CN105688864B - One heavy metal species processing screen cloth and preparation method thereof - Google Patents

One heavy metal species processing screen cloth and preparation method thereof Download PDF

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CN105688864B
CN105688864B CN201610110943.9A CN201610110943A CN105688864B CN 105688864 B CN105688864 B CN 105688864B CN 201610110943 A CN201610110943 A CN 201610110943A CN 105688864 B CN105688864 B CN 105688864B
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screen cloth
preparation
heavy metal
setting
dendritic
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CN105688864A (en
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唐文清
曾荣英
方淑英
易露
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Hengyang Normal University
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Hengyang Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • B01D39/086—Filter cloth, i.e. woven, knitted or interlaced material of inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/10—Open-work fabrics
    • D04B21/12—Open-work fabrics characterised by thread material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604—Arrangement of the fibres in the filtering material
    • B01D2239/0613—Woven
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D10B2331/041—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET] derived from hydroxy-carboxylic acids, e.g. lactones

Abstract

The present invention relates to heavy metal species processing screen cloth and preparation method thereof, it is obtained by tricot machine 3 D weaving, and the thickness of screen cloth is 5~200mm, and screen cloth permeable amount is 1800~3000mms‑1, bursting strength is 2000~4500N；Using being produced on German import KARL MAYER RD6DPLM type double rib warp looms, by warping, required heavy metal processing screen cloth is prepared in three steps of braiding and arrangement.The present invention uses the dissaving polymer with 30 phosphonic acids end groups, by the method for weaving of screen cloth, sewage disposal screen cloth to be prepared for modifying agent, has absorption property excellent, sewage treating efficiency is high, can be recycled.

Description

One heavy metal species processing screen cloth and preparation method thereof
Technical field
The present invention relates to technical field of textile production, is a heavy metal species processing screen cloth and its preparation side specifically Method.
Background technology
Continuous progressive and industry with society develops rapidly, and the pollution caused by heavy metal wastewater thereby discharge is to ecosystem System and public health constitute serious threat, and the heavy metal in water body becomes one of China's environmental problem the most serious, because This, the improvement to heavy metal wastewater thereby is paid much attention to be subject to domestic and international researcher.In order to more effectively prevent weight in water body Metallic pollution, China have put into effect multinomial legal system, the improvement for heavy metal in water.The processing method of heavy metal wastewater thereby at present Mainly there are chemical precipitation, ion exchange, solvent extraction, chemistry redox and absorption method etc., wherein absorption method has and is easy to grasp The advantages that work, low energy consumption, low-residual, high adsorption capacity and repeatable usability is most economical, efficient and widely uses and deeply grinds The technology studied carefully it.It is a variety of including activated carbon, chitosan, natural zeolite, biological adsorption agent, chelating resin etc. at present Adsorbent is widely used in the processing of heavy metal wastewater thereby, and the adsorption capacity of these adsorbents depends on the thing of its own Rationality matter and surface functional group.
Compared with traditional resin, foam and traditional fibre, polymer fiber is due to high-specific surface area, high hole Rate, it is easily prepared and be easy to physical/chemical modification the advantages that, it is also increasingly extensive in the application of heavy metal containing wastewater treatment.Use at present In the fibrous material of heavy metal adsorption, the mainly multi-functional material such as hydroxyl, amino, as cellulose, polyacrylonitrile with And polyimides etc.；And for traditional fibrous material, due in its preparation process by spinning again through weaving etc. process, Film or fabric is prepared so as to which the processing in Heavy Metals in Waters could be applied, its spinning is complicated through weaving process again, and Process is more.Therefore develop it is a kind of can realize material shape and the fluff material technology of preparing of functions, and applied to weight The absorption of metal, for water pollution fast reaction, the quick emergency that handles is of great significance.
Web materials have excellent engineering three-dimensional tissue structures, you can beneficial to the filtering of sewage, while are also beneficial to mud etc. It is filtered through；It is more to be used for the research of sewage for screen cloth at present, but is concentrated mainly on fiber of the exploitation with low latitudes and prepares Screen cloth, improves the specific surface area of fiber in itself；The present invention uses the dissaving polymer with 30 phosphonic acids end groups as modifying agent, By the method for weaving of screen cloth, sewage disposal screen cloth is prepared, has absorption property excellent, sewage treating efficiency is high, can Recycle.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a heavy metal species processing screen cloth and its preparation side Method.
The purpose of the present invention is what is be achieved through the following technical solutions：
One heavy metal species processing screen cloth, it is obtained by tricot machine 3 D weaving, and the thickness of screen cloth is 5~200mm, net Cloth permeable amount is 1800~3000mms-1, bursting strength is 2000~4500N.
