CN105960280A - Metal adsorbent having nonwoven fabric form, and production method for same - Google Patents

Metal adsorbent having nonwoven fabric form, and production method for same Download PDF

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Publication number
CN105960280A
CN105960280A CN201580007145.7A CN201580007145A CN105960280A CN 105960280 A CN105960280 A CN 105960280A CN 201580007145 A CN201580007145 A CN 201580007145A CN 105960280 A CN105960280 A CN 105960280A
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CN
China
Prior art keywords
metal
glycidyl
macromolecule
woven fabrics
adsorbing material
Prior art date
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Pending
Application number
CN201580007145.7A
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Chinese (zh)
Inventor
井上嘉则
梶原健宽
齐藤雅春
藤井隆幸
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Kanebo Ltd
Filcon
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Kanebo Ltd
Filcon
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Publication of CN105960280A publication Critical patent/CN105960280A/en
Pending legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • 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
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • B01J20/28014—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 form
    • B01J20/28023—Fibres or filaments
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3278—Polymers being grafted on the carrier
    • 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
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • 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
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • 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
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/007—Addition polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • 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
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
    • D06M2400/01—Creating covalent bondings between the treating agent and the fibre

Abstract

Provided are a metal adsorbent having a nonwoven fabric form, for use in adsorption and recovery of metals in solution, wherein the metal adsorbent having a nonwoven fabric form is produced by passing through: a) a step for preparing a polymer having glycidyl groups in the molecules thereof; b) a step for kneading the polymer having glycidyl groups, and a polyolefin fiber matrix polymer having a flow initiation temperature of 200 DEG C or below; c) a step for forming a nonwoven fabric by a melt blowing process or spunbonding process; and d) a step for reacting long-chain metalloligands having amino groups or imino groups, with the glycidyl groups on the nonwoven fabric fiber surfaces, or with halohydrin groups formed by reacting a hydrogen halide with these the glycidyl groups, to introduce metal-adsorbing functional groups. The metal adsorbent has high adsorbent capacity and high chemical resistance, can be endowed with a variety of metal-adsorbing properties, and can be readily processed into various forms. Also provided is a production method for the metal adsorbent.

Description

Nonwoven cloth-like metal-adsorbing material and manufacture method thereof
Technical field
The present invention relates to be suitable to absorption and recovery plant draining, use water, Environmental Water, manufacturing process's water On the metal in solution widely, have that high adsorption capacity, chemical-resistant be high, variation is held Easily, nonwoven cloth-like metal-adsorbing material and the manufacture method thereof of rich and varied form can be processed into.
Background technology
Appeal to construct Circular Society Construction the most always.Aluminum cylinder or the plastics such as cylinder of steel, PET, two The classification of primary cell, stationery, bottle class etc. is reclaimed and recirculation is personal problem, and recirculation rate is also Rise year by year.On the other hand, with rare metals such as rare earth element, indium, niobium, manganese as representative, Metallic element including including platinum family, copper, zinc, aluminum etc. is referred to as " key metal ", in high-tech Skill industry etc. are particularly important key material.In them, although substantially establish copper, The recirculating system of zinc, aluminum etc., but about other metallic elements, the most do not establish practical Time limit.This is because, such as, first, the concentration of the valuable metal in garbage or waste water is low, Therefore the efficiency in abstraction process is low.It addition, such as, complex procedures, cost be high, noble metal with Outer metal cannot be adjusted, and is also a problem.In view of pursuing the social situations of metals resources, there is valency Recovery and the constructing of recirculating system of metal are the task of top priority, simultaneously need to exploitation and establishment are effectively The absorption of valuable metal and isolation technics.
In general, metal removing and reclaim in use coagulation, co-precipitation, solvent extraction, The methods such as granulated adsorbent material.In view of equipment and carrying capacity of environment or even regeneration, use from The method of sub-exchange resin or chelating resin equigranular adsorbing material is effective.Especially because chela Resin affinity with metal more higher than having with Ion Exchange Resin Phase, is therefore gold The optimal adsorption material (non-patent literature 1～3) belonged to.At present, iminodiacetic acid (salt) acid type, low point The various chelating tree such as sub-polyamine type, phosphoramidic acid type, isothiuronium salts (イ ソ チ オ ニ ウ system) type Fat is commercially sold, and main utilization is applicable to adsorb the iminodiacetic acid (salt) acid type of metal widely Chelating resin.But, the coordination between iminodiacetic acid (salt) acid type chelating resin and metallic element is formed Power is the biggest, and the situation that can not get high-recovery in actual use is many.Further, since The adsorption rate of the metal of iminodiacetic acid (salt) acid type chelating resin is also slow, therefore, it is difficult to process rapidly big The process water of amount.And then, owing to this iminodiacetic acid (salt) acid type chelating resin is granular, thus necessary It is filled in specific tank body use, according to use condition and arrange environment, it is difficult to the situation of application A lot.
