CN105778116B - PEG- acrylate dendritic polymer and preparation method thereof - Google Patents
PEG- acrylate dendritic polymer and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses PEG- acrylate dendritic polymer and preparation method thereof.The present invention is using acrylate, polyethylene glycol and primary amine thio-alcohol as raw material; by transesterification reaction; the 4.5th generation PEG- acrylate dendritic polymer is prepared in alkene-sulfydryl and the reaction of alkene-double bond click chemistry, wherein using amido protecting group, hydroxyl or carbon-carbon double bond as surface functional group.Dendritic polymer of the present invention has biggish cavity, not only serve as the coated carrier of organic dyestuff, drug and nano inoganic particle, and there is a large amount of functional group on surface, it can be used as additive and the mobile performance for improving product be blended in other polymers, and be used for anti-penetration wastewater disposal antisludging agent, Industrial Catalysis.
Description
Technical field
The present invention relates to a kind of dendritic polymers, and in particular to PEG- acrylate dendritic polymer and preparation method thereof,
The preparation method prepares the quasi polymer using alkene-mercaptan click-reaction and Michael addition reaction.
Background technique
In the same macromolecular combination of dendritic morphology and linear structure for carry medicine and nanocrystal cladding from group
Dress process is brought a possibility that new, and structure has fabulous geometrical symmetry, and the available essence of the volume of molecule, shape
True control.Due to the unique texture of dendritic polymer, so that it is had dendritic polymer low viscosity, high rheological variation and a large amount of ends
A series of unique physics such as end functional group and chemical characteristic, have broad application prospects in fields such as advanced design of material.
And there are still certain deficiencies for the dendritic polymer for the preparation that succeeded at present:
(1) complicated condition synthesized, condition are harsh
The synthesis process of existing dendritic macromolecules needs the reaction process of more stringent reaction condition and complexity, such as
Add that hydrogen, deprotection, high temperature, process is tediously long, needs the processes such as multi step strategy, increases the difficulty of synthesis, limit dendritic macromolecules
MOLECULE DESIGN a possibility that.So these synthesizing mean reaction conditions are strictly the major defects of existing synthesis process.
(2) algebra synthesized is higher, and space bit is bigger, and the defect of branch is more serious
From MOLECULE DESIGN structural level, the dendritic polymer of precision architecture can be designed that.But with branch
The continuous repetition of unit, the steric hindrance of intramolecular constantly increase, and are that molecular structure cannot reach essence to generate some defects
True property.
(3) toxicity of the dendritic polymer containing a large amount of nitrogen-atoms or aromatic ring
Containing a large amount of nitrogen-atoms, into organism after will form cation, the cation and cell on the surface of this macromolecular
The interaction of film surface anion, destroys the biological chemical environment of cell, thus presents certain bio-toxicity.Band
The dendritic polymer of aromatic ring is difficult to be degraded quickly in vivo, it is also difficult to be fully drained, thus be detained in vivo
Time it is elongated, it is unfavorable to organism health.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology, and it is mild to provide a kind of reaction condition, high conversion rate, green
The PEG- acrylate dendritic polymer and preparation method thereof of environmental protection, the dendritic polymer have the spy of low viscosity, high rheological variation
Point.
PEG- acrylate dendritic polymer of the present invention, using acrylate, polyethylene glycol (PEG) and primary amine thio-alcohol as
Raw material, by transesterification reaction, alkene-sulfydryl and the reaction of alkene-double bond click chemistry are prepared and are attached most importance to polyethylene glycol-acrylate
Multiple unit, amido (BOC amido protecting group) surface functional group.Specifically converted with acrylate and PEG by transesterification enzymatic
Alkene-mercaptan and alkene-double bond click-reaction are carried out again, synthesize the PEG- propylene without algebra using by divergent method and convergence hair
Acid esters dendritic polymer branched monomer.PEG- acrylate dendritic polymer, the polymer can be used as organic dyestuff, drug and nothing
The coated carrier of machine nanoparticle, the mobility of high molecular polymer blending and modifying adjust additive, anti-penetration wastewater disposal scale inhibition
Agent.
The object of the invention is achieved through the following technical solutions:
PEG- acrylate dendritic polymer has the following structure formula, and the amplifier chain segment table on the left side shows dendritic polymerization in formula
The bottom end of object, the amplifier chain segment table on the right show the branch of dendritic polymer, and the end of the branch of end is amido protecting group-
NHBoc, the structure of other branches at different levels is all the same as the amplification segment on the right；
R1Indicate hydrogen bond or methyl, R2Expression-CH2CH2Or-CH2CH2CH2-；The value of n is 3~20.
Preferably, the molecular weight of the PEG- acrylate dendritic polymer is 1.3 ten thousand~70,000.
Preferably, the PEG- acrylate dendritic polymer is NHBoc for the end group of product Gn, and end group number Ne isInternal layer number of repeat unit Nr isWherein,Show that branching connects branch's number NbN-1 power, wherein n indicate
The algebra of synthesis, n=1,2,3,4,5, b indicate branch.
Preferably, the branching of the PEG- acrylate dendritic polymer connects branch's number NbIt is 2.
Preferably, the PEG- acrylate dendritic polymer is for the half of product for product GmEnd group one end be hydroxyl
Base, the other end are amido protecting group, and end group number Ne isInternal layer number of repeat unit Nr is Indicate branch
Change connection branch's number NbM-0.5 power, wherein m indicate synthesis algebra, m=1.5,2.5,3.5,4.5, b indicate branch.
The preparation method of the PEG- acrylate dendritic polymer, comprising the following steps:
(1) transesterification reaction prepares raw material polyethylene glycol methacrylate-styrene polymer: first with the meter of substance, by 1 part of poly- second two
Alcohol is dissolved in organic solvent, is configured to the solution of 0.3~1.5mmol/mL, and 1~5 part of acrylate is then added, stirs evenly
Afterwards, transesterification enzyme is added, the transesterification of 5~15mg is added in every milliliter of solution, and 30~70 DEG C of stirrings are lower to react 24~48h；Reaction terminates
Afterwards, filtering vacuum distillation, remaining liq are eluted by chromatography, the eluant, eluent of petrol ether/ethyl acetate, obtain product
For polyethylene glycol acrylate；
(2) click-reaction prepares branched monomer 1: with the meter of substance, 1 part of polyethylene glycol acrylic monoester being dissolved in polarity
In organic solvent, the solution for becoming 2~20mmol/mL is prepared, it is organic molten that 1~5 part of sulfydryl primary amine compound is dissolved in polarity
In agent, the solution for becoming 2~20mmol/mL is prepared, and 0~3 part of basic catalyst is added；It is passed through argon gas, carries out deoxygenation；In room
2~10h is stirred to react under temperature；After reaction, vacuum distillation removes organic phase under the conditions of 30~50 DEG C, and remaining liq passes through
Column chromatography for separation, is eluted with the eluant, eluent of ethyl acetate/methanol, and product branched monomer 1 is obtained after vacuum drying；
(3) click-reaction prepares branched monomer 2: with the meter of substance, 1 part of polyethylene glycol acrylic monoester being dissolved in polarity
In organic solvent, the solution for becoming 2~20mmol/mL is prepared, 1~6 part of Boc- amineothiot class compound, which is dissolved in polarity, to be had
In solvent, the solution for becoming 2~20mmol/mL is prepared, and 0~3 part of basic catalyst is added；Deoxygenation；It is stirred at room temperature
React 2~10h；After reaction, vacuum distillation removes organic phase under the conditions of 30~50 DEG C, and remaining liq passes through column chromatography point
From the eluant, eluent of ethyl acetate/methanol is eluted, and product branched monomer 2 is obtained after vacuum drying；
(4) the branch G0.5 of dendritic polymer is prepared: with the meter of substance, the product branching list that 1 part of step (2) is obtained
