CN101280032B - Preparation of quaternaries hyper branched polycation electrolyte - Google Patents
Preparation of quaternaries hyper branched polycation electrolyte Download PDFInfo
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- CN101280032B CN101280032B CN2007101351804A CN200710135180A CN101280032B CN 101280032 B CN101280032 B CN 101280032B CN 2007101351804 A CN2007101351804 A CN 2007101351804A CN 200710135180 A CN200710135180 A CN 200710135180A CN 101280032 B CN101280032 B CN 101280032B
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Abstract
The invention discloses a synthesis method to prepare hyperbranched polycation electrolyte based on self-condensing atom transfer radical (co)polymerization and is characterized in that the method makes use of an initiated monomer containing quaternary ammonium salt structures to obtain hyperbranched polycation electrolytes through the aqueous phase self-condensing atom transfer radical copolymerization of the initiated monomer, or through the aqueous phase self-condensing atom transfer radical copolymerization of other cationic unsaturated monomers. The method can obtain the polycation electrolyte simultaneously provided with high branching degree and high charge density in one step, and is simple in procedures; the obtained hyperbranched polycation electrolyte can be used for phase transfer catalysis, flow modification, immune diagnostic reagent and other occasions.
Description
Technical field
The present invention relates to initiation type monomer by containing quaternary ammonium salt structure in water or nonelectrolyte mixed aqueous solution from condensation vinyl atom transfer polymerization or with other positively charged ion unsaturated monomer from the copolymerization of condensation vinyl atom transfer, prepare the electrolytical method of hyper branched polycation.
Background technology
Polyelectrolyte refers to through covalent linkage and connects, has macromolecular compound ionic or ionogenic group, according to its with the character and the distributing position that maybe can produce electric charge, can be divided into: (1) only carries the polyanion electrolyte of negative charge; (2) only carry the polycation electrolyte of positive charge; (3) polymer chain contains positive and negative charge simultaneously, but positive and negative charge is distributed in respectively on the different monomeric units, and this base polymer is called polyamphoteric electrolyte; (4) polymer chain contains positive and negative charge simultaneously, and positive and negative charge is distributed on the same repeating unit, and this type of ionogen is called poly-trimethyl-glycine.Owing to contain ionic group on the polyelectrolyte structure, be different from other neutral polymkeric substance, so it shows the character that is different from general neutral polymer, as the viscosity of polyelectrolyte solution, pH and ionic strength sensibility etc.Because these characteristics of polyelectrolyte make it have a wide range of applications at aspects such as water treatment, paper industry, petroleum industry, textile industries.
The notion of hyperbranched polymer is that Flory proposed in nineteen fifty-two: he points out AB
xThe monomeric polycondensation of (x 〉=2) type will generate the highly branched polymkeric substance of solubility, and this polymkeric substance is not perfect dendritic macromole, but defective hyperbranched polymer.1987, the Kim of DuPont company etc. utilized the method for polycondensation at first to obtain first kind of hyperbranched polymer that industrial use is arranged.Nineteen ninety-five, the method that Fr é chet etc. has reported a kind of new synthesis of super branched polymkeric substance from the condensation vinyl polymerization (self-condensing vinyl polymerization, SCVP).Used monomer is AB
*Type, wherein A is a vinyl, B
*For causing the active group of vinyl polymerization.Monomer be initiator be again branch point, monomer activates under the effect of catalyzer, produces a plurality of living radicals, causes next step reaction, along with the carrying out of polyreaction, branch point increases, and finally forms hyperbranched polymer.Atom transfer radical polymerization is just to have obtained rapidly development since its invention, also Just because of this, is obtaining a large amount of results and breakthrough by preparing from condensation atom transfer radical polymerization (SCATRP) aspect the hyperbranched polymer.
For the electrolytical synthetic method of hyperbranched poly, up to the present, report less; Utilizing the hyperbranched polyethyleneimine that obtains from the ring-opening polymerization of condensation positively charged ion of ethyleneimine such as BASF AG is present unique a kind of industrialized polycation electrolyte, but obvious this method only is applicable to the annular monomer of only a few; On the other hand, utilize the method for polyfunctionality monomer polycondensation, also can obtain overspending magnificent polyquaternium cationoid ionogen.Similarly, the monomer structure complexity, the preparation difficulty that are fit to this method.
