CN107857846B - A kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer - Google Patents
A kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer, polyethylene glycol macromole evocating agent first is prepared with small molecule dihydroxy initiator, then utilizing " grafting from " strategy to be prepared for, structure is clear, the relatively narrow amphipathic graft copolymer of molecular weight distribution.The beneficial effects of the present invention are: the present invention provides one kind, to be prepared for main chain hydrophilic, the method of the polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer of pendant hydrophobic, the graft copolymer of this method synthesis has grafting density adjustable, the controllable feature of branch segment molecular weight.
Description
Technical field
The invention belongs to chemical material fields, are related to a kind of polyethylene glycol grafting amphipathic grafting of polybutyl methacrylate
The preparation method of copolymer.
Background technique
Graft copolymer is two kinds of macromoleculars incompatible with each other by main chain and side chain be connected chemically be formed by it is poly-
Close object.The comprehensive performance that usually there is graft polymers both of which polymers to have, and there is unique molecular structure and form.
The performance of graft polymers is decided by the main, composed structure of branch and length and branch number.
Amphipathic graft copolymer refers in same graft copolymer macromolecular chain simultaneously containing hydrophilic and oleophylic two
The polymer of kind chemical structure difference segment.By being graft-polymerized, the mechanical property of base polymer material, viscoplasticity, infiltration
Property, crystallinity, SOLUTION PROPERTIES, the physical and chemical properties such as printing and dyeing apparent variation will occur.On the one hand, because of its unique materialization
Property, amphipathic graft copolymer are often used as the surface modifier of polymer and expanding material are blended.On the other hand, due to amphiphilic
Property copolymer the nano-sized aggregates with abundant pattern can be self-assembly of in selective solvent, in medicament slow release, urge
The numerous areas such as agent carrier, microreactor have wide practical use, therefore it is similarly subjected to more and more pay close attention to.At present
Most of relevant report be all about amphipathic nature block polymer, it is fewer to the research of amphiphilic graft polymers, more
It is to be rarely reported that main chain is hydrophilic, the amphipathic graft copolymer of pendant hydrophobic.
In addition, the synthesis of the controllable graft polymers of compound with regular structure is a difficult problem on polymer chemistry, and with each
The successful discovery of kind living control polymerization reaction technology, to prepare the accurate graft polymers of various structures, together
When be also that amphiphilic graft polymers self assembly behavioral study provides convenience.Atom transfer radical polymerization (ATRP) is with mild
Reaction condition, polymer architecture and molecular weight are easily controllable, efficiency of initiation is high, to monomer it is adaptable the advantages that be grafted
Big advantage has been embodied in the synthesis of polymer.Main chain not only can be generated by ATRP can also generate branch；Not only may be used
To be individually used for generating graft polymers, it can be also combined with other methods and generate graft polymers.
The present invention first passes through the brominated initiator of monohydroxy lactate synthesis small molecule dihydroxy, and further synthetic macromolecule is brominated
Initiator finally utilizes " grafting from " strategy, is prepared for that structure is specific, molecular weight point using AGRET ATRP method
The relatively narrow amphipathic graft copolymer of cloth.The density of this method hydrophilic backbone polyethylene glycol grafting site is adjustable, side chain molecule
Amount can be designed and be controlled well using ARGETATRP.
Summary of the invention
The technical problem to be solved by the present invention is based on the above issues, the present invention provides a kind of polyethylene glycol grafting poly- first
The preparation method of base butyl acrylate amphipathic graft copolymer.
The present invention solves a technical solution used by its technical problem: a kind of polyethylene glycol grafting polymethyl
The preparation method of acid butyl ester amphipathic graft copolymer, comprising the following steps:
(1) preparation of small molecule dihydroxy initiator
Solvent I, trihydroxy monomer, acid binding agent are added in reaction vessel, are placed in ice-water bath, mechanical stirring, to system
Internal temperature drops to 3 DEG C hereinafter, acylbromide is slowly added dropwise, and recession is added dropwise and removes ice-water bath, ambient temperature overnight reaction post-processes
Small molecule initiator is weighed after vacuum drying oven is dry.
