CN110330609A - A kind of aqueous solution open environment anionic polymerisation process - Google Patents
A kind of aqueous solution open environment anionic polymerisation process Download PDFInfo
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- CN110330609A CN110330609A CN201910653617.6A CN201910653617A CN110330609A CN 110330609 A CN110330609 A CN 110330609A CN 201910653617 A CN201910653617 A CN 201910653617A CN 110330609 A CN110330609 A CN 110330609A
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- -1 vinyl sulfone compound Chemical class 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical group CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000003205 fragrance Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 150000007530 organic bases Chemical class 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 12
- 229920000151 polyglycol Polymers 0.000 description 12
- 239000010695 polyglycol Substances 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 229960003237 betaine Drugs 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007995 HEPES buffer Substances 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229920001464 poly(sodium 4-styrenesulfonate) Polymers 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- RTQUAUBDJBWXEQ-UHFFFAOYSA-N 3-sulfonylprop-2-enoic acid Chemical compound OC(=O)C=C=S(=O)=O RTQUAUBDJBWXEQ-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920006250 telechelic 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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 invention discloses a kind of methods of anionic polymerisation under aqueous solution open environment, the method is using vinyl sulfone compound as initiator, organic base is catalyst, and 25~100 DEG C of reaction 1-72h realize the aqueous environment anionic polymerisation containing α-electron-withdrawing group alkene.This method wide application range of substrates；Reaction condition is mild, operates without anhydrous and oxygen-free, and controllability is strong；It is a kind of aqueous environment anionic polymerisation process having a high potential.
Description
Technical field
The invention belongs to the field of polymers, and in particular to anionic polymerisation process under open environment in a kind of aqueous solution.
Technical background
High molecular material is widely used in the research of daily life and every field.High molecular material is usually
It is prepared by monomer by polymerization reaction, common polymerization reaction includes free radical polymerization, cationic polymerization and anionic polymerisation.
Living anion polymerization have the characteristics that without terminate, without chain tra nsfer, be that prepare the uniform polymer standards product of molecular weight, block total
The ideal method of polymers and the telechelic polymer that can be rolled into a ball with special hat.
The olefinic monomer of anionic polymerisation usually has electron-withdrawing, makes double bond with certain electropositive, has electrophilic
Property, by alkali metal or the catalyst with anion and monomer form anion active center, and activated centre passes through chain growth
Reaction generates macromolecule.In anionic polymerisation, monomer forms anion active species once initiation, just with the progress of identical mode
Chain growth, generally without termination or chain tra nsfer, until monomer exhausts, therefore referred to as living polymerization.Compared to free radical polymerization, yin
Ionic polymerization monomer utilization ratio is higher.Common anionic polymerization catalyst mainly has two major classes, and one kind is alkali metal, passes through alkali
Outer-shell electron is transferred directly to monomer by metal, forms free radical-anion, and it is anti-to be further formed dianion progress chain growth
It answers；One kind is organo-metallic compound, such as butyl lithium, and potassium tert-butoxide and Grignard Reagent etc., organo-metallic compound is in the solution
Alkyl carbanion or alkoxy anion are formed, changes anion and monomer reaction generates anion, further realize chain growth.
In addition, other nucleopilic reagents, such as R3N and R3P etc. also can trigger monomer and generate amphoteric ion, but its activity is weaker, can only cause
Very active monomer polymerization.Reaction mechanism based on anionic polymerisation, existing anionic polymerisation usually all have non-proton
It is carried out in solvent, is terminated and reacted by Bronsted acid.Reaction needs to carry out in anhydrous system, to prevent Anionic Active kind
Termination.
Summary of the invention
The present invention is intended to provide anionic polymerisation process under a kind of aqueous solution open environment, the method includes walking as follows
Rapid: using the vinyl sulfone compound with II structure of general formula as initiator, cause has general formula I under the action of catalyst
The water phase anionic polymerisation of polymer monomer can be realized in 25-100 DEG C of reaction 1-72h containing α-electron-withdrawing group alkene
High molecular material is made in aqueous environment anionic polymerisation, has general formula III structure.
Reaction route is as follows:
Wherein, X is electron-withdrawing group, is spread out selected from sulfuryl, acrylate, acrylamide or fragrance containing electron-withdrawing group
Biology；Y is selected from hydrogen atom, methyl or ethyl；R is organic deriveding group；R ' is organic deriveding group, preferably water-soluble organic
Deriveding group, more preferably oligomeric ethylene glycol.
For in technique described above scheme, in preferred situation, the initiator polymerize as polymer monomer
Chain initiator, have vinylsulfone group.
