CN112961278A - Functionalized vinyl pyrrolidone copolymer and preparation method thereof - Google Patents
Functionalized vinyl pyrrolidone copolymer and preparation method thereof Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 24
- 150000003254 radicals Chemical class 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 41
- LLLWMXQKXWIRDZ-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one Chemical compound C=CN1CCCC1=O.C=CN1CCCC1=O LLLWMXQKXWIRDZ-UHFFFAOYSA-N 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 229920005604 random copolymer Polymers 0.000 description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 238000010526 radical polymerization reaction Methods 0.000 description 22
- 229920001400 block copolymer Polymers 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000004062 sedimentation Methods 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000002685 polymerization catalyst Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- JBKINHFZTVLNEM-UHFFFAOYSA-N 2-bromoethoxy-tert-butyl-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OCCBr JBKINHFZTVLNEM-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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- 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 invention relates to the technical field of synthesis and polymerization of functional monomers, in particular to a preparation method of a functional vinyl pyrrolidone copolymer, which comprises the following steps: mixing vinyl pyrrolidone monomer and organic lithium salt at low temperature, reacting, heating to room temperature, dropwise adding bromine salt, quenching after reaction, extracting, purifying and drying to obtain the functionalized vinyl pyrrolidone monomer. Preparing a catalyst solution; and (2) taking functionalized vinyl pyrrolidone and vinyl pyrrolidone monomers as raw materials, and carrying out catalytic polymerization reaction by using the catalyst solution to obtain the vinyl pyrrolidone copolymer. The copolymer prepared by the invention is an amphiphilic adjustable copolymer, and the hydrophilicity of the copolymer is reduced along with the increase of the content of the functionalized monomer; the copolymer can also be deprotected to form a macroinitiator, and can initiate the polymerization of other monomers according to the requirements to prepare polymers with different topological structures, so that the copolymer can be widely applied to different fields, especially the biomedical field, and a simple and convenient preparation way is provided for improving the performance of high polymer materials.
Description
Technical Field
The invention relates to the technical field of synthesis and polymerization of functional monomers, in particular to a functional vinyl pyrrolidone copolymer and a preparation method thereof.
Background
Polyvinylpyrrolidone is a nonionic water-soluble high molecular compound formed by polymerizing monomer vinylpyrrolidone under certain conditions, and has excellent solubility, good biocompatibility and chemical stability. Therefore, polyvinylpyrrolidone has been widely used in the fields of medicines, cosmetics, foods, separation membranes, photosensitive materials, and the like. However, the price is relatively high, and therefore, research on copolymerization modification of vinyl pyrrolidone becomes a current research hotspot.
The hydrogen at the third position of the vinyl pyrrolidone is more active, a substitution reaction can be carried out under certain conditions, reaction sites are provided for modification of the vinyl pyrrolidone, and based on small difference of free radical reaction between the vinyl pyrrolidone and the functionalized vinyl pyrrolidone, the functional group connected to the vinyl pyrrolidone can not significantly influence the free radical reactivity of a vinyl bond, so that the derivative has better functional group tolerance, and can be quantitatively and selectively post-modified under relatively mild and no side reaction conditions to prepare a polymer containing multiple functional groups and having a definite structure.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a functionalized vinyl pyrrolidone copolymer, which is a preparation method with both functionalized monomer synthesis and copolymerization technologies and provides a simple method for preparing the functionalized copolymer.
In order to solve the technical problems, the invention provides a preparation method of a functionalized vinylpyrrolidone copolymer, which comprises the following steps:
1) preparation of functionalized vinylpyrrolidone: mixing the solution of vinyl pyrrolidone and the organic lithium salt solution at low temperature, reacting for a certain time, heating to room temperature, slowly dropwise adding bromine salt, reacting for a certain time, quenching, extracting with an organic solvent, purifying and drying.
2) The functionalized vinyl pyrrolidone and the vinyl pyrrolidone are copolymerized by a free radical method as follows: dispersing a catalyst in an organic solvent to obtain a catalyst solution; the functionalized vinyl pyrrolidone and vinyl pyrrolidone monomers are used as raw materials, and the catalyst solution is used for catalyzing polymerization reaction at 50-100 ℃ to obtain the vinyl pyrrolidone copolymer.
Preferably, in the above preparation method of a functionalized vinylpyrrolidone copolymer, in step 1), the functionalized vinylpyrrolidone copolymer has a structure represented by formula (I):
wherein R is1And R2Represents hydrogen, alkane or functionalized straight-chain alkane.