(2) preparation of polyethylene glycol macromole evocating agent
Dihydroxy initiator and solvent II are added in reaction vessel, after to be triggered dose of dissolution, diisocyanate list is added
Body, 70 DEG C are reacted, and sampling carries out fourier infrared test tracking isocyano (- NCO) response situation during reaction, are reacted to different
Cyanate radical relative amount is basically unchanged, and being incorporated in the dried polyethylene glycol of vacuum drying oven, the reaction was continued, continues to sample with infrared
Spectrum tracking, until NCO content is substantially zeroed, reaction was completed, obtains polyethylene glycol macromole evocating agent.
(3) preparation of amphipathic graft copolymer (PEG-g-PBMA):
By polyethylene glycol macromole evocating agent, monomer methacrylic acid butyl ester (BMA), ligand, catalyst, reducing agent, molten
Agent, vacuumizes logical nitrogen circulation while stirring and is placed in 70 DEG C of oil bath pans three times and polymerize, and during which gas-chromatography is used in sampling
Instrument tracks monomer conversion.After reaction, ethyl acetate is that mobile phase crosses neutral alumina pillar to remove copper ion, is collected
It is precipitated after liquid revolving, is precipitated by sedimentation agent of petroleum ether, obtain product drying and processing.
Further, solvent I described in step (1) is toluene, methyl phenyl ethers anisole, n,N-Dimethylformamide, tetrahydrofuran, second
One or more of acetoacetic ester or 1-Methyl-2-Pyrrolidone；Trihydroxy monomer is triethanolamine, trimethylolpropane or sweet
One or more of oil；Acid binding agent is organic acid binding agent (triethylamine, pyridine, N, N- diisopropylethylamine (DIEA)) or inorganic
One or more of acid binding agent (sodium hydroxide, sodium acetate, sodium carbonate, potassium carbonate)；Acylbromide is alpha-brominated isobutyl acylbromide or α-
One of bromo propionyl bromide.
Further, acid binding agent described in step (1): the molar ratio of acylbromide is 1:1；Trihydroxy monomer: the molar ratio of acylbromide
For 5~20:1；The dosage of solvent I is 5~15 times of acid binding agent, acylbromide and trihydroxy monomer summation.
Further, diisocyanate monomer described in step (2) is methyl diphenylene diisocyanate (MDI), toluene
Diisocyanate (TDI), isophorone diisocyanate (IPDI), naphthalene -1,5- diisocyanate (NDI), 2,6- diisocyanate
Ester methyl caproate (LDI), 1,6- hexyl diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI), methyl cyclohexane
One or more of group diisocyanate (HTDI), benzene dimethylene diisocyanate (XDI).
Further, solvent II described in step (2) be toluene, methyl phenyl ethers anisole, n,N-Dimethylformamide, tetrahydrofuran,
One or more of ethyl acetate or 1-Methyl-2-Pyrrolidone.
Further, polyethylene glycol described in step (2) be PEG400, PEG1000, PEG2000, PEG6000,
One or more of PEG10000.
Further, small molecule dihydroxy initiator, polyethylene glycol and diisocyanate monomer described in step (2) according to
Molar ratio NCO/OH=1~1.5/1 feeds intake.
Further, the feed ratio of polyethylene glycol described in step (2) and small molecule initiator determines graft copolymer
Grafting density.Polyethylene glycol: the mass ratio of small molecule initiator is 5~20:1.
Further, catalyst described in step (3) is the transition metal halide CuCl of oxidation state2、CuBr2、FeCl3
Or FeBr3；Ligand is five methyl diethylentriamine, three second tetramine of hexamethyl, bis- (dimethyl aminoethyl) ethers, bipyridine
One of amine or three-(N, N- dimethyl aminoethyl) amine；Reducing agent is one in stannous octoate, ascorbic acid or glucose
Kind.
