CN110128578A - The light-operated reversible complexing of aqueous solution polymerize and the preparation of polymer nano-particle - Google Patents
The light-operated reversible complexing of aqueous solution polymerize and the preparation of polymer nano-particle Download PDFInfo
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- CN110128578A CN110128578A CN201910516532.3A CN201910516532A CN110128578A CN 110128578 A CN110128578 A CN 110128578A CN 201910516532 A CN201910516532 A CN 201910516532A CN 110128578 A CN110128578 A CN 110128578A
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- methacrylate
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- 229920000642 polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 title abstract description 15
- 230000002441 reversible effect Effects 0.000 title description 9
- 230000000536 complexating effect Effects 0.000 title description 7
- 239000000178 monomer Substances 0.000 claims abstract description 33
- -1 methyl acrylic ester Chemical class 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000005286 illumination Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 10
- 150000001351 alkyl iodides Chemical class 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 239000011630 iodine Substances 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 229920000151 polyglycol Polymers 0.000 claims description 6
- 239000010695 polyglycol Substances 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- HRGQEKKNLHJZGZ-UHFFFAOYSA-N 2-methylpropyl 2-cyanoacetate Chemical group CC(C)COC(=O)CC#N HRGQEKKNLHJZGZ-UHFFFAOYSA-N 0.000 claims description 4
- OFJWFSNDPCAWDK-UHFFFAOYSA-N 2-phenylbutyric acid Chemical compound CCC(C(O)=O)C1=CC=CC=C1 OFJWFSNDPCAWDK-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims 1
- 229920001400 block copolymer Polymers 0.000 claims 1
- 229920001515 polyalkylene glycol Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 5
- 230000001939 inductive effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 150000003254 radicals Chemical class 0.000 abstract description 4
- 239000000693 micelle Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000003708 ampul Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229940113088 dimethylacetamide Drugs 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 description 2
- DBESYUOJKJZGLV-UHFFFAOYSA-N 2-iodo-2-methylpropanenitrile Chemical compound CC(C)(I)C#N DBESYUOJKJZGLV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QDERNBXNXJCIQK-UHFFFAOYSA-N ethylisopropylamiloride Chemical compound CCN(C(C)C)C1=NC(N)=C(C(=O)N=C(N)N)N=C1Cl QDERNBXNXJCIQK-UHFFFAOYSA-N 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C08F2438/00—Living radical polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of visible light-inducing iodine of water-soluble monomer in aqueous solution to regulate and control reversibly inactivated free radical polymerisation process and polymer nano-particle preparation, the following steps are included: in protective atmosphere, by Water-soluble methyl acrylic ester monomer and alkyl iodide initiator, it is added to the water and is reacted at 20-30 DEG C, illumination wavelength is 390-590nm, Water-soluble methyl acrylic polymer is obtained after the reaction was completed, oil-soluble methacrylate-based monomer is added and carries out chain extending reaction, it obtains amphipathic nature block polymer and spherical micelle nanoparticle can be automatically assembled into aqueous solution.The present invention directly polymerize in water, polymerize that component is simple, polymerizing condition is mild, the polymerization of methacrylate-based monomer and the preparation of polymer nano-particle can be realized without extra catalyst, prepared polymer molecular weight narrow distribution, stable spherical polymer nanoparticle is obtained, polymerization process has " activity " free radical polymerization characteristic.
Description
Technical field
The present invention relates to technical field of polymer preparation more particularly to the reversible complexing polymerization of light-operated aqueous solution and polymer nanos
The preparation of rice corpuscles.
Background technique
In recent years, the development of RDRP (reversibly inactivated free radical polymerization) method is swift and violent, become synthesis have specific structure and
A strong tools of polydispersity polymer can be designed.Up to the present, various RDRP methods such as nitrogen oxidation stability living radical
It polymerize (NMP), atom transfer radical polymerization (ATRP), reversible addion-fragmentation chain transfer (RAFT) polymerization and reversible complexing are poly-
Close the effective ways that (RCMP) etc. has become preparation " activity " polymer.RCMP be it is a kind of by alkyl iodide and additional organic amine,
The reversible complexing of the catalyst such as NaI, iodine drone salt carries out the RDRP technology of number of free radical regulation, because of its mild item
Part, extensive monomer applicability, no residual transition metal and it is easily operated the features such as gradually cause the pass of many scientists
Note.