The preparation method of one heavy metal species processing screen cloth, it is concretely comprised the following steps：
(a) preparation of hyperbranched dendritic polymer
Hyperbranched dendritic polymer, its chemical structural formula are：
Based technique for in-situ remediation, is not take up arable land, does not influence agricultural production and income, and cost is low, effect on environment is small, Soil environment is not destroyed, is very suitable for the agricultural land soil for being subject to mild or moderate cadmium, lead, copper, zinc pollution for handling large area, if It can successfully realize industrialization and large-area applications, will realize important breakthrough in heavy metal pollution in-situ immobilization field, and be our province Rice field cadmium, the reparation of lead-contaminated soil, the content of beary metal in reduction rice, the agriculture volume increase of realization, increasing peasant income etc. will all rise To huge impetus.
And the hyperbranched dendritic polymer with high algebraically, since phosphonyl group content is high in molecule, with heavy metal from Sub- chelation is strong, and the chelating quantity of single molecular metal ion is big, and the chelation group molecule space volume of formation is big therefore resistance to Ph stability is good, and resistance to migration is good, due to dendritic structure especially during chelation, to the heavy metal in molecule With very excellent ion blocking effect and filter ions effect, therefore design more dendritic structures and more phosphonic acids Chelation group, its chelation is stronger, and antiacid alkaline stability is stronger, therefore present invention design has 30 phosphonyl groups, and With 3 major branches, 9 withes passivator to the repairing effect of heavy metal substantially since conventional metal is passivated renovation agent；
Hyperbranched dendritic polymer its preparation method comprises the following steps that：
(1) preparation of star terminal double bond dendritic
Using tetramethylol methane tetraacrylate and melamine as raw material, low molecule class alcohol is solvent, in band stirring and condensation In the reaction unit of reflux, protected down with nitrogen, the temperature for controlling reaction system is -10~5 DEG C, first that the alcohol of melamine is molten Liquid is divided into three equal parts, and the alcoholic solution of melamine is then added dropwise into the alcoholic solution of tetramethylol methane tetraacrylate in batches, the When the alcoholic solution of melamine is once added dropwise, the temperature for controlling dropwise addition process is -10~-5 DEG C, and time for adding is 30~60min, When the alcoholic solution of melamine being added dropwise for the second time, the temperature for controlling dropwise addition process is -5~0 DEG C, and time for adding is 30~45min, When the alcoholic solution of melamine is added dropwise in third time, the temperature for controlling dropwise addition process is 0~5 DEG C, and time for adding is 20~30min, After the alcoholic solution of melamine is added dropwise each time, reaction system reacts 4~10h at a temperature of moving to 25 DEG C；Melamine is whole It is added dropwise after drop finishes, reaction system is moved at 25 DEG C, the reaction was continued 10~20h；Light golden yellow is had after the completion of reaction in system Product separates out, filtering, and is washed with methanol, and light golden yellow product is dried in vacuo at 40 DEG C, and it is double to obtain light golden yellow star end Key dendritic；
The tetramethylol methane tetraacrylate and the molar ratio of melamine are 1:0.25~0.30；
The low molecule class alcoholic solution is methanol, ethanol, aqueous isopropanol；
The molar fraction of the alcoholic solution of the tetramethylol methane tetraacrylate is 0.25~1.25mol/L；
The molar fraction of the alcoholic solution of the melamine is 0.10~1.50mol/L；
(2) star end amido dendritic
With stirring, in the reactor of reflux condensing tube, controlling reaction temperature is 0~5 DEG C, protects and stirs in nitrogen Under the conditions of, the methanol solution of ethylenediamine is first added, then again adds star terminal double bond dendritic prepared by step (1) Enter, stir, be uniformly mixed.Then at 25 DEG C, 20~30h is reacted, then 3~5h is evaporated under reduced pressure under conditions of 80~100 DEG C Methanol and unnecessary ethylenediamine are removed, obtains faint yellow viscous product, as star end amido dendritic, star end amine Chemical formula reaction equation such as Fig. 1 of base dendritic；
The molar fraction of ethylenediamine is 0.5~5.0mol/L in the ethylenediamine methanol solution；
The star terminal double bond dendritic and the molar ratio of ethylenediamine are 1:10~12；
Melamine and ethylene diamine compound source are wide, and cost is low, are chemically reacted gently in preparation process, preparation process can Control, therefore the cost in preparation process is low, beneficial to industrialized production and large-scale promotion, has for the marketization for lifting product Very big cost advantage.
