CN107857846A - 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
- Publication number
- CN107857846A CN107857846A CN201711177897.5A CN201711177897A CN107857846A CN 107857846 A CN107857846 A CN 107857846A CN 201711177897 A CN201711177897 A CN 201711177897A CN 107857846 A CN107857846 A CN 107857846A
- Authority
- CN
- China
- Prior art keywords
- polyethylene glycol
- graft copolymer
- preparation
- grafting
- amphipathic graft
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to a kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer, first prepare polyethylene glycol macromole evocating agent with small molecule dihydroxy initiator, then utilize " grafting from " strategy be prepared for structure clearly, the amphipathic graft copolymer of molecular weight distribution relative narrower.The beneficial effects of the invention are as follows：It is prepared for that main chain is hydrophilic the invention provides one kind, the method for the polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer of pendant hydrophobic, the graft copolymer of this method synthesis has the characteristics of grafting density is adjustable, and branch segment molecular weight is controllable.
Description
Technical field
The invention belongs to chemical material field, is related to a kind of polyethylene glycol grafting amphipathic grafting of polybutyl methacrylate
The preparation method of copolymer.
Background technology
Graft copolymer is two kinds of macromoleculars incompatible with each other by main chain and side chain be connected chemically to be formed it is poly-
Compound.Graft polymers generally has both of which polymers possessed combination property, and with unique molecular structure and form.
The performance of graft polymers is decided by main, the composition structure and length of side chain, and side chain number.
Amphipathic graft copolymer refers in same graft copolymer macromolecular chain simultaneously containing hydrophilic and oleophylic two
The polymer of kind chemical constitution 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 obvious change will occur.On the one hand, because of its unique materialization
Property, amphipathic graft copolymer are often used as the surface modifier and blending bulking agent of polymer.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 increasing concern.At present
Most of relevant report is all on amphipathic nature block polymer, and the research to amphiphilic graft polymers is fewer, 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 so that prepare the accurate graft polymers of various structures and be possibly realized, together
When also for amphiphilic graft polymers self assembly behavioral study provide conveniently.ATRP (ATRP) is with gentle
Reaction condition, polymer architecture and molecular weight are easily controllable, efficiency of initiation is high, the advantages that strong adaptability of monomer is being grafted
Big advantage has been embodied in the synthesis of polymer.Main chain can be not only generated by ATRP can also generate side chain；Not only may be used
To be individually used for generating graft polymers, generation graft polymers can be also combined with other method.
The present invention first passes through the brominated initiator of monohydroxy lactate synthesis small molecule dihydroxy, and further synthetic macromolecule is brominated
Initiator, finally utilize " grafting from " strategies, using AGRET ATRP methods be prepared for structure clearly, molecular weight point
The amphipathic graft copolymer of cloth relative narrower.The density of this method hydrophilic backbone polyethylene glycol grafting site is adjustable, side chain molecule
Amount can be designed and controlled well using ARGETATRP.
The content of the invention
The technical problem to be solved in the present invention is：Based on above mentioned problem, the present invention provides a kind of polyethylene glycol and is grafted poly- first
The preparation method of base butyl acrylate amphipathic graft copolymer.
A technical scheme is used by the present invention solves its technical problem：A kind of polyethylene glycol is grafted polymethyl
The preparation method of acid butyl ester amphipathic graft copolymer, comprises the following steps：
(1) preparation of small molecule dihydroxy initiator
Solvent I, trihydroxy monomer, acid binding agent are added in reaction vessel, is placed in ice-water bath, mechanical agitation, treats system
Internal temperature drops to less than 3 DEG C, and acylbromide is slowly added dropwise, and recession is added dropwise and removes ice-water bath, ambient temperature overnight reaction, post-processes
Small molecule initiator, vacuum drying oven are weighed after drying.