On the other hand, illumination is as a kind of environmentally protective, easy to operate, low-cost stimulation mode, in many systems
In be widely used.Have more at present about light-operated RCMP at ontology (Chem.Commun.2016,52,10850.)
And the organic solvents such as N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide (DMAC)
(Polym.Chem.2016,7,3576.) document report being polymerize in.Polymer nano-particle coating, medicament transport,
Gene diagnosis etc. is widely used, therefore the synthesis methodology research of polymer nano-particle has been developed as a hot topic
Research topic.Water uses it to carry out aqueous solution polymerization, green, inexpensive, ring as medium as a kind of natural green solvent
It protects, safety.However, how light-operated RCMP technical application is carried out polymerization into aqueous solution yet there are no document report.
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of light-operated reversible complexings of aqueous solution to polymerize and polymerize
The preparation of object nanoparticle, the present invention under visible light illumination, are directly polymerize in water, polymerize that component is simple, polymerization item
Part is mild, and the polymerization of methacrylate-based monomer and the preparation of polymer nano-particle can be realized without extra catalyst,
Prepared polymer molecular weight narrow distribution, obtains stable spherical polymer nanoparticle, and polymerization process has " activity "
Free radical polymerization characteristic.
The first purpose of this invention is to regulate and control the reversible complexing polymerization of aqueous solution using visible light-inducing iodine, provides one
The preparation method of kind Water-soluble methyl acrylic polymer, comprising the following steps:
It is in protective atmosphere, the alkyl iodide initiator of Water-soluble methyl acrylic ester monomer and formula (1) is soluble in water,
Obtained solution is reacted at 20-30 DEG C under illumination condition, illumination wavelength 390-590nm obtains formula after the reaction was completed
(2) Water-soluble methyl acrylic polymer shown in；Wherein, formula (1)-(2) are as follows:
Wherein, m=10-200；
R1Selected from isobutyl cyano or α-ethyl phenylacetate base；
R is selected from poly glycol monomethyl ether base, ethoxy or hydroxypropyl.
Further, work as R1When for isobutyl cyano, alkyl iodide initiator is the iodo- 2- methyl propionitrile (CP-I) of 2-；Work as R1For α-
When ethyl phenylacetate base, alkyl iodide initiator is alpha-iodine ethyl phenylacetate (EIPA).
Further, Water-soluble methyl acrylic ester monomer be Methylacrylic acid polyethylene glycol single armor ether ester (PEGMA),
Hydroxyethyl methacrylate (HEMA) or hydroxy propyl methacrylate (HPMA).Preferably, Water-soluble methyl esters of acrylic acid list
Body is PEGMA.
Further, the molar ratio of Water-soluble methyl acrylic ester monomer and alkyl iodide initiator is 10~200:1.It is excellent
The molar ratio of selection of land, Water-soluble methyl acrylic ester monomer and alkyl iodide initiator is 10~100:1.
Further, reaction time 3-36h.
Further, in solution, the concentration of Water-soluble methyl acrylic ester monomer is 1.0-4.0mol/L.
Further, the molecular weight distributing index of Water-soluble methyl acrylic polymer is 1.05-1.21.
Further, light source used in illumination of the present invention is LED light.Preferably, illumination wavelength 465nm.
A second object of the present invention is to provide a kind of preparation methods of polymer nano-particle, comprising the following steps:
Cause using Water-soluble methyl acrylic polymer prepared by the above-mentioned preparation method of the present invention as macromolecular
Agent, in protective atmosphere, by oil-soluble methacrylate-based monomer under the action of the macromole evocating agent, in water in
20-30 DEG C issues the third contact of a total solar or lunar eclipse according to polymerization, and illumination wavelength 390-590nm obtains the amphiphilic block of formula (3) after the reaction was completed
Object, the amphipathic nature block polymer in water assemble in situ at the polymer nano-particle；Wherein, formula (3) is as follows:
Wherein, m=10-200；N=20-300；
R1Selected from isobutyl cyano or α-ethyl phenylacetate base；
R is selected from poly glycol monomethyl ether base, ethoxy or hydroxypropyl；
R2Selected from benzyl or C1-C6 alkyl.