Preferably, in the above preparation method of the functionalized vinylpyrrolidone copolymer, in the step 1), the molar ratio of vinylpyrrolidone to lithium salt to bromine salt is 1:1-2: 1-10.
Preferably, in the preparation method of the functionalized vinylpyrrolidone copolymer, in the step 1), the low temperature is-40 to 0 ℃, and the low temperature reaction time is 1 to 5 hours.
Preferably, in the above preparation method of the functionalized vinylpyrrolidone copolymer, in the step 1), the dropping time is 0.5 to 5 hours, and the reaction time at room temperature is 6 to 20 hours.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 1), the quenching agent is a saturated aqueous inorganic salt solution.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 1), the extractant is a saturated inorganic salt aqueous solution, and is extracted 3 to 6 times with an equal volume of organic solvent.
Preferably, in the above preparation method of a functionalized vinylpyrrolidone copolymer, in step 1), the purification method is recrystallization, column chromatography, distillation, or the like.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 1), the organic solvent is dried with an inorganic salt, including anhydrous magnesium sulfate, calcium chloride, phosphorus pentoxide, and the like.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the catalyst for radical copolymerization comprises azobisisobutyronitrile, azobisisoheptonitrile, peroxide, ammonium persulfate, and the like.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the catalyst is dispersed in an organic solvent to obtain a catalyst solution, wherein the boiling point of the organic solvent is 70-140 ℃.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the ratio of functionalized vinylpyrrolidone: the ratio of vinyl pyrrolidone is 0-100: 10.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the reaction temperature for copolymerization is 50 to 100 ℃.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the feeding sequence of the two monomers is a one-pot method.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the feeding sequence of the two monomers is a stepwise feeding method.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the copolymerization reaction time is 6 to 48 hours.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the copolymerization reaction is terminated by using an acidified organic solvent.
Preferably, in the above method for preparing the functionalized vinylpyrrolidone copolymer, after the termination of copolymerization, the copolymer is precipitated by using an organic solvent at a low temperature or room temperature.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the copolymer is precipitated 3 to 6 times with an organic solvent.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), after the copolymer is settled, the copolymer is dried for 12 to 48 hours.
Preferably, in the above method for preparing a functionalized vinylpyrrolidone copolymer, in step 2), the copolymer is deprotected to obtain a copolymer containing a functionalized group such as a hydroxyl group and an amine group.
The invention has the following beneficial effects:
the bipolymer prepared according to the process of the invention is: the single-functional vinyl pyrrolidone-vinyl pyrrolidone random copolymer, the single-functional vinyl pyrrolidone-vinyl pyrrolidone block copolymer, the double-functional vinyl pyrrolidone-vinyl pyrrolidone random copolymer and the double-functional vinyl pyrrolidone-vinyl pyrrolidone block copolymer can obtain binary copolymers with different functional groups or different sequence distributions and different content compositions simply by changing the feeding sequence and the feeding amount of functional groups or monomers. The microstructure of a polymer directly determines its properties and applications. The introduction of the functional group in the patent endows the polymer with the possibility of post-modification, thereby providing a simple and convenient method for modifying the polymer. The polymer is regulated and controlled in sequence composition and content, and the hydrophilicity, the thermal stability, the glass transition temperature and other properties of the copolymer can be effectively regulated, so that the polymer material can be widely applied. Therefore, the preparation method of the functionalized vinylpyrrolidone-vinylpyrrolidone copolymer provided by the invention is very innovative.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the bifunctional vinylpyrrolidone monomer synthesized in the preparation example 2 of the functionalized monomer. FIG. 2 is a NMR spectrum of a bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer example 1.
FIG. 3 is a Fourier transform infrared spectrum of a bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer example 1.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples describing preferred embodiments of the invention, but it is to be understood that these descriptions are intended only to further illustrate the features and advantages of the invention and are not intended to limit the scope of the claims which follow.
Example 1 preparation of monofunctional vinylpyrrolidone
Under ice bath, respectively reacting 99% and 4.5ml of vinyl pyrrolidone solution with 24% of THF solution of lithium bis (trimethylsilyl) amide for 1h, heating to room temperature, slowly dropwise adding 96% and 2.1ml of (2-bromoethoxy) -tert-butyldimethylsilane for 1h, reacting for 15h, quenching, extracting with diethyl ether, removing the solvent by rotary evaporation, purifying by column chromatography (petroleum ether/ethyl acetate is used as a developing agent), obtaining a second component, and drying to obtain the monofunctional vinyl pyrrolidone.
