CN102585065A - Simple method for preparing crystalline poly-sulphonic acid betaine - Google Patents
Simple method for preparing crystalline poly-sulphonic acid betaine Download PDFInfo
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Abstract
The invention discloses a simple method for preparing crystalline poly-sulphonic acid betaine and belongs to the field of polymer chemistry. According to the invention, a high-crystallinity polymer is obtained by carrying out free radical polymerization on a sulphonic acid betaine monomer in an aqueous solution of 30-50 DEG C; and the polymer can be cultured at low temperature less than a freezing point to form a polymer polycrystal solid. The method is simple and convenient; the obtained polymer can be applied to a medicament for improving the blood compatibility of the medicament and enhancing medicament effect, and can be applied to an oil field under high-temperature high-salt condition for exerting drag reduction effect; in addition, due to regular arrangement structure of the obtained polymer, the side group of the betaine easily contacts metal ions so that the obtained polymer is good in sewage treatment effect; and when the obtained polymer is grafted on the surface of a substance, the side group of the obtained polymer easily contacts exterior, thereby taking good antiseptic and anti-bacterial effects.
Description
Technical field
The present invention relates to a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine, belong to chemical field.
Background technology
Crystallization has very big influence to polymer properties; The high-crystallinity Vestolen PP 7052 has high firmness; Amount of deflection is low under the high temperature, creep property good; Process the barrier property (Michael T.H., Jay K. K., Robert G. P.V. United States Patent 5500282) that film helps improving film.Crystalline polymer can be applied in the medical treatment; When organism temperature is higher than polymer melting temperature; Polymkeric substance is a moving phase; When organism temperature was lower than polymer melting temperature, polymkeric substance was a coagulation phase, utilized the metamorphosis of polymkeric substance can treat embolism and hemostasis (Edward E. S. United States Patent 5469867; Tang Nade ﹒ K ﹒ Bu Landengmu, Zhan's nurse think ﹒ E ﹒ Mikaela this, fine jade ﹒ Ce Ertingge, Ai Like ﹒ V ﹒ Heidi Schmid, Luo Baite ﹒ K ﹒ Shu Erci.The side chain crystallizable polymers that is used for medical use, Chinese invention patent: CN200780002684.7).
Yet make the polymer scale crystal method all more numerous and diverse so far, Lee etc. prepare crystallinity hydrogenation through hydrogenated ring-opened polymerization and gather (acetylene-1,3-pentamethylene); Gather (acetylene-1; The 3-pentamethylene) is unformed polymkeric substance, through being transformed into crystalline polyolefin (Lee L.-B. W., Register R. A. Macromolecules 2005 after the hydrogenation under the HTHP; 38,1216-1222).Ricci etc. study CoCl
2(P
iPrPh
2)
2-MAO system catalysis (E)-1,3-pentadiene polymerization has obtained fusing point and is 168 ℃ crystalline polymer (Ricci G, Motta T.; Boglia A., Alberti E., Zetta L.; Bertini F., Arosio P., Famulari A.; Meille S. V. Macromolecules 2005,38,8345-8352).Matsumoto etc. have studied the solid state polymerization of diethylammonium muconic acid, let the regular arrangement of monomer earlier, make monomer ordered arrangement in polymkeric substance through polymerization then; By the time crystalline polymer (Matsumoto A., Yokoi K., Aoki S.; Tashiro K., Kamae T., Kobavashi M. Macromolecules 1998; 31,2129-2136).Li etc. have studied the crystallization of polyethylene oxide under field of flow is induced, and can inducing molecule chain orientation nucleation form shish-kebab and have brilliant (the Zhao B.-J. of uncrimping chain of high tensile through field of flow; Li X.-Y., Huang Y.-H., Ma Z.; Shao C.-G., An H.-N., Yan T.-Z.; Li L.-B. Macromolecules 2009,42,1428-1432).Nice Mu Jiadi etc. discloses and a kind ofly makes the method for polymer crystallization (Di Malibaisiteer makes the method for polymkeric substance nucleation, Chinese invention patent: CN200780012801.8) for Nice Mu Jiadi, Abraham A Selin through adding the nucleation microemulsion.MP dust card top grade discloses the thermal crystalline of a kind of molten polyester polymer in fluid, and polyester is introduced the Tg liquid medium that temperature is higher than polyester polymers, is being higher than under the vp of liquid medium; Make polymkeric substance sufficient crystallising (MP dust; MT Jie Ernigan, CL Wei Ersi, LC Wim Wenders; The thermal crystalline of molten polyester polymer in fluid, Chinese invention patent: CN200410085231.3).In addition; Can also be through the crystallinity of external force improved effect polymkeric substance; Liu Li discloses and has a kind ofly made polysulfonamides fibre crystalline method through ultrasonic wave field; (Liu Li utilizes ultrasonic wave field to improve the method for performance of polysulfone polyamide fiber crystallization, Chinese invention patent: CN201010152480.5) to have improved the percent crystallinity of polysulfonamides fibre greatly through outer field action.