Further, butyl methacrylate described in step (3): the molar ratio of initiator is 20:1~500:1, methyl
Butyl acrylate: the molar ratio of catalyst is 1:0.0005~1:0.00005, and catalyst: the molar ratio of ligand is 1:10~1:
30, catalyst: the molar ratio of reducing agent is 1:10~1:25, and solvent usage is the 50% of butyl methacrylate quality.
The beneficial effects of the present invention are:
It is prepared for that main chain is hydrophilic the present invention provides one kind, the polyethylene glycol of pendant hydrophobic is grafted polybutyl methacrylate
The graft copolymer of the method for amphipathic graft copolymer, this method synthesis has grafting density adjustable, and side chain molecular weight is controllable
The characteristics of.
Specific embodiment
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1:
(1) preparation of small molecule dihydroxy initiator
Solvents tetrahydrofurane 800mL, triethanolamine 74.6g are added into the four-hole boiling flask equipped with thermometer, agitating paddle
(0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical stirring, declines to system internal temperature
To 3 DEG C hereinafter, alpha-brominated isobutyl acylbromide 11.50g (0.05mol) is slowly added to as much as possible with constant pressure funnel, it is added dropwise
After remove ice-water bath, ambient temperature overnight reaction.Filter paper is filtered to remove the salt of generation after reaction, and filtrate decompression rotates molten
Agent tetrahydrofuran, concentrate are dissolved with ethyl acetate, and parlkaline aluminium oxide pillar is collected and rotates to obtain product.Vacuum drying oven
It weighs after drying, product about 8.3g, yield about 56%.
(2) preparation of macromole evocating agent PEG1000 (0.5)
PEG1000/ initiator=10g/0.5g, obtained macromole evocating agent are denoted as PEG1000 (0.5), 0.5 in bracket
For the quality of the 10gPEG small molecule initiator reacted.
Dihydroxy initiator 0.5g (1.677mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
The mixed solvent of 15g, toluene 14g, pyrrolidones 1g dissolve, and hexamethylene diisocyanate (HDI) 2.357g is added
(0.014mol) is placed in 70 DEG C of oil bath pans and reacts, and sampling carries out fourier infrared test tracking isocyano during reaction
(- NCO) response situation, reaction to isocyano relative amount are basically unchanged, and the 10g poly- second two dried in vacuum drying oven is added
The reaction was continued for alcohol (PEG1000), continues sampling and is tracked with infrared spectroscopy, until NCO content is substantially zeroed, reaction was completed, is gathered
Ethylene glycol macromole evocating agent PEG1000 (0.5).
(3) preparation of amphipathic graft copolymer PEG1000 (0.5)-g-PBMA (5000)
PEG macromole evocating agent PEG1000 (0.5) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 5.87g (0.0413mol), ligand PMDETA 0.072g (0.413mmol), catalyst CuBr2 4.614mg
(0.0206mmol), reducing agent stannous octoate 0.083g (0.206mmol), solvent butanone 10g, vacuumize logical nitrogen while stirring
Circulation, which is placed on three times in 70 DEG C of oil bath pans, to be polymerize.Period sampling tracks monomer conversion with gas chromatograph.Reaction knot
Shu Hou, ethyl acetate are that mobile phase crosses neutral alumina pillar to remove copper ion, precipitate after collection liquid revolving, are with petroleum ether
Sedimentation agent is precipitated, and product drying and processing is obtained.