Body 1 is dissolved in organic solvent, prepares the solution for becoming 0.1~10mmol/mL, and 0~3 part of acid binding agent is added；Then by 1~5
Part acryloyl chloride is dissolved in organic solvent, the solution for becoming 0.1~10mmol/mL is prepared, under agitation by acryloyl chloride
Solution is injected into 2 solution of branched monomer, and 12~36h is reacted under 20~60 DEG C of stirring conditions, after reaction, reaction solution decompression
Distillation, remaining liq obtain quasi- branch G0.5 (the 0.5th generation branched structure) by silica gel post separation；
(5) the branch G1.5 of dendritic polymer is prepared: with the meter of substance, the product branching list that 1 part of step (2) is obtained
Body 1 is dissolved in organic solvent, prepares the solution for becoming 0.1~10mmol/mL, and 0~3 part of basic catalyst is added；Then will
The quasi- branch G0.5 that 0.5~5 part of step (4) obtains is dissolved in organic solvent, prepares the solution for becoming 0.1~10mmol/mL,
1 solution of branched monomer is added dropwise in quasi- branch G0.5 solution under stirring condition, after reaction, reaction solution vacuum distillation is remaining
Liquid obtains branch G1.5 (the 1.5th generation branched structure) by silica gel post separation；
(6) it prepares the branch G2.5 of dendritic polymer: with the meter of substance, 1 part of G1.5 being taken to be dissolved in organic solvent, prepare
As the solution of 0.1~10mmol/mL, 0~3 part of acid binding agent injects 1~5 part of acryloyl chloride with syringe, after injection,
12~36h is stirred at room temperature, and after reaction, filtering, vacuum distillation removes solvent, is removed with methylene chloride and water extraction water-soluble
Property impurity, oil reservoir liquid obtains product by column chromatography for separation；It takes 1 part of above-mentioned product to be dissolved in organic solvent, takes 0.5~5 part
Branched monomer 1 is dissolved in organic solvent, 0~3 part of basic catalyst, and 60~100h is stirred at 20~60 DEG C, after reaction, with
Petrol ether/ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains branch G2.5 (the 2.5th generation branch knot
Structure)；
(7) it prepares the branch G3.5 of dendritic polymer: first with the meter of substance, 1 part of G2.5 being taken to be dissolved in organic solvent,
The solution for becoming 0.1~10mmol/mL is prepared, 0~3 part of acid binding agent injects 1~5 part of acryloyl chloride with syringe, and injection finishes
Afterwards, 12~36h is stirred at room temperature, and after reaction, filtering, vacuum distillation removes solvent, is removed with methylene chloride and water extraction
Water-solubility impurity, oil reservoir liquid obtain product by column chromatography for separation；It takes 1 part of the product to be dissolved in organic solvent, takes 0.5
~5 parts of branched monomers 1 are dissolved in organic solvent, 0~3 part of basic catalyst, and 60~100h is stirred at 20~60 DEG C, and reaction terminates
Afterwards, eluant, eluent is made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, obtain product G3.5 branched structure
(the 3.5th generation branched structure)；
(8) it prepares the branch G4.5 of dendritic polymer: with the meter of substance, 1 part of G3.5 being taken to be dissolved in organic solvent, prepare
As the solution of 0.1~10mmol/mL, 0~3 part of acid binding agent injects 1~5 part of acryloyl chloride with syringe, after injection,
12~36h is stirred at room temperature, and after reaction, filtering, vacuum distillation removes solvent, is removed with methylene chloride and water extraction water-soluble
Property impurity, oil reservoir liquid obtains product by column chromatography for separation；It takes 1 part of the product to be dissolved in organic solvent, takes 0.5~5 part
Branched monomer 1 is dissolved in organic solvent, 0~3 part of basic catalyst, and 60~100h is stirred at 20~60 DEG C, after reaction, with
Petrol ether/ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains branch G4.5 (the 4.5th generation branch knot
Structure).
Preferably, the average molecular weight of the polyethylene glycol is 200-1000.
Preferably, the acrylate is methyl methacrylate, ethyl methacrylate, methyl acrylate or third
Olefin(e) acid ethyl ester.
Preferably, the transesterification enzyme is Novozyme 435, and the organic solvent is ether, methylene chloride and tetrahydrofuran
One of or it is a variety of；The basic catalyst is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium methoxide, sodium ethoxide, triethylamine
With one of pyridine or a variety of；The polar organic solvent is one kind of methanol, ethyl alcohol, ether, methylene chloride and tetrahydrofuran
Or it is a variety of；The sulfydryl primary amine compound include mercaptoethylmaine, to sulfydryl phenyl ethylamine, 3- sulfydryl -1- propylamine and its they
One of hydrochloride is a variety of.
Preferably, the sulfydryl primary amine compound is 2- (Boc- amino) ethyl mercaptan and 3- mercapto-propyl-(Boc- ammonia
Base) one of or it is a variety of；The acid binding agent include one of triethylamine, pyridine, n,N-diisopropylethylamine, potassium carbonate or
It is a variety of.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the PEG- acrylate dendritic polymer of preparation of the invention combines the advantage of convergence method and divergent method, first
Afterwards should be with alkene-sulfydryl and alkene-double bond click-reaction using transesterification hair, reaction condition is mild, and molecular structure is accurate, conversion ratio
Height, it is environmentally protective.
(2) the PEG- acrylate dendritic polymer of preparation of the invention, relative to traditional dendritic height of polyamidoamine
For molecule (PAMAM) etc., the content of nitrogen-atoms in molecular structure is greatly reduced, to reduce its bio-toxicity.
(3) the PEG- acrylate dendritic polymer of preparation of the invention is the combination of dendritic morphology and linear structure, tool
Standby dendritic polymer have a series of unique physics such as biggish cavity, low viscosity, high rheological variation and a large amount of functional end-groups and
Chemical characteristic, acts not only as the coated carrier of organic dyestuff, drug and inorganic nano-particle, and as additive and
The mobile performance for improving product is blended in other polymers, and in anti-penetration wastewater disposal antisludging agent, Industrial Catalysis and petrochemical industry
Equal advanced materials design field has broad application prospects.
Detailed description of the invention
Fig. 1 is the 4.5th generation of embodiment 1 branch's nuclear structure magnetic carbon spectrogram.
Specific embodiment
The present invention will be further described with reference to embodiments, but the scope of protection of present invention is not limited to reality
Apply the range of example statement.In embodiment, the volume of petroleum ether and ethyl acetate in eluent petroleum ether/ethyl acetate mix reagent
Than 30~40:1.
Embodiment 1
(1) preparation of PEG200 monomethacrylate acid monoester: taking 3g PEG200 to be dissolved in 15mL tetrahydrofuran, is added
435,50 DEG C of stirring constant temperature magnetic force of 2.5g methyl methacrylate and 150mg Novozyme react 25 hours under the conditions of stirring.Instead
It should be tracked in the process using thin-layered chromatography, after reaction, be filtered to remove transesterification enzyme, filtrate is depressurized with Rotary Evaporators
Solvent is distilled off, eluant, eluent is then made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, is obtained
PEG200 monomethacrylates product is weak yellow liquid, average molecular weight 270g/mol.
(2) preparation of branched monomer 1: PEG200 methacrylic monoesters 2.7g is dissolved in 5mL tetrahydrofuran, is added
0.50g catalyst sodium hydroxide, 1.3g mercaptoethylamine hydrochloride are passed through argon gas, and reaction 4h is stirred at room temperature.Reaction terminates
Afterwards, product is extracted with methylene chloride and water, (is verified with thin-layer chromatography) until there is no mercaptoethylamine hydrochloride in water.With nothing
Water magnesium sulfate removes the moisture in organic phase.Organic phase under the conditions of 30 DEG C after revolving water removal, obtains branching after vacuum drying
1 product of monomer is weak yellow liquid, average molecular weight 340g/mol.
(3) preparation of branched monomer 2: PEG200 methacrylic monoesters 2.7g is dissolved in 5mL tetrahydrofuran, is added
0.50g catalyst sodium hydroxide, 1.8g 2- (Boc- amino) ethyl mercaptan, is passed through argon gas, and reaction 5h is stirred at room temperature.Reaction
After, eluant, eluent is made for the petrol ether/ethyl acetate mix reagent of 35:1 with volume ratio, is separated by silica gel column chromatography.?
It is weak yellow liquid, average molecular weight 450g/mol to 2 product of branched monomer.