(2) preparation of polyethylene glycol macromole evocating agent
Dihydroxy initiator and solvent II are added in reaction vessel, after to be triggered dose of dissolving, add diisocyanate list
Body, 70 DEG C of reactions, sampling progress fourier infrared test tracking isocyano (- NCO) response situation, reacts to different during reaction
Cyanate radical relative amount is basically unchanged, and is incorporated in the dried polyethylene glycol of vacuum drying oven and is continued to react, and continues to sample with infrared
Spectrum tracks, substantially zeroed to NCO content, terminates reaction, 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), part, catalyst, reducing agent, molten
Agent, vacuumizes logical nitrogen circulation and is placed in afterwards three times in 70 DEG C of oil bath pans and polymerize while stirring, during which sampling gas-chromatography
Instrument tracks monomer conversion.After reaction terminates, ethyl acetate is that mobile phase crosses neutral alumina pillar to remove copper ion, is collected
Precipitated after liquid revolving, precipitated by sedimentation agent of petroleum ether, obtain product drying and processing.
Further, the solvent I described in step (1) is toluene, methyl phenyl ethers anisole, DMF, tetrahydrofuran, second
One or more in acetoacetic ester or 1-Methyl-2-Pyrrolidone；Trihydroxy monomer is triethanolamine, trimethylolpropane or sweet
One or more in oil；Acid binding agent is organic acid binding agent (triethylamine, pyridine, N, N- diisopropylethylamine (DIEA)) or inorganic
One or more in acid binding agent (sodium hydroxide, sodium acetate, sodium carbonate, potassium carbonate)；Acylbromide be alpha-brominated isobutyl acylbromide or α-
One kind in bromo propionyl bromide.
Further, the acid binding agent described in step (1)：The mol ratio of acylbromide is 1：1；Trihydroxy monomer：The mol 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, the diisocyanate monomer described in step (2) is methyl diphenylene diisocyanate (MDI), toluene
Diisocyanate (TDI), IPDI (IPDI), naphthalene -1,5- diisocyanate (NDI), the isocyanic acids of 2,6- bis-
Ester methyl caproate (LDI), 1,6- hexyl diisocyanates (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI), methyl cyclohexane
One or more in group diisocyanate (HTDI), XDI (XDI).
Further, the solvent II described in step (2) be toluene, methyl phenyl ethers anisole, DMF, tetrahydrofuran,
One or more in ethyl acetate or 1-Methyl-2-Pyrrolidone.
Further, the polyethylene glycol described in step (2) be PEG400, PEG1000, PEG2000, PEG6000,
One or more in PEG10000.
Further, small molecule dihydroxy initiator, polyethylene glycol and the diisocyanate monomer described in step (2) according to
Mol ratio NCO/OH=1~1.5/1 is fed intake.
Further, the rate of charge of the 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, the catalyst described in step (3) is the transition metal halide CuCl of oxidation state2、CuBr2、FeCl3
Or FeBr3；Part is five methyl diethylentriamine, the second tetramine of hexamethyl three, double (dimethyl aminoethyl) ethers, bipyridine
One kind in amine or three-(N, N- dimethyl aminoethyl) amine；Reducing agent is one in stannous octoate, ascorbic acid or glucose
Kind.
Further, the butyl methacrylate described in step (3)：The mol ratio of initiator is 20：1~500：1, methyl
Butyl acrylate：The mol ratio of catalyst is 1：0.0005~1：0.00005, catalyst：The mol ratio of part is 1：10~1：
30, catalyst：The mol ratio of reducing agent is 1：10~1：25, solvent load is the 50% of butyl methacrylate quality.
The beneficial effects of the invention are as follows：
It is prepared for that main chain is hydrophilic the invention provides one kind, the polyethylene glycol grafting polybutyl methacrylate of pendant hydrophobic
The method of amphipathic graft copolymer, the graft copolymer of this method synthesis have that grafting density is adjustable, and side chain molecular weight is controllable
The characteristics of.
Embodiment
Presently in connection with specific embodiment, the invention will be further described, following examples be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1：
(1) preparation of small molecule dihydroxy initiator
To equipped with thermometer, agitating paddle four-hole boiling flask in add solvents tetrahydrofurane 800mL, triethanolamine 74.6g
(0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical agitation, treats that system internal temperature declines
To less than 3 DEG C, alpha-brominated isobutyl acylbromide 11.50g (0.05mol) is slowly added to as much as possible with constant pressure funnel, is added dropwise
After remove ice-water bath, ambient temperature overnight reaction.Reaction terminates the salt that rear filter paper is filtered to remove generation, and filtrate decompression rotates molten
Agent tetrahydrofuran, concentrate are dissolved with ethyl acetate, parlkaline aluminum oxide pillar, are collected and are rotated to obtain product.Vacuum drying oven
Weighed after drying, product about 8.3g, yield about 56%.