EXAMPLE 2 preparation of bifunctional vinylpyrrolidone
Under ice bath, respectively reacting a vinyl pyrrolidone solution with the concentration of 99 percent and 4.5ml with a THF solution with the concentration of 24 percent and 25.80g of lithium bis (trimethylsilyl) amide for 1h, heating to room temperature, slowly dropwise adding 96 percent and 2.1ml of (2-bromoethoxy) -tert-butyldimethylsilane for 1h, quenching the reaction for 15h, extracting with diethyl ether, removing the solvent by rotary evaporation, purifying by column chromatography (using petroleum ether/ethyl acetate as a developing agent), and drying the obtained first component to obtain the bifunctional vinyl pyrrolidone.
EXAMPLE 3 preparation of free radical catalytic System
Preparation of (mono) free radical polymerization catalyst System 1
Preparation of free radical polymerization catalyst System 1: at 25 ℃, 10 mu mol of azobisisobutyronitrile and 10mL of toluene solvent are added into 25mL of anhydrous and anaerobic polymerization container, the molar ratio of the azodiisobutyronitrile to the free radical initiator provided by the invention is 500: 1-2000: 1, and the mixture is uniformly stirred to obtain a catalytic system 1.
Preparation of (II) free radical polymerization catalyst System 2
Preparation of free radical polymerization catalyst system 2: at 25 ℃, 10 mu mol of azobisisoheptonitrile and 10mL of toluene solvent are added into 25mL of anhydrous and anaerobic treated polymerization container, the molar ratio of the azodiisoheptanonitrile to the free radical initiator provided by the invention is 500: 1-2000: 1, and the mixture is uniformly stirred to obtain a catalytic system 2.
Preparation of (III) free-radical polymerization catalyst System 3
Preparation of free radical polymerization catalyst system 3: at 25 ℃, 10 mu mol of dibenzoyl peroxide and 10mL of toluene solvent are added into 25mL of anhydrous and anaerobic polymerization container, the molar ratio of the dibenzoyl peroxide to the free radical initiator provided by the invention is 500: 1-2000: 1, and the mixture is uniformly stirred to obtain a catalytic system 3.
Preparation of (tetra) free radical polymerization catalyst System 4
Preparation of the free-radical polymerization catalyst system 4: at 25 ℃, 10 mu mol of di-tert-butyl peroxide and 10mL of toluene solvent are added into 25mL of anhydrous and anaerobic polymerization container, the molar ratio of the di-tert-butyl peroxide to the free radical initiator provided by the invention is 500: 1-2000: 1, and the mixture is uniformly stirred to obtain a catalytic system 4.
(V) preparation of the free radical polymerization catalyst System 5
Preparation of the free radical polymerization catalyst system 5: at 25 ℃, 10 mu mol of ammonium persulfate and 10mL of toluene solvent are added into 25mL of anhydrous and anaerobic treated polymerization container, the molar ratio of the ammonium persulfate to the free radical initiator provided by the invention is 500: 1-2000: 1, and the mixture is uniformly stirred to obtain a catalytic system 5.
EXAMPLE 4 bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer
(A)
Taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 0.5mmol of bifunctional vinyl pyrrolidone and 10mmol of vinyl pyrrolidone, and carrying out polymerization reaction at 60 ℃ for 24 h. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of n-hexane for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer, and then placing the random copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer.
(II)
And (2) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 1.0mmol of bifunctional vinyl pyrrolidone and 10mmol of vinyl pyrrolidone, and carrying out polymerization reaction at 60 ℃ for 24 h. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of n-hexane for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer, and then placing the random copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer.
(III)
And (2) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 1.5mmol of bifunctional vinyl pyrrolidone and 10mmol of vinyl pyrrolidone, and carrying out polymerization reaction at 60 ℃ for 24 h. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of n-hexane for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer, and then placing the random copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer.
(IV)
And (2) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 2.0mmol of bifunctional vinyl pyrrolidone and 10mmol of vinyl pyrrolidone, and carrying out polymerization reaction at 60 ℃ for 24 h. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of n-hexane for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer, and then placing the random copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer.
(V)
Taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 2.5mmol of bifunctional vinyl pyrrolidone and 10mmol of vinyl pyrrolidone, and carrying out polymerization reaction at 60 ℃ for 24 h. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of n-hexane for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer, and then placing the random copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer.