(3) synthesis of hyperbranched dendritic polymer
By phosphorous acid be added in concentrated hydrochloric acid be uniformly mixed, control phosphorous acid in concentrated hydrochloric acid concentration be 0.25~ 1.25mol/L, concentrated hydrochloric acid is the hydrochloric acid solution of 10~12mol/L, and then under the conditions of 0~10 DEG C, star end amido tree is added dropwise The aqueous solution of dendritic polymer, the aqueous solution mass fraction of the star end amido dendritic is 20~45%, star The aqueous solution of shape end amido dendritic is added dropwise process and is added dropwise to complete in 30min；Then again in 85~90 DEG C of stirring Under the conditions of, formalin is added dropwise, rear reaction system, then the insulation reaction 1~2 under the conditions of 90 DEG C is added dropwise in formalin Hour, 105~110 DEG C, when reflux 2~4 is small, after reflux are finally warming up to, closing volume device, opens HCl absorption bottles, Reaction mixture is concentrated, 105~110 DEG C of thickening temperature, after being concentrated into no HCl releasings, is cooled to room temperature, obtains solid content as 25 ~55% light yellow transparent liquid, is product hyperbranched dendritic polymer, the synthesis of hyperbranched dendritic polymer Reaction equation is as shown in Figure 2；
Wherein solid content is the mass percent of hyperbranched dendritic polymer in the solution, is that hyperbranched dendritic gathers The mass percent of compound in aqueous；
(b) preparation of modified PLA fibers
Water miscible PLA is used as raw material, using water as solvent, is dissolved under the conditions of 60~80 DEG C, controls PLA spinning The mass fraction of liquid is 20~25%, then adds the hyperbranched dendritic polymer of above-mentioned steps (a) synthesis, after dissolving, Wet spinning is carried out, using the aqueous solution of sodium sulphate as solidification liquid, is solidified through solidification liquid, modification is prepared in stretching and winding PLA fibers；
The wet spinning speed is 1.0~15m/min, 25~35 DEG C of spinning solution temperature；The solidifying process is adopted With solidifying twice, solidification liquid concentration is 1.0~1.5g/L in first of process of setting, and setting temperature is in first of process of setting 40~50 DEG C, the fiber retention time is 12~18s in first of process of setting；Solidification liquid concentration is in second process of setting 0.9~1.3g/L, setting temperature is 85~95 DEG C in second process of setting, in second process of setting the residence time for 10~ 15s；The drawing process is divided into first time wet tensile, second of dry drawing stretching process, stretching times during first time wet tensile Number is 0.5~1.0 times, and draft temperature is 120~150 DEG C, and multiple is stretched during second of dry tensile for 1.5~2.0 Times, draft temperature is 180~230 DEG C；
PLA fibers have excellent water-swellable energy, beneficial to the hyperbranched branch with end phosphonyl group of chelation Contact of the shaped polymer with heavy metal ion, so that suction-operated of the screen cloth to heavy metal ion is improved, while in wet spinning During, since PLA fibers form substantial amounts of micropore in process of setting, the recessed grain and micropore of fiber surface are lifted, so as to carry High phosphonic acids end group hyperbranched dendritic polymer with the heavy metal contact surface in sewage, lift the suction-operated of screen cloth.
(c) preparation of heavy metal processing screen cloth
Using being produced on German import KARL MAYER RD6DPLM type double rib warp looms, by warping, weave and whole Required heavy metal processing screen cloth is prepared in three steps of reason；It is 0.08~0.18g/ that tension in Warping is controlled during warping Den, and through warp thread during weaving, weft yarn and ties up yarn and is manufactured into screen cloth, and warp thread is in vertical shape structure, and weft yarn is horizontal Structure, warp thread and weft yarn are connected by tying up yarn, and the density of warp thread is 300~450/cm, the density of weft yarn for 300~450/ Cm, the density for tying up yarn are 500~600/cm, and warp thread is modified PLA fibers, and weft yarn is polyester monofilament, and it is that modified PLA is fine to tie up yarn Dimension；
Using screen cloth structure, in sewage disposal process, the warp thread on vertical direction can be good at and the weight in sewage Metal is contacted, and is avoided conventional fabrics due to being reduced caused by overlay structure with waste water surface, is caused adsorption effect The problem of decrease；The polyester monofilament of weft yarn provides structural strength for screen cloth at the same time, realizes the unification of the function and performance of screen cloth；
Compared with prior art, the positive effect of the present invention is：
Of the invention heavy metal species processing screen cloth and preparation method thereof, using screen cloth structure, in sewage disposal process, It can be good at being contacted with the heavy metal in sewage using the warp thread on vertical direction, avoid conventional fabrics due to overlapping The problem of being reduced caused by structure with waste water surface, causing adsorption effect to weaken；Phosphonyl group is held using with 30 Hyperbranched dendritic polymer is the modifying agent of PLA fibers, and using the water-swellable energy that PLA is excellent, and PLA fibers are in wet method Substantial amounts of micropore is formed in spinning process of setting, the recessed grain and micropore of fiber surface is lifted, gathers so as to improve hyperbranched dendritic Compound with the heavy metal contact surface in sewage, the suction-operated of screen cloth is lifted, by wet spinning process using hyperbranched Polymer macromolecule steric hindrance acts on and intermolecular interaction of hydrogen bond fixes the phosphonic acids of hyperbranched dendritic polymer End group, avoids the migration of modifying agent, simultaneously because spherical hyperbranched dendritic polymer is during spinning super drawing Effect is rolled, moves to fiber surface, reduces hyperbranched dendritic polymer and the contact resistance of the heavy metal ion in water body, Beneficial to more stable chelate compound is formed, the sewage disposal performance of screen cloth is lifted；Place for Heavy Metals in Waters ion The fields such as reason have broad application prospects.