The preparation of (4) the 0.5th generation branched structures: taking 0.45g branched monomer 2 to be dissolved in 1.5mL methylene chloride, 0.14g carbon
Sour potassium injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h at room temperature, after reaction, filters, decompression
Solvent is distilled off, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid is first evaporated under reduced pressure to be chromatographed by column afterwards
Separation, obtains G0.5 branch (the 0.5th generation branched structure), is weak yellow liquid, average molecular weight 500g/mol.
The preparation of (5) the 1.5th generation branched structures: taking 0.5g G0.5 to be dissolved in methylene chloride, takes 0.4g branched monomer 1 molten
In methylene chloride, 0.05g catalyst sodium hydroxide is added, 50h is stirred at 50 DEG C, after reaction, after reaction, with body
Product is separated by silica gel column chromatography than being that the petrol ether/ethyl acetate mix reagent of 35:1 makees eluant, eluent, obtains G1.5 branch
(the 1.5th generation branched structure) is weak yellow liquid, molecular weight 1300g/mol.
The preparation of (6) the 2.5th generation branched structures: taking 1.3g G1.5 branched structure to be dissolved in methylene chloride, 0.014g carbonic acid
Potassium injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h at room temperature, and after reaction, filtering, decompression is steamed
Solvent is removed in distillation, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid obtains product by column chromatography for separation.
It takes above-mentioned product 1.31g to be dissolved in 2ml methylene chloride, 0.35g branched monomer 1 is taken to be dissolved in 2ml methylene chloride, 0.05g catalysis
Agent sodium hydroxide stirs 60h at 50 DEG C, after reaction, is made with the petrol ether/ethyl acetate mix reagent that volume ratio is 35:1
Eluant, eluent is separated by silica gel column chromatography, obtains G1.5 branch (the 2.5th generation branched structure), is weak yellow liquid, and molecular weight is
3000g/mol。
The preparation of (7) the 3.5th generation branched structures: taking 0.3g G2.5 branched structure to be dissolved in 1ml methylene chloride, is added
0.014g potassium carbonate injects 0.012g acryloyl chloride with syringe, after injection, stirs 10h at room temperature, after reaction,
Filtering, vacuum distillation remove solvent, remove water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid passes through column chromatography point
From obtaining product.It takes above-mentioned product 0.31g to be dissolved in 1ml methylene chloride, 0.04g branched monomer 1 is taken to be dissolved in 1ml methylene chloride
In, 0.005g catalyst sodium hydroxide stirs 70h at 50 DEG C, is petroleum ether/acetic acid of 35:1 with volume ratio after reaction
Ethyl ester mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains G3.5 branch (the 3.5th generation branched structure), molecular weight
For 6500g/mol.
The preparation of (8) the 4.5th generation branched structures: taking 0.65g G3.5 branch to be dissolved in methylene chloride, and 0.014g carbon is added
Sour potassium injects 0.012g acryloyl chloride with syringe, after injection, stirs 10h at room temperature, after reaction, filters, decompression
Solvent is distilled off, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid is produced by column chromatography for separation
Object.It takes above-mentioned product 0.66g to be dissolved in methylene chloride, 0.04g branched monomer 1 is taken to be dissolved in methylene chloride, 0.005g catalyst
Sodium hydroxide is stirred 80h at 50 DEG C, after reaction, is washed with volume ratio for the petrol ether/ethyl acetate mix reagent of 35:1
De- agent, is separated by silica gel column chromatography, and obtaining product G4.5 branched structure, (the 4.5th generation branched structure, nuclear-magnetism carbon spectrum are shown in figure
1), molecular weight 13452g/mol.The nuclear-magnetism carbon spectrum of 4.5th generation branched structure is shown in Fig. 1.As shown in Figure 1,175.10ppm,
Three characteristic peaks at 172.3ppm and 155.75ppm belong on acrylate respectively and amido protecting group on carbonyl (C=O)
Carbon；Characteristic peak at 28.38ppm belongs to the carbon of end group methyl, the carbon of methyl on the characteristic peak ownership side chain at 16.82ppm；With
The characteristic peak for first methylene that two ester groups are connected is 72.59ppm and 63.71ppm；69.10ppm be belong to
Second mesomethylene carbon that ester group is connected, 70.28ppm~70.68ppm belong to remaining methylene on peg molecule chain
Carbon on base.
PEG- acrylate dendritic polymer manufactured in the present embodiment combines the advantage of convergence method and divergent method, successively makes
With transesterification hair should with alkene-sulfydryl and alkene-double bond click-reaction because the reaction of primary amine and acrylate can low temperature even
It is reacted under room temperature, mild condition；The product that every single step reaction obtains carries out column separation, and molecular structure is controllable, so molecule knot
Structure is accurate；Sulfydryl-strong the selectivity of vinyl click-reaction, side reaction is few in reaction process, high conversion rate；Reaction process does not have
Environmentally harmful substance is generated, it is environmentally protective.4.5th generation PEG- acrylate dendritic polymer architecture of the present embodiment synthesis
Formula is following formula 2.
Branched structure right structure in equation 2 aboveRepresent the repetitive structure between N-N, left structureGeneration
The bottom terminal portion of table dendritic polymer.
Fan-shaped in the branched structure conformation of the present embodiment dendritic polymerization, dendritic polymer itself has biggish sky
A series of unique physics such as chamber, low viscosity, high rheological variation and a large amount of functional end-groups and chemical characteristic.The polymerization of this spline structure
Object acts not only as the coated carrier of organic dyestuff, drug and inorganic nano-particle, and poly- with other as additive
It closes object and the mobile performance for improving product is blended, and is advanced in anti-penetration wastewater disposal antisludging agent, Industrial Catalysis and petrochemical industry etc.
Design of material field has broad application prospects.PEG- acrylate dendritic polymer manufactured in the present embodiment, relative to biography
For dendritic macromolecule of the polyamidoamine of system (PAMAM) etc., the content of nitrogen-atoms in molecular structure is greatly reduced, thus
Reduce its bio-toxicity.
The present embodiment dendritic polymer itself has cavity structure, can coat organic matter and inorganic matter.The present embodiment obtains
The product end group arrived is amido protecting group (- NHBOC).If the polymer is subjected to amido protection group reaction, and
The polymer that available end after Michael's addition etc. is reacted is hydroxyl is carried out with polyethylene glycol methacrylate-styrene polymer.
The present embodiment dendritic polymer has biggish cavity, not only serves as organic dyestuff, drug and inorganic nanoparticles
The coated carrier of son, and there is a large amount of functional group on surface, can be used as additive and the stream for improving product is blended in other polymers
Dynamic performance, and it is used for anti-penetration wastewater disposal antisludging agent, Industrial Catalysis.
Embodiment 2
(1) preparation of PEG400 monomethacrylates: taking 6g PEG400 to be dissolved in 15mL tetrahydrofuran, and 2.5g is added
435,50 DEG C of stirring constant temperature magnetic force of methyl methacrylate and 150mg Novozyme react 25 hours under the conditions of stirring.It reacted
It is tracked in journey using thin-layered chromatography, after reaction, is filtered to remove transesterification enzyme, filtrate is evaporated under reduced pressure with Rotary Evaporators
Solvent is removed, eluant, eluent is then made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, PEG200 is obtained
Monomethacrylates product is weak yellow liquid, average molecular weight 470g/mol.
(2) preparation of branched monomer 1: PEG400 methacrylic monoesters 4.7g is dissolved in 50mL methanol, 1.0g sulfydryl
Ethamine is passed through argon gas, and reaction 3h is stirred at room temperature.After reaction, product is extracted with methylene chloride and water, until not having in water
Have and (is verified with thin-layer chromatography) until mercaptoethylmaine salt.The moisture in organic phase is removed with anhydrous magnesium sulfate.Under the conditions of 30 DEG C
Organic phase after revolving water removal, obtains 1 product of branched monomer after vacuum drying, be weak yellow liquid, average molecular weight 547g/
mol。
(3) preparation of branched monomer 2: PEG400 methacrylic monoesters 4.7g is dissolved in 50mL methanol, and 1.1g is added
Catalyst sodium carbonate, 1.8g 2- (Boc- amino) ethyl mercaptan, is passed through argon gas, and reaction 3h is stirred at room temperature.After reaction,
Make eluant, eluent with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography.2 product of branched monomer is obtained, is yellowish
Color liquid, average molecular weight 647g/mol.