Embodiment 2:
(1) preparation of small molecule initiator
Solvents tetrahydrofurane 800mL, triethanolamine 74.6g are added into the four-hole boiling flask equipped with thermometer, agitating paddle
(0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical stirring, declines to system internal temperature
To 3 DEG C hereinafter, alpha-brominated propionyl bromide 10.79g (0.05mol) is slowly added to as much as possible with constant pressure funnel, drip
Ice-water bath, ambient temperature overnight reaction are gone in complete recession.Filter paper is filtered to remove the salt of generation after reaction, and filtrate decompression rotates solvent
Tetrahydrofuran, concentrate are dissolved with ethyl acetate, and parlkaline aluminium oxide pillar is collected and rotates to obtain product.Vacuum drying oven is dry
Weighing, product about 8.3g, yield about 56% after dry.
(2) preparation of macromole evocating agent PEG1000 (1.0)
PEG1000/ initiator=10g/1.0g, obtained macromole evocating agent are denoted as PEG1000 (1.0), 1.0 in bracket
For the quality of the 10gPEG1000 small molecule initiator reacted.
Dihydroxy initiator 1.0g (3.354mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
The mixed solvent of 30g, toluene 28g, pyrrolidones 2g dissolve, and hexamethylene diisocyanate (HDI) 2.691g is added
(0.016mol) is placed in 70 DEG C of oil bath pans and reacts, and sampling carries out fourier infrared test tracking isocyano during reaction
(- NCO) response situation, reaction to isocyano relative amount are basically unchanged.Add the 10g poly- second dried in vacuum drying oven
The reaction was continued for glycol (PEG1000), continues sampling and is tracked with infrared spectroscopy, until NCO content is substantially zeroed, reaction was completed, obtains
Polyethylene glycol macromole evocating agent PEG1000 (1.0).
(3) preparation of amphipathic graft copolymer PEG1000 (1.0)-g-PBMA (5000)
PEG macromole evocating agent PEG1000 (1.0) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 5.52g (0.0388mol), ligand PMDETA 0.0672g (0.388mmol), catalyst CuBr2 4.35mg
(0.0194mmol), reducing agent stannous octoate 0.0786g (0.194mmol), solvent butanone 10g, vacuumize logical nitrogen while stirring
Gas circulation, which is placed on three times in 70 DEG C of oil bath pans, to be polymerize.Period sampling tracks monomer conversion with gas chromatograph.Reaction
After, ethyl acetate is that mobile phase crosses neutral alumina pillar to remove copper ion, is precipitated after collection liquid revolving, with petroleum ether
It is precipitated for sedimentation agent, obtains product drying and processing.
Embodiment 3:
(1) preparation of small molecule initiator
Solvents tetrahydrofurane 800mL, trimethylolpropane are added into the four-hole boiling flask equipped with thermometer, agitating paddle
67.09g (0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical stirring, to temperature inside system
Degree drops to 3 DEG C hereinafter, alpha-brominated isobutyl acylbromide 11.50g (0.05mol) is slowly added as much as possible with constant pressure funnel
Enter, recession is added dropwise and goes ice-water bath, ambient temperature overnight reaction.Filter paper is filtered to remove the salt of generation, filtrate decompression after reaction
Solvents tetrahydrofurane is rotated, concentrate is dissolved with ethyl acetate, and parlkaline aluminium oxide pillar is collected and rotates to obtain product.
It weighs after vacuum drying oven is dry, product about 8.3g, yield about 56%.
(2) preparation of macromole evocating agent PEG1000 (2.0)
PEG1000/ initiator=10g/2.0g, obtained macromole evocating agent are denoted as PEG1000 (2.0), 2.0 in bracket
For the quality of the 10gPEG small molecule initiator reacted.
Dihydroxy initiator 2.0g (6.708mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
The mixed solvent of 60g, toluene 56g, pyrrolidones 4g dissolve, and hexamethylene diisocyanate (HDI) 3.364g is added
(0.0200mol) is placed in 70 DEG C of oil bath pans and reacts, and sampling carries out fourier infrared test tracking isocyano during reaction
(- NCO) response situation, reaction to isocyano relative amount are basically unchanged, and the 10g poly- second two dried in vacuum drying oven is added
The reaction was continued for alcohol (PEG1000), continues sampling and is tracked with infrared spectroscopy, until NCO content is substantially zeroed, reaction was completed, is gathered
Ethylene glycol macromole evocating agent PEG1000 (2.0).