In order to solve above-mentioned problem, and tackle various requirement, for chelating resin, Need to improve metal adsorption characteristic further, simultaneously need to the variation of the form of investigation adsorbing material. One of resolution policy as such problem, as the form of chelating resin, has been carried out about fibre The research of dimension shape metal-adsorbing material.For threadiness adsorbing material, its adsorption site limits to In fiber surface, the most in general will not produce often to become for granulated adsorbent material and ask The problem of the diffusion resistant within pore of topic.Therefore, threadiness adsorbing material demonstrates rapidly Adsorption/desorption characteristic, further, since be threadiness, therefore can be to cloth and silk (cloth, fabric, nothing Spin cloth etc.) or paper etc. be processed, it is also possible to carry out secondary operations further.
Disclose the manufacture method of several threadiness adsorbing material.Patent Document 1 discloses logical Cross the method introducing sequestering functional group in chemical graft normal direction fibrous member, at patent documentation 2 Generate with Patent Document 3 discloses the free radical utilizing lonizing radiation to irradiate and utilize graft polymerization method To fibrous member surface introduce sequestering functional group method, Patent Document 4 discloses The method injecting low molecule chelating agen under High Temperature High Pressure in general fiber.Manufactured by these methods Fibrous adsorbing material there is sufficient function, although infer liquid to be treated can be located rapidly Reason, but have problems on manufacturing.Chemical graft process is defined in the graftable kinds of fibers of use, And manufacturing process is loaded down with trivial details.Lonizing radiation Graft Method, compared with chemical graft process, has and is applicable to respectively The advantage planting fiber, but consider from the operating aspect of lonizing radiation, owing to needs are made in certain circumstances Industry, thus not claiming is easy and cheap manufacture method.It addition, the injection of chelating agen and impregnation Method also has the advantage of available various fiber, but owing to needs are impregnated with at high temperature under high pressure, Thus shortage general applicability.
Patent documentation 5 is inhaled with Patent Document 6 discloses the fibrous metal using blend spinning method The manufacture method of enclosure material.According to patent documentation 5, in polyvinyl alcohol, add long chain type part (divide The compound of the display metal adsorption performance of subchain length), after wet method or dry spinning, further Formolation and the method that manufactures fibrous metal adsorbing material, this manufacture method can use existing Equipment, inexpensively and in large quantities manufactures fibrous metal adsorbing material.It addition, according to patent documentation 6, Disclose interpolation long chain type part in viscose rayon in the same manner as patent documentation 5, spun by wet type The method that silk legal system makes fibrous metal adsorbing material, this manufacture method is in the same manner as patent documentation 5 Can use existing equipment inexpensively and manufacture fibrous metal adsorbing material in large quantities.By this The fibrous metal adsorbing material of a little method manufactures is fibrous, thus can manufacture non-woven fabrics (ginseng According to patent documentation 6), by gained non-woven fabrics being carried out further secondary operations, it is possible to produce each Plant the metal-adsorbing material of the form of various kinds.
Fibrous metal adsorbing material disclosed in patent documentation 5 and patent documentation 6 is easily fabricated, Further, since employ long chain type part, compared with iminodiacetic acid (salt) acid type chelating resin, display Go out high coordination Forming ability, and there is high element selectivity.
But, the fibrous metal adsorbing material of artificial silk mother metal manufactured in patent documentation 6 is deposited In problem below.That is, in general the processed solution as metal recovery object be to contain The acid solution of hydrochloric acid, sulphuric acid, nitric acid etc..Accordingly, because artificial silk is being exposed to strong acid disposition Decompose time under condition, thus the fibrous metal adsorbing material of artificial silk mother metal making in acid condition With being limited.Artificial silk is decomposed by the microorganism in environment etc., thus the threadiness of artificial silk mother metal There is the problem that can not use the most continuously or not be resistant to repeatedly regenerate use in metal-adsorbing material.