Brief description of the drawings
Fig. 1 is chemical formula reaction equation such as Fig. 1 prepared by star terminal double bond dendritic
Fig. 2 is chemical formula reaction equation prepared by star end amido dendritic；
Fig. 3 is the reaction equation of the synthesis of hyperbranched dendritic polymer；
The nuclear magnetic resonance 1H-NMR collection of illustrative plates of Fig. 4 star terminal double bond dendritics；
The nuclear-magnetism 1H-NMR collection of illustrative plates of Fig. 5 stars end amido dendritic；
The nuclear magnetic resonance 1H-NMR collection of illustrative plates of Fig. 6 hyperbranched dendritic polymer；
Embodiment
The embodiment of heavy metal species processing screen cloth of the invention presented below and preparation method thereof.
Embodiment 1
One heavy metal species processing screen cloth, it is obtained by tricot machine 3 D weaving, and the thickness of screen cloth is 5~200mm, net Cloth permeable amount is 1800~3000mms-1, bursting strength is 2000~4500N.
The preparation method of one heavy metal species processing screen cloth, it is concretely comprised the following steps：
(a) preparation of hyperbranched dendritic polymer
Hyperbranched dendritic polymer, its chemical structural formula are：
Hyperbranched dendritic polymer its preparation method comprises the following steps that：
(1) preparation of star terminal double bond dendritic
Using tetramethylol methane tetraacrylate and melamine as raw material, low molecule class alcohol is solvent, in band stirring and condensation In the reaction unit of reflux, protected down with nitrogen, the temperature for controlling reaction system is -10~5 DEG C, first that the alcohol of melamine is molten Liquid is divided into three equal parts, and the alcoholic solution of melamine is then added dropwise into the alcoholic solution of tetramethylol methane tetraacrylate in batches, the When the alcoholic solution of melamine is once added dropwise, the temperature for controlling dropwise addition process is -10~-5 DEG C, and time for adding is 30~60min, When the alcoholic solution of melamine being added dropwise for the second time, the temperature for controlling dropwise addition process is -5~0 DEG C, and time for adding is 30~45min, When the alcoholic solution of melamine is added dropwise in third time, the temperature for controlling dropwise addition process is 0~5 DEG C, and time for adding is 20~30min, After melamine alcoholic solution is added dropwise each time, reaction system reacts 4~10h at a temperature of moving to 25 DEG C；Melamine all drips After adding drop to finish, reaction system is moved at 25 DEG C, the reaction was continued 10~20h；Light golden yellow production is had after the completion of reaction in system Thing separates out, filtering, and is washed with methanol, and light golden yellow product is dried in vacuo at 40 DEG C, obtains light golden yellow star terminal double bond Dendritic；Chemical formula reaction equation such as Fig. 1 prepared by star terminal double bond dendritic；
The tetramethylol methane tetraacrylate and the molar ratio of melamine are 1:0.25；
The low molecule class alcoholic solution is methanol, ethanol, aqueous isopropanol；
The molar fraction of the alcoholic solution of the tetramethylol methane tetraacrylate is 0.25mol/L；
The molar fraction of the alcoholic solution of the melamine is 0.10mol/L；
(2) star end amido dendritic
With stirring, in the reactor of reflux condensing tube, controlling reaction temperature is 0~5 DEG C, protects and stirs in nitrogen Under the conditions of, the methanol solution of ethylenediamine is first added, then again adds star terminal double bond dendritic prepared by step (1) Enter, stir, be uniformly mixed.Then at 25 DEG C, 20~30h is reacted, then 3~5h is evaporated under reduced pressure under conditions of 80~100 DEG C Methanol and unnecessary ethylenediamine are removed, obtains faint yellow viscous product, as star end amido dendritic, star end amine Chemical formula reaction equation such as Fig. 2 prepared by base dendritic；
The molar fraction of ethylenediamine is 0.5mol/L in the ethylenediamine methanol solution；
The star terminal double bond dendritic and the molar ratio of ethylenediamine are 1:10；
(3) synthesis of hyperbranched dendritic polymer
By phosphorous acid be added in concentrated hydrochloric acid be uniformly mixed, control phosphorous acid in concentrated hydrochloric acid concentration be 0.25~ 1.25mol/L, concentrated hydrochloric acid is the hydrochloric acid solution of 10~12mol/L, and then under the conditions of 0~10 DEG C, star end amido tree is added dropwise The aqueous solution of dendritic polymer, the aqueous solution mass fraction of the star end amido dendritic is 20~45%, star The aqueous solution of shape end amido dendritic is added dropwise process and is added dropwise to complete in 30min；Then again in 85~90 DEG C of stirring Under the conditions of, formalin is added dropwise, rear reaction system, then the insulation reaction 1~2 under the conditions of 90 DEG C is added dropwise in formalin Hour, 105~110 DEG C, when reflux 2~4 is small, after reflux are finally warming up to, closing volume device, opens HCl absorption bottles, Reaction mixture is concentrated, 105~110 DEG C of thickening temperature, after being concentrated into no HCl releasings, is cooled to room temperature, obtains solid content as 25 ~55% light yellow transparent liquid, be product hyperbranched dendritic polymer, hyperbranched dendritic Macroscopic single crystal it is anti- Answer equation as shown in Figure 3；
Wherein solid content is the mass percent of hyperbranched dendritic polymer in the solution, is that hyperbranched dendritic gathers The mass percent of compound in aqueous；
(b) preparation of modified PLA fibers
Water miscible PLA is used as raw material, using water as solvent, is dissolved under the conditions of 60~80 DEG C, controls PLA spinning The mass fraction of liquid is 20~25%, then adds the hyperbranched dendritic polymer of above-mentioned steps (a) synthesis, after dissolving, Wet spinning is carried out, using the aqueous solution of sodium sulphate as solidification liquid, is solidified through solidification liquid, modification is prepared in stretching and winding PLA fibers；
The wet spinning speed is 1.0~15m/min, 25~35 DEG C of spinning solution temperature；The solidifying process is adopted With solidifying twice, solidification liquid concentration is 1.0~1.5g/L in first of process of setting, and setting temperature is in first of process of setting 40~50 DEG C, the fiber retention time is 12~18s in first of process of setting；Solidification liquid concentration is in second process of setting 0.9~1.3g/L, setting temperature is 85~95 DEG C in second process of setting, in second process of setting the residence time for 10~ 15s；The drawing process is divided into first time wet tensile, second of dry drawing stretching process, stretching times during first time wet tensile Number is 0.5~1.0 times, and draft temperature is 120~150 DEG C, and multiple is stretched during second of dry tensile for 1.5~2.0 Times, draft temperature is 180~230 DEG C；
PLA fibers have excellent water-swellable energy, beneficial to the hyperbranched branch with end phosphonyl group of chelation Contact of the shaped polymer with heavy metal ion, so that suction-operated of the screen cloth to heavy metal ion is improved, while in wet spinning During, since PLA fibers form substantial amounts of micropore in process of setting, the recessed grain and micropore of fiber surface are lifted, so as to carry High phosphonic acids end group hyperbranched dendritic polymer with the heavy metal contact surface in sewage, lift the suction-operated of screen cloth.
(c) preparation of heavy metal processing screen cloth
Using being produced on German import KARL MAYER RD6DPLM type double rib warp looms, by warping, weave and whole Required heavy metal processing screen cloth is prepared in three steps of reason；It is 0.08~0.18g/ that tension in Warping is controlled during warping Den, and through warp thread during weaving, weft yarn and ties up yarn and is manufactured into screen cloth, and warp thread is in vertical shape structure, and weft yarn is horizontal Structure, warp thread and weft yarn are connected by tying up yarn, and the density of warp thread is 300~450/cm, the density of weft yarn for 300~450/ Cm, the density for tying up yarn are 500~600/cm, and warp thread is modified PLA fibers, and weft yarn is polyester monofilament, and it is that modified PLA is fine to tie up yarn Dimension；
Using screen cloth structure, in sewage disposal process, the warp thread on vertical direction can be good at and the weight in sewage Metal is contacted, and is avoided conventional fabrics due to being reduced caused by overlay structure with waste water surface, is caused adsorption effect The problem of decrease；The polyester monofilament of weft yarn provides structural strength for screen cloth at the same time, realizes the unification of the function and performance of screen cloth；
The nuclear magnetic resonance 1H-NMR collection of illustrative plates of Fig. 4 star terminal double bond dendritics, is polymerize by star terminal double bond dendroid The 1H-NMR collection of illustrative plates of the molecular structural formula binding molecule of thing, the chemical shift of each hydrogen-like is as shown in the figure, wherein melamine in molecule The chemical shift of middle amino on amine is 4.05ppm (e), and melamine and tetramethylol methane tetraacrylate there occurs Michael addition reactions, make to produce new chemical bond in molecule, the characteristic absorption peak of methylene, its correspondingization occur Displacement study is 2.48ppm (g) and 3.45ppm (f), and the peak area and methylene of the amino characteristic absorption peak e on melamine The ratio between the peak area of characteristic absorption peak g and f be 1:2.02:2.01, all kinds of amino and methylene in corresponding molecular structure Unit structure ratio is 1:2:2, thus a double bond in melamine and tetramethylol methane tetraacrylate there occurs Michael addition reactions, generate target product star terminal double bond dendritic.