Preferably, R1Selected from isobutyl cyano, R is selected from poly glycol monomethyl ether base, R2Selected from benzyl, methyl or normal-butyl.
Further, oil-soluble methacrylate-based monomer is benzyl methacrylate (BnMA), methyl methacrylate
Ester (MMA) or butyl methacrylate (BMA).Preferably, oil-soluble methacrylate-based monomer is BnMA.
Further, the molar ratio of oil-soluble methacrylate-based monomer and macromole evocating agent is 20~300:1.It is excellent
The molar ratio of selection of land, oil-soluble methacrylate-based monomer and macromole evocating agent is 50~100:1.
Further, the concentration of oil-soluble methacrylate-based monomer described in water is 0.5-4.0mol/L.
Further, polymer nano-particle is spherical micelle nanoparticle, partial size 30-150nm.
Further, reaction time 10-24h.
Further, the molecular weight distributing index of amphipathic nature block polymer is 1.10-1.29.
Further, light source used in illumination of the present invention is LED light.Preferably, illumination wavelength 465nm.
According to the above aspect of the present invention, the present invention has at least the following advantages:
The present invention provides the preparation methods of Water-soluble methyl acrylic polymer, and cause as macromolecular
Agent, further prepares polymer nano-particle, the preparation method of above two substance, using pure water as solvent, inexpensive, green, ring
Protect, safety, be not required to extra catalyst, polymerization component is simple, light source is used as using room temperature LED etc., reaction condition it is mild, it can be achieved that
The visible light-inducing RCMP of Water-soluble methyl acrylic ester monomer, having obtained narrow molecular weight distribution, polymer molecular weight can set
The water-soluble polymer and polymer nano-particle of meter.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is PPEGMA1H NMR test result；
Fig. 2 is PPEGMA-b-PBnMA1H NMR test result；
Fig. 3 (a) is the elution curve figure for the polymer that chain extension is tested and the PPEGMA- that (b) is observed by TEM
The shape appearance figure of b-PBnMA assembly；
Fig. 4 is the kinetics of polymerization figure in PPEGMA preparation process.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
In following embodiment of the present invention, used raw material PEGMA, HEMA, HPMA, BnMA needed neutral alumina pillar
Polymerization inhibitor is removed, the preservation of refrigerator upper layer is then placed into.Other reagents directly use after being obtained through commercial channels.
In the present invention, using following test method:
1, the number-average molecular weight (M of resulting polymersn,GPC) and molecular weight distribution (Mw/Mn) solidifying by TOSOH HLC-8320
Glue penetration chromatograph (GPC) measures, apparatus preparation TOSOH differential refraction detector, guard column (4.6 × 20mm,
TSKgel guard column SuperMP-N) He Lianggen test pole (4.6 × 150mm, TSKgelSupermultiporeHZ-
N), testable molecular weight ranges are from 5 × 102To 5 × 105g/mol.Using DMF+0.01mol/L LiBr as mobile phase when test,
Temperature is 40 DEG C, flow velocity 0.6mL/min.Sample is tested by the absorption of TOSOH autosampler, is selected when analyzing data
The line style PS bought from TOSOH is selected as standard specimen.The preparation process for testing the sample of GPC is as follows: taking the mixed with polymers of 20 μ L
Solution removes solvent, is then dissolved polymer with DMF by freeze-drying, and polymer solution is passed through a neutral alumina
Duckpin and syringe equipped with 0.45 μm of filter, in polymer solution injection test bottle that finally will be pure.
2, the nuclear magnetic spectrogram of resulting polymers is tested to obtain by Bruker 300MHz Nuclear Magnetic Resonance, with D2O or
DMSO-d6For deuterated reagent, (25 DEG C) tests at room temperature, tetramethylsilane (TMS) is internal standard.