And then, the fibrous metal adsorbing material of the polyvinyl alcohol mother metal disclosed in patent documentation 5 is deposited In problem below.That is, polyvinyl alcohol improves acidproof and alkali resistance by formolation, but right The patience of organic solvent may not be high.Therefore, the fibrous metal adsorbing material pair of polyvinyl alcohol mother metal The recovery of the valuable metal (such as, coupling reaction palladium catalyst) in organic solvent and removing etc. For, there is it and apply the problem being restricted.
After the fibrous adsorbing material prepared by above-mentioned spin processes uses the fibrillation such as cylinder carding machine, can By the known method non-woven fabrics such as needle point method or water spray, then made many by secondary operations The adsorbing material of sample form.But, in the method manufacturing such non-woven fabrics, need spinning work The multistage operations such as sequence, fibrillation operation and non-woven fabrics chemical industry sequence, manufacturing process is loaded down with trivial details.And then, In the non-woven fabrics prepared by such method, the chopped fiber generated in fibrillation and non-woven fabrics chemical industry sequence (Soft flocks) are contained in non-woven fabrics.Metal recovery from the solution using this non-woven fabrics is processing Water produces spilling of Soft flocks, it is therefore desirable to from adsorption treatment water, remove Soft flocks.Therefore, This removal step must be added in metal recovery operation.Particularly, will manufactured by this non-woven fabrics When the metal-adsorbing material that method manufactures is for pure water or by the purified treatment of water etc., Soft flocks are to place That manages water spills the problem becoming the most deep.
Spill countermeasure as the Soft flocks in the non-woven fabrics of artificial silk mother metal, can enumerate at gained fiber The fiber that during fibrillation of shape adsorbing material, the heat of mixing is fusible, after making non-woven fabrics, is carried out at heating The method of reason.By this heat treated, by with the hot melt being mixed with fibrous metal adsorbing material Fibers melt is bonding, is fixed between fiber.The generation of Soft flocks can be reduced by the method, But spilling of Soft flocks can not be completely inhibited.Further, since the fiber that the heat of mixing is fusible, cause The Fibriform adsorbents amount of per unit weight declines, thus causes the decline of metal adsorption amount.
Prior art literature
Patent documentation
Patent documentation 1: JP 2001-113272 publication
Patent documentation 2: No. 4119966 publications of patent
Patent documentation 3: No. 3247704 publications of patent
Patent documentation 4: JP 2007-247104 publication
Patent documentation 5: JP 2011-056349 publication
Patent documentation 6: JP 2011-056350 publication
Non-patent literature
Non-patent literature 1: north bar is just relaxing, " chelating resin ion exchange resin " talks about society サ イ エンティフィク(1976)
Non-patent literature 2: younger sister's tail, Ah portion's light are male, Suzuki is tall, " ion exchange-high separation The basis of technology ", talk society サ イ エ Application テ ィ Off ィ Network (1991)
Non-patent literature 3: refreshing rugged supervision, ion exchange association of Japan, " tip ion exchange Technology whole ", census of manufacturing meeting (2009)
Summary of the invention
The problem that invention is to be solved
The present invention completes the most in view of the above problems, its objective is to provide a kind of nonwoven cloth-like Metal-adsorbing material and manufacture method thereof, described nonwoven cloth-like metal-adsorbing material is used for adsorbing and returning Receiving the metal in solution, have high adsorption capacity, chemical-resistant is high, can pass through chemical modification Give diversified metal adsorption characteristic, and, it is not necessary to use special equipment and loaded down with trivial details behaviour Make and existing manufacture equipment can be used to manufacture, and then rich and varied shape can be easily processed into Formula.
Solve the means of problem
The present inventor, through further investigation, it was found that by the following method, can make Producing and have high adsorption capacity, chemical-resistant is high, can be processed into the nothing of colourful form Spinning cloth-like metal-adsorbing material, described method includes: melting mixing has the high score of glycidyl Son and the polyolefin series fiber mother metal macromolecule that flowing initial temperature is less than 200 DEG C, by melt-blown After method (also referred to as mel t-blown) or spun-bond process make non-woven fabrics, make to be present in the fibre of non-woven fabrics The halo alcohol radical that this glycidyl hydrogen halides is maybe processed and generates by the glycidyl in dimension table face React with the long chain type metal ligand with amino or imino group, introduce attractability of metal functional group.