For in technique described above scheme, in preferred situation, the polymer monomer has the knot of general formula I
Structure, X is electron-withdrawing group in formula, is selected from sulfurylAcrylateAcrylamideOr it is electric containing inhaling
The fragrance derivatives of subbase group, such asY is selected from hydrogen atom H, methyl CH3, ethyl
CH2CH3；
For in technique described above scheme, in preferred situation, the catalyst is three substitution organic amines, it is selected from
1- methylimidazole, triethylenediamine, hexa, N, N- dimethylamino naphthyridine.
For in technique described above scheme, in preferred situation, the dosage of the catalyst is polymer monomer object
The 0.1%-10% of the amount of matter.
For in technique described above scheme, in preferred situation, the dosage of the initiator is polymer monomer
The 0.1%-5% of the amount of substance.
For in technique described above scheme, in preferred situation, preferred 35-60 DEG C of the reaction temperature.
For in technique described above scheme, in preferred situation, the reaction time preferred 12-72h.
For that in preferred situation, can lead to during water phase anionic polymerisation in technique described above scheme
It crosses and solution is adjusted to acid termination reaction, such as add hydrochloric acid that solution is adjusted to acid termination reaction.
The invention further relates to the polymer materials that the Sustainable use above method is prepared, and have general formula III structure.
The present invention provides anionic polymerisation process under a kind of aqueous solution open environment, are with active ethylene group sulphones
Initiator forms internal salt structure by organic base catalytic, and carbanion causes monomer polymerization in solution in internal salt structure, real
Chain termination reaction may be implemented by adjusting solution condition in existing chain growth, and controllability is strong, and monomer utilization ratio is high, aqueous phase reactions ring
Border is friendly, and mild condition is a kind of huge anionic polymerization of application potential.
The utility model has the advantages that
Anionic polymerisation process under aqueous solution open environment of the present invention, has relative to conventional anion polymerization
Following advantage:
(1) catalyst is done using organic base, avoids the use of normal starter (such as potassium tert-butoxide, butyl lithium etc.), mentions
High operational safety；
(2) reaction condition is mild, and open environment reaction does not need anhydrous and oxygen-free operation, and easy to operate, controllability is strong；
(3) aqueous phase reactions, it is environmental-friendly；
To sum up, this method substrate applicability is wide, easy to operate, and mild condition is environmental-friendly, be it is a kind of have a high potential it is wide
Spectrality aqueous environment anionic polymerisation process.
Detailed description of the invention
Fig. 1 is that three poly glycol monomethyl ether vinyl sulfones are initiator, and methacrylic sulfonic acids glycine betaine (SBMA) is single
Body, 1- methylimidazole are polymethylacrylic acid sulphonic acid betaine (pSBMA) made from catalyst1HNMR spectrogram.
Fig. 2 is that three poly glycol monomethyl ether vinyl sulfones are initiator, and methacrylic sulfonic acids glycine betaine (SBMA) is single
Body, 1- methylimidazole are the gel aqueous phase permeation chromatography figure of polymethylacrylic acid sulphonic acid betaine (pSBMA) made from catalyst.
Fig. 3 is that three poly glycol monomethyl ether vinyl sulfones are initiator, and hydroxyethyl methacrylate (HEMA) is monomer, 1-
Methylimidazole is the gel aqueous phase permeation chromatography figure of poly hydroxy ethyl acrylate (pHEMA) made from catalyst.
Fig. 4 is that three poly glycol monomethyl ether vinyl sulfones are initiator, and N,N-DMAA is monomer, 1- methyl
Imidazoles is poly- N made from catalyst, the gel aqueous phase permeation chromatography figure of N- dimethylacrylamide.
Fig. 5 is that three poly glycol monomethyl ether vinyl sulfones are initiator, and sodium p styrene sulfonate is monomer, 1- methylimidazole
For the gel aqueous phase permeation chromatography figure of poly (sodium 4-styrenesulfonate) made from catalyst.
Specific embodiment
Following nonlimiting examples can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
The present invention provides anionic polymerisation process under a kind of aqueous solution open environment, the chain initiator is vinyl
Sulfone group compound, have II structure of general formula, R ' be organic deriveding group, preferably water-soluble organic deriveding group, more preferably
For oligomeric ethylene glycol；The polymer monomer has the structure of general formula I, and X is electron-withdrawing group in formula, is selected from sulfuryl, acrylic acid
Ester, acrylamide, or the fragrance derivatives containing electron-withdrawing group, including but not limited to
Y is selected from hydrogen atom, methyl, ethyl；The catalyst is three to replace organic amines, preferred 1- methylimidazole, triethylenediamine, six
Methenamine, N, N- dimethylamino naphthyridine.