3, UV-vis is measured by Shimadzu UV-2600 ultraviolet-visible spectrophotometer, H2O is solvent.
4, the shape appearance figure of polymer nano-particle is obtained by FEI TecnaiG22 transmission electron microscope (TEM), is added
Fast voltage is 120kV.It takes the mixed with polymers solution of 4 μ L in the ampoule bottle of a dried and clean, the H of 5mL is added2O dilution, so
Solution (0.5mg/mL) after drawing 10 μ L dilution afterwards drips on the carbon-coated copper mesh of 200 mesh.After standing 40 seconds, with prior shearing
Good filter paper siphons away extra solvent below copper mesh.In order to preferably observe the pattern of polymer nano-particle, need with dense
Degree is that the phosphotungstic acid aqueous solution of 1.0%w/w dyes it.Therefore, the phosphotungstic acid aqueous solution drop for drawing 10 μ L is being dripped
Have on the copper mesh of polymer nano-particle, is siphoned away again with filter paper shear in advance from copper mesh lower section after standing 20 seconds extra molten
Agent is finally dried at room temperature.
Embodiment 1: the preparation of polymethylacrylic acid poly glycol monomethyl ether ester (PPEGMA)
[PEGMA] in molar ratio0/[CP-I]0=50/1, respectively by PEGMA (1.09g, 2.18mmol), CP-I (8.5mg,
0.04mmol), H2O (1.0mL) is added in the ampoule bottle of 5mL cleaning, is put into a clean stirrer.Mixed solution is
Colorless and transparent homogeneous phase solution, ampoule bottle, which is placed in liquid nitrogen, freezes solution, is then evacuated 20~30 seconds, then be passed through argon gas,
Make its dissolution of thawing at room temperature, by gas displacement three times, the oxygen in ampoule bottle is eliminated, and be at argon atmosphere
Under, ampoule bottle is moved at gun slot rapidly, is sealed ampoule bottle with flame envelope.The ampoule bottle for sealing mouth is placed on and is installed in advance
Blue LED lamp band (wavelength 464nm, 15mW/cm2) lamp panel in, try to get to the heart of a matter and place blender, beside lamp panel place an electricity
Fan keeps polymerization temperature at room temperature.Ampoule bottle is moved to dark place, breaks pipe, moved with liquid-transfering gun by reaction to certain time
50 μ L polymer solutions are taken to be dissolved in D2O is carried out1H NMR test, calculates conversion ratio.The mixed with polymers solution for taking 20 μ L, through being subcooled
It is lyophilized dry, removes solvent, be dissolved in DMF progress GPC test.
Fig. 1 is PPEGMA after purification1H NMR test result；
Embodiment 2: the preparation (chain extension experiment) of polymer nanoparticle PPEGMA-b-PBnMA
[PEGMA] in molar ratio0/[CP-I]0=10/1, respectively by PEGMA (0.55g, 1.09mmol), CP-I
(19.1mg, 0.11mmol), H2O (1.0mL) is added in the ampoule bottle of 5mL cleaning, is put into a clean stirrer, presses
According to the condition of embodiment 1, in argon atmosphere, after reacting 6h under same illumination condition, pipe is broken, is taken out a certain amount of
Reaction solution remains to test, then using obtained PPEGMA as macromole evocating agent, directly by BnMA (0.37mL, 2.18mmol),
H2O (3.50mL) is mixed with reaction solution, is transferred in new ampoule bottle, and ampoule bottle is made to be under argon atmosphere and close with flame
Envelope.The ampoule bottle for sealing mouth is allowed to continue in blue LED lamp band (wavelength 464nm, 15mW/cm2) the lower reaction of irradiation.It is molten to play first oil
Property BnMA and polymerization system it is immiscible, after a certain period of time, reaction solution is in uniform white emulsion shape for reaction, after 18h, by ampoule bottle
Dark place is moved to, pipe is broken, pipettes 1.0mL polymer with liquid-transfering gun, purified by petroleum ether precipitation, and resulting polymers are dissolved in
DMSO-d6It carries out1H NMR test.