The same two kinds of methods are compared, the people such as Muller AHE of Germany Bayreuth university have proposed two-step approach and have prepared the electrolytical method of hyper branched polycation, promptly utilize initiation type monomer and diethylaminoethyl methacrylate to carry out having prepared hyperbranched polymethyl acrylic acid lignocaine ethyl ester from condensation atom transfer radical copolymerization (SCATRCP), and then carry out quaterisation with halogenated alkane, just obtained the hyper branched polycation polyelectrolyte immediately, its synthetic route is as follows respectively:
Obviously, above method needed for two steps, and efficient is not high; For the hyperbranched poly ionogen, most important textural factor is the degree of branching and electric density simultaneously, but aforesaid method can't be taken into account.Because it is the uncharged initiation type monomer of utilization and other monomer copolymerization.Obtain the high degree of branching, then need strengthen the initiation type monomer consumption, cause electric density not high; As improving electric density, will improve the comonomer consumption, this just causes the degree of branching not high.As seen, the major cause that both can't take into account is to regulate the initiation type monomer neutral of the degree of branching, and the monomer that produces electric charge in other words can't branching.So if ionizable monomer energy branching, then the polymkeric substance of its generation can improve electric density, also can realize the high degree of branching.The 3rd because the initiation type monomer in this method is non-water-soluble, and with this type of initiation type monomer directly and other ionic comonomer carry out SCATRCP and can't realize because charged monomer almost can only be dissolved in the water.
The inventor utilize a class based on the water SCATRP of the water-soluble initiation type monomer self of quaternary ammonium salt or with the SCATRCP of other water-soluble cationic unsaturated monomer, prepare hyper branched polycation ionogen with good aqueous solubility, compare with other method that has been in the news, owing to utilize water to make solvent, little to environmental stress, and can obtain the high degree of branching and high charge density simultaneously; Resulting hyper branched polycation ionogen can be used for occasions such as phase-transfer catalysis, flow modifier, immune diagnostic reagent.
Summary of the invention
The objective of the invention is: carry out water SCATRP or SCATRCP prepares the hyper branched polycation ionogen by water-soluble initiation type monomer, and provide synthetic this base polymer convenient and be easy to the method for suitability for industrialized production.
For achieving the above object, the technical solution used in the present invention is: utilize water miscible quaternary ammonium salt initiation type monomer MEBDAB or MECDAC, in water or nonelectrolyte mixed aqueous solution, carry out the SCATRP of himself, perhaps carry out SCATRCP and obtain the hyper branched polycation ionogen with other cationic monomer.
The implementation method of SCATRP or SCATRCP is as follows: described initiation type monomer is dissolved in water, water/ethanol or the water/tetrahydrofuran compound, does not add or add other positively charged ion unsaturated monomer, add catalyzer (CuCl, CuBr or FeCl
2) and complexing agent (bPy, TMEDA or PMDETA), initiation type monomer is 100: 0～10: 100 with the proportioning of other cationic monomer, the mole proportioning of monomer, catalyzer, complexing agent is 200: 1: 2～100: 3: 6, feed high-purity argon gas or nitrogen again in this system after about 10 minutes, airtight flask, behind 50～90 ℃ of reaction 2～24h, polymerization system is poured in the acetone of 5 times of systems and obtained throw out, it is filtered the back in vacuum drying oven, dry, promptly obtain the hyper branched polycation ionogen.
The rheological property of resulting hyper branched polycation aqueous electrolyte liquid is different from the character of conventional linear aqueous solutions of polymers, and its shear viscosity of such aqueous solutions of polymers increases along with the increase of shearing rate.The character of this uniqueness has crucial potential value for aspects such as oil production, medicament slow release, coating and polymer processing modifications.
Because the application of technique scheme, the present invention has following advantage:
1. the present invention has realized in water and water/alcohol mixed solvent by obtaining the hyper branched polycation ionogen from condensation atom transfer radical polymerization (SCATRP) or from condensation atom transfer radical copolymerization (SCATRCP) reaction, for its industrial applications provides very economic method, help the protection of environment simultaneously;
2. the character of synthetic hyper branched polycation aqueous electrolyte liquid of the present invention is different traditional aqueous solutions of polymers, and its relative shear viscosity of such aqueous solutions of polymers remains unchanged substantially along with the increase of shearing rate, has certain salt resistance simultaneously.