The preparation of (4) the 0.5th generation branched structures: taking 0.45g branched monomer 2 to be dissolved in 1.5mL methylene chloride, is added
0.12g acid binding agent triethylamine injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h at room temperature, reaction terminates
Afterwards, the triethylamine hydrochloride that filtering reaction generates, vacuum distillation remove solvent, remove remaining three second with methylene chloride and water extraction
Amine and triethylamine salt, oil reservoir liquid is first evaporated under reduced pressure passes through column chromatography for separation afterwards, obtains product G0.5 branched structure (the 0.5th generation
Branched structure), it is weak yellow liquid, average molecular weight 700g/mol.
The preparation of (5) the 1.5th generation branched structures: taking 0.5g G0.5 to be dissolved in methylene chloride, and 0.4g monomer 1 is taken to be dissolved in two
In chloromethanes, 0.1g catalyst sodium carbonate stirs 50h at 50 DEG C, after reaction, after reaction, with petroleum ether/acetic acid
Ethyl ester mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G1.5 branched structure (the 1.5th generation branch knot
Structure), it is weak yellow liquid, molecular weight 1950g/mol.
The preparation of (6) the 2.5th generation branched structures: taking 1.3g G1.5 branched structure to be dissolved in methylene chloride, and 0.12g is added
Acid binding agent triethylamine injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h, after reaction, mistake at room temperature
The triethylamine hydrochloride that filter reaction generates, vacuum distillation remove solvent, with methylene chloride and water extraction remove remaining triethylamine and
Triethylamine salt, oil reservoir liquid obtain product by column chromatography for separation.It takes above-mentioned product 1.31g to be dissolved in 2ml methylene chloride, takes
0.35g branched monomer 1 is dissolved in 2ml methylene chloride, and 0.1g catalyst sodium carbonate is added, stirs 60h at 50 DEG C, reaction terminates
Afterwards, eluant, eluent is made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, obtain product G2.5 branched structure
(the 2.5th generation branched structure) is weak yellow liquid, molecular weight 4565g/mol.
The preparation of (7) the 3.5th generation branched structures: taking 0.3g G2.5 branched structure to be dissolved in 1ml methylene chloride, is added
0.012g acid binding agent triethylamine injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h, reaction knot at room temperature
Shu Hou, the triethylamine hydrochloride that filtering reaction generates, vacuum distillation remove solvent, remove residue three with methylene chloride and water extraction
Ethamine and triethylamine salt, oil reservoir liquid obtain product by column chromatography for separation.Above-mentioned product 0.31g is taken to be dissolved in 1ml methylene chloride
In, it takes 0.04g branched monomer 1 to be dissolved in 1ml methylene chloride, 0.01g catalyst sodium carbonate is added, stirs 70h at 50 DEG C, reacts
After, eluant, eluent is made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, product G3.5 branch is obtained
Structure (the 3.5th generation branched structure), molecular weight 9780g/mol.
The preparation of (8) the 4.5th generation branched structures: taking 0.65g G3.5 branched structure to be dissolved in methylene chloride, is added
0.012g acid binding agent triethylamine injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h, reaction knot at room temperature
Shu Hou, after reaction, the triethylamine hydrochloride that filtering reaction generates, vacuum distillation remove solvent, are extracted with methylene chloride and water
Remaining triethylamine and triethylamine salt are removed, oil reservoir liquid obtains product by column chromatography for separation.Take above-mentioned product 0.66g molten
In methylene chloride, 0.04g branched monomer 1 is taken to be dissolved in methylene chloride, 0.01g catalyst sodium carbonate is added, is stirred at 50 DEG C
80h makees eluant, eluent with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, obtain product after reaction
G4.5 branched structure (the 4.5th generation branched structure), obtains product G4.5 branched structure, molecular weight 20230g/mol.
The present embodiment product is in structure and the difference of embodiment 1, the first monomer concentration in synthesizing branched monomer
Difference, 2 monomer concentration of embodiment are 2mmol/mL, and embodiment 1 is 20mmol/mL；The molecular weight of next reaction raw materials PEG is not
Together, embodiment 2 is PEG400, and embodiment 1 is PEG200, so the polymer molecular weight that the former synthesizes every generation is bigger than the latter.
The product structure that the present embodiment obtains is substantially similar compared with formula 2, and the main distinction is small point of each of branched structure
The average molecular weight of branch PEG chain segment is 400, therefore comparing the main distinction with Fig. 1 is first Asia being connected with two ester groups
The relative intensity of the ownership methyl peak 28.38ppm of the characteristic peak 72.59ppm and 63.71ppm and end group amido protecting group of methyl
It is opposite to become larger.
Embodiment 3
It the use of PEG600, methyl methacrylate, 3- sulfydryl -1- propylamine is raw material, basic catalyst is sodium methoxide, ties up acid
Agent n,N-diisopropylethylamine, tetrahydrofuran or methylene chloride prepare PEG- acrylate dendritic polymer, system as solvent
Preparation Method is as follows:
(1) preparation of PEG600 monomethacrylates: taking 9g PEG 600 to be dissolved in 15mL tetrahydrofuran, and 2.5g is added
435,50 DEG C of stirring constant temperature magnetic force of methyl methacrylate and 150mg Novozyme react 25 hours under the conditions of stirring.It reacted
It is tracked in journey using thin-layered chromatography, after reaction, is filtered to remove transesterification enzyme, filtrate is evaporated under reduced pressure with Rotary Evaporators
Solvent is removed, eluant, eluent is then made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, PEG600 is obtained
Monomethacrylates product is weak yellow liquid, average molecular weight 670g/mol.
(2) preparation of branched monomer 1: PEG600 monomethacrylate acid monoester 6.7g is dissolved in 3mL dimethyl sulfoxide, is added
Enter 0.8g catalyst sodium methoxide, 0.92g 3- sulfydryl -1- propylamine is passed through argon gas, and reaction 3h is stirred at room temperature.Reaction terminates
Afterwards, product is extracted with methylene chloride and water, (is verified with thin-layer chromatography) until there is no mercaptoethylamine hydrochloride in water.With nothing
Water magnesium sulfate removes the moisture in organic phase.Organic phase under the conditions of 30 DEG C after revolving water removal, obtains branching after vacuum drying
1 product of monomer is weak yellow liquid, average molecular weight 762g/mol.
(3) preparation of branched monomer 2: PEG600 monomethacrylate acid monoester 2g is dissolved in 3mL dimethyl sulfoxide, is added
0.8g catalyst sodium methoxide, 2.0g 3- mercapto-propyl-(Boc- amino), is passed through argon gas, and reaction 5h is stirred at room temperature.Reaction
After, eluant, eluent is made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography.Obtain the production of branched monomer 2
Object is weak yellow liquid, average molecular weight 860g/mol.
The preparation of (4) the 0.5th generation branched structures: taking 0.85g branched monomer 2 to be dissolved in 2mL methylene chloride, and 0.13g is added
Acid binding agent n,N-diisopropylethylamine injects 0.12g g acryloyl chloride with syringe, after injection, stirs 10h at room temperature,
After reaction, it filters, vacuum distillation removes solvent, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid is first
By column chromatography for separation after vacuum distillation, product G0.5 branched structure (the 0.5th generation branched structure) is obtained, is weak yellow liquid,
Average molecular weight is 918g/mol.
The preparation of (5) the 1.5th generation branched structures: taking 0.9g G0.5 to be dissolved in methylene chloride, and 0.75g monomer 1 is taken to be dissolved in two
In chloromethanes, 0.08g catalyst sodium methoxide is added, stirs 50h at 50 DEG C, after reaction, after reaction, with petroleum ether/
Ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G1.5 branched structure (the 1.5th generation branch
Structure), it is weak yellow liquid, molecular weight 2600g/mol.