Fig. 2 is PPEGMA-b-PBnMA1H NMR test result can clearly be seen in BnMA from nuclear magnetic spectrogram
The characteristic peak for the hydrogen being connected with phenyl ring, this shows that the present invention has obtained amphipathic nature block polymer PPEGMA-b-PBnMA.
The mixed with polymers solution for taking 20 μ L removes solvent by freeze-drying, is dissolved in progress GPC test in DMF.Fig. 3
(a) the elution curve figure before and after PPEGMA polymer chain extension and the PPEGMA-b-PBnMA assembly (b) observed by TEM
Shape appearance figure.Fig. 3 (a) show PPEGMA before chain extension, molecular weight 5000g/mol, molecular weight distributing index 1.09
(curve 1)；After chain extension, the molecular weight of obtained PPEGMA-b-PBnMA is 9100g/mol, molecular weight distributing index 1.10
(curve 2).Polymer molecular weight obviously increases the success for similarly showing amphipathic nature block polymer PPEGMA-b-PBnMA
Synthesis.It tests to have obtained the shape appearance figure of assembly by TEM.Amphipathic nature block polymer assemble in situ shape in aqueous solution
The partial size of spherical micelle nanoparticle is 58.9nm.
In chain extension experiment, other methyl acrylic ester lists in addition to BnMA are also may be selected in used polymerized monomer
Body, such as MMA, BMA, also can be obtained polymer nano-particle.
Embodiment 3: dynamic experiment
[PEGMA] in molar ratio0/[CP-I]0=50/1, respectively by PEGMA (1.09g, 2.18mmol), CP-I (8.5mg,
0.04mmol), H2O (1.0mL) is added in the ampoule bottle of 5mL cleaning, is put into a clean stirrer.Mixed solution is
Colorless and transparent homogeneous phase solution, ampoule bottle, which is placed in liquid nitrogen, freezes solution, is then evacuated 20~30 seconds, then be passed through argon gas,
Make its dissolution of thawing at room temperature, by gas displacement three times, the oxygen in ampoule bottle is eliminated, and be at argon atmosphere
Under, ampoule bottle is moved at gun slot rapidly, is sealed ampoule bottle with flame envelope.By measure different reaction time (6h, 8h,
12h, 16h, for 24 hours) under monomer conversion ratio, obtain kinetics of polymerization figure as shown in Figure 4.In Fig. 4 (a), right-to-left, polymerization
Time is sequentially increased, and molecular weight and molecualr weight distribution corresponding to right-to-left curve is followed successively by 13800g/mol, and 1.08；
15800g/mol, 1.09；18400g/mol, 1.11；20000g/mol, 1.14；21000g/mol, 1.17.It can be with from Fig. 4 (a)
Find out, variation of the molecular weight of polymer from the longer delivery time to the shorter delivery time show the molecular weight of polymer from
The small process to become larger；In Fig. 4 (b), ln ([M]0/ [M]) as the extension of time is in nearly level-one linear relationship；It can from Fig. 4 (c)
To find out, the molecular weight of polymer is with the increase of conversion ratio, the substantially trend that increases of presentation line style, molecular weight distribution also compared with
Narrow (Mw/Mn<1.20).Since the molecular weight of polymer is smaller, so being tested by GPC, the molecule being calculated using PS as standard specimen
There are biggish errors with theoretical molecular weight for amount.Kinetics of polymerization shows in the case where blue LED lamp band irradiates hydrophily in aqueous solution
The photoinduction iodine of monomer regulates and controls the feature that reversibly inactivated free radical polymerization meets " activity " polymerization.