Reaction route is as follows:
Following specific embodiments are that the content of the present invention will be further explained, be should not be construed as to any shape of the present invention
The restriction of formula.
Three poly glycol monomethyl ether vinyl sulfone (M-EG in following embodiments3- VS) according to document
The step of (Biointerphases, 2017,12,02C414) is reported synthesizes.
Embodiment 1: with three poly glycol monomethyl ether vinyl sulfone (M-EG3- VS) it is initiator, methacrylic sulfonic acids sweet tea
Dish alkali (SBMA) is that monomer prepares polymethylacrylic acid sulphonic acid betaine (pSBMA)
By M-EG3- VS, SBMA monomer and 1- methylimidazole are dissolved in 12mL according to the ratio of concentration ratio 2mM:100mM:10mM
In HEPES buffer solution (pH 8.0), 35 DEG C are added hydrochloric acid after reaction 48 hours and terminate reaction in acid to solution.Use retention point
It is lyophilized, uses after the ultrafiltration membrane dialysis that son amount is 3000Da1HNMR and water phase GPC characterization, as shown in Figure 1 and Figure 2.
As can be seen that reaction product corresponds to the position h methyl peak at the peak 1.00ppm from nuclear magnetic resonance spectroscopy (Fig. 1)；?
There is new peak in 1.94ppm, the methylene peak of the position pSBMAg after corresponding SBMA monomer polymerization；The peak 2.20ppm corresponds to the position f methylene
Base peak；The methylene peak of the corresponding position e adjacent with sulfonic group in the peak 2.90ppm；The peak 3.15ppm corresponds to two first on the quaternary ammonium of the position d
Base peak；The peak 3.50ppm and the peak 3.70ppm respectively correspond the position b, c methylene peak；It is neighbouring with ester group that the peak 4.40ppm corresponds to the position a
Methylene peak, it was demonstrated that polymerization reaction occur.As can be seen that reaction obtains the number-average molecular weight of product from water phase GPC (Fig. 2)
It (Mn) is 313583, monodispersity index (PDI) is 1.391.
Embodiment 2: with three poly glycol monomethyl ether vinyl sulfone (M-EG3- VS) it is initiator, hydroxyethyl methacrylate
(HEMA) poly hydroxy ethyl acrylate (pHEMA) is prepared for monomer
By M-EG3- VS, HEMA monomer and 1- methylimidazole are dissolved according to the ratio of concentration ratio 2mM:100mM:10mM
In 12mLHEPES buffer (pH 8.0), 35 DEG C hydrochloric acid is added after reaction 48 hours and terminates reaction in acid to solution, freeze-drying,
It is characterized using water phase GPC.Polymerization reaction occurs as can be seen from Figure 3, and the number-average molecular weight (Mn) that reaction obtains product is 1291,
Monodispersity index (PDI) is 1.072.
Embodiment 3: with three poly glycol monomethyl ether vinyl sulfone (M-EG3- VS) it is initiator, N, N- dimethyl allene acyl
Amine is that monomer prepares poly- N, N- dimethylacrylamide
By M-EG3- VS, N,N-DMAA monomer and 1- methylimidazole are according to concentration ratio 2mM:100mM:10mM
Ratio be dissolved in 12mLHEPES buffer (pH 8.0), 35 DEG C are added hydrochloric acid after reaction 48 hours and terminate to solution in acid
Reaction, freeze-drying, is characterized using water phase GPC.Polymerization reaction occurs as can be seen from Figure 4, and reaction obtains the number-average molecular weight of product
It (Mn) is 1266, monodispersity index (PDI) is 1.022.
Embodiment 4: with three poly glycol monomethyl ether vinyl sulfone (M-EG3- VS) it is initiator, sodium p styrene sulfonate is
Monomer prepares poly (sodium 4-styrenesulfonate)
By M-EG3- VS, sodium p styrene sulfonate monomer and 1- methylimidazole according to concentration ratio 2mM:100mM:10mM ratio
Example is dissolved in 12mLHEPES buffer (pH 8.0), and 35 DEG C are added hydrochloric acid after reaction 48 hours and terminate reaction in acid to solution,
Freeze-drying, is characterized using water phase GPC.Polymerization reaction occurs as can be seen from Figure 5, and the number-average molecular weight (Mn) that reaction obtains product is
1278, monodispersity index (PDI) is 1.024.