The preparation of (6) the 2.5th generation branched structures: taking 2.55g G1.5 branched structure to be dissolved in methylene chloride, and 0.13g is added
Acid binding agent n,N-diisopropylethylamine injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h at room temperature, instead
After answering, filtering, vacuum distillation removes solvent, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid passes through
Column chromatography for separation obtains product.It takes above-mentioned product 2.65g to be dissolved in 2ml methylene chloride, 0.8g branched monomer 1 is taken to be dissolved in 2ml bis-
In chloromethanes, 0.08g catalyst sodium methoxide is added, stirs 58h at 50 DEG C, after reaction, is mixed with petrol ether/ethyl acetate
Reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G2.5 branched structure (the 2.5th generation branched structure), molecular weight
For 6070g/mol.
The preparation of (7) the 3.5th generation branched structures: taking 0.6g G2.5 branched structure to be dissolved in 4ml methylene chloride, is added
0.013g acid binding agent n,N-diisopropylethylamine is injected 0.012g acryloyl chloride with syringe, after injection, is stirred at room temperature
12h, after reaction, filtering, vacuum distillation remove solvent, remove water-solubility impurity, oil reservoir liquid with methylene chloride and water extraction
By column chromatography for separation, product is obtained.It takes above-mentioned product 4g to be dissolved in 4ml methylene chloride, 0.08g branched monomer 1 is taken to be dissolved in 1ml
In methylene chloride, 0.008g catalyst sodium methoxide is added, 70h is stirred at 50 DEG C, after reaction, with petrol ether/ethyl acetate
Mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G3.5 branched structure (the 3.5th generation branched structure), point
Son amount is 13000g/mol.
The preparation of (8) the 4.5th generation branched structures: taking 1.28g G3.5 branched structure to be dissolved in methylene chloride, and 0.13g is added
Acid binding agent n,N-diisopropylethylamine injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h at room temperature, instead
After answering, after reaction, filtering, vacuum distillation removes solvent, removes water-solubility impurity, oil with methylene chloride and water extraction
Layer liquid obtains product by column chromatography for separation.It takes above-mentioned product 1.29g to be dissolved in methylene chloride, takes 0.08g branched monomer 1
It is dissolved in methylene chloride, 0.008g catalyst sodium methoxide is added, 80h is stirred at 50 DEG C, after reaction, with petroleum ether/acetic acid
Ethyl ester mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G4.5 branched structure (the 4.5th generation branch knot
Structure), molecular weight 26902g/mol.
This example product in structure with the difference of embodiment 1: first in sulfydryl vinyl reaction raw materials it is different, it is real
Applying example 1 is mercaptoethylamine hydrochloride, and embodiment 3 is 3- sulfydryl -1- propylamine, and the branched structure synthesized thus is different；
The product structure that the present embodiment obtains and formula 2 are unanimous on the whole, and the main distinction is each subbranch PEG of branched structure
The average molecular weight of segment is the feature that 400 and Fig. 1 compares that the main distinction is first methylene being connected with two ester groups
The relative intensity of peak 72.59ppm and 63.71ppm and the ownership methyl peak 28.38ppm of end group amido protecting group are varied, N
The ownership peak of more methylene between S.
Secondly reaction raw materials PEG molecular weight is different, and embodiment 3 is PEG600, and embodiment 1 is PEG200, so the former closes
It is bigger than the latter at the polymer molecular weight of every generation.
Embodiment 4
It the use of PEG800, methyl methacrylate, mercaptoethylmaine (mercaptoethylamine hydrochloride) is raw material, sodium ethoxide is alkalinity
Catalyst, pyridine is as acid binding agent and tetrahydrofuran or methylene chloride as solvent preparation PEG- acrylate dendritic polymerization
Object, the preparation method is as follows:
(1) preparation of PEG800 monomethacrylates: taking 12g PEG800 to be dissolved in 15mL tetrahydrofuran, and 2.5g is added
435,50 DEG C of stirring constant temperature magnetic force of methyl methacrylate and 150mg Novozyme react 25 hours under the conditions of stirring.It reacted
It is tracked in journey using thin-layered chromatography, after reaction, is filtered to remove transesterification enzyme, filtrate is evaporated under reduced pressure with Rotary Evaporators
Solvent is removed, eluant, eluent is then made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, PEG800 is obtained
Monomethacrylates product is weak yellow liquid, average molecular weight 870g/mol.
(2) preparation of branched monomer 1: being dissolved in 10mL dimethylformamide for PEG800 monomethacrylate acid monoester 8.7g,
0.7g catalyst sodium ethoxide is added, 1.3g mercaptoethylamine hydrochloride is passed through argon gas, and reaction 3h is stirred at room temperature.Reaction terminates
Afterwards, product is extracted with methylene chloride and water, (is verified with thin-layer chromatography) until there is no mercaptoethylamine hydrochloride in water.With nothing
Water magnesium sulfate removes the moisture in organic phase.Organic phase under the conditions of 30 DEG C after revolving water removal, obtains branching after vacuum drying
1 product of monomer is weak yellow liquid, average molecular weight 947g/mol.
(3) preparation of branched monomer 2: being dissolved in 3mL dimethylformamide for PEG800 monomethacrylate acid monoester 2g, is added
0.7g catalyst sodium ethoxide, 1.8g 2- (Boc- amino) ethyl mercaptan, is passed through argon gas, and reaction 3h is stirred at room temperature.Reaction terminates
Afterwards, eluant, eluent is made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography.2 product of branched monomer is obtained, is
Weak yellow liquid, average molecular weight 1047g/mol.
The preparation of (4) the 0.5th generation branched structures: taking 1.05g branched monomer 2 to be dissolved in 3mL methylene chloride, and 0.08g is added
Acid binding agent pyridine injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h at room temperature, after reaction, decompression
Solvent is distilled off, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid is first evaporated under reduced pressure to be chromatographed by column afterwards
Separation, obtains product G0.5 branched structure (the 0.5th generation branched structure), is weak yellow liquid, average molecular weight 1103g/
mol。
The preparation of (5) the 1.5th generation branched structures: taking 1.1g G0.5 to be dissolved in methylene chloride, and 1g monomer 1 is taken to be dissolved in dichloro
In methane, 0.07g catalyst sodium ethoxide is added, 50h is stirred at 50 DEG C, after reaction, after reaction, with petroleum ether/second
Acetoacetic ester mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G1.5 branched structure (the 1.5th generation branch knot
Structure), molecular weight 3153g/mol.
The preparation of (6) the 2.5th generation branched structures: taking 3.2g G1.5 branched structure to be dissolved in methylene chloride, and 0.08g is added
Acid binding agent pyridine injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h, after reaction, mistake at room temperature
It filters, vacuum distillation removes solvent, removes water-solubility impurity with methylene chloride and water extraction, and oil reservoir liquid passes through column chromatography for separation,
Obtain product.It takes above-mentioned product 3.3g to be dissolved in 2ml methylene chloride, 1g branched monomer 1 is taken to be dissolved in 2ml methylene chloride, be added
0.07g catalyst sodium ethoxide is stirred 60h at 50 DEG C, after reaction, is eluted with petrol ether/ethyl acetate mix reagent
Agent is separated by silica gel column chromatography, obtains product G2.5 branched structure (the 2.5th generation branched structure), molecular weight 7365g/
mol。
The preparation of (7) the 3.5th generation branched structures: taking 0.7g G2.5 branched structure to be dissolved in 1ml methylene chloride, is added
0.01g acid binding agent pyridine injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h at room temperature, reaction terminates
Afterwards, it filters, vacuum distillation removes solvent, is removed with methylene chloride and water extraction and is removed water-solubility impurity, oil reservoir liquid passes through column
Chromatography obtains product.It takes above-mentioned product 0.71g to be dissolved in 1ml methylene chloride, 0.1g branched monomer 1 is taken to be dissolved in 1ml dichloro
In methane, 0.007g catalyst sodium ethoxide is added, stirs 70h at 50 DEG C, after reaction, is mixed with petrol ether/ethyl acetate
Reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G3.5 branched structure (the 3.5th generation branched structure), molecular weight
For 15789g/mol.