(2) macromole evocating agent PEG1000 (0.5) preparation
PEG1000/ initiators=10g/0.5g, obtained macromole evocating agent are designated as PEG1000 (0.5), 0.5 in bracket
For the quality of the 10gPEG small molecule initiators reacted.
Dihydroxy initiator 0.5g (1.677mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
15g, toluene 14g, pyrrolidones 1g mixed solvent dissolving, add hexamethylene diisocyanate (HDI) 2.357g
(0.014mol), it is placed in 70 DEG C of oil bath pans and reacts, sampling progress fourier infrared test tracking isocyano during reaction
(- NCO) response situation, react to isocyano relative amount and be basically unchanged, add 10g in the dried poly- second two of vacuum drying oven
Alcohol (PEG1000) continues to react, and continues sampling and is tracked with infrared spectrum, substantially zeroed to NCO content, terminates reaction, is gathered
Ethylene glycol macromole evocating agent PEG1000 (0.5).
(3) amphipathic graft copolymer PEG1000 (0.5)-g-PBMA (5000) preparation
PEG macromole evocating agents PEG1000 (0.5) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 5.87g (0.0413mol), part 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 is placed in 70 DEG C of oil bath pans afterwards three times 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, are precipitated after collection liquid revolving, using petroleum ether as
Sedimentation agent is precipitated, and obtains product drying and processing.
Embodiment 2：
(1) preparation of small molecule initiator
To equipped with thermometer, agitating paddle four-hole boiling flask in add solvents tetrahydrofurane 800mL, triethanolamine 74.6g
(0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical agitation, treats that system internal temperature declines
To less than 3 DEG C, alpha-brominated propionyl bromide 10.79g (0.05mol) is slowly added to as much as possible with constant pressure funnel, dripped
Ice-water bath, ambient temperature overnight reaction are gone in complete recession.Reaction terminates the salt that rear filter paper is filtered to remove generation, and filtrate decompression rotates solvent
Tetrahydrofuran, concentrate are dissolved with ethyl acetate, parlkaline aluminum oxide pillar, are collected and are rotated to obtain product.Vacuum drying oven is done
Weighed after dry, product about 8.3g, yield about 56%.
(2) macromole evocating agent PEG1000 (1.0) preparation
PEG1000/ initiators=10g/1.0g, obtained macromole evocating agent are designated as PEG1000 (1.0), 1.0 in bracket
For the quality of the 10gPEG1000 small molecule initiators reacted.
Dihydroxy initiator 1.0g (3.354mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
30g, toluene 28g, pyrrolidones 2g mixed solvent dissolving, add hexamethylene diisocyanate (HDI) 2.691g
(0.016mol), it is placed in 70 DEG C of oil bath pans and reacts, sampling progress fourier infrared test tracking isocyano during reaction
(- NCO) response situation, react to isocyano relative amount and be basically unchanged.10g is added in the dried poly- second of vacuum drying oven
Glycol (PEG1000) continues to react, and continues sampling and is tracked with infrared spectrum, substantially zeroed to NCO content, terminates reaction, obtains
Polyethylene glycol macromole evocating agent PEG1000 (1.0).
(3) amphipathic graft copolymer PEG1000 (1.0)-g-PBMA (5000) preparation
PEG macromole evocating agents PEG1000 (1.0) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 5.52g (0.0388mol), part 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 is placed in 70 DEG C of oil bath pans afterwards three times to be polymerize.Period sampling tracks monomer conversion with gas chromatograph.Reaction
After end, ethyl acetate is that mobile phase crosses neutral alumina pillar to remove copper ion, is precipitated after collection liquid revolving, with petroleum ether
Precipitated for sedimentation agent, obtain product drying and processing.
Embodiment 3:
(1) preparation of small molecule initiator
To equipped with thermometer, agitating paddle four-hole boiling flask in add solvents tetrahydrofurane 800mL, trimethylolpropane
67.09g (0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical agitation, treats temperature inside system
Degree drops to less than 3 DEG C, and 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.Reaction terminates the salt that rear filter paper is filtered to remove generation, filtrate decompression
Solvents tetrahydrofurane is rotated, concentrate is dissolved with ethyl acetate, parlkaline aluminum oxide pillar, is collected and is rotated to obtain product.