(VI)
5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5 is placed in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, 3.0mmol of bifunctional vinyl pyrrolidone and 10mmol of vinyl pyrrolidone are added simultaneously, and the polymerization reaction is carried out for 24 hours at the temperature of 60 ℃. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of n-hexane for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer, and then placing the random copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer.
Example 5 Dual functionalized vinylpyrrolidone-vinylpyrrolidone Block copolymer
(A)
And (3) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, adding 0.5mmol of bifunctional vinyl pyrrolidone, carrying out polymerization reaction at 60 ℃ for 24 hours, adding 10mmol of vinyl pyrrolidone, and continuing the polymerization reaction for 24 hours. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of ethanol for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer, and then placing the block copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer.
(II)
And (3) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 1.0mmol of bifunctional vinylpyrrolidone, carrying out polymerization reaction at 60 ℃ for 24 hours, adding 10mmol of vinylpyrrolidone, and continuing the polymerization reaction for 24 hours. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of ethanol for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer, and then placing the block copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer.
(III)
And (3) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 1.5mmol of bifunctional vinylpyrrolidone, carrying out polymerization reaction at 60 ℃ for 24 hours, adding 10mmol of vinylpyrrolidone, and continuing the polymerization reaction for 24 hours. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of ethanol for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer, and then placing the block copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer.
(IV)
And (3) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 2.0mmol of bifunctional vinylpyrrolidone, carrying out polymerization reaction at 60 ℃ for 24 hours, adding 10mmol of vinylpyrrolidone, and continuing the polymerization reaction for 24 hours. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of ethanol for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer, and then placing the block copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer.
(V)
And (3) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 2.5mmol of bifunctional vinylpyrrolidone, carrying out polymerization reaction at 60 ℃ for 24 hours, adding 10mmol of vinylpyrrolidone, and continuing the polymerization reaction for 24 hours. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of ethanol for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer, and then placing the block copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer.
(VI)
And (3) taking 5mL of the prepared toluene solution of the free radical polymerization catalytic system 1-5, placing the solution in a polymerization bottle which is subjected to anhydrous and anaerobic treatment, simultaneously adding 3.0mmol of bifunctional vinylpyrrolidone, carrying out polymerization reaction at 60 ℃ for 24 hours, adding 10mmol of vinylpyrrolidone, and continuing the polymerization reaction for 24 hours. Adding 1mL of ethanol solution with the volume concentration of 10% hydrochloric acid to terminate the polymerization reaction, pouring the reaction solution into 100mL of ethanol for sedimentation to obtain the bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer, and then placing the block copolymer in a vacuum oven for drying for 48 hours to obtain the dried constant-weight bifunctional vinylpyrrolidone-vinylpyrrolidone block copolymer.
Example 6 characterization
Hydrogen nuclear magnetic resonance spectrum of the product (1H-NMR), Fourier transform infrared spectroscopy (FT-IR), etc., as shown in FIGS. 1-3.
FIG. 1 is a view of a bifunctional vinylpyrrolidone monomerHydrogen spectrum of nuclear magnetic resonance1H-NMR(300MHz，CDCl3,298K),δ0.014(12H,-Si(CH3)2),0.86(18H,-C(CH3)2),1.79(4H,-CH2CH2O-),2.18(2H,-CH2CH2N-),3.39(2H,-CH2N-),3.68(4H,-CH2O-),4.40(2H,-CH＝CH2),7.07ppm(1H,-CH＝CH2). The above characterization confirmed the successful synthesis of functionalized vinylpyrrolidone monomers, which confirmed the presence of various functional groups in the monomers.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer1H-NMR(300MHz,CDCl3,298K):δ0.88(12H,-Si(CH3)2-),1.26(18H,-C(CH3)3),1.71(2H,-NCH2CH2-),1.80(4H,-CCH2CH2-),2.04(2H,-CHCH2-),2.36(2H,-CH2CH2N-),3.21(2H,-NCH2CH2-),3.71(1H,-NCHCH2-),3.88ppm(4H,-CCH2CH2-). The above characterization confirms the successful synthesis of the functionalized vinylpyrrolidone-vinylpyrrolidone random copolymer, and confirms the existence of each functional group of the polymer.
FIG. 3 is a Fourier transform Infrared Spectroscopy (FT-IR) of a bifunctional vinylpyrrolidone-vinylpyrrolidone random copolymer, as can be seen:
the above characterization confirmed the successful synthesis of functionalized vinylpyrrolidone-vinylpyrrolidone random copolymer, again evidencing the presence of various functional groups of the polymer.