Description of drawings
Fig. 1 is polymers obtained after carrying out SCATRP reaction 2h under 90 ℃ for MEBDAB
1H-NMR figure, [MEBDAB]/[CuBr]/[PMDETA]=100/1/2;
Fig. 2 is polymers obtained after carrying out SCATRP reaction 24h under 90 ℃ for MEBDAB
1H-NMR figure, [MEBDAB]/[CuBr]/[PMDETA]=100/1/2;
Fig. 3 is polymers obtained for MECDAC carries out SCATRP under 90 ℃
1H-NMR figure, [MECDAC]/[CuCl]/[bPy]=100/1/2;
Down to carry out SCATRCP polymers obtained with MEDMAB at 90 ℃ for MEBDAB for Fig. 4
1H-NMR figure, [MEBDAB]/[MEDMAB]/[CuBr]/[PMDETA]=50/50/1/2;
Down to carry out SCATRCP polymers obtained with MBDMAC at 90 ℃ for MEBDAB for Fig. 5
1H-NMR figure, [MEBDAB]/[MBDMAC]/[CuBr]/[bPy]=50/50/1/2
Fig. 6 is polymers obtained after down carrying out SCATRCP with MHDMAB at 90 ℃ for MEBDAB
1H-NMR figure;
Down to carry out SCATRCP polymers obtained with MBDMAC at 90 ℃ for MECDAC for Fig. 7
1H-NMR figure, [MECDAC]/[MBDMAC]/[CuBr]/[bPy]=100/200/3/6;
Fig. 8 be MEBDAB 90 ℃ down and MEDMAB at FeCl
2It is polymers obtained that/bPy is that catalyst system carries out SCATRCP
1H-NMR figure, [MEBDAB]/[MEDMAB]/[FeCl
2]/[bPy]=100/100/1/2;
Down to be at CuBr/TMEDA that catalyst system carries out SCATRCP polymers obtained with MEDMAB at 90 ℃ for MEBDAB for Fig. 9
1H-NMR figure, [MEBDAB]/[MEDMAB]/[CuBr]/[TMEDA]=100/100/1/2;
Figure 10 be MEBDAB 90 ℃ down and MEDMAB at FeCl
2It is polymers obtained that/bPy is that catalyst system carries out SCATRCP
1H-NMR figure, [MEBDAB]/[MEDMAB]/[FeCl
2]/[bPy]=10/100/1.1/2.2;
Figure 11 is linear polypropylene acid sodium and hyperbranched PMEBDAB aqueous solution shear rheology relation, and the concentration of polymkeric substance is 3g/L, wherein PMEBDAB
IThe polymerization degree and the degree of branching be respectively 6 and 0.568, hyperbranched PMEBDAB
IIThe polymerization degree and the degree of branching be respectively 145 and 0.4;
Figure 12 is DSC figure linear and hyperbranched PMEBDAB, wherein PMEBDAB
IIIThe polymerization degree and the degree of branching be respectively 10 and 0.6, hyperbranched PMEBDAB
IVThe polymerization degree and the degree of branching be respectively 124 and 0.39.
Figure 13: prepare hyper branched polycation ionogen process synoptic diagram with the catalytic MEBDAB water of CuBr/PMDETA SCATRP:
The SCATRCP of Figure 14: MEBDAB and positively charged ion unsaturated monomer prepares hyper branched polycation ionogen synoptic diagram, A wherein, A
*, B
*, a, the structure of b sees that Figure 13 is described.
Embodiment
Relate to positively charged ion unsaturated monomer title in the concrete case study on implementation, structural formula is as follows respectively with abbreviation:
1. title: N-methylacryoyloxyethyl-N-ethane-N, N-dimethyl brometo de amonio structural formula:
Abbreviation: MEDMAB
2. title: N-methylacryoyloxyethyl-N-hexyl-N, N-dimethyl brometo de amonio structural formula:
Abbreviation: MHDMAB
3.N-methylacryoyloxyethyl-N-benzyl N, N dimethyl-ammonium chloride structural formula:
Abbreviation: MBDMAC
Embodiment one: utilize the SCATRP of MEBDAB to prepare hyper branched polycation ionogen PMEBDAB
With MEBDAB (4.31g, 10mmol), CuBr (14.4mg, 0.1mmol), PMDETA (34.6mg, 0.2mmol) and 8ml water/ethanol (volume ratio 1/1) add in the round-bottomed flask, vacuumize applying argon gas repeatedly, be sealed in 90 ℃ of reaction 2h down then.After reaction finishes, polymerization system is precipitated in acetone, after the filtration again with washing with acetone three times to remove catalyzer, 70 ℃ of following vacuum-dryings, gained purple solid is the hyper branched polycation ionogen, poly-N-methylacryoyloxyethyl-N-(alpha-brominated isobutyl acyl-oxygen) ethyl-N, N-dimethyl brometo de amonio, (PMEBDAB).The structure of PMEBDAB comprises the molecular weight and the degree of branching, utilizes
1H-NMR analyzes, and sees accompanying drawing 1.Chemical shift is the proton (CH of two keys at 5.6 and 6.0 peak among the figure
2=); Chemical shift is the methene proton (O=C-O-CH that links to each other with ester group at 3.6～3.9 peak
2-); Chemical shift at 3.45～3.47 peak is and-N
+Methene proton (the N that group links to each other
+-CH
2-); Chemical shift at 3.0～3.1 peak is and-methyl proton (N that the N+-group links to each other
+-(CH
3)
2); Chemical shift at 1.7～2.0 peak be with bromine ortho position methyl proton (
Or
Be designated as a), chemical shift at 1.5～1.7 peak be methene proton on the main chain (
); Chemical shift at 0.9 peak be the methyl proton that links to each other with main chain (
Be designated as b).For hyperbranched polymer by the SCATRP preparation, can be by the peak area and (N of two keys among the nuclear-magnetism figure
+-(CH
3)
2) ratio of peak area calculates the polymerization degree of polymkeric substance.The polymerization degree of polymkeric substance (DP) is about 2 by calculating as can be known.Degree of branching basis
1Among the H-NMR ratio at a peak and b peak come quantificational expression (Matyjaszewski K., Macromolecules 1997,30,7034-7041), the degree of branching=a/ (a+b), can calculate the degree of branching is 0.49.