Vacuum drying oven is weighed after drying, product about 8.3g, yield about 56%.
(2) macromole evocating agent PEG1000 (2.0) preparation
PEG1000/ initiators=10g/2.0g, obtained macromole evocating agent are designated as PEG1000 (2.0), 2.0 in bracket
For the quality of the 10gPEG small molecule initiators reacted.
Dihydroxy initiator 2.0g (6.708mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
60g, toluene 56g, pyrrolidones 4g mixed solvent dissolving, add hexamethylene diisocyanate (HDI) 3.364g
(0.0200mol), it is placed in 70 DEG C of oil bath pans and reacts, sampling progress fourier infrared test tracking isocyano during reaction
(- NCO) response situation, react to isocyano relative amount and be basically unchanged, add 10g in the dried poly- second two of vacuum drying oven
Alcohol (PEG1000) continues to react, and continues sampling and is tracked with infrared spectrum, substantially zeroed to NCO content, terminates reaction, is gathered
Ethylene glycol macromole evocating agent PEG1000 (2.0).
(3) amphipathic graft copolymer PEG1000 (2.0)-g-PBMA (5000) preparation
PEG macromole evocating agents PEG1000 (2.0) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 4.91g (0.0345mol), part 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 is placed in 70 DEG C of oil bath pans afterwards three times 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, are precipitated after collection liquid revolving, using petroleum ether as
Sedimentation agent is precipitated, and obtains product drying and processing.
Embodiment 4:
(1) preparation of small molecule initiator
To equipped with thermometer, agitating paddle four-hole boiling flask in add solvents tetrahydrofurane 800mL, triethanolamine 74.6g
(0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical agitation, treats that system internal temperature declines
To less than 3 DEG C, alpha-brominated isobutyl acylbromide 11.50g (0.05mol) is slowly added to as much as possible with constant pressure funnel, is added dropwise
After remove ice-water bath, ambient temperature overnight reaction.Reaction terminates the salt that rear filter paper is filtered to remove generation, and filtrate decompression rotates molten
Agent tetrahydrofuran, concentrate are dissolved with ethyl acetate, parlkaline aluminum oxide pillar, are collected and are rotated to obtain product.Vacuum drying oven
Weighed after drying, product about 8.3g, yield about 56%.
(2) macromole evocating agent PEG1000 (1.0) preparation
PEG1000/ initiators=10g/1.0g, obtained macromole evocating agent are designated as PEG1000 (1.0), 1.0 in bracket
For the quality of the 10gPEG1000 small molecule initiators reacted.
Dihydroxy initiator 1.0g (3.354mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
30g, toluene 28g, pyrrolidones 2g mixed solvent dissolving, add hexamethylene diisocyanate (HDI) 2.691g
(0.016mol), it is placed in 70 DEG C of oil bath pans and reacts, sampling progress fourier infrared test tracking isocyano during reaction
(- NCO) response situation, react to isocyano relative amount and be basically unchanged.10g is added in the dried poly- second of vacuum drying oven
Glycol (PEG1000) continues to react, and continues sampling and is tracked with infrared spectrum, substantially zeroed to NCO content, terminates reaction, obtains
Polyethylene glycol macromole evocating agent PEG1000 (1.0).
(3) amphipathic graft copolymer PEG1000 (1.0)-g-PBMA (10000) preparation
PEG macromole evocating agents PEG1000 (1.0) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 11.03g (0.0776mol), part 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 is placed in 70 DEG C of oil bath pans afterwards three times 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, are precipitated after collection liquid revolving, using petroleum ether as
Sedimentation agent is precipitated, and obtains product drying and processing.
Embodiment 5:
(1) preparation of small molecule initiator
To equipped with thermometer, agitating paddle four-hole boiling flask in add solvents tetrahydrofurane 800mL, triethanolamine 74.6g
(0.50mol), acid binding agent triethylamine 5.06g (0.05mol), is placed in ice-water bath, mechanical agitation, treats that system internal temperature declines
To less than 3 DEG C, alpha-brominated isobutyl acylbromide 11.50g (0.05mol) is slowly added to as much as possible with constant pressure funnel, is added dropwise
After remove ice-water bath, ambient temperature overnight reaction.Reaction terminates the salt that rear filter paper is filtered to remove generation, and filtrate decompression rotates molten
Agent tetrahydrofuran, concentrate are dissolved with ethyl acetate, parlkaline aluminum oxide pillar, are collected and are rotated to obtain product.Vacuum drying oven
Weighed after drying, product about 8.3g, yield about 56%.