(3) preparation of amphipathic graft copolymer PEG1000 (2.0)-g-PBMA (5000)
PEG macromole evocating agent PEG1000 (2.0) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 4.91g (0.0345mol), ligand PMDETA 0.068g (0.345mmol), catalyst CuBr2 4.40mg
(0.0173mmol), reducing agent stannous octoate 0.080g (0.173mmol), solvent butanone 10g, vacuumize logical nitrogen while stirring
Circulation, which is placed on three times in 70 DEG C of oil bath pans, to be polymerize.Period sampling tracks monomer conversion with gas chromatograph.Reaction knot
Shu Hou, ethyl acetate are that mobile phase crosses neutral alumina pillar to remove copper ion, precipitate after collection liquid revolving, are with petroleum ether
Sedimentation agent is precipitated, and product drying and processing is obtained.
Embodiment 4:
(1) preparation of small molecule initiator
Solvents tetrahydrofurane 800mL, triethanolamine 74.6g are added into the four-hole boiling flask equipped with thermometer, agitating paddle
(0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical stirring, declines to system internal temperature
To 3 DEG C hereinafter, alpha-brominated isobutyl acylbromide 11.50g (0.05mol) is slowly added to as much as possible with constant pressure funnel, it is added dropwise
After remove ice-water bath, ambient temperature overnight reaction.Filter paper is filtered to remove the salt of generation after reaction, and filtrate decompression rotates molten
Agent tetrahydrofuran, concentrate are dissolved with ethyl acetate, and parlkaline aluminium oxide pillar is collected and rotates to obtain product.Vacuum drying oven
It weighs after drying, product about 8.3g, yield about 56%.
(2) preparation of macromole evocating agent PEG1000 (1.0)
PEG1000/ initiator=10g/1.0g, obtained macromole evocating agent are denoted as PEG1000 (1.0), 1.0 in bracket
For the quality of the 10gPEG1000 small molecule initiator reacted.
Dihydroxy initiator 1.0g (3.354mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
The mixed solvent of 30g, toluene 28g, pyrrolidones 2g dissolve, and hexamethylene diisocyanate (HDI) 2.691g is added
(0.016mol) is placed in 70 DEG C of oil bath pans and reacts, and sampling carries out fourier infrared test tracking isocyano during reaction
(- NCO) response situation, reaction to isocyano relative amount are basically unchanged.Add the 10g poly- second dried in vacuum drying oven
The reaction was continued for glycol (PEG1000), continues sampling and is tracked with infrared spectroscopy, until NCO content is substantially zeroed, reaction was completed, obtains
Polyethylene glycol macromole evocating agent PEG1000 (1.0).
(3) preparation of amphipathic graft copolymer PEG1000 (1.0)-g-PBMA (10000)
PEG macromole evocating agent PEG1000 (1.0) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 11.03g (0.0776mol), ligand PMDETA 0.134g (0.776mmol), catalyst CuBr28.69mg
(0.0388mmol), reducing agent stannous octoate 0.157g (0.388mmol), solvent butanone 15g, vacuumize logical nitrogen while stirring
Circulation, which is placed on three times in 70 DEG C of oil bath pans, to be polymerize.Period sampling tracks monomer conversion with gas chromatograph.Reaction knot
Shu Hou, ethyl acetate are that mobile phase crosses neutral alumina pillar to remove copper ion, precipitate after collection liquid revolving, are with petroleum ether
Sedimentation agent is precipitated, and product drying and processing is obtained.