The crystallinity of polymkeric substance depends on the taxis of polymkeric substance to a great extent.Natta etc. synthesize high stereoregular Vestolen PP 7052 through polycoordination the earliest, and this crystalling propylene degree height (Natta G., Pasquon I., Zambelli A. Journal of American Chemical Society. 1962,84,1488-1490).Ishihara etc. also synthesize normal PS between height through polycoordination; Different with in the past through anionoid polymerization or common radical polymerization gained PS, this very easily crystallization of PS tacticity height (Ishihara N., Seimiya T.; Kuramoto M.; Uoi M. Macromolecules 1986,19,2465-2466).Tacticity is high more to help polymer crystallization more, so people have carried out the tacticity that a series of researchs improve polymkeric substance, in the hope of obtaining crystalline polymer.Lewis acid is a kind of good stereoregular regulation and control catalyzer, and Kamigaito etc. have studied at Y (OTf)
3The isotactic active free radical polymerization of middle DMAA (DMAA); Obtain degree of isotacticity and be 80% polydimethylacrylamiin (PDMAA) (Sugiyama Y; Satoh K; Kamigaito M. Journal Polymer Science Part A:Polymer Chemistry, 2006,44:2086-2098).Solvent also has very big influence to the taxis of polymkeric substance, and Kakuchi etc. have studied under the low temperature ATRP of TEB 3K (MMA) in hexafluoroisopropanol, control through solvent; Obtained degree of syndiotacticity and be 84% polymethylmethacrylate (PMMA) (Miura Y; Satoh T, Narumi A, et al. Macromolecules; 2005,38:1041-1043).
The betaines polymkeric substance is to contain electroneutral bisexual ion purification characteristic trimethyl-glycine side group, has amphiphilic polymers (the McCormick C. L. of anti-polyelectrolyte solution character; Lowe A. B. Chemical Reviews, 2002,102,4177-4189).Under different pH, charge effect on the inner salt bond structure of chain internode and the macromolecular chain can cause the polymer dissolution degree to change along with the molecular chain conformational change; Making it in solution, to have the unrivaled theoretical investigation of most of non-ionic polyalcohols is worth and potential application (Lowe A. B.; McCormick C. L., The Journal of Physical Chemistry B, 2001; 105,2281-2284).
The betaines polymkeric substance is an electroneutral, and in the aqueous solution, the effect of molecule intrachain electrostatic attraction is associated molecule intrachain zwitterion group, and molecular chain shrinks, and the hydromeehanics size reduces, and molecular conformation is tight, and viscosity is little; In salts solution, the small molecule salt shielding has destroyed the electrostatic attraction between the zwitterion group, and molecular conformation becomes gradually and unfolds; Viscosity increases; Present anti-polyelectrolyte solution character (Kourosh K., Sara F. D., Polymers for Advanced Technologies 16; 2005,659-666).
Owing to have the characteristic of polyamphoteric electrolyte; Poly-sulphonic acid betaine like protein, nucleic acid etc., not only has histocompatibility, blood compatibility more near the natural biological polymer; Also have biochemical characteristics such as antibiotic, anti-protein adsorption, good application is arranged on biomedicine.Styrenic and methacrylic poly-sulphonic acid betaine have anticoagulant property, and ability antiplatelet adhesivity can be improved the blood compatibility (Zhou Jing, Shen Jian, Lin Sicong, SCI, 2002,23,2393) of giving birth to doctor's material.The betaines polymkeric substance can interact with small molecules such as metals ion, tensio-active agent, medicine, dyestuff etc. or macromole such as protein etc. and form complex compounds, can it be discharged again under certain condition, can be applied to separate purify and be used as pharmaceutical carrier.When temperature is lower than lower critical solution temperature; The PDMAPS aggregated particle can be caught DNA, and released dna when temperature is higher than lower critical solution temperature realizes that p-sulfonic acid betaines polymkeric substance is to DNA control and release (Asami O.; Hidemitsu F.; Macromolecular Rapid Communications 27,2006,1 242-246).
The sulphonic acid betaine amphoteric ion polymer can be used as additive for drilling fluid; Overcome common amphoteric ion polymer at high temperature and high salt condition decline leakage ability and the defective (Yang Xiaohua, the Wang Zhonghua that suppress subsiding property difference; The preparation method of amphoteric ion sulphonate polymer drilling well treatment agent at night; Chinese invention patent: CN 200710180497 X, 2007.11.7).In addition, because having excellent salt resistance, the sulphonic acid betaine amphiphilic polymers can be used to improve oil recovery rate (Wang Lin, Su Changming, Li Jiafen, Luo Lan, Tian Yuqin, Li Juan.A kind of amphoteric ion polymer and preparation method thereof, Chinese invention patent: CN 200910236268.4,2009.10.23).
But by the end of so far, report all be the betaines monomer with other monomer copolymerizations or high temperature under homopolymerization, N; N-dimethyl--N-methylacryoyloxyethyl-N-propyl sulfonic acid ammonium salt, Jia Jibingxisuanyizhi and acrylic amide are that sulphonic acid betaine class amphoteric ion polymer is reported (Fauke, A.R., Buriks the earliest altogether in the aqueous solution; R. S.; United States Patent 3819589), McCormick etc. have studied the addition under the high temperature in the aqueous solution of sulphonic acid betaine monomer reversible-chain transfer radical polymerization (Donovan M. S., Sumerlin B. S.; Lowe A. B.; McCormick C.L. Macromolecules 2002,35,8663-8666).But these high temperature betaines polymkeric substance following or the copolymerization gained all is (Ding W., Lv C. F., the Sun Y. of unformed shape; Liu X. J.; Yu T., Qu G. M., Luan H. X. Journal Polymer Science Part A:Polymer Chemistry. 2011; 49,432-440.).
The inventor passes through radical polymerization at a lower temperature at this, obtains the high crystalline poly-sulphonic acid betaine, and this base polymer can be turned out the poly-sulphonic acid betaine crystal.
Summary of the invention
The object of the present invention is to provide a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine, this base polymer can be cultivated and obtain the poly-sulphonic acid betaine crystal.
Because the initiator that often adopts thermal induction to decompose in the conventional radical polymerization is so often polymerization temperature is higher.The sulphonic acid betaine monomer carries out under comparatively high temps that radical polymerization then obtained can't crystalline amorphous state polymkeric substance.In order to reduce polymeric reaction temperature, used initiator system is based on the single electron transfer active free radical polymerization (SET-LRP) of out-shell electron transfer and the redox initiation radical polymerization of shifting based on inner electron among the present invention.
A kind of simple method for preparing the crystallinity poly-sulphonic acid betaine, carry out according to following step:
Prepare the crystallinity poly-sulphonic acid betaine through the SET-LRP polymerization: a certain amount of monomer, initiator, catalyzer, part and solvent are added in the container; After treating that monomer fully dissolves, logical nitrogen number minute, sealed vessel; The oil bath pan of putting into assigned temperature heats; Behind reaction 0.5 ~ 1h, polymerization system is put in the low temperature below freezing low temperature cultivated 7 days-14 days, can obtain poly-sulphonic acid betaine polycrystalline solid.
Monomer in the wherein above-mentioned reaction: initiator: part=200:1:3 (mol ratio), catalyzer copper wire 10.0cm;
Initiator is the alpha-brominated isopropylformic acid of SET-LRP initiator (BiBA) in the wherein above-mentioned reaction.
Part is PMDETA in the wherein above-mentioned reaction,
Monomer is N in the wherein above-mentioned reaction; N-dimethyl--N-methylacryoyloxyethyl-N-butyl sulfonic acid ammonium (DMABS), N; N-dimethyl--N-methylacryoyloxyethyl-N-propyl sulfonic acid ammonium (DMAPS) or N; N-dimethyl--N methacrylamide base propyl group-N-propyl sulfonic acid ammonium (DMMPPS), monomer concentration is 1.00 ~ 2.86mol/L.
Solvent is a zero(ppm) water in the wherein above-mentioned reaction.
A kind of preparation method of crystallinity poly-sulphonic acid betaine, perhaps carry out according to following step:
Prepare the crystallinity poly-sulphonic acid betaine through redox initiation radical polymerization: redox initiator, monomer and solvent are added in the round-bottomed flask; After treating that monomer fully dissolves; Be placed on temperature and be in 30 ~ 50 ℃ the oil bath pan and heat, behind reaction 1h ~ 1d, polymerization system is poured in the acetone; Be put into refrigerator and cultivated 7 days-14 days, can obtain poly-sulphonic acid betaine polycrystalline solid at low temperature.
Monomer is N in the wherein above-mentioned reaction; N-dimethyl--N-methylacryoyloxyethyl-N-butyl sulfonic acid ammonium (DMABS), N; N-dimethyl--N-methylacryoyloxyethyl-N-propyl sulfonic acid ammonium (DMAPS), N; N-dimethyl--N methacrylamide base propyl group-N-propyl sulfonic acid ammonium (DMMPPS), its concentration is 1.00mol/L.
Reductive agent in the wherein above-mentioned reaction: oxygenant: monomer=1.2:1:100 (mol ratio).
Reductive agent is N in the wherein above-mentioned reaction, N, N ', N ", N "-pentamethyl-two subunit triamines (PMDETA), oxygenant is ammonium persulphate (APS).
The structural formula of monomer DMABS of the present invention, DMAPS, DMMPPS is as follows:
Advantage of the present invention: through harsh reaction conditions such as HTHP or to obtain crystalline polymer through the external force inducing action different, the present invention only can obtain crystalline polymer through low-temp reaction with in the past, and condition is simple, and is quick.
Description of drawings
Fig. 1 is PDMABS
80DSC heat balance diagram and XRD phasor
Fig. 2 is PDMABS
50DSC heat balance diagram and XRD phasor
Fig. 3 is PDMAPS
50DSC heat balance diagram and XRD phasor
Fig. 4 is PDMMPPS
50DSC heat balance diagram and XRD phasor
Fig. 5 is PDMABS
40DSC heat balance diagram and XRD phasor
Fig. 6 is PDMAPS
40DSC heat balance diagram and XRD phasor
Fig. 7 is PDMMPPS
40DSC heat balance diagram and XRD phasor
Fig. 8 is PDMABS
30DSC heat balance diagram and XRD phasor
Fig. 9 is PDMAPS
30DSC heat balance diagram and XRD phasor
Figure 10 is PDMMPPS
30DSC heat balance diagram and XRD phasor
Figure 11 is PDMABS
SET-LRPDSC heat balance diagram and XRD phasor
Figure 12 is PDMAPS
SET-LRPDSC heat balance diagram and XRD phasor
Figure 13 is PDMMPPS
SET-LRPDSC heat balance diagram and XRD phasor
The practical implementation method
Below in conjunction with specific embodiment the present invention is done further elaboration in detail.
Comparative example: take by weighing 0.200mmol APS, 0.0200mol DMABS, H respectively
2O 20.0 mL and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 80 ℃ of oil bath pan reacting by heating.Pour in the acetone behind 1 h, polymerization system is poured in the acetone, be put into refrigerator and cultivated about 7 days-14 days, can only obtain white jelly at low temperature.The gluey thing of the polymkeric substance of separating out is used the zero(ppm) water repetitive scrubbing, remove unreacted monomer, filter, dry in the baking oven, be designated as PDMABS
80Fig. 1 is PDMABS
80DSC heat balance diagram and XRD phasor, visible by figure, PDMABS
80Heat balance diagram do not have melting peak, the XRD phasor does not have tangible peak crystallization yet, and PDMABS is described
80Be amorphous state.
Embodiment one: take by weighing 0.240mmol APS, 0.200mmol PDMETA, 0.0200mol DMABS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 50 ℃ of oil bath pan reacting by heating, pour in the acetone behind 1 h; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMABS
50Fig. 2 is PDMABS
50DSC heat balance diagram and XRD phasor, by PDMABS
50The DSC heat balance diagram visible, PDMABS
50At 90 ℃ and 193 ℃ two remarkable melting peaks are arranged, PDMABS is described
50Be crystalline state and have multiple crystal formation; From PDMABS
50The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMABS
50Be crystalline structure and contain multiple crystal formation.
Embodiment two: take by weighing 0.240mol APS, 0.200mol PDMETA, 0.0200mol DMAPS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 50 ℃ of oil bath pan reacting by heating, pour in the acetone behind 1 h; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMAPS
50Fig. 3 is PDMAPS
50DSC heat balance diagram and XRD phasor are by PDMAPS
50The DSC heat balance diagram visible, PDMAPS
50At 92 ℃ and 193 ℃ two remarkable melting peaks are arranged, PDMAPS is described
50Be crystalline state and have multiple crystal formation; From PDMAPS
50The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMAPS
50Be crystalline structure and contain multiple crystal formation.
Embodiment three: take by weighing 0.240mmol g APS, 0.200mmol g PDMETA, 0.0200mol DMMPPS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 50 ℃ of oil bath pan reacting by heating, pour in the acetone behind 1 h; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMMPPS
50Fig. 4 is PDMMPPS
50DSC heat balance diagram and XRD phasor are by PDMMPPS
50The DSC heat balance diagram visible, PDMMPPS
50At 88 ℃ and 194 ℃ two remarkable melting peaks are arranged, PDMMPPS is described
50Be crystalline state and have multiple crystal formation; From PDMMPPS
50The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMMPPS
50Be crystalline structure and contain multiple crystal formation.
Embodiment four: take by weighing 0.240mmol APS, 0.200mmol PDMETA, 0.0200mol DMABS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 40 ℃ of oil bath pan reacting by heating, pour in the acetone behind the 5h; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMABS
40Fig. 5 is PDMABS
40DSC heat balance diagram and XRD phasor are by PDMABS
40The DSC heat balance diagram visible, PDMABS
40At 88 ℃ and 193 ℃ two remarkable melting peaks are arranged, PDMABS is described
40Be crystalline state and have multiple crystal formation; From PDMABS
40The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMABS
40Be crystalline structure and contain multiple crystal formation.
Embodiment five: take by weighing 0.240mmol APS, 0.200mmol PDMETA, 0.0200mol DMAPS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 40 ℃ of oil bath pan reacting by heating, pour in the acetone behind 5 h; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMAPS
40Fig. 6 is PDMAPS
40DSC heat balance diagram and XRD phasor are by PDMAPS
40The DSC heat balance diagram visible, PDMAPS
40At 88 ℃ and 193 ℃ two remarkable melting peaks are arranged, PDMAPS is described
40Be crystalline state and have multiple crystal formation; From PDMAPS
40The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMAPS
40Be crystalline structure and contain multiple crystal formation.
Embodiment six: take by weighing 0.240mmol APS, 0.200mmol PDMETA, 0.0200mol DMMPPS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 40 ℃ of oil bath pan reacting by heating, pour in the acetone behind 5 h; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be PDMMPPS
40Fig. 7 is PDMMPPS
40DSC heat balance diagram and XRD phasor are by PDMMPPS
40The DSC heat balance diagram visible, PDMMPPS
40At 93 ℃ and 194 ℃ two remarkable melting peaks are arranged, PDMMPPS is described
40Be crystalline state and have multiple crystal formation; From PDMMPPS
40The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMMPPS
40Be crystalline structure and contain multiple crystal formation.
Embodiment seven: take by weighing 0.240mmol APS, 0.200mmolPDMETA, 0.0200mol DMABS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 30 ℃ of oil bath pan reacting by heating, pour in the acetone behind 1 d; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMABS
30Fig. 8 is PDMABS
30DSC heat balance diagram and XRD phasor are by PDMABS
30The DSC heat balance diagram visible, PDMABS
30At 93 ℃ and 193 ℃ two remarkable melting peaks are arranged, PDMABS is described
30Be crystalline state and have multiple crystal formation; From PDMABS
30The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMABS
30Be crystalline structure and contain multiple crystal formation.
Embodiment eight: take by weighing 0.240mmol APS, 0.200mmol PDMETA, 0.0200mol DMAPS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 30 ℃ of oil bath pan reacting by heating, pour in the acetone behind 1 d; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMAPS
30Fig. 9 is PDMAPS
30DSC heat balance diagram and XRD phasor are by PDMAPS
30The DSC heat balance diagram visible, PDMAPS
30At 89 ℃ and 194 ℃ two remarkable melting peaks are arranged, PDMAPS is described
30Be crystalline state and have multiple crystal formation; From PDMAPS
30The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMAPS
30Be crystalline structure and contain multiple crystal formation.
Embodiment nine: take by weighing 0.240mmol APS, 0.200mmol PDMETA, 0.0200mol DMMPPS, 20.0 mL H respectively
2O and magnetic agitation join in the single necked round bottom flask of 50 mL, put into 30 ℃ of oil bath pan reacting by heating, pour in the acetone behind 1 d; Being put into refrigerator cultivated about 7 days-14 days at low temperature; The alum shape crystal block of separating out is collected, and dissolving-deposition-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMMPPS
30Figure 10 is PDMMPPS
30DSC heat balance diagram and XRD phasor are by PDMMPPS
30The DSC heat balance diagram visible, PDMMPPS
30At 94 ℃ and 192 ℃ two remarkable melting peaks are arranged, PDMMPPS is described
30Be crystalline state and have multiple crystal formation; From PDMMPPS
30The XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMMPPS
30Be crystalline structure and contain multiple crystal formation.
Embodiment ten: take by weighing 0.125mmol BiBA, 0.375mmol PMDETA, 0.0250molDMABS, 7.00mL H respectively
2O, 10.00 cm copper wires and magnetic agitation join in the 50 mL single necked round bottom flask, seal behind applying argon gas 5 min, put into 50 ℃ oil bath reacting by heating; Putting into freezer compartment of refrigerator low temperature behind the 30min cultivated about 7 days-14 days; The alum shape crystal block of separating out is collected, and dissolution-crystallization once more, to remove the residual monomer that possibly comprise in the crystal block; And filtering drying, be designated as PDMABS
SET-LRPFigure 11 is PDMABS
SET-LRPDSC heat balance diagram and XRD phasor are by PDMABS
SET-LRPThe DSC heat balance diagram visible, PDMABS
SET-LRPAt 180 ℃ remarkable melting peak is arranged, PDMABS is described
SET-LRPBe crystalline state; From PDMABS
SET-LRPThe XRD phasor can find out its obvious diffraction peak, further specify PDMABS
SET-LRPBe crystalline state.
Embodiment 11: take by weighing 0.100mmol BiBA, 0.300mmol PMDETA, 0.0200mol DMAPS, 20.0 mL H respectively
2O, 10.00 cm copper wires and magnetic agitation join in the 50 mL single necked round bottom flask; Seal behind applying argon gas 5 min, put into and put into freezer compartment of refrigerator low temperature behind 50 ℃ the oil bath reacting by heating 1h and cultivated about 7 days-14 days, the alum shape crystal block of separating out is collected; And dissolution-crystallization once more; Removing the residual monomer that possibly comprise in the crystal block, and filtering drying, be designated as PDMAPS
SET-LRPFigure 12 is PDMAPS
SET-LRPDSC heat balance diagram and XRD phasor are by PDMAPS
SET-LRPThe DSC heat balance diagram visible, PDMAPS
SET-LRPAt 160 ℃ and 180 ℃ two remarkable melting peaks are arranged, PDMAPS is described
SET-LRPBe crystalline state and have multiple crystal formation; From PDMAPS
SET-LRPThe XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMAPS
SET-LRPBe crystalline structure and contain multiple crystal formation.
Embodiment 12: take by weighing 0.100mmol BiBA, 0.300mmol PMDETA, 0.0200mol DMMPPS, 20.0 mL H respectively
2O, 10.00 cm copper wires and magnetic agitation join in the 50 mL single necked round bottom flask; Seal behind applying argon gas 5 min, put into and put into freezer compartment of refrigerator low temperature behind 50 ℃ the oil bath reacting by heating 1h and cultivated about 7 days-14 days, the alum shape crystal block of separating out is collected; And dissolution-crystallization once more; Removing the residual monomer that possibly comprise in the crystal block, and filtering drying, be designated as PDMMPPS
SET-LRPFigure 13 is PDMMPPS
SET-LRPDSC heat balance diagram and XRD phasor are by PDMMPPS
SET-LRPThe DSC heat balance diagram visible, PDMMPPS
SET-LRPAt 89 ℃ and 193 ℃ two remarkable melting peaks are arranged, PDMMPPS is described
SET-LRPBe crystalline state and have multiple crystal formation; From PDMMPPS
SET-LRPThe XRD phasor can find out that it has a plurality of obvious diffraction peak, further specifies PDMMPPS
SET-LRPBe crystalline structure and contain multiple crystal formation.
Claims (9)
1. simple method for preparing the crystallinity poly-sulphonic acid betaine is characterized in that carrying out according to following step:
Prepare the crystallinity poly-sulphonic acid betaine through the SET-LRP polymerization: a certain amount of monomer, initiator, catalyzer, part and solvent are added in the container; After treating that monomer fully dissolves, logical nitrogen number minute, sealed vessel; The oil bath pan of putting into assigned temperature heats; Behind reaction 0.5 ~ 1h, polymerization system is put in the low temperature below freezing low temperature cultivated 7 days-14 days, can obtain poly-sulphonic acid betaine polycrystalline solid.
2. a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine according to claim 1 is characterized in that wherein said monomer: initiator: the part molar ratio computing is 200:1:3, catalyzer copper wire 10.0cm; Wherein said initiator is alpha-brominated isopropylformic acid.
3. a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine according to claim 1 is characterized in that wherein said part is PMDETA.
4. a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine according to claim 1; It is characterized in that wherein said monomer is N; N-dimethyl--N-methylacryoyloxyethyl-N-butyl sulfonic acid ammonium, N; N-dimethyl--N-methylacryoyloxyethyl-N-propyl sulfonic acid ammonium or N, N-dimethyl--N methacrylamide base propyl group-N-propyl sulfonic acid ammonium, monomer concentration is 1 ~ 2.86mol/L.
5. a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine according to claim 1 is characterized in that wherein said solvent is a zero(ppm) water.
6. the preparation method of a crystallinity poly-sulphonic acid betaine is characterized in that carrying out according to following step:
Prepare the crystallinity poly-sulphonic acid betaine through redox initiation radical polymerization: redox initiator, monomer and solvent are added in the round-bottomed flask; After treating that monomer fully dissolves; Be placed on temperature and be in 30 ~ 50 ℃ the oil bath pan and heat, behind reaction 1h ~ 1d, polymerization system is poured in the acetone; Be put into refrigerator and cultivated 7 days-14 days, can obtain poly-sulphonic acid betaine polycrystalline solid at low temperature.
7. a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine according to claim 6; It is characterized in that wherein said monomer is N; N-dimethyl--N-methylacryoyloxyethyl-N-butyl sulfonic acid ammonium, N; N-dimethyl--N-methylacryoyloxyethyl-N-propyl sulfonic acid ammonium, N, N-dimethyl--N methacrylamide base propyl group-N-propyl sulfonic acid ammonium, its concentration is 1mol/L.
8. a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine according to claim 6 is characterized in that wherein said reductive agent: oxygenant: monomeric mol ratio is 1.2:1:100.
9. a kind of simple method for preparing the crystallinity poly-sulphonic acid betaine according to claim 6 is characterized in that wherein said reductive agent is N, N, N ', N ", N "-pentamethyl-two subunit triamines, oxygenant is an ammonium persulphate.
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| CN103483479B (en) * | 2013-10-10 | 2015-11-18 | 河北工业大学 | A kind of single electron transfer active free radical polymerization prepares the method for PDMAEMA |
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