(2) macromole evocating agent PEG2000 (1.0) preparation
PEG2000/ initiators=10g/1.0g, obtained macromole evocating agent are designated as PEG2000 (1.0), 1.0 in bracket
For the quality of the 10gPEG2000 small molecule initiators reacted.
Dihydroxy initiator 1.0g (3.354mmol) is added into the flask equipped with reflux condensing tube, with containing ethyl acetate
30g, toluene 28g, pyrrolidones 2g mixed solvent dissolving, add hexamethylene diisocyanate (HDI) 1.682g
(0.010mol), it is placed in 70 DEG C of oil bath pans and reacts, sampling progress fourier infrared test tracking isocyano during reaction
(- NCO) response situation, react to isocyano relative amount and be basically unchanged, add 10g in the dried poly- second two of vacuum drying oven
Alcohol (PEG2000) continues to react, and continues sampling and is tracked with infrared spectrum, substantially zeroed to NCO content, terminates reaction, is gathered
Ethylene glycol macromole evocating agent PEG2000 (1.0).
(3) amphipathic graft copolymer PEG2000 (1.0)-g-PBMA (5000) preparation
PEG macromole evocating agents PEG2000 (1.0) 4.5g, monomer methacrylic acid butyl ester are added into reaction flask
(BMA) 5.95g (0.0418mol), part 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 is placed in 70 DEG C of oil bath pans afterwards three times to be polymerize.Period sampling tracks monomer conversion with gas chromatograph.Reaction
After end, ethyl acetate is that mobile phase crosses neutral alumina pillar to remove copper ion, is precipitated after collection liquid revolving, with petroleum ether
Precipitated for sedimentation agent, obtain product drying and processing.
The GPC results of polyethylene glycol macromole evocating agent see the table below 1 corresponding to embodiment 1,2,3：
The GPC results of the polyethylene glycol macromole evocating agent of table 1
PEG-g-PBMA GPC results see the table below 2 corresponding to embodiment 1,2,3：
Table 2PEG-g-PBMA GPC results
Claims (9)
1. a kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer, including following step
Suddenly：
(1) preparation of small molecule dihydroxy initiator
Solvent I, trihydroxy monomer, acid binding agent are added in reaction vessel, is placed in ice-water bath, mechanical agitation, treats inside system
Temperature drops to less than 3 DEG C, and 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, vacuum drying oven are weighed after drying.
(2) preparation of polyethylene glycol macromole evocating agent
Dihydroxy initiator and solvent II are added in reaction vessel, after to be triggered dose of dissolving, addition diisocyanate monomer, 70
DEG C reaction, during reaction sampling carry out fourier infrared test tracking isocyano (- NCO) response situation, react to isocyanic acid
Root relative amount is basically unchanged, and is incorporated in the dried polyethylene glycol of vacuum drying oven and is continued to react, continues sampling infrared spectrum
Tracking, it is substantially zeroed to NCO content, terminate reaction, obtain 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), part PMDETA, catalyst, reducing agent is pungent
Sour stannous, solvent butanone, vacuumize logical nitrogen circulation and are placed in afterwards three times in 70 DEG C of oil bath pans and polymerize while stirring, during which take
Sample with gas chromatograph track monomer conversion, reaction terminate after, ethyl acetate be mobile phase cross neutral alumina pillar with except
Copper ion is removed, is precipitated after collection liquid revolving, is 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, DMF, tetrahydrofuran, acetic acid
One or more in ethyl ester or 1-Methyl-2-Pyrrolidone；Trihydroxy monomer is triethanolamine, trimethylolpropane or glycerine
In one or more；Acid binding agent is organic acid binding agent (triethylamine, pyridine, N, N- diisopropylethylamine (DIEA)) or inorganic tied up
One or more in sour agent (sodium hydroxide, sodium acetate, sodium carbonate, potassium carbonate)；Acylbromide is alpha-brominated isobutyl acylbromide or α-bromine
For one kind in 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 mol ratio of acylbromide is 1：1；Trihydroxy monomer：The mol ratio of acylbromide is