Embodiment 5:
(1) preparation of small molecule initiator
Solvents tetrahydrofurane 800mL, triethanolamine 74.6g are added into the four-hole boiling flask equipped with thermometer, agitating paddle
(0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical stirring, declines to system internal temperature
To 3 DEG C hereinafter, alpha-brominated isobutyl acylbromide 11.50g (0.05mol) is slowly added to as much as possible with constant pressure funnel, it is added dropwise
After remove ice-water bath, ambient temperature overnight reaction.Filter paper is filtered to remove the salt of generation after reaction, and filtrate decompression rotates molten
Agent tetrahydrofuran, concentrate are dissolved with ethyl acetate, and parlkaline aluminium oxide pillar is collected and rotates to obtain product.Vacuum drying oven
It weighs after drying, product about 8.3g, yield about 56%.
(2) preparation of macromole evocating agent PEG2000 (1.0)
PEG2000/ initiator=10g/1.0g, obtained macromole evocating agent are denoted as PEG2000 (1.0), 1.0 in bracket
For the quality of the 10gPEG2000 small molecule initiator reacted.
Dihydroxy initiator 1.0g (3.354mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
The mixed solvent of 30g, toluene 28g, pyrrolidones 2g dissolve, and hexamethylene diisocyanate (HDI) 1.682g is added
(0.010mol) is placed in 70 DEG C of oil bath pans and reacts, and sampling carries out fourier infrared test tracking isocyano during reaction
(- NCO) response situation, reaction to isocyano relative amount are basically unchanged, and the 10g poly- second two dried in vacuum drying oven is added
The reaction was continued for alcohol (PEG2000), continues sampling and is tracked with infrared spectroscopy, until NCO content is substantially zeroed, reaction was completed, is gathered
Ethylene glycol macromole evocating agent PEG2000 (1.0).
(3) preparation of amphipathic graft copolymer PEG2000 (1.0)-g-PBMA (5000)
PEG macromole evocating agent PEG2000 (1.0) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 5.95g (0.0418mol), ligand PMDETA 0.0724g (0.418mmol), catalyst CuBr2 4.68mg
(0.0209mmol), reducing agent stannous octoate 0.0847g (0.209mmol), solvent butanone 10g, vacuumize logical nitrogen while stirring
Gas circulation, which is placed on three times in 70 DEG C of oil bath pans, to be polymerize.Period sampling tracks monomer conversion with gas chromatograph.Reaction
After, ethyl acetate is that mobile phase crosses neutral alumina pillar to remove copper ion, is precipitated after collection liquid revolving, with petroleum ether
It is precipitated for sedimentation agent, obtains product drying and processing.
The GPC result of the corresponding polyethylene glycol macromole evocating agent of embodiment 1,2,3 see the table below 1:
The GPC result of 1 polyethylene glycol macromole evocating agent of table
The GPC result of the corresponding PEG-g-PBMA of embodiment 1,2,3 see the table below 2:
The GPC result of table 2PEG-g-PBMA
Claims (9)
1. a kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer, including following step
It is rapid:
(1) preparation of small molecule dihydroxy initiator
Solvent I, trihydroxy monomer, acid binding agent are added in reaction vessel, are placed in ice-water bath, mechanical stirring, inside system
Temperature drops to 3 DEG C hereinafter, acylbromide is slowly added dropwise, and recession is added dropwise and removes ice-water bath, ambient temperature overnight reaction post-processes to obtain small point
Sub- initiator is weighed after vacuum drying oven is dry；
(2) preparation of polyethylene glycol macromole evocating agent
Dihydroxy initiator and solvent II are added in reaction vessel, after to be triggered dose of dissolution, addition diisocyanate monomer, 70
DEG C reaction, sampling carries out fourier infrared test tracking isocyano (- NCO) response situation during reaction, and reaction is to isocyanic acid
Root relative amount is basically unchanged, and being incorporated in the dried polyethylene glycol of vacuum drying oven, the reaction was continued, continues sampling infrared spectroscopy
Tracking, until NCO content is substantially zeroed, reaction was completed, obtains polyethylene glycol macromole evocating agent；
(3) preparation of amphipathic graft copolymer (PEG-g-PBMA):
Polyethylene glycol macromole evocating agent, monomer methacrylic acid butyl ester (BMA), ligand, catalyst, reducing agent octanoic acid is sub-
Tin, solvent butanone, vacuumize logical nitrogen circulation while stirring and are placed in 70 DEG C of oil bath pans three times and polymerize, and during which sampling is used
Gas chromatograph tracks monomer conversion, and after reaction, ethyl acetate is that mobile phase crosses neutral alumina pillar to remove copper
Ion, collection liquid precipitate after rotating, are precipitated by sedimentation agent of petroleum ether, obtain product drying and processing.