The nuclear-magnetism 1H-NMR collection of illustrative plates of Fig. 5 stars end amido dendritic, by star end amido dendritic Nuclear magnetic spectrum understands that the double bond in molecule, there occurs Michael addition reactions, makes double bond all disappear, and produce with ethylenediamine Methylene, as make the chemical shift of double bond by 5.83ppm (a, c) and 6.37ppm (b) be transferred to 2.95ppm (a ', c ') and 2.37ppm (b '), and characteristic absorption peak of the molecule without double bond, while the ammonia in ethylenediamine molecular structure is detected in molecule The characteristic absorption peak of base (j) and ethyl (h).Therefore illustrate that star terminal double bond dendritic member ethylenediamine occurs Michael addition reactions, reaction are carried out by design direction.
The nuclear magnetic resonance 1H-NMR collection of illustrative plates of Fig. 6 hyperbranched dendritic polymer, phosphonous acid are sent out in acid condition with formaldehyde Raw addition reaction, makes the characteristic absorption peak of reaction generation methylene, and the hydroxyl characteristic absorption peak of the phosphonous acid produced in molecule is 1.84ppm (m), and do not detect the characteristic absorption peak in amino molecule；Star end amido branch in collection of illustrative plates in molecule at the same time The methylene of secondary amino group on the melamine of shaped polymer and phosphonous acid and formaldehyde reaction production is 3.11ppm (i), star end The chemical shift of amino and phosphonous acid and the methylene of formaldehyde reaction production on the aminoethyl amino of amido dendritic For 2.44ppm (k), and the peak area ratio of the peak area of i and k are 0.33:3.05, the Asia of existing corresponding different chemical shifts The number ratio of methyl is 1:9, hence it is demonstrated that amino uniform phosphonous acid is reacted in synthesized passivation agent molecule, produce There is the hyperbranched polymer molecule of phosphonous acid structure, as react and carried out according to design direction, generate required over-expense Change dendritic.
Embodiment 2
One heavy metal species processing screen cloth, it is obtained by tricot machine 3 D weaving, and the thickness of screen cloth is 5~200mm, net Cloth permeable amount is 1800~3000mms-1, bursting strength is 2000~4500N.
The preparation method of one heavy metal species processing screen cloth, it is concretely comprised the following steps：
(a) preparation of hyperbranched dendritic polymer
Hyperbranched dendritic polymer, its chemical structural formula are：
Hyperbranched dendritic polymer its preparation method comprises the following steps that：
(1) preparation of star terminal double bond dendritic
Using tetramethylol methane tetraacrylate and melamine as raw material, low molecule class alcohol is solvent, in band stirring and condensation In the reaction unit of reflux, protected down with nitrogen, the temperature for controlling reaction system is -10~5 DEG C, first that the alcohol of melamine is molten Liquid is divided into three equal parts, and the alcoholic solution of melamine is then added dropwise into the alcoholic solution of tetramethylol methane tetraacrylate in batches, the When the alcoholic solution of melamine is once added dropwise, the temperature for controlling dropwise addition process is -10~-5 DEG C, and time for adding is 30~60min, When the alcoholic solution of melamine being added dropwise for the second time, the temperature for controlling dropwise addition process is -5~0 DEG C, and time for adding is 30~45min, When the alcoholic solution of melamine is added dropwise in third time, the temperature for controlling dropwise addition process is 0~5 DEG C, and time for adding is 20~30min, After melamine alcoholic solution is added dropwise each time, reaction system reacts 4~10h at a temperature of moving to 25 DEG C；Melamine all drips After adding drop to finish, reaction system is moved at 25 DEG C, the reaction was continued 10~20h；Light golden yellow production is had after the completion of reaction in system Thing separates out, filtering, and is washed with methanol, and light golden yellow product is dried in vacuo at 40 DEG C, obtains light golden yellow star terminal double bond Dendritic；Preparation chemical reaction mode such as Fig. 1 of star terminal double bond dendritic；
The tetramethylol methane tetraacrylate and the molar ratio of melamine are 1:0.25~0.30；
The low molecule class alcoholic solution is methanol, ethanol, aqueous isopropanol；
The molar fraction of the tetramethylol methane tetraacrylate alcoholic solution is 1.25mol/L；
The molar fraction of the melamine alcoholic solution is 1.50mol/L；
(2) star end amido dendritic
With stirring, in the reactor of reflux condensing tube, controlling reaction temperature is 0~5 DEG C, protects and stirs in nitrogen Under the conditions of, the methanol solution of ethylenediamine is first added, then again adds star terminal double bond dendritic prepared by step (1) Enter, stir, be uniformly mixed；Then at 25 DEG C, 20~30h is reacted, then 3~5h is evaporated under reduced pressure under conditions of 80~100 DEG C Methanol and unnecessary ethylenediamine are removed, obtains faint yellow viscous product, as star end amido dendritic, star end amine The chemical equation of base dendritic such as Fig. 2；
The molar fraction of ethylenediamine is 5.0mol/L in the ethylenediamine methanol solution；
The star terminal double bond dendritic and the molar ratio of ethylenediamine are 1:12；
Melamine and ethylene diamine compound source are wide, and cost is low, are chemically reacted gently in preparation process, preparation process can Control, therefore the cost in preparation process is low, beneficial to industrialized production and large-scale promotion, has for the marketization for lifting product Very big cost advantage.
(3) synthesis of hyperbranched dendritic polymer
By phosphorous acid be added in concentrated hydrochloric acid be uniformly mixed, control phosphorous acid in concentrated hydrochloric acid concentration be 0.25~ 1.25mol/L, concentrated hydrochloric acid is the hydrochloric acid solution of 10~12mol/L, and then under the conditions of 0~10 DEG C, star end amido tree is added dropwise The aqueous solution of dendritic polymer, the aqueous solution mass fraction of the star end amido dendritic is 20~45%, star The aqueous solution of shape end amido dendritic is added dropwise process and is added dropwise to complete in 30min；Then again in 85~90 DEG C of stirring Under the conditions of, formalin is added dropwise, rear reaction system, then the insulation reaction 1~2 under the conditions of 90 DEG C is added dropwise in formalin Hour, 105~110 DEG C, when reflux 2~4 is small, after reflux are finally warming up to, closing volume device, opens HCl absorption bottles, Reaction mixture is concentrated, 105~110 DEG C of thickening temperature, after being concentrated into no HCl releasings, is cooled to room temperature, obtains solid content as 25 ~55% light yellow transparent liquid, is product hyperbranched dendritic polymer, the synthesis of hyperbranched dendritic polymer Reaction equation is as shown in Figure 3：
(b) preparation of modified PLA fibers
Water miscible PLA is used as raw material, using water as solvent, is dissolved under the conditions of 60~80 DEG C, controls PLA spinning The mass fraction of liquid is 20~25%, then adds the hyperbranched dendritic polymer of above-mentioned steps (a) synthesis, after dissolving, Wet spinning is carried out, using the aqueous solution of sodium sulphate as solidification liquid, is solidified through solidification liquid, modification is prepared in stretching and winding PLA fibers；
The wet spinning speed is 1.0~15m/min, 25~35 DEG C of spinning solution temperature；The solidifying process is adopted With solidifying twice, solidification liquid concentration is 1.0~1.5g/L in first of process of setting, and setting temperature is in first of process of setting 40~50 DEG C, the fiber retention time is 12~18s in first of process of setting；Solidification liquid concentration is in second process of setting 0.9~1.3g/L, setting temperature is 85~95 DEG C in second process of setting, in second process of setting the residence time for 10~ 15s；The drawing process is divided into first time wet tensile, second of dry drawing stretching process, stretching times during first time wet tensile Number is 0.5~1.0 times, and draft temperature is 120~150 DEG C, and multiple is stretched during second of dry tensile for 1.5~2.0 Times, draft temperature is 180~230 DEG C；
PLA fibers have excellent water-swellable energy, beneficial to the hyperbranched branch with end phosphonyl group of chelation Contact of the shaped polymer with heavy metal ion, so that suction-operated of the screen cloth to heavy metal ion is improved, while in wet spinning During, since PLA fibers form substantial amounts of micropore in process of setting, the recessed grain and micropore of fiber surface are lifted, so as to carry High phosphonic acids end group hyperbranched dendritic polymer with the heavy metal contact surface in sewage, lift the suction-operated of screen cloth.
(c) preparation of heavy metal processing screen cloth
Using being produced on German import KARL MAYER RD6DPLM type double rib warp looms, by warping, weave and whole Required heavy metal processing screen cloth is prepared in three steps of reason；It is 0.08~0.18g/ that tension in Warping is controlled during warping Den, and through warp thread during weaving, weft yarn and ties up yarn and is manufactured into screen cloth, and warp thread is in vertical shape structure, and weft yarn is horizontal Structure, warp thread and weft yarn are connected by tying up yarn, and the density of warp thread is 450/cm, and the density of weft yarn is 450/cm, ties up yarn Density is 600/cm, and warp thread is modified PLA fibers, and weft yarn is polyester monofilament, and it is modified PLA fibers to tie up yarn；
Using screen cloth structure, in sewage disposal process, the warp thread on vertical direction can be good at and the weight in sewage Metal is contacted, and is avoided conventional fabrics due to being reduced caused by overlay structure with waste water surface, is caused adsorption effect The problem of decrease；The polyester monofilament of weft yarn provides structural strength for screen cloth at the same time, realizes the unification of the function and performance of screen cloth；
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, without departing from the inventive concept of the premise, can also make some improvements and modifications, these improvements and modifications also should be regarded as In protection scope of the present invention.

Claims (3)

1. the preparation method of a heavy metal species processing screen cloth, it is characterised in that it is concretely comprised the following steps：
(a) preparation of hyperbranched dendritic polymer
Hyperbranched dendritic polymer, its chemical structural formula are：
(b) preparation of modified PLA fibers
Water miscible PLA is used as raw material, using water as solvent, is dissolved under the conditions of 60~80 DEG C, control PLA spinning solutions Mass fraction is 20~25%, then adds the hyperbranched dendritic polymer of above-mentioned steps (a) synthesis, after dissolving, is carried out Wet spinning, using the aqueous solution of sodium sulphate as solidification liquid, solidifies through solidification liquid, and modified PLA fibres are prepared in stretching and winding Dimension；
(c) preparation of heavy metal processing screen cloth
Using being produced on German import KARL MAYER RD6DPLM type double rib warp looms, by warping, braiding and arrangement three Required heavy metal processing screen cloth is prepared in a step；It is 0.08~0.18g/den that tension in Warping is controlled during warping, And through warp thread during weaving, weft yarn and tie up yarn and be manufactured into screen cloth, warp thread is in vertical shape structure, the horizontal knot of weft yarn Structure, warp thread and weft yarn are connected by tying up yarn, and the density of warp thread is 300~450/cm, the density of weft yarn for 300~450/ Cm, the density for tying up yarn are 500~600/cm, and warp thread is modified PLA fibers, and weft yarn is polyester monofilament, and it is that modified PLA is fine to tie up yarn Dimension.
2. the preparation method of heavy metal species processing screen cloth as claimed in claim 1, it is characterised in that
The hyperbranched dendritic polymer its preparation method comprises the following steps that：
(1) preparation of star terminal double bond dendritic
(2) star end amido dendritic
(3) synthesis of hyperbranched dendritic polymer
Phosphorous acid is added in concentrated hydrochloric acid and is uniformly mixed, it is 0.25~1.25mol/L to control phosphorous acid concentration in concentrated hydrochloric acid, Concentrated hydrochloric acid is the hydrochloric acid solution of 10~12mol/L, and then under the conditions of 0~10 DEG C, star end amido dendritic is added dropwise Aqueous solution, the aqueous solution mass fraction of the star end amido dendritic is 20~45%, star end amido tree The aqueous solution of dendritic polymer is added dropwise process and is added dropwise to complete in 30min；Then again under 85~90 DEG C of stirring condition, it is added dropwise Formalin, rear reaction system is added dropwise in formalin, then when insulation reaction 1~2 is small under the conditions of 90 DEG C, finally rises Temperature is to 105~110 DEG C, and when reflux 2~4 is small, after reflux, closing volume device opens HCl absorption bottles, and concentration reaction is mixed Close liquid, 105~110 DEG C of thickening temperature, is concentrated into after no HCl releases, is cooled to room temperature, obtain solid content be 25~55% it is light Yellow transparent liquid, is product hyperbranched dendritic polymer.
3. the preparation method of heavy metal species processing screen cloth as claimed in claim 1, it is characterised in that
The wet spinning speed is 1.0~15m/min, 25~35 DEG C of spinning solution temperature；The solidifying process uses two Secondary solidification, solidification liquid concentration is 1.0~1.5g/L in first of process of setting, in first of process of setting setting temperature for 40~ 50 DEG C, the fiber retention time is 12~18s in first of process of setting；In second process of setting solidification liquid concentration for 0.9~ 1.3g/L, setting temperature is 85~95 DEG C in second process of setting, and the residence time is 10~15s in second process of setting； The drawing process is divided into first time wet tensile, second of dry drawing stretching process, and draw ratio is during first time wet tensile 0.5~1.0 times, draft temperature is 120~150 DEG C, and draw ratio is 1.5~2.0 during second of dry tensile Times, draft temperature is 180~230 DEG C.
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