The preparation of (8) the 4.5th generation branched structures: taking 1.6g G3.5 branched structure to be dissolved in methylene chloride, and 0.01g is added
Acid binding agent pyridine injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h at room temperature, after reaction, instead
After answering, filtering, vacuum distillation removes solvent, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid passes through
Column chromatography for separation obtains product.It takes above-mentioned product 1.61g to be dissolved in methylene chloride, 0.1g branched monomer 1 is taken to be dissolved in methylene chloride
In, 0.007g catalyst sodium ethoxide is added, 80h is stirred at 50 DEG C, after reaction, with petrol ether/ethyl acetate mix reagent
Make eluant, eluent, separated by silica gel column chromatography, obtains product G4.5 branched structure (the 4.5th generation branched structure), molecular weight is
32637g/mol。
The present embodiment product is in structure and the difference of embodiment 1 is that reaction raw materials PEG molecular weight is different, embodiment 4
For PEG800, embodiment 1 is PEG200, so the polymer molecular weight that the former synthesizes every generation is bigger than the latter.The present embodiment obtains
The product structure arrived and formula 2 are unanimous on the whole, and the main distinction is that the average molecular weight of each subbranch PEG chain segment of branched structure is
400 and Fig. 1 compared to the main distinction be first methylene being connected with two ester groups characteristic peak 72.59ppm and
The relative intensity of 63.71ppm and the ownership methyl peak 28.38ppm of end group amido protecting group are varied.
Embodiment 5
Using PEG1000, ethyl methacrylate, 3- sulfydryl -1- propylamin hydrochloride be raw material, triethylamine be catalyst and
Tetrahydrofuran or methylene chloride prepare PEG- acrylate dendritic polymer as solvent, the preparation method is as follows:
(1) preparation of PEG1000 acrylate: taking 15g PEG1000 to be dissolved in 15mL tetrahydrofuran, and 2.5g methyl is added
435,50 DEG C of stirring constant temperature magnetic force of methyl acrylate and 150mg Novozyme react 25 hours under the conditions of stirring.In reaction process
It is tracked using thin-layered chromatography, after reaction, is filtered to remove transesterification enzyme, filtrate is evaporated under reduced pressure with Rotary Evaporators and is removed
Then solvent is made eluant, eluent with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, PEG1000 propylene is obtained
Acid esters product is weak yellow liquid, average molecular weight 1070g/mol.
(2) preparation of branched monomer 1: PEG1000 monomethacrylate acid monoester 1.07g is dissolved in 7mL dimethyl sulfoxide,
0.9g catalyst sodium ethoxide is added, 1.3g 3- sulfydryl -1- propylamin hydrochloride is passed through argon gas, and reaction 3h is stirred at room temperature.Instead
After answering, product is extracted with methylene chloride and water, (is tested with thin-layer chromatography until not having mercaptoethylamine hydrochloride in water
Card).The moisture in organic phase is removed with anhydrous magnesium sulfate.Organic phase under the conditions of 30 DEG C after revolving water removal, after vacuum drying
1 product of branched monomer is obtained, is weak yellow liquid, average molecular weight 1160g/mol.
(3) preparation of branched monomer 2: PEG1000 monomethacrylate acid monoester 2g is dissolved in 3mL dimethyl sulfoxide, is added
Enter 1.2g catalyst of triethylamine, 1.8g 2- (Boc- amino) ethyl mercaptan is passed through argon gas, and reaction 3h is stirred at room temperature.Reaction knot
Shu Hou makees eluant, eluent with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography.2 product of branched monomer is obtained,
For weak yellow liquid, average molecular weight 1262g/mol.
The preparation of (4) the 0.5th generation branched structures: taking 1.25g branched monomer 2 to be dissolved in 3mL methylene chloride, and 0.12g is added
Acid binding agent triethylamine injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h, after reaction, mistake at room temperature
The triethylamine hydrochloride that filter reaction generates, vacuum distillation remove solvent, with methylene chloride and water extraction remove remaining triethylamine and
Triethylamine salt, oil reservoir liquid is first evaporated under reduced pressure passes through column chromatography for separation afterwards, obtains product G0.5 branched structure (the 0.5th generation branch
Structure), it is weak yellow liquid, average molecular weight 1320g/mol.
The preparation of (5) the 1.5th generation branched structures: taking 1.3g G0.5 to be dissolved in methylene chloride, takes 1.2g branched monomer 1 molten
In methylene chloride, 0.12g catalyst of triethylamine is added, 50h is stirred at 50 DEG C, after reaction, after reaction, with petroleum
Ether/ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G1.5 branched structure (the 1.5th generation point
Branch structure), it is weak yellow liquid, molecular weight 3800g/mol.
The preparation of (6) the 2.5th generation branched structures: taking 3.8g G1.5 branched structure to be dissolved in methylene chloride, and 0.2g is added and ties up
Sour agent triethylamine injects 0.12g acryloyl chloride with syringe, after injection, stirs 10h at room temperature, after reaction, filtering
The triethylamine hydrochloride generated is reacted, vacuum distillation removes solvent, removes remaining triethylamine and three with methylene chloride and water extraction
Ethylamine salt, oil reservoir liquid obtain product by column chromatography for separation.It takes above-mentioned product 3.9g to be dissolved in 2ml methylene chloride, takes 1.2g
Branched monomer 1 is dissolved in 2ml methylene chloride, and 0.12g catalyst of triethylamine is added, stirs 60h at 50 DEG C, after reaction, with
Petrol ether/ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G1.5 branched structure the (the 2.5th
For branched structure), molecular weight 8870g/mol.
The preparation of (7) the 3.5th generation branched structures: taking 0.88g G2.5 branched structure to be dissolved in 4ml methylene chloride, is added
0.4g acid binding agent triethylamine injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h at room temperature, reaction terminates
Afterwards, the triethylamine hydrochloride that filtering reaction generates, vacuum distillation remove solvent, remove remaining three second with methylene chloride and water extraction
Amine and triethylamine salt, oil reservoir liquid obtain product by column chromatography for separation.It takes above-mentioned product 4g to be dissolved in 4ml methylene chloride, takes
0.012g branched monomer 1 is dissolved in 1ml methylene chloride, and 0.012g g catalyst of triethylamine is added, stirs 70h at 50 DEG C, reacts
After, eluant, eluent is made with petrol ether/ethyl acetate mix reagent, is separated by silica gel column chromatography, product G3.5 branch is obtained
Structure (the 3.5th generation branched structure), molecular weight 19000g/mol.
The preparation of (8) the 4.5th generation branched structures: taking 1.88g G3.5 branched structure to be dissolved in methylene chloride, is added
0.012g acid binding agent triethylamine injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h, reaction knot at room temperature
Shu Hou, after reaction, the triethylamine hydrochloride that filtering reaction generates, vacuum distillation remove solvent, are extracted with methylene chloride and water
Remaining triethylamine and triethylamine salt are removed, oil reservoir liquid obtains product by column chromatography for separation.Take above-mentioned product 1.89g molten
In methylene chloride, 0.012g branched monomer 1 is taken to be dissolved in methylene chloride, 0.012g catalyst of triethylamine is added, is stirred at 50 DEG C
80h is mixed, after reaction, eluant, eluent is made with petrol ether/ethyl acetate mix reagent, is separated, is produced by silica gel column chromatography
Object G4.5 branched structure obtains product G4.5 branched structure (the 4.5th generation branched structure), molecular weight 39302g/mol.
The present embodiment product in structure with the difference of embodiment 1: first in sulfydryl vinyl reaction raw materials it is different,
Embodiment 1 is mercaptoethylamine hydrochloride, and embodiment 5 is 3- sulfydryl -1- propylamin hydrochloride, and the branched structure synthesized thus is different
Sample；The product structure that the present embodiment obtains substantially is consistent with formula 2, and the main distinction is each subbranch PEG of branched structure
The average molecular weight of segment is the feature that 400 and Fig. 1 compares that the main distinction is first methylene being connected with two ester groups
The relative intensity of peak 72.59ppm and 63.71ppm and the ownership methyl peak 28.38ppm of end group amido protecting group change, N
The ownership peak of more methylene between S.Secondly reaction raw materials PEG molecular weight is different, and embodiment 5 is PEG1000, implements
Example 1 is PEG200, so the polymer molecular weight that the former synthesizes every generation is bigger than the latter.