Embodiment 5: with three poly glycol monomethyl ether vinyl sulfone (M-EG3- VS) it is initiator, n-isopropyl acrylamide
Polyisopropyl acrylamide is prepared for monomer
By M-EG3- VS, n-isopropyl acrylamide monomer and triethylenediamine are according to concentration ratio 2mM:100mM:2mM's
Ratio is dissolved in 12mLHEPES buffer (pH 8.0), 35 DEG C be added after reaction 48 hours hydrochloric acid to solution in it is acid terminate it is anti-
It answers, is lyophilized after being dialysed using the ultrafiltration membrane that molecular cut off is 3000Da.The white powder of acquisition is poly- isopropyl acrylamide
Amine
Embodiment 6: with three poly glycol monomethyl ether vinyl sulfone (M-EG3- VS) it is initiator, methacrylic sulfonic acids sweet tea
Dish alkali (SBMA) is that monomer prepares polymethylacrylic acid sulphonic acid betaine (pSBMA)
By M-EG3- VS, SBMA monomer and N, N- dimethylamino naphthyridine are molten according to the ratio of concentration ratio 2mM:100mM:2mM
In 12mL HEPES buffer solution (pH 8.0), 35 DEG C are added hydrochloric acid after reaction 48 hours and terminate reaction in acid to solution.Rotation
Ethyl alcohol recrystallization is added after dereaction solvent is evaporated off, obtaining white precipitate is pSBMA.
For any person skilled in the art, without departing from the scope of the technical proposal of the invention, all
Many possible changes and modifications are made to technical solution of the present invention using the technology contents of the disclosure above, or are revised as equivalent
The equivalent embodiment of variation.Therefore, anything that does not depart from the technical scheme of the invention, according to the technical essence of the invention to
Any simple modifications, equivalents, and modifications that upper embodiment is done should all still fall within the range of technical solution of the present invention protection
It is interior.
Claims (10)
1. anionic polymerisation process under a kind of aqueous solution open environment, which is characterized in that described method includes following steps: with tool
The vinyl sulfone compound for having general formula II is initiator, causes the polymer with general formula I under the action of catalyst
The water phase anionic polymerisation of monomer, 25-100 DEG C of reaction 1-72h；
Wherein, X is electron-withdrawing group or the fragrance derivatives containing electron-withdrawing group；
Y is hydrogen atom, methyl or ethyl；
R, R ' is organic deriveding group.
2. the method according to claim 1, wherein the X is selected from
3. the method according to claim 1, wherein the R ' is water-soluble organic deriveding group.
4. the method according to claim 1, wherein the catalyst is selected from 1- methylimidazole, three ethylenes two
Amine, hexa, N, N- dimethylamino naphthyridine.
5. the method according to claim 1, wherein the dosage of the catalyst is polymer monomer substance
The 0.1~10% of amount.
6. the method according to claim 1, wherein the dosage of the initiator is polymer monomer substance
The 0.1~5% of amount.
7. the method according to claim 1, wherein the reaction temperature is 35-60 DEG C.
8. the method according to claim 1, wherein the reaction time is 12-72h.
9. the method according to claim 1, wherein being reacted by the way that solution is adjusted to acid terminate.
10. the high molecular material of method preparation described in claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910653617.6A CN110330609B (en) | 2019-07-18 | 2019-07-18 | Anionic polymerization method for aqueous solution in open environment |
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| CN201910653617.6A CN110330609B (en) | 2019-07-18 | 2019-07-18 | Anionic polymerization method for aqueous solution in open environment |
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| CN114716719A (en) * | 2022-03-10 | 2022-07-08 | 大连理工大学 | Method for carrying out surface modification on polyester material in aqueous solution by using polymer chain |
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| GB1069087A (en) * | 1963-05-31 | 1967-05-17 | Monsanto Co | Polyamides |
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| CN103087363A (en) * | 2011-11-04 | 2013-05-08 | 中国石油化工股份有限公司 | Liquid polyisoprene, preparation method and application thereof |
| CN105820095A (en) * | 2016-04-24 | 2016-08-03 | 大连理工大学 | Preparation method of vinyl sulfone derivatives |
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| GB1069087A (en) * | 1963-05-31 | 1967-05-17 | Monsanto Co | Polyamides |
| US20080308204A1 (en) * | 2007-06-18 | 2008-12-18 | Hogan Terrence E | Functional polymers prepared with sulfur-containing initiators |
| CN103087363A (en) * | 2011-11-04 | 2013-05-08 | 中国石油化工股份有限公司 | Liquid polyisoprene, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114716719A (en) * | 2022-03-10 | 2022-07-08 | 大连理工大学 | Method for carrying out surface modification on polyester material in aqueous solution by using polymer chain |
| CN114716719B (en) * | 2022-03-10 | 2023-09-01 | 大连理工大学 | Method for surface modification of polyester material in aqueous solution by using polymer chain |
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