Embodiment two: utilize the SCATRP of MEBDAB to prepare hyper branched polycation ionogen PMEBDAB
With MEBDAB (4.31g, 10mmol), CuBr (14.4mg, 0.1mmol), PMDETA (34.6mg, 0.2mmol) and 8ml water/ethanol (volume ratio 1/1) add in the round-bottomed flask, vacuumize applying argon gas repeatedly, be sealed in 90 ℃ of reactions 24 hours down then.After reaction finishes, polymerization system is precipitated in acetone, after the filtration again with washing with acetone three times removing catalyzer, 70 ℃ of following vacuum-dryings, gained purple solid is hyper branched polycation ionogen, PMEBDAB.The structure of PMEBDAB comprises the molecular weight and the degree of branching, utilizes
1H-NMR analyzes, and sees accompanying drawing 2.Chemical shift is the proton (CH of two keys at 5.6 and 6.0 peak among the figure
2=); Chemical shift is the methene proton (O=C-O-CH that links to each other with ester group at 3.6～3.9 peak
2-); Chemical shift at 3.45～3.47 peak is and-N
+Methene proton (the N that group links to each other
+-CH
2-); Chemical shift at 3.0～3.1 peak is and-methyl proton (N that the N+-group links to each other
+-(CH
3)
2); Chemical shift at 1.7～2.0 peak be with bromine ortho position methyl proton (
Or
, be designated as a), chemical shift at 1.5～1.7 peak be methene proton on the main chain (
); Chemical shift at 0.9 peak be the methyl proton that links to each other with main chain (
, be designated as b).For hyperbranched polymer by the SCATRP preparation, can be by the peak area and (N of two keys among the nuclear-magnetism figure
+-(CH
3)
2) ratio of peak area calculates the polymerization degree of polymkeric substance.The DP of polymkeric substance is about 70 by calculating as can be known.Degree of branching basis
1The ratio at a peak and b peak comes quantificational expression among the H-NMR, the degree of branching=a/ (a+b), and can calculate the degree of branching is 0.43.
Embodiment three: utilize the SCATRP of MECDAC to prepare hyper branched polycation ionogen PMECDAC
With MECDAC (1.66g, 5mmol), CuCl (4.95mg, 0.05mmol), (15.6mg 0.1mmol) adds among 6ml water/THF (volume ratio 1/1) bPy, vacuumizes applying argon gas repeatedly, is sealed in 90 ℃ of reactions 18 hours down then.After reaction finishes, polymerization system is precipitated in acetone, after the filtration again with washing with acetone three times removing catalyzer, 70 ℃ of following vacuum-dryings, the gained white solid is hyper branched polycation ionogen, PMECDAC.The product structure of PMECDAC comprises the molecular weight and the degree of branching, utilizes
1H-NMR analyzes, and sees accompanying drawing 3.Chemical shift is phenyl ring proton (C at 7.6 peak among the figure
6H
4-); Chemical shift is two key proton (CH at 5.6 and 6.0 peak
2=); Chemical shift is the methene proton hydrogen (CH that links to each other for phenyl ring at 4.6 peak
2-C
6H
4-CH
2-); Chemical shift is the proton (O-CH that links to each other with ester group at 3.7 peak
2-); Chemical shift at 3.5 peaks is and ammonium ortho position methene proton (N
+(CH
3)
2-CH
2-); Chemical shift at 3.0 peak is and ammonium ortho position methyl proton hydrogen (N
+-(CH
3)
2); Chemical shift at 2.0 peak be with chlorine ortho position methyl proton (
, be designated as a); Chemical shift at 1.5～1.8 peaks be methylene radical on the main chain proton (
); Chemical shift at 0.9 peak be link to each other with main chain methyl proton (
, be designated as b).For hyperbranched polymer by the SCATRP preparation, can be by the peak area and (N of two keys among the nuclear-magnetism figure
+-(CH
3)
2) ratio of peak area calculates the polymerization degree of polymkeric substance.The DP of polymkeric substance is about 300 by calculating as can be known.The degree of branching also can basis
1The ratio at a peak and b peak comes quantificational expression among the H-NMR figure: the degree of branching=a/ (a+b) can calculate the degree of branching and be about 0.39.
Embodiment four: utilize the SCATRCP of MEBDAB and MEDMAB to prepare hyper branched polycation ionogen PMEBDAB-co-PMEDMAB
With MEBDAB (0.862g, 2mmol), and MEDMAB (0.532g, 2mmol), CuBr (5.76mg, 0.04mmol), bPy (6.24mg, 0.08mmol), and 4ml water/ethanol (volume ratio is 1/1) joins in the round-bottomed flask, the sealing, vacuumize applying argon gas repeatedly, the reaction vessel after the deoxygenation at a certain temperature 90 ℃ carry out polyreaction.Behind the 12h, polymerization system is precipitated in acetone, and clean 2～3 times with acetone, filter vacuum-drying, the gained solid is hyper branched polycation ionogen, PMEBDAB-co-PMEDMAB.The structure of product comprises the molecular weight and the degree of branching, utilizes
1H-NMR analyzes, and sees accompanying drawing 4.Chemical shift is two key proton (CH at 5.68 and 6.06 peak among the figure
2=); Proton (the CH of chemical shift on the methylene radical that the peak between 3.32～3.96 is with ammonium links to each other
2-CH
2-N
+-CH
2-CH
3,-CH
2-CH
2-N
+-CH
2-CH
2-); Chemical shift at 3.0～3.19 peak is and ammonium ortho position methyl proton hydrogen (N
+-(CH
3)
2); Chemical shift at 2.5 peak for the proton of the methylene radical on the contiguous bromine atoms (
); Chemical shift at 2.0～1.8 peak be with bromine ortho position methyl proton (
Or
, be designated as a); Chemical shift at 1.5～1.8 peaks be methylene radical on the main chain proton (
); Chemical shift is the chemical shift of proton (N of methyl on the monobromethane at the peak between 1.25～1.34
+-CH
2-CH
3); Peak 1.0 be link to each other with main chain methyl proton (
With
, be designated as b).For hyperbranched polymer by the SCATRP preparation, can be by the peak area and (N of two keys among the nuclear-magnetism figure
+-(CH
3)
2) ratio of peak area calculates the polymerization degree of polymkeric substance.The DP of polymkeric substance is about 103 by calculating as can be known.The degree of branching also can basis
1The ratio at a peak and b peak comes quantificational expression among the H-NMR figure: the degree of branching=a/ (a+b) can calculate the degree of branching and be about 0.38.
Embodiment five: utilize the SCATRCP of MEBDAB and MBDMAC to prepare hyper branched polycation ionogen PMEBDAB-co-PMBDMAC
With MEBDAB (0.862g, 2mmol), and MBDMAC (0.567g, 2mmol), CuBr (5.76mg, 0.04mmol), bPy (12.48mg, 0.08mmol), and 4ml water/ethanol (volume ratio is 1/1) joins in the round-bottomed flask, the sealing, vacuumize applying argon gas repeatedly, the reaction vessel after the deoxygenation at a certain temperature 90 ℃ carry out polyreaction.Behind the 12h, polymerization system is precipitated in acetone, and clean 2～3 times with acetone, filter vacuum-drying, the gained solid is hyper branched polycation ionogen, PMEBDAB-co-PMBDMAC.The structure of product comprises the molecular weight and the degree of branching, utilizes
1H-NMR analyzes, and sees accompanying drawing 5.Chemical shift is phenyl ring proton (C at 7.5 peak among the figure
6H
5-); Chemical shift is two key proton (CH at 5.68 and 6.06 peak
2=); Chemical shift is link to each other for phenyl ring methene proton hydrogen and the methene proton hydrogen (CH that links to each other with ester group at 4.54 peak
2-C
6H
5With-O-CH
2-); Chemical shift at 3.48～4.0 peak is and ammonium ortho position methene proton (CH
2-N
+-CH
2-CH
2,-O-CH
2-CH
2-N
+-); Chemical shift at 3.0～3.19 peak is and ammonium ortho position methyl proton hydrogen (N
+-(CH
3)
2); Chemical shift at 2.5 peak for the proton of the methylene radical on the contiguous bromine atoms (
); Chemical shift at 2.0～1.8 peak be with bromine ortho position methyl proton (
Or
, be designated as a); Chemical shift at 1.5～1.8 peaks be methylene radical on the main chain proton (
); Chemical shift at 0.9 peak be link to each other with main chain methyl proton (
With
, be designated as b).For hyperbranched polymer by the SCATRP preparation, can be by the peak area and (N of two keys among the nuclear-magnetism figure
+-(CH
3)
2) ratio of peak area calculates the polymerization degree of polymkeric substance.The DP of polymkeric substance is about 20 by calculating as can be known.The degree of branching also can basis
1The ratio at a peak and b peak comes quantificational expression among the H-NMR figure: the degree of branching=a/ (a+b) can calculate the degree of branching and be about 0.39.
Embodiment six: utilize the SCATRCP of MEBDAB and MHDMAB to prepare hyper branched polycation ionogen PMEBDAB-co-PMHDMAB
With MEBDAB (0.862g, 2mmol), and MHDMAB (0.567g, 2mmol), CuBr (5.76mg, 0.04mmol), bPy (12.48mg, 0.08mmol), and 4ml distilled water joins in the round-bottomed flask, the sealing, vacuumize applying argon gas repeatedly, the reaction vessel after the deoxygenation at a certain temperature 90 ℃ carry out polyreaction.Stopped reaction behind the 13h precipitates polymerization system in acetone, and cleans 2～3 times with acetone, filters vacuum-drying, and the gained solid is hyper branched polycation ionogen, PMEBDAB-co-PMHDMAB.The structure of product comprises the molecular weight and the degree of branching, utilizes
1H-NMR analyzes, and sees Fig. 6.Chemical shift is phenyl ring proton (C at 7.5 peak among the figure
6H
5-); Chemical shift is two key proton (CH at 5.68 and 6.06 peak
2=); Chemical shift is link to each other for phenyl ring methene proton hydrogen and the methene proton hydrogen (CH that links to each other with ester group at 4.54 peak
2-C
6H
5With-O-CH
2-); Chemical shift at 3.48～4.0 peak is and ammonium ortho position methene proton (CH
2-N
+-CH
2-CH
2,-O-CH
2-CH
2-N
+-); Chemical shift at 3.0～3.19 peak is and ammonium ortho position methyl proton hydrogen (N
+-(CH
3)
2); Chemical shift at 2.5 peak for the proton of the methylene radical on the contiguous bromine atoms (
); Chemical shift at 2.0～1.8 peak be with bromine ortho position methyl proton (
Or
, be designated as a); Chemical shift at 1.5～1.8 peaks be methylene radical on the main chain proton (
); Chemical shift at 0.9 peak be link to each other with main chain methyl proton (
With
, be designated as b).For hyperbranched polymer by the SCATRP preparation, can be by the peak area and (N of two keys among the nuclear-magnetism figure
+-(CH
3)
2) ratio of peak area calculates the polymerization degree of polymkeric substance.The DP of polymkeric substance is about 18 by calculating as can be known.The degree of branching also can basis
1The ratio at a peak and b peak comes quantificational expression among the H-NMR figure: the degree of branching=a/ (a+b) can calculate the degree of branching and be about 0.39.
Embodiment seven: utilize the SCATRCP of MECDAC and MBDMAC to prepare hyper branched polycation ionogen PMECDAC-co-PMBDMAC
With MECDAC (0.332g, 1mmol), and MBDMAC (0.567g, 2mmol), CuCl (2.97mg, 0.03mmol), bPy (9.36mg, 0.06mmol), and 4ml water/ethanol mixed solvent joins in the round-bottomed flask, the sealing, vacuumize applying argon gas repeatedly, the reaction vessel after the deoxygenation at a certain temperature 90 ℃ carry out polyreaction.Stopped reaction behind the 16h precipitates polymerization system in acetone, and cleans 2～3 times with acetone, filters vacuum-drying, and the gained solid is hyper branched polycation ionogen, PMECDAC-co-PMBDMAC.The structure of product comprises the molecular weight and the degree of branching, utilizes
1H-NMR analyzes, and sees accompanying drawing 7.The peak of chemical shift about 7.5 is phenyl ring proton (C among the figure
6H
5-); Chemical shift is two key proton (CH at 5.64 and 6.03 peak
2=); Chemical shift is link to each other for phenyl ring methene proton hydrogen and the methene proton hydrogen (CH that links to each other with ester group at 4.57 peak
2-C
6H
5With-O-CH
2-); Chemical shift at 3.4～4.0 peak is and ammonium ortho position methene proton (CH
2-N
+-CH
2-CH
2,-O-CH
2-CH
2-N
+-); Chemical shift at 3.0～3.19 peak is and ammonium ortho position methyl proton hydrogen (N
+-(CH
3)
2); Chemical shift at 2.1 peak be with bromine ortho position methyl proton (
Or
, be designated as a); Chemical shift at 1.5～1.8 peaks be methylene radical on the main chain proton (
); Chemical shift at 0.9 peak be link to each other with main chain methyl proton (
With
, be designated as b).For hyperbranched polymer by the SCATRP preparation, can be by the peak area and (N of two keys among the nuclear-magnetism figure
+-(CH
3)
2) ratio of peak area calculates the polymerization degree of polymkeric substance.The DP of polymkeric substance is about 9 by calculating as can be known.The degree of branching also can basis
1The ratio at a peak and b peak comes quantificational expression among the H-NMR figure: the degree of branching=a/ (a+b) can calculate the degree of branching and be about 0.29.
Embodiment eight: utilize the SCATRCP of MEBDAB and MEDMAB to prepare hyper branched polycation ionogen PMEBDAB-co-PMEDMAB
With MEBDAB (0.862g, 2mmol), MEDMAB (0.532g, 2mmol), FeCl
2(2.54mg, 0.02mmol), bPy (6.24mg, 0.04mmol), and 4ml water/ethanol (volume ratio is 1/1) joins in the round-bottomed flask, sealing vacuumizes applying argon gas repeatedly, the reaction vessel after the deoxygenation at a certain temperature 90 ℃ carry out polyreaction.Behind the 16h, polymerization system is precipitated in acetone, and clean 2～3 times with acetone, filter vacuum-drying, the gained solid is hyper branched polycation ionogen, PMEBDAB-co-PMEDMAB.The structural characterization of product is seen accompanying drawing 8 with embodiment four, and its polymerization degree is 490, and the degree of branching is 0.44.
Embodiment nine: utilize the SCATRCP of MEBDAB and MEDMAB to prepare hyper branched polycation ionogen PMEBDAB-co-PMEDMAB
With MEBDAB (0.862g, 2mmol), and MEDMAB (0.532g, 2mmol), CuBr (2.88mg, 0.02mmol), TMEDA (4.64mg, 0.04mmol), and 4ml water/ethanol (volume ratio is 1/1) joins in the round-bottomed flask, the sealing, vacuumize applying argon gas repeatedly, the reaction vessel after the deoxygenation at a certain temperature 90 ℃ carry out polyreaction.Behind the 16h, polymerization system is precipitated in acetone, and clean 2～3 times with acetone, filter vacuum-drying, the gained solid is hyper branched polycation ionogen, PMEBDAB-co-PMEDMAB.The structural characterization of product is seen accompanying drawing 9 with embodiment four, and its polymerization degree is 138, and the degree of branching is 0.39.
Embodiment ten: utilize the SCATRCP of MEBDAB and MEDMAB to prepare hyper branched polycation ionogen PMEBDAB-co-PMEDMAB
With MEBDAB (0.2115g, 0.5mmol), MEDMAB (1.33g, 5mmol), FeCl
2(3.5mg, 0.055mmol), bPy (17.16mg, 0.11mmol), and 4ml water/ethanol (volume ratio is 1/1) joins in the round-bottomed flask, sealing vacuumizes applying argon gas repeatedly, the reaction vessel after the deoxygenation at a certain temperature 90 ℃ carry out polyreaction.Behind the 10h, polymerization system is precipitated in acetone, and clean 2～3 times with acetone, filter vacuum-drying, the gained solid is hyper branched polycation ionogen, PMEBDAB-co-PMEDMAB.The structural characterization of product is seen accompanying drawing 10 with embodiment four, and its polymerization degree is 13, and the degree of branching is 0.43.
Embodiment 11: the shear rheology of the different polyelectrolyte aqueous solution
Press the hyperbranched PMEBDAB of the two kinds of different degrees of branching of method preparation among the embodiment two, two kinds of hyperbranched PMEBDAB reacted respectively 6 hours and 19 hours, wherein PMEBDAB
IThe polymerization degree and the degree of branching of (reacting 6 hours) are respectively 6 and 0.568, hyperbranched PMEBDAB
IIThe polymerization degree and the degree of branching of (reacting 19 hours) are respectively 145 and 0.4.Accurate weighing linear polypropylene acid sodium, hyperbranched PMEBDAB
IWith hyperbranched PMEBDAB
IIEach 0.075 gram is dissolved in respectively in the volumetric flask of sodium chloride solution of the distilled water of 25ml and 1M, is carrying out rheometer test under 25 ℃ on Anton Paar Physica MCR 301 rheometers then, and range of shear rate is from 0.1to 3000s
-1The results are shown in accompanying drawing 11.Can find out of the increase of the shear viscosity of the sodium polyacrylate aqueous solution from figure (a) and (b) along with shearing rate, be tangible shear shinning phenomenon, and do not reduce along with the increase of shearing rate for its shear viscosity of hyperbranched PMEBDAB, keep constant basically.This causes mainly due to lacking between the almost spherical structure of hyperbranched polymer and molecular chain to twine.In addition, adding NaCl has obviously reduced the shear viscosity of linear polypropylene acid sodium aqueous solution, mainly because " polyelectrolyte effect " causes, adding NaCl outward then influences not quite the shear viscosity of the hyperbranched PMEBDAB aqueous solution, shows that the latter has better salt resistance for this.
Embodiment 12: the mensuration of the second-order transition temperature (Tg) of linear PMEBDAB and two kinds of hyperbranched PMEBDAB
Prepare other two kinds of hyperbranched PMEBDAB by the method among the embodiment two, two kinds of hyperbranched PMEBDAB reacted respectively 6 hours and 19 hours, wherein PMEBDAB
IIIThe polymerization degree and the degree of branching of (reacting 8 hours) are respectively 10 and 0.6, hyperbranched PMEBDAB
IVThe polymerization degree and the degree of branching of (reacting 16 hours) are respectively 124 and 0.39.The polymkeric substance that obtains is gone up test T in Perkin-Elmer Pyris-1 differential scanning calorimeter (DSC)
g, temperature range is 50～200 ℃, rate of heating is 10 ℃/min.The T of linear PMEBDAB as can be seen from see accompanying drawing 12
gGreatly about 120 ℃, and hyperbranched PMEBDAB
IIIT
gGreatly about 70 ℃, and hyperbranched PMEBDAB
IVT
gNot in this useful range, also be to be in elastomeric state under the normal temperature then.
Claims (2)
1. preparation of quaternaries hyper branched polycation electrolyte, it is characterized in that: utilize water miscible quaternary ammonium salt initiation type monomer N-methylacryoyloxyethyl-N-bromo isobutyl acyl-oxygen ethyl-N, N-dimethyl brometo de amonio MEBDAB or N-methylacryoyloxyethyl-N-(to chloromethyl) benzyl-N, N-alkyl dimethyl ammonium chloride MECDAC, in water or nonelectrolyte mixed aqueous solution, what carry out himself is SCATRP from the condensation atom transfer radical polymerization, perhaps with other positively charged ion unsaturated monomer be SCATRCP from the condensation atom transfer radical copolymerization, be about to initiation type monomer and be dissolved in water, in water/ethanol or the water/tetrahydrofuran compound, do not add or add other positively charged ion unsaturated monomer, add Catalysts Cu Cl, CuBr or FeCl
2With complexing agent 2,2 '-dipyridyl bPy, Tetramethyl Ethylene Diamine TMEDA or five methyl diethylentriamine PMDETA, feed high-purity argon gas or nitrogen again in this system after 10 minutes, airtight flask behind 50～90 ℃ of reaction 2～24h, is poured polymerization system in the acetone of 5 times of systems and is obtained throw out, it is filtered the back in vacuum drying oven, dry, promptly obtain the quaternaries hyper branched polycation ionogen; Wherein initiation type monomer is 100: 0～10: 100 to the feed ratio scope of other positively charged ion unsaturated monomer, initiation type monomer is 200: 1: 2～100: 3: 6 to catalyzer to the mole proportioning of complexing agent, and described other positively charged ion unsaturated monomer has following structure:
R=CH wherein
3, R '=C
nH
2n+1, n=2～6 or CH
2C
6H
5, X=Cl or Br.
2. preparation of quaternaries hyper branched polycation electrolyte according to claim 1, it is characterized in that described initiation type monomer comprises N-methylacryoyloxyethyl-N-bromo isobutyl acyl-oxygen ethyl-N, N-dimethyl brometo de amonio MEBDAB, it has following chemical structure:
Or N-methylacryoyloxyethyl-N-(to chloromethyl) benzyl-N, N-alkyl dimethyl ammonium chloride MECDAC, it has following chemical structure:
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