1~20：1；The dosage of solvent I is 5~15 times of acid binding agent, acylbromide and trihydroxy monomer 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), IPDI (IPDI), naphthalene -1,5- diisocyanate (NDI), 2,6- diisocyanate oneself
Sour methyl esters (LDI), 1,6- hexyl diisocyanates (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI), methylcyclohexyl two
One or more in isocyanates (HTDI), XDI (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) is PEG400, PEG1000, PEG2000, PEG6000,
One or more in 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
Mol ratio NCO/OH=1~1.5/1 is fed 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 rate of charge of polyethylene glycol and small molecule initiator described in step (2) 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；Part is five methyl diethylentriamine, the second tetramine of hexamethyl three, double (dimethyl aminoethyl) ethers, bipyridine amine
Or three-(N, N- dimethyl aminoethyl) one kind in 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 mol ratio of initiator is 20：1~500：1, methyl
Butyl acrylate：The mol ratio of catalyst is 1：0.0005~1：0.00005, catalyst：The mol ratio of part is 1：10~1：
30, catalyst：The mol ratio of reducing agent is 1：10~1：25, solvent load is the 50% of butyl methacrylate quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711177897.5A CN107857846B (en) | 2017-11-23 | 2017-11-23 | A kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711177897.5A CN107857846B (en) | 2017-11-23 | 2017-11-23 | A kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107857846A true CN107857846A (en) | 2018-03-30 |
| CN107857846B CN107857846B (en) | 2019-10-11 |
Family
ID=61702346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711177897.5A Active CN107857846B (en) | 2017-11-23 | 2017-11-23 | A kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107857846B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499550A (en) * | 2018-12-19 | 2019-03-22 | 浙江工业大学 | A kind of semi-hydrophobic nano-crystal glue medium and preparation method thereof |
| CN112300342A (en) * | 2020-11-04 | 2021-02-02 | 长兴电子（苏州）有限公司 | Novel method for synthesizing hydrophilic comb-shaped macromolecules by photoinitiation |
| CN113057927A (en) * | 2021-03-29 | 2021-07-02 | 中科瑞晟芳香产业研究院(湖北)有限公司 | Hair-strengthening shampoo containing aromatic Chinese herbal medicines |
| CN115197379A (en) * | 2022-07-18 | 2022-10-18 | 福州大学 | Method for regulating and controlling polymer grafting density |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002100439A1 (en) * | 2001-06-08 | 2002-12-19 | Labopharm, Inc. | Water-soluble stabilized self-assembled polyelectrolytes |
| CN101139089A (en) * | 2007-08-09 | 2008-03-12 | 同济大学 | Method for preparing amphipathic nature block polymer decorated nanometer-carbon tube |
| WO2011063171A1 (en) * | 2009-11-23 | 2011-05-26 | Isp Investments Inc. | A reactive solution of polymerizable polymer comprising polymerizable reactive functionalities, process and compositions thereof |
| CN102399353A (en) * | 2011-07-29 | 2012-04-04 | 常州大学 | Preparation method of amphiphilic segmented copolymer |
| CN102643598A (en) * | 2012-04-09 | 2012-08-22 | 四川大学 | Antifouling seal-cleaning aqueous polyurethane leather finishing agent and preparation method thereof |
-
2017
- 2017-11-23 CN CN201711177897.5A patent/CN107857846B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002100439A1 (en) * | 2001-06-08 | 2002-12-19 | Labopharm, Inc. | Water-soluble stabilized self-assembled polyelectrolytes |
| CN101139089A (en) * | 2007-08-09 | 2008-03-12 | 同济大学 | Method for preparing amphipathic nature block polymer decorated nanometer-carbon tube |
| WO2011063171A1 (en) * | 2009-11-23 | 2011-05-26 | Isp Investments Inc. | A reactive solution of polymerizable polymer comprising polymerizable reactive functionalities, process and compositions thereof |
| CN102399353A (en) * | 2011-07-29 | 2012-04-04 | 常州大学 | Preparation method of amphiphilic segmented copolymer |
| CN102643598A (en) * | 2012-04-09 | 2012-08-22 | 四川大学 | Antifouling seal-cleaning aqueous polyurethane leather finishing agent and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499550A (en) * | 2018-12-19 | 2019-03-22 | 浙江工业大学 | A kind of semi-hydrophobic nano-crystal glue medium and preparation method thereof |