To sum up, the present invention is by being added to the water Water-soluble methyl acrylic ester monomer and alkyl iodide initiator in 20-
It is reacted at 30 DEG C, illumination wavelength 390-590nm, the visible light-inducing iodine regulation for realizing water-soluble monomer in aqueous solution is reversible
Free radical polymerisation process is inactivated, several different Water-soluble methyl acrylic polymers is prepared for, oil-soluble first is added
Base acrylic ester monomer carries out chain extending reaction, obtains amphipathic nature block polymer and can primary reconstruction balling-up in aqueous solution
Shape micellar nanoparticles realize the preparation of polymer nano-particle.The present invention is using environmentally protective pure water as solvent, aggregation group
Part is simple, polymerizing condition is mild, is not necessarily to extra catalyst, is successfully realized polymerization and the polymer of methacrylate-based monomer
The preparation of nanoparticle, and prepared polymer molecular weight narrow distribution, obtain stable spherical polymer nanoparticle, gather
Conjunction process has " activity " free radical polymerization characteristic.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of Water-soluble methyl acrylic polymer, which comprises the following steps:
It is in protective atmosphere, the alkyl iodide initiator of Water-soluble methyl acrylic ester monomer and formula (1) is soluble in water, will
To solution reacted at 20-30 DEG C under illumination condition, illumination wavelength 390-590nm obtains formula (2) institute after the reaction was completed
The Water-soluble methyl acrylic polymer shown；Wherein, formula (1)-(2) are as follows:
Wherein, m=10-200；
R1Selected from isobutyl cyano or α-ethyl phenylacetate base；
R is selected from poly glycol monomethyl ether base, ethoxy or hydroxypropyl.
2. preparation method according to claim 1, it is characterised in that: the Water-soluble methyl acrylic ester monomer is first
Base polyalkylene glycol acrylate monomethyl ether ester, hydroxyethyl methacrylate or hydroxy propyl methacrylate.
3. preparation method according to claim 1, it is characterised in that: the Water-soluble methyl acrylic ester monomer and alkane
The molar ratio of base iodine initiator is 10~200:1.
4. preparation method according to claim 1, it is characterised in that: reaction time 3-36h.
5. preparation method according to claim 1, it is characterised in that: in solution, Water-soluble methyl acrylic ester monomer
Concentration be 1.0-4.0mol/L.
6. a kind of preparation method of polymer nano-particle, which comprises the following steps:
Using Water-soluble methyl acrylic polymer prepared by preparation method of any of claims 1-5 as
Macromole evocating agent, in protective atmosphere, by oil-soluble methacrylate-based monomer the macromole evocating agent effect
Under, the third contact of a total solar or lunar eclipse is issued in 20-30 DEG C in water according to polymerization, illumination wavelength 390-590nm obtains the two of formula (3) after the reaction was completed
Parent's property block copolymer, the amphipathic nature block polymer in water assemble in situ at the polymer nano-particle；Wherein, formula
(3) as follows:
Wherein, m=10-200；N=20-300；
R1Selected from isobutyl cyano or α-ethyl phenylacetate base；
R is selected from poly glycol monomethyl ether base, ethoxy or hydroxypropyl；
R2Selected from benzyl or C1-C6 alkyl.
7. preparation method according to claim 6, it is characterised in that: the oil-soluble methacrylate-based monomer is first
Base benzyl acrylate, methyl methacrylate or butyl methacrylate.
8. preparation method according to claim 6, it is characterised in that: the oil-soluble methacrylate-based monomer and big
The molar ratio of initiator molecule is 20~300:1.
9. preparation method according to claim 6, it is characterised in that: oil-soluble methacrylate-based monomer described in water
Concentration be 0.5-4.0mol/L.
10. preparation method according to claim 6, it is characterised in that: the partial size of the polymer nano-particle is 30-
150nm。
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| CN111440279B (en) * | 2020-05-26 | 2022-04-01 | 苏州大学 | Preparation method of block polymer with adjustable molecular weight distribution |
| CN112028900A (en) * | 2020-09-10 | 2020-12-04 | 苏州大学 | Synthesis of star polymer and monomolecular micelle by light-operated in-situ bromine-iodine conversion RDRP method |
| CN112028900B (en) * | 2020-09-10 | 2021-08-31 | 苏州大学 | Synthesis of star polymer and monomolecular micelle by light-operated in-situ bromine-iodine conversion RDRP method |
| CN114805798A (en) * | 2022-05-19 | 2022-07-29 | 福州大学 | Heterogeneous catalyst for visible light induced controllable free radical polymerization |
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