2. the preparation side of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer according to claim 1
Method, it is characterised in that: solvent I described in step (1) is toluene, methyl phenyl ethers anisole, n,N-Dimethylformamide, tetrahydrofuran, acetic acid
One or more of ethyl ester or 1-Methyl-2-Pyrrolidone；Trihydroxy monomer is triethanolamine, trimethylolpropane or glycerol
One or more of；Acid binding agent is triethylamine, pyridine, N, N- diisopropylethylamine (DIEA), sodium hydroxide, sodium acetate, carbon
One or more of sour sodium, potassium carbonate；Acylbromide is one of alpha-brominated isobutyl acylbromide or alpha-brominated propionyl bromide.
3. the preparation side of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer according to claim 1
Method, it is characterised in that: acid binding agent described in step (1): the molar ratio of acylbromide is 1:1；Trihydroxy monomer: the molar ratio of acylbromide is
1~20:1；The dosage of solvent I is 5~15 times of acid binding agent, acylbromide and trihydroxy monomer mass summation.
4. the preparation side of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer according to claim 1
Method, it is characterised in that: diisocyanate monomer described in step (2) is methyl diphenylene diisocyanate (MDI), toluene two is different
Cyanate (TDI), isophorone diisocyanate (IPDI), naphthalene -1,5- diisocyanate (NDI), 2,6- diisocyanate oneself
Sour methyl esters (LDI), 1,6- hexyl diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI), methylcyclohexyl two
One or more of isocyanates (HTDI), benzene dimethylene diisocyanate (XDI).
5. the preparation side of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer according to claim 1
Method, it is characterised in that: polyethylene glycol described in step (2) be PEG400, PEG1000, PEG2000, PEG6000,
One or more of PEG10000.
6. the preparation side of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer according to claim 1
Method, it is characterised in that: small molecule dihydroxy initiator, polyethylene glycol and diisocyanate monomer described in step (2) according to
Molar ratio NCO/OH=1~1.5/1 feeds intake.
7. the preparation side of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer according to claim 1
Method, it is characterised in that: the feed ratio of polyethylene glycol described in step (2) and small molecule initiator determines connecing for graft copolymer
Branch density, polyethylene glycol: the mass ratio of small molecule initiator is 5~20:1.
8. the preparation side of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer according to claim 1
Method, it is characterised in that: catalyst described in step (3) is the transition metal halide CuCl of oxidation state2、CuBr2、FeCl3Or
FeBr3；Ligand is five methyl diethylentriamine, three second tetramine of hexamethyl, bis- (dimethyl aminoethyl) ethers, bipyridine amine
Or three-one of (N, N- dimethyl aminoethyl) amine；Reducing agent is one in stannous octoate, ascorbic acid or glucose
Kind.
9. the preparation side of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer according to claim 1
Method, it is characterised in that: butyl methacrylate described in step (3): the molar ratio of initiator is 20:1~500:1, methyl
Butyl acrylate: the molar ratio of catalyst is 1:0.0005~1:0.00005, and catalyst: the molar ratio of ligand is 1:10~1:
30, catalyst: the molar ratio of reducing agent is 1:10~1:25, and solvent usage is the 50% of butyl methacrylate quality.
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| CN107857846B true CN107857846B (en) | 2019-10-11 |
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