| CN109499550B (en) * | 2018-12-19 | 2022-02-15 | 浙江工业大学 | Semi-hydrophobic nano crystal glue medium and preparation method thereof |
| CN112300342A (en) * | 2020-11-04 | 2021-02-02 | 长兴电子（苏州）有限公司 | Novel method for synthesizing hydrophilic comb-shaped macromolecules by photoinitiation |
| CN112300342B (en) * | 2020-11-04 | 2022-04-01 | 长兴电子（苏州）有限公司 | Method for synthesizing hydrophilic comb-shaped macromolecules by photoinitiation |
| CN113057927A (en) * | 2021-03-29 | 2021-07-02 | 中科瑞晟芳香产业研究院(湖北)有限公司 | Hair-strengthening shampoo containing aromatic Chinese herbal medicines |
| CN115197379A (en) * | 2022-07-18 | 2022-10-18 | 福州大学 | Method for regulating and controlling polymer grafting density |
| CN115197379B (en) * | 2022-07-18 | 2023-09-22 | 福州大学 | Method for regulating and controlling polymer grafting density |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107857846B (en) | 2019-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107857846B (en) | A kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer | |
| Ke et al. | Controlled synthesis of linear and comb-like glycopolymers for preparation of honeycomb-patterned films | |
| Li et al. | Synthesis of biodegradable pentaarmed star-block copolymers via an asymmetric BIS-TRIS core by combination of ROP and RAFT: From star architectures to double responsive micelles | |
| CN104356318B (en) | A kind of starlike thermoplastic elastomer (TPE) of lignin-base and preparation method thereof | |
| Yu et al. | Open-air preparation of cross-linked CO 2-responsive polymer vesicles by enzyme-assisted photoinitiated polymerization-induced self-assembly | |
| CN105504322B (en) | A kind of method being improved with PTMC and PPDO to polyvinyl alcohol film water resistance and compliance | |
| CN110943249A (en) | Polymer electrolyte and lithium ion battery | |
| CN108310984A (en) | A kind of anti-pollution hydrophilic PVDF Modified Membrane and preparation method thereof | |
| Munoz-Bonilla et al. | Glycoparticles and bioactive films prepared by emulsion polymerization using a well-defined block glycopolymer stabilizer | |
| CN102633961A (en) | Preparation method of segmented copolymer from vinylidene chloride copolymer and polyethylene glycol | |
| Shen et al. | Synthesis of graft copolymer of ethyl cellulose through living polymerization and its self-assembly | |
| Fodor et al. | Poly (N‐vinylimidazole)‐l‐poly (tetrahydrofuran) amphiphilic conetworks and gels. II. Unexpected dependence of the reactivity of poly (tetrahydrofuran) macromonomer cross‐linker on molecular weight in copolymerization with N‐vinylimidazole | |
| CN103396521A (en) | Synthesis and micellization application of amphiphilic beta-cyclodextrin star polymer | |
| CN103483480A (en) | Artificial cell membrane materials applied to photoinduction stem grafting and synthesis method thereof | |
| CN112961273B (en) | Epoxy tea oil monomer-based reversible addition-fragmentation chain transfer emulsion polymerization method, polymer prepared by using method and application of polymer | |
| CN100412101C (en) | Amphipathic fluoride block copolymer and production thereof | |
| CN112608472A (en) | Terminal functionalized polymer and method for carrying out CuAAC polymerization by utilizing copper acetylide | |
| CN101104653A (en) | Process for preparing polymer modified carbon nano-tube | |
| CN107163203B (en) | A kind of multiform looks organic nano particle and its preparation method and application | |
| CN107903348A (en) | A kind of preparation method of polyethylene glycol grafting polymethyl methacrylate amphipathic graft copolymer | |
| CN103044697B (en) | Method for preparing microphase structural latex film | |
| CN114805822B (en) | Polymer molecular brush with multiblock side chains and preparation method and application thereof | |
| CN110804137A (en) | Block polymer containing perfluoropolyether structure | |
| CN105885082A (en) | Method for preparing surface glycosyl modified porous material by utilizing highly-introverted emulsion template method | |
| CN101838374A (en) | Method for preparing crosslinked polymer nanometer micelle with structure simulating outer cell membranes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |