CN103741477B - A kind of sulfonic group modified polytetrafluoroethylene fibre self-assembly preparation method thereof - Google Patents
A kind of sulfonic group modified polytetrafluoroethylene fibre self-assembly preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of sulfonic group modified polytetrafluoroethylene fibre self-assembly preparation method thereof with powerful coordination and absorption property.The feature of this sulfonic group modified polytetrafluoroethylene fibre is that using the self-assembly system be made up of diallyl dimethyl ammoniumchloride (PDDA) and kayexalate (PSS) to carry out process to acrylic acid modified polytetrafluoroethylene fibre forms.The cooperation of its iron ion or adsorbance can be made by regulation and control more than 3.50mmol/g in the self assembly number of plies of fiber surface, and its dry break strength can remain on more than 92N.This preparation method adopts following technique: 1. the preliminary treatment of acrylic acid modified polytetrafluoroethylene fibre; 2. the preparation of cationic polyelectrolyte solution; 3. the preparation of anionic polyelectrolyte solution; 4. cationic self-assembly process; 5. the self-assembly process of anion; 6. LBL self-assembly technique; 7. aftertreatment technology.The sulfonic group modified polytetrafluoroethylene fibre using above-mentioned technique to prepare can not only be strong with the coordination ability of iron ion under cryogenic, and there is excellent physical and mechanical properties, for the heterogeneous Fenton reaction catalyst preparing high Fe content is laid a good foundation.
Description
Technical field
The present invention relates to chemical industry absorption and catalyst technology, be specially a kind of sulfonic group modified polytetrafluoroethylene fibre self-assembly preparation method thereof with powerful coordination and absorption property.
Background technology
Fenton oxidation technology is a kind of effective ways can removing the persistence organic pollutants such as dyestuff from waste water, and it can make these pollutants occur to degrade fast and completely and mineralising.The degradation reaction that support materials surface and the heterogeneous Fenton reaction catalyst made not only can urge them is significantly fixed on by iron ion, but also it is strong and be easy to the advantages such as recovery to have pH applicability, therefore the research and development of heterogeneous Fenton catalyst are the keys improving Fenton oxidation technology at present.And fibre metal complex has preparation simply as heterogeneous Fenton photochemical catalyst, easy to use and cheap feature doubly receives the concern of people.Research shows, the fibrous material that synthesis has powerful coordination property to iron ion is the key preparing fibre metal complex, this is because these fibrous materials with powerful coordination property can make the heterogeneous Fenton photochemical catalyst obtained have higher iron ion content by complexation reaction.And the heterogeneous Fenton photochemical catalyst of research these ferric ion content verified has higher catalytic activity usually [see Dong Yongchun etc., the application of iron modified acrylic fibres catalyst in Degradation of Azo Dyes reaction, textile journal, 2009,30 (1): 82-87].We prove in nearest research, use polytetrafluoroethylene (PTFE) (PTFE) fiber and the Fe of polyacrylic acid grafted modification
3+the iron ion content of the complex that ion is formed generally be no more than 2.50mmol/g [see 1. Dong Yongchun etc., the preparation of modified ptfe fibre metal complex and Photocatalytic Degradation Property thereof, Acta PhySico-Chimica Sinica, 2013,29 (01): 157-166, 2. Dong Yongchun etc., the photocatalytic degradation reaction of REACTIVE Red 195 within the scope of the existence of iron modified Teflon fiber complex heterogeneous catalysis and wide pH value, ColorationTechnology, 2013, 129 (6): 403-411 (YongchunDongetal., PhotoassisteddegradationofCIReactiveRed195usinganFe (III)-graftedpolytetrafluoroethylenefibrecomplexasanovelhetero geneousFentoncatalystoverawidepHrange, ColorationTechnology, 2013, 129 (6): 403-411)].Although acrylic acid can be improved at the percent grafting of fiber surface by regulating graft reaction, so not only can the carrying out of effects on surface graft reaction bring very large difficulty and increase substantially preparation cost, and damage can be brought to the physical and mechanical properties of fiber.Therefore, the present invention, in order to improve the coordination ability of modified ptfe fiber and iron ion and prepare the fibre metal complex of ferric ion content, devises a kind of method by self-assembling technique preparation with the fibrous material of powerful coordination property.So-called layer-by-layer (Layer-by-LayerSelf-Assembly, LBLSA), namely the method for successively alternating deposit is utilized, by the intermolecular weak interaction of each layer (as electrostatic attraction, hydrogen bond, coordinate bond etc.), layer and layer is made spontaneously to form and be formed structural integrity, stable performance, the molecule aggregate with certain specific function or supramolecular structure.It has many advantages, and as being not particularly limited film forming matrix, do not need special equipment, the selection of film forming driving force is more, and the film of preparation has good machinery and chemical stability, the composition of film and thickness controlled etc.Then have employed at us with electrostatic interaction is that the molecule deposition LBL self-assembly method of motive force prepares sulfonic group modified PTFE fiber.Namely first prepare acrylic acid modified polytetrafluoroethylene fibre, then respectively with kayexalate (PSS) and diallyl dimethyl ammoniumchloride (PDDA) for anion and cationic polyelectrolyte carry out LBL self-assembly that multilayer PDDA/PSS replaces to obtain sulfonic group modified polytetrafluoroethylene fibre to acrylic acid modified polytetrafluoroethylene fibre again.This method can utilize that compound is various, sedimentary condition is easy, and deposition process is controlled.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is: provide a kind of sulfonic group modified polytetrafluoroethylene fibre self-assembly preparation method thereof.Fiber of the present invention having powerful coordination property for the preparation of during fiber iron complex to iron ion, has when namely carrying out complexation reaction with iron ion that adsorbance is large, adsorption time is short and to temperature and the advantage such as pH value dependence is weak.The more important thing is, because fiberoptic fiber of the present invention still has outstanding oxidative resistance and mechanical strength, there is mechanical strength change little when its fiber iron complex is used as heterogeneous Fenton reaction catalyst, metal ion difficult drop-off, within the scope of wide pH value, there is catalytic activity, and the advantage such as reusability is good.In addition, the very low and environment friendly of the concentration of medicament contained by the anion that this preparation method uses and cationic polyelectrolyte solution, preparation and preparation manipulation are simply, cheap.In addition, preparation method's technique of the present invention is relatively simple, and moderate cost, easily operates, and using adaptability is good, is conducive to industrialization promotion.
The technical scheme that the present invention solves described catalyst technology problem is: the self-assembly preparation method thereof (hereinafter referred to as preparation method) designing a kind of sulfonic group modified polytetrafluoroethylene fibre, it is characterized in that preparation method of the present invention is made up of the preparation of preliminary treatment, cationic polyelectrolyte solution, the preparation of anionic polyelectrolyte solution, cationic self-assembly process, the self-assembly process of anion, seven steps such as LBL self-assembly technique and aftertreatment technology; The wherein diallyl dimethyl ammoniumchloride (PDDA) of cationic polyelectrolyte solution by 5.0g/L and the mixed aqueous solution of 0.50mol/L sodium chloride preparation, the mixed aqueous solution that anionic polyelectrolyte solution is prepared by kayexalate (PSS) and the 0.50mol/L sodium chloride of 5.0g/L; Polyelectrolyte solution outward appearance is colourless transparent liquid, and pH value is about 6.0-7.0, and proportion is approximately 1.0; LBL self-assembly technique can repeatedly be carried out repeatedly, to obtain the sulfonic group modified polytetrafluoroethylene fibre with the different number of plies.The sulfonic group modified polytetrafluoroethylene fibre outward appearance that this preparation method obtains is fiber shape, and fracture strength is respectively 93.51-95.29N.
The technical scheme that the present invention solves described preparation method's technical problem is: the self-assembly preparation method thereof designing a kind of sulfonic group modified polytetrafluoroethylene fibre of the present invention, and it adopts following technique:
1. pretreating process: under room temperature and stirring condition, first use is taken out after 10 minutes containing the acrylic acid modified polytetrafluoroethylene fibre of nonionic surfactant water-soluble liquid carrying out washing treatment that volumetric concentration is 2.0g/L, and then use distilled water to carry out washing 5 times to it, finally by its vacuum drying 24 hours at 50 DEG C;
2. the preparation of cationic polyelectrolyte solution: diallyl dimethyl ammoniumchloride (PDDA) and sodium chloride are made an addition in distilled water respectively and forms mixed solution, the concentration of wherein PDDA is made to be 5g/L, the molar concentration of sodium chloride is 0.5mol/L, set aside for use.
3. the preparation of anionic polyelectrolyte solution: kayexalate (PSS) and sodium chloride are made an addition in distilled water respectively and form mixed solution, makes the concentration of wherein PSS be 5g/L, and the molar concentration of sodium chloride is 0.5mol/L, set aside for use.
4. cationic self-assembly process: immerse in described cationic polyelectrolyte solution through pretreated fiber by above-mentioned, the ratio of its fibre weight (gram) and cationic polyelectrolyte liquor capacity (milliliter) is made to be 1: 50,50 DEG C, pH value be 6.0 and stirring condition under carry out self-assembling reaction and take out after 20 minutes, then it is dried at 40-60 DEG C and obtains CATION self assembly fiber.
5. the self-assembly process of anion: the above-mentioned fiber through CATION self assembly is immersed in described anionic polyelectrolyte solution, the ratio of its fibre weight (gram) and anionic polyelectrolyte liquor capacity (milliliter) is made to be 1: 50,50 DEG C, pH value be 6.0 and stirring condition under carry out self-assembling reaction and take out after 20 minutes, then it is dried at 40-60 DEG C and obtains anion self assembly fiber.
6. LBL self-assembly technique: the above-mentioned fiber through anion self assembly is repeated process in order according to step 4 and 5, so repeats 1-9 time, obtain the LBL self-assembly fiber of the different number of plies.
7. aftertreatment technology: under room temperature and stirring condition, first use containing the volumetric concentration nonionic surfactant water-soluble liquid carrying out washing treatment that is 2.0g/L above-mentioned after LBL self-assembly fiber take out after 10 minutes, and then use distilled water to carry out washing 5 times to it, finally its vacuum drying at 50 DEG C is obtained sulfonic group modified polytetrafluoroethylene fibre in 24 hours.
Compared with prior art, the molecule deposition film that sulfonic group modified polytetrafluoroethylene fibre surface coverage prepared by the present invention has multilayer PDDA/PSS to replace, and in the PSS layer on its top layer, there is a large amount of sulfonic acid groups, this is for itself and iron ion form coordination structure and complete suction-operated and lay a good foundation.Fiber of the present invention not only with iron ion coordination or the dependence of adsorption reaction process to temperature little, and the heterogeneous Fenton photochemical catalyst obtained can be made to have higher iron ion content by coordination or adsorption reaction, this means that catalyst has higher catalytic activity.The more important thing is, because fiber of the present invention still has outstanding oxidative resistance and mechanical strength, there is mechanical strength change little when its fiber iron complex is used as heterogeneous Fenton reaction catalyst, metal ion difficult drop-off, catalytic activity is high, and the advantage such as reusability is good.In addition, the very low and environment friendly of the concentration of medicament contained by the anion that preparation method of the present invention uses and cationic polyelectrolyte solution, preparation and preparation manipulation are simply, cheap.In addition, preparation method's technique of the present invention is relatively simple, and moderate cost, easily operates, and using adaptability is good, is conducive to industrialization promotion.
Accompanying drawing explanation
Fig. 1, Fig. 2 and Fig. 3 be adopt preparation method of the present invention and prior art place to prepare respectively modified Teflon fiber to the coordination of iron ion or adsorption effect comparison diagram.(method of testing: the coordination of 0.10mol/L ferric chloride aqueous solutions or the absorption certain hour that 1.0g fiber sample are placed in 50mL, then takes out fiber sample and uses distilled water to wash 3 times.) especially, it should be noted that, adopt the method for the invention to prepare the sulfonic group modified polytetrafluoroethylene fibre that the LBL self-assembly number of plies is respectively 2,6 and 10, and they are correspondingly designated as BLB-PTFE-SO respectively
3h (2), BLB-PTFE-SO
3h (6) and BLB-PTFE-SO
3h (10), and use the catalyst of prior art process to be designated as PAA-g-PTFE.The present invention adopts and measures the iron ion use level in above-mentioned gained complex with the following method: after coordination or adsorption reaction complete, by reaction residue and subsequent wash liquid mixing constant volume, then use the concentration of aas determination iron ion wherein, and then calculate the use level of iron ion in gained fiber iron complex respectively.
The modified Teflon fiber that Fig. 4 adopts preparation method of the present invention and prior art place to prepare respectively is at different temperatures to coordination or the adsorption effect comparison diagram of iron ion.(method of testing is same as described above).
Fig. 5 is the ultimate strength comparison diagram of the modified Teflon fiber using preparation method of the present invention and prior art place to prepare.Wherein BLB (2), BLB (6), BLB (10) and PAA represent BLB-PTFE-SO respectively
3h (2), BLB-PTFE-SO
3h (6), BLB-PTFE-SO
3h (10) and PAA-g-PTFE.(test condition: with reference to standard GB/T/T3923.1-1997; Place 24 hours at 25 DEG C before sample test).
Detailed description of the invention
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing thereof:
The self-assembly preparation method thereof (hereinafter referred to as preparation method) of a kind of sulfonic group modified polytetrafluoroethylene fibre of the present invention's design, is characterized in that preparation method of the present invention is made up of seven steps such as the self-assembly process of the preparation of preliminary treatment, cationic polyelectrolyte solution, the preparation of anionic polyelectrolyte solution, cationic self-assembly process, anion, LBL self-assembly technique and aftertreatment technologys; The wherein diallyl dimethyl ammoniumchloride (PDDA) of cationic polyelectrolyte solution by 5g/L and the mixed aqueous solution of 0.50mol/L sodium chloride preparation, the mixed aqueous solution that anionic polyelectrolyte solution is prepared by kayexalate (PSS) and the 0.50mol/L sodium chloride of 5.0g/L; Polyelectrolyte solution outward appearance is colourless transparent liquid, and pH value is about 6.0-7.0, and proportion is approximately 1.0; LBL self-assembly technique can repeatedly be carried out repeatedly, to obtain the sulfonic group modified polytetrafluoroethylene fibre with the different number of plies.The sulfonic group modified polytetrafluoroethylene fibre outward appearance that this preparation method obtains is fiber shape, and fracture strength is respectively 93.51-95.29cN.
The sulfonic group modified polytetrafluoroethylene fibre (hereinafter referred to as fiber) prepared with the technology of the present invention is for series of products: by changing the number of plies of fiber surface self assembly layer by layer, prepare the sulfonic group modified polytetrafluoroethylene fibre product of the series with the different number of plies.Adopt the sulfonic group modified polytetrafluoroethylene fibre sulfonic acid surfactant base content prepared of layer-by-layer can be controlled by the number of plies of its self assembly, the content of the number of plies more multilist light fibers sulfonic acid surfactant base is higher, and they are also different from the coordination property of iron ion.Such as, the fiber of the low number of plies and iron ion show as excellent fracture strength and lower coordination property when carrying out complexation reaction, the complex Surface Fe ion concentration obtained is lower, this means that it is lower as catalytic activity during heterogeneous Fenton photochemical catalyst, be applicable to the process of the waste water from dyestuff of low concentration; The fiber of the medium number of plies and iron ion have best combination property when carrying out complexation reaction, show as excellent fracture strength and the highest coordination property, the complex Surface Fe ion concentration obtained is the highest, this means that it is the highest as catalytic activity during heterogeneous Fenton photochemical catalyst, be applicable to long time treatment waste water from dyestuff; The fiber of high-layer and iron ion show as very outstanding fracture strength and higher coordination property when carrying out complexation reaction, the complex Surface Fe ion concentration obtained is higher, this means that it is higher as catalytic activity during heterogeneous Fenton photochemical catalyst, be applicable to the waste water from dyestuff processing high concentration.As required, the sulfonic group modified polytetrafluoroethylene fibre product of actual preparation is not limited to this number of plies value range.Meanwhile, though fiber of the present invention is threadiness, also other shapes are easily made as, as granule or particulate etc.
Different from fiber prepared by prior art, fiber of the present invention adopts layer-by-layer to prepare, referred to as BLB-PTFE-SO
3h (X), (BLB wherein represents the modification of employing layer-by-layer, and PTFE represents polytetrafluoroethylene fibre, SO
3h represents sulfonic group modified, and X is the self assembly number of plies).Its most obvious architectural feature is the molecule deposition film that fiber surface of the present invention is coated with multilayer PDDA/PSS and replaces, and has a large amount of sulfonic acid groups in the PSS layer on its top layer, and this is for itself and iron ion form coordination structure and complete suction-operated and lay a good foundation.This makes the fiber obtained have excellent combination property, not only show and be easy to form the iron complex with high coordination property with iron ion, and it has very high ultimate strength.Compared with the fiber of prior art, fiber of the present invention is not only little with the dependence of iron ion complexation reaction process to temperature, and the heterogeneous Fenton photochemical catalyst obtained can be made to have higher iron ion content by complexation reaction, this means that catalyst can have higher catalytic activity.
Experimental study shows, fiber of the present invention has higher use level to iron ion, especially with the fiber (BLB-PTFE-SO of second embodiment of the invention
3h (6)) show the most outstanding.This proves that fiber of the present invention has stronger coordination property to iron ion, the heterogeneous Fenton photochemical catalyst obtained can be made to have higher iron ion content by complexation reaction under identical reaction time and temperature conditions, make catalyst have higher catalytic activity.
Following experimental study shows, when the fiber of fiber of the present invention for 1.0g or prior art being placed in the 0.10mol/L ferric chloride aqueous solutions of 50mL, after making both carry out coordination or adsorption reaction certain hour under 50 DEG C of conditions, investigate iron ion use level (Q in the fiber iron complex obtained
fe) the difference that is changed significantly.From Fig. 1, Fig. 2 and Fig. 3, in the complexation reaction starting stage, fiber all improves along with the prolongation of complexation reaction time gradually to the use level of iron ion, and the reaction time more than 150 minutes after no longer to increase and convergence is stablized, this illustrates reaction between the two after 150 minutes close to completing.The fiber (PAA-g-PTFE) of prior art is with the complexation reaction of iron ion, and when the iron ion content of reaction its fiber surface after 180 minutes is about 1.54mmol/g, and the self assembly number of plies of the present invention is the fiber (BLB-PTFE-SO of 2
3h (2)) react 180 minutes with iron ion after the iron ion content on its surface be about 1.44mmol/g (see Fig. 1).And the self assembly number of plies of the present invention is the fiber (BLB-PTFE-SO of 6
3h (6)) react 180 minutes with iron ion after the iron ion content on its surface be about 3.55mmol/g, far above the fiber of prior art, this illustrates BLB-PTFE-SO
3h (6) has high coordination property, can be had the heterogeneous Fenton photochemical catalyst (see Fig. 2) of ferric ion content by complexation reaction preparation.The self assembly number of plies of the present invention is the fiber (BLB-PTFE-SO of 10
3h (10)) react 180 minutes with iron ion after the iron ion content on its surface be about 2.75mmol/g, compared with the fiber higher than prior art, this illustrates BLB-PTFE-SO
3h (10) has higher coordination property, can prepare the heterogeneous Fenton photochemical catalyst (see Fig. 3) had compared with ferric ion content by complexation reaction.
For understanding the dependence of coordination property to temperature of the fiber of fiber of the present invention or prior art, the fiber of fiber of the present invention for 1.0g or prior art is placed in the 0.10mol/L ferric chloride aqueous solutions of 50mL, makes both under condition of different temperatures, carry out coordination or iron ion use level (Q in the fiber iron complex obtained is investigated in adsorption reaction after 180 minutes
fe) change.As shown in Figure 4, along with the rising fiber of temperature almost linearly increases to the use level of iron ion.And at the same temperature compared with the fiber of prior art, fiber (BLB-PTFE-SO of the present invention
3h (6) and BLB-PTFE-SO
3h (10)) use level of iron ion is significantly improved.It should be noted that, when reaction temperature is increased to 50 DEG C from 20 DEG C, the fiber of prior art approximately adds 5 times to iron ion use level, and fiber BLB-PTFE-SO of the present invention
3h (2) adds 1.8 times to iron ion use level is approximately corresponding, and BLB-PTFE-SO
3h (6) and BLB-PTFE-SO
3h (10) is approximately corresponding adds 0.5 times, is starkly lower than the former.This illustrates fiber (BLB-PTFE-SO of the present invention
3h (6) and BLB-PTFE-SO
3h (10)) to iron ion, still there is very high use level under cryogenic, and little to the dependence of temperature, this means to use fiber of the present invention can be had the heterogeneous Fenton photochemical catalyst of ferric ion content by complexation reaction preparation at a lower temperature.The physical and mechanical properties of fibrous ligands as ultimate strength be ensure its reusable key parameter of catalyst that formed, measure the ultimate strength with the sulfonic group modified polytetrafluoroethylene fibre of the different self assembly number of plies, result is see Fig. 5.As seen from the figure, fiber (BLB-PTFE-SO of the present invention
3h (2), BLB-PTFE-SO
3h (6), BLB-PTFE-SO
3h (10)) ultimate strength compare with the ultimate strength of the fiber (PAA-g-PTFE) of prior art, change hardly.This illustrates that the fiber of fiber of the present invention and prior art still has good physical and mechanical properties, and prepared catalyst can make its current mechanical force tolerating the longer time when reusing and chemical erosion effect.
The present invention devises a kind of self-assembly preparation method thereof of sulfonic group modified polytetrafluoroethylene fibre, and it adopts following technique:
1. pretreating process: under room temperature and stirring condition, first use is taken out after 10 minutes containing the acrylic acid modified polytetrafluoroethylene fibre of nonionic surfactant water-soluble liquid carrying out washing treatment that volumetric concentration is 2.0g/L, and then use distilled water to carry out washing 5 times to it, finally by its vacuum drying 24 hours at 50 DEG C;
2. the preparation of cationic polyelectrolyte solution: diallyl dimethyl ammoniumchloride (PDDA) and sodium chloride are made an addition in distilled water respectively and forms mixed solution, the concentration of wherein PDDA is made to be 5.0g/L, the molar concentration of sodium chloride is 0.50mol/L, set aside for use.
3. the preparation of anionic polyelectrolyte solution: kayexalate (PSS) and sodium chloride are made an addition in distilled water respectively and form mixed solution, makes the concentration of wherein PSS be 5g/L, and the molar concentration of sodium chloride is 0.50mol/L, set aside for use.
4. cationic self-assembly process: immerse in described cationic polyelectrolyte solution through pretreated fiber by above-mentioned, the ratio of its fibre weight (gram) and cationic polyelectrolyte liquor capacity (milliliter) is made to be 1: 50,50 DEG C, pH value be 6.0 and stirring condition under carry out self-assembling reaction and take out after 20 minutes, then it is dried at 40-60 DEG C and obtains CATION self assembly fiber.
5. the self-assembly process of anion: the above-mentioned fiber through CATION self assembly is immersed in described anionic polyelectrolyte solution, the ratio of its fibre weight (gram) and anionic polyelectrolyte liquor capacity (milliliter) is made to be 1: 50,50 DEG C, pH value be 6.0 and stirring condition under carry out self-assembling reaction and take out after 20 minutes, then it is dried at 40-60 DEG C and obtains anion self assembly fiber.
6. LBL self-assembly technique: the above-mentioned fiber through anion self assembly is repeated process in order according to step 4 and 5, so repeats 1-9 time, obtain the LBL self-assembly fiber of the different number of plies.
7. aftertreatment technology: under room temperature and stirring condition, first use containing the volumetric concentration nonionic surfactant water-soluble liquid carrying out washing treatment that is 2.0g/L above-mentioned after LBL self-assembly fiber take out after 10 minutes, and then use distilled water to carry out washing 5 times to it, finally its vacuum drying at 50 DEG C is obtained sulfonic group modified polytetrafluoroethylene fibre in 24 hours.
Preparation method of the present invention and prior art in essence unlike, the molecule deposition film that sulfonic group modified polytetrafluoroethylene fibre surface coverage prepared by the present invention has multilayer PDDA/PSS to replace, and in the PSS layer on its top layer, there is a large amount of sulfonic acid groups, this is for itself and iron ion form coordination structure and complete suction-operated and lay a good foundation.Fiber of the present invention not only little with the dependence of iron ion complexation reaction process to temperature, and can make the heterogeneous Fenton photochemical catalyst obtained have higher iron ion content by complexation reaction, this means that catalyst has higher catalytic activity.The more important thing is, because this fiber still has outstanding oxidative resistance and mechanical strength, there is mechanical strength change little when its fiber iron complex is used as heterogeneous Fenton reaction catalyst, metal ion difficult drop-off, catalytic activity is high, and the advantage such as reusability is good.In addition, the very low and environment friendly of the concentration of medicament contained by the anion that preparation method of the present invention uses and cationic polyelectrolyte solution, preparation and preparation manipulation are simply, cheap.In addition, preparation method's technique of the present invention is relatively simple, and moderate cost, easily operates, and using adaptability is good, is conducive to industrialization promotion.
The present invention does not address part and is applicable to prior art.The method that wherein involved in the present invention acrylic acid modified polytetrafluoroethylene fibre is provided by patent ZL201110434060.0 (a kind of modified Teflon fibre metal composition catalyst and preparation method) is prepared:
1. the preliminary treatment of polytetrafluoroethylene fibre: under room temperature and stirring condition, first use takes out washing oven dry containing the nonionic surfactant water-soluble liquid carrying out washing treatment polytetrafluoroethylene fibre that volumetric concentration is 2.0g/L after 10 minutes.And then use acetone to carry out cleaning to polytetrafluoroethylene fibre to take out after 20 minutes, finally by its vacuum drying 24 hours at 50 DEG C;
2. the graft modification reaction of polytetrafluoroethylene fibre: the described pretreated polytetrafluoroethylene fibre of accurate weighing predetermined weight, and immersed acrylic monomers that concentration is 300-700g/L and concentration is in the iron ammonium sulfate mixed aqueous solution of 15-50g/L.Described polytetrafluoroethylene (PTFE) weight (gram) is 1: 30 with the ratio of the volume (milliliter) of mixed aqueous solution; Then in system, pass into nitrogen 5-10 minute with the air driven in it and use polytetrafluoroethylene (PTFE) adhesive tape system to be sealed.Finally this sealing system is placed in the Co of 0.5-1.0kGy/h
60radiation treatment 50-100 hour is carried out at ambient temperature in gamma-rays.After reaction, pink graft modification polytetrafluoroethylene fibre is taken out and use hot water and acetone to carry out washing 3-5 time and remain in monomer and the polymer of fiber surface with removal, and vacuum drying 24 hours is for subsequent use at 50 DEG C;
The dry break strength that the present invention measures gained fiber with reference to standard GB/T/T3923.1-1997 is 90.4N.
Introduce specific embodiments of the invention below, but the claims in the present invention are not by the restriction of these specific embodiments:
Embodiment 1
1. pretreating process: under room temperature and stirring condition, first use is taken out after 10 minutes containing the acrylic acid modified polytetrafluoroethylene fibre of nonionic surfactant water-soluble liquid carrying out washing treatment that volumetric concentration is 2.0g/L, and then use distilled water to carry out washing 5 times to it, finally by its vacuum drying 24 hours at 50 DEG C;
2. the preparation of cationic polyelectrolyte solution: diallyl dimethyl ammoniumchloride (PDDA) and sodium chloride are made an addition in distilled water respectively and forms mixed solution, the concentration of wherein PDDA is made to be 5g/L, the molar concentration of sodium chloride is 0.50mol/L, set aside for use.
3. the preparation of anionic polyelectrolyte solution: kayexalate (PSS) and sodium chloride are made an addition in distilled water respectively and form mixed solution, makes the concentration of wherein PSS be 5.0g/L, and the molar concentration of sodium chloride is 0.50mol/L, set aside for use.
4. cationic self-assembly process: immerse in described cationic polyelectrolyte solution through pretreated fiber by above-mentioned, the ratio of its fibre weight (gram) and cationic polyelectrolyte liquor capacity (milliliter) is made to be 1: 50,50 DEG C, pH value be 6.0 and stirring condition under carry out self-assembling reaction and take out after 20 minutes, then it is dried at 60 DEG C and obtains CATION self assembly fiber.
5. the self-assembly process of anion: the above-mentioned fiber through CATION self assembly is immersed in described anionic polyelectrolyte solution, the ratio of its fibre weight (gram) and anionic polyelectrolyte liquor capacity (milliliter) is made to be 1: 50,50 DEG C, pH value be 6.0 and stirring condition under carry out self-assembling reaction and take out after 20 minutes, then it is dried at 40-60 DEG C and obtains anion self assembly fiber.
6. LBL self-assembly technique: by the above-mentioned fiber through anion self assembly according to step 4 and 5 reprocessing 1 time in order.
7. aftertreatment technology: under room temperature and stirring condition, first use is taken out after 10 minutes containing the above-mentioned fiber after LBL self-assembly of nonionic surfactant water-soluble liquid carrying out washing treatment that volumetric concentration is 2.0g/L, and then use distilled water to carry out washing 5 times to it, finally its vacuum drying at 50 DEG C is obtained sulfonic group modified polytetrafluoroethylene fibre, referred to as BLB-PTFE-SO in 24 hours
3h (2).
Embodiment 2
1. technique is identical with the step 1 in embodiment 1 respectively.
2. technique is identical with the step 2 in embodiment 1 respectively.
3. technique is identical with the step 3 in embodiment 1 respectively.
4. technique is identical with the step 4 in embodiment 1 respectively.
5. technique is identical with the step 5 in embodiment 1 respectively.
6. repeating number of repetition described in is 5 times.
7. technique is identical with the step 7 in embodiment 1 respectively, obtains sulfonic group modified polytetrafluoroethylene fibre referred to as BLB-PTFE-SO
3h (6).
Embodiment 3
1. technique is identical with the step 1 in embodiment 1 respectively.
2. technique is identical with the step 2 in embodiment 1 respectively.
3. technique is identical with the step 3 in embodiment 1 respectively.
4. technique is identical with the step 4 in embodiment 1 respectively.
5. technique is identical with the step 5 in embodiment 1 respectively.
6. repeating number of repetition described in is 9 times.
7. technique is identical with the step 7 in embodiment 1 respectively, obtains sulfonic group modified polytetrafluoroethylene fibre referred to as BLB-PTFE-SO
3h (10).
Comparative example:
The present embodiment is Contrast on effect example.Use prior art to prepare acrylic acid modified polytetrafluoroethylene fibre, its preparation method is provided by patent ZL201110434060.0 (a kind of modified Teflon fibre metal composition catalyst and preparation method):
1. the preliminary treatment of polytetrafluoroethylene fibre: under room temperature and stirring condition, first use takes out washing oven dry containing the nonionic surfactant water-soluble liquid carrying out washing treatment polytetrafluoroethylene fibre that volumetric concentration is 2.0g/L after 10 minutes.And then use acetone to carry out cleaning to polytetrafluoroethylene fibre to take out after 20 minutes, finally by its vacuum drying 24 hours at 50 DEG C;
2. the graft modification reaction of polytetrafluoroethylene fibre: the described pretreated polytetrafluoroethylene fibre of accurate weighing predetermined weight, and immersed acrylic monomers that concentration is 300-700g/L and concentration is in the iron ammonium sulfate mixed aqueous solution of 15-50g/L.Described polytetrafluoroethylene (PTFE) weight (gram) is 1: 30 with the ratio of the volume (milliliter) of mixed aqueous solution; Then in system, pass into nitrogen 5-10 minute with the air driven in it and use polytetrafluoroethylene (PTFE) adhesive tape system to be sealed.Finally this sealing system is placed in the Co of 0.5-1.0kGy/h
60radiation treatment 50-100 hour is carried out at ambient temperature in gamma-rays.After reaction, pink graft modification polytetrafluoroethylene fibre is taken out and use hot water and acetone to carry out washing 3-5 time and remain in monomer and the polymer of fiber surface with removal, and vacuum drying 24 hours is for subsequent use at 50 DEG C;
Under the condition of the ferric trichloride of 50mL0.10mol/L, 1.0g fiber, 50 DEG C and pH=2-3, the fiber of fiber of the present invention and prior art is carried out complexation reaction with iron ion respectively, reacts the iron ion use level (Q measured after 180 minutes in gained complex
fe).The present invention adopts and measures the iron ion use level in above-mentioned gained complex with the following method: after complexation reaction completes, reaction residue and described cleaning solution (distilled water) are mixed constant volume, then use the concentration of complexometric titration iron ion wherein, and then calculate the use level of iron ion in gained complex respectively.And the fracture strength of the fiber of fiber of the present invention and prior art is measured with reference to standard GB/T/T3923.1-1997, place 24 hours at 25 DEG C before sample test.
Table 1 fiber of the present invention and the fiber of prior art and the coordination ability of iron ion and fracture strength
As can be seen from Table 1, although BLB-PTFE-SO
3the iron ion use level of H (2) is lower than the iron ion use level of PAA-g-PTFE, but BLB-PTFE-SO
3h (6) and BLB-PTFE-SO
3the iron ion use level of H (10) is significantly higher than the iron ion use level of PAA-g-PTFE.This illustrates when the self assembly number of plies is increased to certain number of plies, and fiber of the present invention has higher use level to iron ion, especially with the fiber (BLB-PTFE-SO of second embodiment of the invention
3h (6)) show the most outstanding.This proves that fiber of the present invention has stronger coordination property to iron ion, can make the heterogeneous Fenton photochemical catalyst obtained have higher iron ion content by complexation reaction under identical reaction time and temperature conditions further.The more important thing is, fiber (BLB-PTFE-SO of the present invention
3h (2), BLB-PTFE-SO
3h (6), BLB-PTFE-SO
3h (10)) ultimate strength compare with the ultimate strength of the fiber (PAA-g-PTFE) of prior art, change hardly.This illustrates that the fiber of fiber of the present invention and prior art still has good physical and mechanical properties, and the catalyst prepared by it can make its current mechanical force tolerating the longer time when reusing and chemical erosion effect.