Embodiment 6
Using PEG2000, methyl acrylate, mercaptoethylmaine, 3- mercapto-propyl-(Boc- amino) raw material, triethylamine is to urge
Agent and tetrahydrofuran or methylene chloride prepare PEG- acrylate dendritic polymer as solvent, the preparation method is as follows:
(1) preparation of PEG200 acrylate: taking 30g 2000 to be dissolved in 15m tetrahydrofuran, and 2.3g acrylic acid first is added
435,50 DEG C of stirring constant temperature magnetic force of ester and 150mg Novozyme react 25 hours under the conditions of stirring.Thin layer is used in reaction process
Chromatography is tracked, and after reaction, is filtered to remove transesterification enzyme, filtrate is evaporated under reduced pressure with Rotary Evaporators and removes solvent, so
Eluant, eluent is made with petrol ether/ethyl acetate mix reagent afterwards, is separated by silica gel column chromatography, the production of PEG200 acrylate is obtained
Object is weak yellow liquid, average molecular weight 2056g/mol.
(2) preparation of branched monomer 1: PEG2000 acrylic monoester 20.6g is dissolved in 10mL methylene chloride, 1.3g mercapto
Base ethylamine hydrochloride, is passed through nitrogen, and reaction 9h is stirred at room temperature.After reaction, product is extracted with methylene chloride and water, directly
It (is verified with thin-layer chromatography) until there is no mercaptoethylamine hydrochloride into water.The moisture in organic phase is removed with anhydrous magnesium sulfate.
Organic phase under the conditions of 30 DEG C after revolving water removal, obtains 1 product of branched monomer after vacuum drying, be weak yellow liquid, average
Molecular weight is 2133g/mol.
(3) preparation of branched monomer 2: PEG2000 acrylic monoester 20.6g is dissolved in 3mL dimethyl sulfoxide, 2.0g
3- mercapto-propyl-(Boc- amino), is passed through argon gas, and reaction 10h is stirred at room temperature.After reaction, with petroleum ether/acetic acid
Ethyl ester mix reagent makees eluant, eluent, is separated by silica gel column chromatography.2 product of branched monomer is obtained, is weak yellow liquid, it is average
Molecular weight is 2245g/mol.
The preparation of (4) the 0.5th generation branched structures: taking 2.3g branched monomer 2 to be dissolved in 3mL methylene chloride, and 0.012g is added
Acid binding agent sodium carbonate injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h at room temperature, after reaction,
Vacuum distillation removes solvent, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid is first evaporated under reduced pressure passes through column afterwards
Chromatography obtains product G0.5 branched structure (the 0.5th generation branched structure), is weak yellow liquid, and average molecular weight is
2300g/mol。
The preparation of (5) the 1.5th generation branched structures: taking 2.3g G0.5 to be dissolved in methylene chloride, and 2.3g monomer 1 is taken to be dissolved in two
In chloromethanes, 0.12g catalyst sodium carbonate is added, stirs 50h at 50 DEG C, after reaction, after reaction, with petroleum ether/
Ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G1.5 branched structure (the 1.5th generation branch
Structure), molecular weight 6735g/mol.
The preparation of (6) the 2.5th generation branched structures: taking 6.7g G1.5 branched structure to be dissolved in methylene chloride, and 0.012g is added
Acid binding agent sodium carbonate injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h at room temperature, after reaction,
Vacuum distillation removes solvent, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid is obtained by column chromatography for separation
Product.It takes above-mentioned product 6.8g to be dissolved in 3ml methylene chloride, 2.2g branched monomer 1 is taken to be dissolved in 2ml methylene chloride, be added
0.2g catalyst of triethylamine stirs 60h at 50 DEG C, after reaction, makees eluant, eluent with stone petroleum ether/methanol mix reagent, leads to
Silica gel column chromatography separation is crossed, product G1.5 branched structure (the 1.5th generation branched structure), molecular weight 15715g/mol are obtained.
The preparation of (7) the 3.5th generation branched structures: taking 1.5g G2.5 branched structure to be dissolved in 4ml methylene chloride, is added
0.012g acid binding agent sodium carbonate injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h, reaction knot at room temperature
Shu Hou, vacuum distillation remove solvent, remove water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid passes through column chromatography point
From obtaining product.It takes above-mentioned product 1.51g to be dissolved in 1ml methylene chloride, 0.23g branched monomer 1 is taken to be dissolved in 1ml methylene chloride
In, 0.012g g catalyst of triethylamine is added, stirs 70h at 50 DEG C, after reaction, is made with petroleum ether/methanol mix reagent
Eluant, eluent is separated by silica gel column chromatography, obtains product G3.5 branched structure (the 3.5th generation branched structure), molecular weight is
33675g/mol。
The preparation of (8) the 4.5th generation branched structures: taking 3.4g G3.5 branched structure to be dissolved in methylene chloride, and 0.012g is added
Acid binding agent sodium carbonate injects 0.012g acryloyl chloride with syringe, after injection, stirs 12h at room temperature, after reaction,
Vacuum distillation removes solvent, removes water-solubility impurity with methylene chloride and water extraction, oil reservoir liquid is obtained by column chromatography for separation
Product.It takes above-mentioned product 4g to be dissolved in methylene chloride, 0.23g branched monomer 1 is taken to be dissolved in methylene chloride, 0.012g catalysis is added
Agent triethylamine stirs 80h at 50 DEG C, after reaction, makees eluant, eluent with petroleum ether/methanol mix reagent, pass through silica gel column layer
Analysis separation, obtains product G4.5 branched structure, obtains product G4.5 branched structure (the 4.5th generation branched structure), molecular weight is
69595g/mol。
This example product is in structure and the difference of embodiment 1: be first the raw material of acrylic ester synthesizing monoesters not
Together, embodiment 6 uses methyl acrylate, and embodiment 1 uses methyl methacrylate；The product structure and formula that the present embodiment obtains
2 is unanimous on the whole, and the main distinction is that the average molecular weight of each subbranch PEG chain segment of branched structure is 400 master to be compared with Fig. 1
It distinguishes the characteristic peak 72.59ppm and 63.71ppm for being first methylene being connected with two ester groups and end group amido is protected
The relative intensity for protecting the ownership methyl peak 28.38ppm of base changes, the ownership peak of more methylene between N and S.Its
Secondary response raw material PEG molecular weight is different, and embodiment 6 is PEG2000, and embodiment 1 is PEG200, so the former synthesizes every generation
Polymer molecular weight is bigger than the latter.
Claims (8)
1.PEG- acrylate dendritic polymer, which is characterized in that have the following structure formula, the amplifier chain segment table on the left side shows in formula
The bottom end of dendritic polymer, the amplifier chain segment table on the right show the branch of dendritic polymer, and the end of the branch of end is amine
Base protecting group-NHBoc, the structure of other branches at different levels is all the same as the amplification segment on the right；
R1Indicate hydrogen bond or methyl, R2Expression-CH2CH2Or-CH2CH2CH2-；The value of n is 3~20.
2. PEG- acrylate dendritic polymer according to claim 1, which is characterized in that the PEG- acrylate
The molecular weight of dendritic polymer is 1.3 ten thousand~70,000.
3. PEG- acrylate dendritic polymer according to claim 1, which is characterized in that the PEG- acrylate branch
Shaped polymer for product half for product GmEnd group one end be hydroxyl, the other end is amido protecting group, and end group number Ne isInternal layer number of repeat unit Nr is Indicate that branching connects branch's number NbM-0.5 power, wherein m table
Show that the algebra of synthesis, m=1.5,2.5,3.5,4.5, b indicate branch.
4. the preparation method of the described in any item PEG- acrylate dendritic polymer of claim 1-3, it is characterised in that including
Following steps:
(1) transesterification reaction prepares raw material polyethylene glycol methacrylate-styrene polymer: first with the meter of substance, 1 part of polyethylene glycol is molten
In organic solvent, it is configured to the solution of 0.3~1.5mmol/mL, 1~5 part of acrylate is then added and adds after mixing evenly
Enter transesterification enzyme, the transesterification enzyme of 5~15mg is added in every milliliter of solution, and 30~70 DEG C of stirrings are lower to react 24~48h；After reaction,
Filtering vacuum distillation, remaining liq are eluted by chromatography, the eluant, eluent of petrol ether/ethyl acetate, and obtaining product is
Polyethylene glycol acrylate；
(2) click-reaction prepares branched monomer 1: with the meter of substance, it is organic that 1 part of polyethylene glycol acrylic monoester being dissolved in polarity
In solvent, the solution for becoming 2~20mmol/mL is prepared, 1~5 part of sulfydryl primary amine compound is dissolved in polar organic solvent,
The solution for becoming 2~20mmol/mL is prepared, and 0~3 part of basic catalyst is added；It is passed through argon gas, carries out deoxygenation；At room temperature
It is stirred to react 2~10h；After reaction, vacuum distillation removes organic phase under the conditions of 30~50 DEG C, and remaining liq passes through column layer
Analysis separation, is eluted with the eluant, eluent of ethyl acetate/methanol, product branched monomer 1 is obtained after vacuum drying；
(3) click-reaction prepares branched monomer 2: with the meter of substance, it is organic that 1 part of polyethylene glycol acrylic monoester being dissolved in polarity
In solvent, the solution for becoming 2~20mmol/mL is prepared, it is organic molten that 1~6 part of Boc- amineothiot class compound is dissolved in polarity
In agent, the solution for becoming 2~20mmol/mL is prepared, and 0~3 part of basic catalyst is added；Deoxygenation；Reaction 2 is stirred at room temperature
~10h；After reaction, vacuum distillation removes organic phase under the conditions of 30~50 DEG C, and remaining liq passes through column chromatography for separation, second
Acetoacetic ester/methanol eluant, eluent is eluted, and product branched monomer 2 is obtained after vacuum drying；
(4) the branch G0.5 of dendritic polymer is prepared: with the meter of substance, the product branched monomer 1 that 1 part of step (2) is obtained
It is dissolved in organic solvent, prepares the solution for becoming 0.1~10mmol/mL, and 0~3 part of acid binding agent is added；Then by 1~5 part third
Alkene acyl chlorides is dissolved in organic solvent, the solution for becoming 0.1~10mmol/mL is prepared, under agitation by acryloyl chloride solution
It is injected into 2 solution of branched monomer, 12~36h is reacted under 20~60 DEG C of stirring conditions, after reaction, reaction solution decompression is steamed
It evaporates, remaining liq obtains quasi- branch G0.5 by silica gel post separation；
(5) the branch G1.5 of dendritic polymer is prepared: with the meter of substance, the product branched monomer 1 that 1 part of step (2) is obtained
It is dissolved in organic solvent, prepares the solution for becoming 0.1~10mmol/mL, and 0~3 part of basic catalyst is added；Then by 0.5
The quasi- branch G0.5 that~5 parts of steps (4) obtain is dissolved in organic solvent, is prepared the solution for becoming 0.1~10mmol/mL, is being stirred
1 solution of branched monomer is added dropwise in quasi- branch G0.5 solution under the conditions of mixing, after reaction, reaction solution vacuum distillation, raffinate
Body obtains branch G1.5 by silica gel post separation；
(6) it prepares the branch G2.5 of dendritic polymer: with the meter of substance, taking 1 part of G1.5 to be dissolved in organic solvent, preparation becomes
The solution of 0.1~10mmol/mL, 0~3 part of acid binding agent inject 1~5 part of acryloyl chloride, after injection, room temperature with syringe
12~36h of lower stirring, after reaction, filtering, vacuum distillation remove solvent, are removed with methylene chloride and water extraction water-soluble miscellaneous
Matter, oil reservoir liquid obtain product by column chromatography for separation；It takes 1 part of above-mentioned product to be dissolved in organic solvent, takes 0.5~5 part of branching
Monomer 1 is dissolved in organic solvent, 0~3 part of basic catalyst, 60~100h is stirred at 20~60 DEG C, after reaction, with petroleum
Ether/ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains branch G2.5；
(7) it prepares the branch G3.5 of dendritic polymer: first with the meter of substance, 1 part of G2.5 being taken to be dissolved in organic solvent, prepare
As the solution of 0.1~10mmol/mL, 0~3 part of acid binding agent injects 1~5 part of acryloyl chloride with syringe, after injection,
12~36h is stirred at room temperature, and after reaction, filtering, vacuum distillation removes solvent, is removed with methylene chloride and water extraction water-soluble
Property impurity, oil reservoir liquid obtains product by column chromatography for separation；It takes 1 part of the product to be dissolved in organic solvent, takes 0.5~5 part
Branched monomer 1 is dissolved in organic solvent, 0~3 part of basic catalyst, and 60~100h is stirred at 20~60 DEG C, after reaction, with
Petrol ether/ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains product G3.5 branched structure；
(8) it prepares the branch G4.5 of dendritic polymer: with the meter of substance, taking 1 part of G3.5 to be dissolved in organic solvent, preparation becomes
The solution of 0.1~10mmol/mL, 0~3 part of acid binding agent inject 1~5 part of acryloyl chloride, after injection, room temperature with syringe
12~36h of lower stirring, after reaction, filtering, vacuum distillation remove solvent, are removed with methylene chloride and water extraction water-soluble miscellaneous
Matter, oil reservoir liquid obtain product by column chromatography for separation；It takes 1 part of the product to be dissolved in organic solvent, takes 0.5~5 part of branching
Monomer 1 is dissolved in organic solvent, 0~3 part of basic catalyst, 60~100h is stirred at 20~60 DEG C, after reaction, with petroleum
Ether/ethyl acetate mix reagent makees eluant, eluent, is separated by silica gel column chromatography, obtains branch G4.5.
5. the preparation method according to claim 4, which is characterized in that the average molecular weight of the polyethylene glycol is 200-
1000。
6. according to claim 4 require preparation method, which is characterized in that the acrylate be methyl methacrylate,
Ethyl methacrylate, methyl acrylate or ethyl acrylate.
7. the preparation method according to claim 4, which is characterized in that the transesterification enzyme is Novozyme 435, described
Organic solvent is one of ether, methylene chloride and tetrahydrofuran or a variety of；The basic catalyst is sodium hydroxide, hydroxide
One of potassium, sodium carbonate, sodium methoxide, sodium ethoxide, triethylamine and pyridine are a variety of；The polar organic solvent is methanol, second
Alcohol, ether, methylene chloride and tetrahydrofuran it is one or more；The sulfydryl primary amine compound includes mercaptoethylmaine, to sulfydryl
One of phenyl ethylamine, 3- sulfydryl -1- propylamine and its their hydrochloride are a variety of.
8. the preparation method according to claim 4, which is characterized in that the acid binding agent is all triethylamine, pyridine, N, N- bis-
One of wopropyl ethyl amine and potassium carbonate are a variety of.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5227432A (en) * | 1987-03-28 | 1993-07-13 | Basf Lacke & Farben Ag | Branched acrylate copolymer with polymerizable double bonds and methods for the production of the acrylate copolymer |
| CN1946772A (en) * | 2004-04-20 | 2007-04-11 | 德瑞迪克纳米科技公司 | Dendritic polymers with enhanced amplification and interior functionality |
| CN102604118A (en) * | 2012-02-10 | 2012-07-25 | 华南理工大学 | Polyethylene glycol dendritic polymers and preparation method thereof |
| CN103304804A (en) * | 2013-05-28 | 2013-09-18 | 中国科学院长春应用化学研究所 | Polyethylene glycol-polyamide-amine-polyamino acid linear-dendritic block polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227432A (en) * | 1987-03-28 | 1993-07-13 | Basf Lacke & Farben Ag | Branched acrylate copolymer with polymerizable double bonds and methods for the production of the acrylate copolymer |
| CN1946772A (en) * | 2004-04-20 | 2007-04-11 | 德瑞迪克纳米科技公司 | Dendritic polymers with enhanced amplification and interior functionality |
| CN102604118A (en) * | 2012-02-10 | 2012-07-25 | 华南理工大学 | Polyethylene glycol dendritic polymers and preparation method thereof |
| CN103304804A (en) * | 2013-05-28 | 2013-09-18 | 中国科学院长春应用化学研究所 | Polyethylene glycol-polyamide-amine-polyamino acid linear-dendritic block polymer and preparation method thereof |
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