While the present invention has been described in detail with reference to the specific embodiments and examples thereof, it should be understood that the present invention is not limited to the details of the method and the examples, but rather, the invention is capable of being practiced without departing from the spirit and scope of the appended claims.
Claims (10)
1. A functionalized vinyl pyrrolidone copolymer is characterized in that the preparation method comprises the following steps:
1) preparation of functionalized vinyl pyrrolidone: mixing a vinyl pyrrolidone solution and an organic lithium salt solution at a low temperature, reacting at the low temperature for a certain time, heating to room temperature, slowly dropwise adding a bromine salt, reacting at the room temperature for a certain time, quenching, extracting with an organic solvent, purifying, and drying to obtain functionalized vinyl pyrrolidone;
2) the functionalized vinyl pyrrolidone and the vinyl pyrrolidone are copolymerized by a free radical method as follows: dispersing a catalyst in an organic solvent to obtain a catalyst solution; taking the functionalized vinyl pyrrolidone obtained in the step 1) and vinyl pyrrolidone monomers as raw materials, and carrying out catalytic polymerization reaction by using the catalyst solution at high temperature to obtain a vinyl pyrrolidone copolymer.
2. A functionalized vinylpyrrolidone copolymer as claimed in claim I, wherein in step 1), the functionalized vinylpyrrolidone has a structure shown in formula (I):
wherein R is1And R2Represents hydrogen, alkane or functionalized straight-chain alkane.
3. The functionalized vinylpyrrolidone copolymer as recited in claim l, wherein in step 1), the molar ratio of vinylpyrrolidone to organic lithium salt to bromine salt is 1:1 to 2:1 to 10.
4. A functionalized vinylpyrrolidone copolymer as recited in claim I, wherein in step 1), the low temperature is-40 to 0 ℃ and the reaction time at the low temperature is 1 to 5 hours.
5. A functionalized vinylpyrrolidone copolymer as recited in claim l, wherein in step 1), the time for dropping bromine salt is 0.5-5h, and the reaction time at room temperature is 6-20 h.
6. A functionalized vinylpyrrolidone copolymer as recited in claim I, wherein in step 2), the catalyst for radical copolymerization is a radical initiator, and is one or more of azobisisobutyronitrile, azobisisoheptonitrile, peroxide and ammonium persulfate.
7. A functionalized vinylpyrrolidone copolymer as recited in claim I, wherein in step 2), the boiling point of the organic solvent is 70 to 140 ℃.
8. A functionalized vinylpyrrolidone copolymer as claimed in claim I, wherein in step 2), the catalyst is present in an amount of 0.1 to 0.5% by mole based on the monomer.
9. A functionalized vinylpyrrolidone copolymer as recited in claim I, wherein in step 2), the ratio of functionalized vinylpyrrolidone to vinylpyrrolidone is from 0 to 100:10 by mole ratio.
10. A functionalized vinylpyrrolidone copolymer as recited in claim I, wherein in step 2), the temperature is 50 to 100 ℃ and the time is 6 to 48 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114478916A (en) * | 2022-02-17 | 2022-05-13 | 辽宁大学 | N-vinyl pyrrolidone-methacrylate random copolymer and preparation method thereof |
| CN117673371A (en) * | 2024-01-31 | 2024-03-08 | 中节能万润股份有限公司 | Preparation method of current collector for non-negative electrode lithium metal battery, current collector and application |
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Non-Patent Citations (1)
| Title |
|---|
| JONAS U. A. ENGSTRÖM ET AL.: "Synthesis of Novel Monomers and Copolymers from 1-Vinylpyrrolidin-2-one: Attractive Materials for Drug Delivery Systems?", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478916A (en) * | 2022-02-17 | 2022-05-13 | 辽宁大学 | N-vinyl pyrrolidone-methacrylate random copolymer and preparation method thereof |
| CN114478916B (en) * | 2022-02-17 | 2023-09-15 | 辽宁大学 | N-vinyl pyrrolidone-methacrylate random copolymer and preparation method thereof |
| CN117673371A (en) * | 2024-01-31 | 2024-03-08 | 中节能万润股份有限公司 | Preparation method of current collector for non-negative electrode lithium metal battery, current collector and application |
| CN117673371B (en) * | 2024-01-31 | 2024-04-30 | 中节能万润股份有限公司 | Preparation method of current collector for non-negative electrode lithium metal battery, current collector and application |
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