In sum, the sulfonic group modified polytetrafluoroethylene fibre using self-assembling technique of the present invention to obtain can not only regulate and control the coordination ability of itself and iron ion by the self assembly number of plies and obtain ferric ion use level, and little with the dependence of iron ion complexation reaction process to temperature.In addition, self assembly technology of preparing of the present invention is on the mechanical strength of the sulfonic group modified polytetrafluoroethylene fibre obtained almost without impact, and this is that the heterogeneous Fenton reaction catalyst preparing ferric ion use level and desirable physical mechanical performance creates condition.
Claims (1)
1. a sulfonic group modified polytetrafluoroethylene fibre self-assembly preparation method thereof, is characterized in that adopting following technique:
(1) pretreating process: under room temperature and stirring condition, first use is taken out after 10 minutes containing the acrylic acid modified polytetrafluoroethylene fibre of nonionic surfactant water-soluble liquid carrying out washing treatment that volumetric concentration is 2.0g/L, and then use distilled water to carry out washing 5 times to it, finally by its vacuum drying 24 hours at 50 DEG C;
(2) preparation of cationic polyelectrolyte solution: diallyl dimethyl ammoniumchloride (PDDA) and sodium chloride are made an addition in distilled water respectively and forms mixed solution, the concentration of wherein PDDA is made to be 5.0g/L, the molar concentration of sodium chloride is 0.50mol/L, set aside for use;
(3) preparation of anionic polyelectrolyte solution: kayexalate (PSS) and sodium chloride are made an addition in distilled water respectively and forms mixed solution, the concentration of wherein PSS is made to be 5.0g/L, the molar concentration of sodium chloride is 0.5mol/L, set aside for use;
(4) cationic self-assembly process: immerse in described cationic polyelectrolyte solution through pretreated fiber by above-mentioned, the ratio of its fibre weight and cationic polyelectrolyte liquor capacity is made to be 1: 50 grams per milliliter, 50 DEG C, pH value be 6.0 and stirring condition under carry out self-assembling reaction and take out after 20 minutes, then it is dried at 40-60 DEG C and obtains CATION self assembly fiber;
(5) self-assembly process of anion: the above-mentioned fiber through CATION self assembly is immersed in described anionic polyelectrolyte solution, the ratio of its fibre weight and anionic polyelectrolyte liquor capacity is made to be 1: 50 grams per milliliter, 50 DEG C, pH value be 6.0 and stirring condition under carry out self-assembling reaction and take out after 20 minutes, then it is dried at 40-60 DEG C and obtains anion self assembly fiber;
(6) LBL self-assembly technique: the above-mentioned fiber through anion self assembly is repeated process in order according to step (4) and (5), so repeats 1-9 time, obtain the LBL self-assembly fiber of the different number of plies;
(7) aftertreatment technology: under room temperature and stirring condition, first use containing the volumetric concentration nonionic surfactant water-soluble liquid carrying out washing treatment that is 2.0g/L above-mentioned after LBL self-assembly fiber take out after 10 minutes, and then use distilled water to carry out washing 5 times to it, finally its vacuum drying at 50 DEG C is obtained sulfonic group modified polytetrafluoroethylene fibre in 24 hours.
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| CN108043458A (en) * | 2018-01-05 | 2018-05-18 | 中国石油大学(华东) | A kind of preparation method and applications of the heterogeneous fenton catalyst of immobilization |
| CN109546161B (en) * | 2018-11-23 | 2021-01-15 | 中国科学院大连化学物理研究所 | Composite bipolar plate for fuel cell and preparation method and application thereof |
| CN113897785B (en) * | 2021-09-24 | 2023-06-09 | 武汉纺织大学 | Preparation method of layer-by-layer self-assembled semiconductor fiber and transistor sensor |
| CN115282933A (en) * | 2022-06-28 | 2022-11-04 | 武汉工程大学 | Sulfamate modified sodium alginate adsorbent and preparation method and application thereof |
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| CN102553644A (en) * | 2011-12-22 | 2012-07-11 | 天津工业大学 | Modified Teflon fiber metal complex catalyst and preparation method thereof |
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| CN102989509A (en) * | 2012-12-18 | 2013-03-27 | 天津工业大学 | Catalyst of sulfonated polystyrene grafted polytetrafluoroethylene fiber metal complex and preparation method thereof |
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| CN101905122A (en) * | 2010-07-23 | 2010-12-08 | 北京工业大学 | Self-assembly method for high-load inorganic nano particle hybridized organic membrane |
| CN102553644A (en) * | 2011-12-22 | 2012-07-11 | 天津工业大学 | Modified Teflon fiber metal complex catalyst and preparation method thereof |
| CN102580566A (en) * | 2012-03-16 | 2012-07-18 | 北京工业大学 | Method for in situ generating inorganic nano particles-polyelectrolyte hybrid membrane |
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