In more detail, the present invention relates to nonwoven cloth-like metal-adsorbing material and the manufacture thereof of the following stated Method.
1) nonwoven cloth-like metal-adsorbing material, manufactures by the following method, and described method includes: will Epoxide number is that the macromolecule with glycidyl of 128～600g/ equivalents is with flowing initial temperature Less than 200 DEG C selected from polyethylene, polypropylene, poly-(ethane-acetic acid ethyenyl ester), saponification degree 85% Polyolefin in following partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) and their mixture is fine Dimension mother metal macromolecule is high molecular with polyolefin series fiber mother metal with the macromolecule with glycidyl Blending ratio is calculated as 10:90～60:40 in mass ratio and carries out melting mixing, by meltblown or spin Bonding makes non-woven fabrics, then make non-woven fabrics fiber surface glycidyl with have amino or The long chain type metal ligand of imino group reacts to introduce attractability of metal functional group, or makes this shrink Glyceryl react with hydrogen halides and change into halo alcohol radical after again with the long-chain with amino or imino group Type metal ligand reacts and introduces attractability of metal functional group.
2) the nonwoven cloth-like metal-adsorbing material described in above-mentioned 1), it is characterised in that there is shrink Glyceryl macromolecule is: selected from having the acrylate of glycidyl or having glycidyl Methacrylate in the homopolymer of monomer or above-mentioned monomer sweet with selected from not having shrink The acrylate of oil base, the methacrylate without glycidyl or vi-ny l aromatic monomers In the copolymer of monomer, and the molecular weight of described homopolymer or copolymer presses Weight-average molecular gauge It is 8,000～100,000.
3) the nonwoven cloth-like metal-adsorbing material described in above-mentioned 1), it is characterised in that there is amino Or the long chain type metal ligand of imino group is selected from polymine, polyallylamine, their part Polymer in carboxymethyl compound and mixture thereof or polymeric blends.
4) manufacture method of nonwoven cloth-like metal-adsorbing material, it is characterised in that be by epoxide number The macromolecule with glycidyl of 128～600g/ equivalents with flowing initial temperature be 200 DEG C with Under selected from polyethylene, polypropylene, poly-(ethane-acetic acid ethyenyl ester), the portion of saponification degree less than 85% Divide the polyolefin series fiber mother metal in saponification poly-(ethane-acetic acid ethyenyl ester) and their mixture high Molecule is to have macromolecule and the high molecular blending ratio of polyolefin series fiber mother metal of glycidyl It is calculated as 10:90～60:40 in mass ratio and carries out melting mixing, made by meltblown or spun-bond process After non-woven fabrics, make the glycidyl of the fiber surface of non-woven fabrics and the length with amino or imino group Chain metal ligand reacts to introduce attractability of metal functional group, or makes this glycidyl and halogen Change hydrogen reaction and after changing into halo alcohol radical again with the long chain type metal ligand with amino or imino group React and introduce attractability of metal functional group, thus manufacture nonwoven cloth-like metal-adsorbing material, wherein,
As having the long chain type metal ligand of amino or imino group, use selected from polymine, Polymer in polyallylamine, their part carboxymethyl compound and mixture thereof or polymer mixed Thing.
5) manufacture method of the nonwoven cloth-like metal-adsorbing material described in above-mentioned 4), it is characterised in that As having the macromolecule of glycidyl, use selected from have glycidyl acrylate or There is the homopolymer of monomer in the methacrylate of glycidyl, or above-mentioned monomer and choosing From do not have glycidyl acrylate, do not have glycidyl methacrylate or The copolymer of the monomer in vi-ny l aromatic monomers, and described homopolymer or the molecular weight of copolymer It is calculated as 8,000～100,000 by weight average molecular weight.
Here, as having the macromolecule of glycidyl, using epoxide number is 128～600g/ to work as The macromolecule of amount.Here, as having the macromolecule of glycidyl, can enumerate that to have shrink sweet The homopolymer of the monomer of oil base or there is the monomer of glycidyl and not there is glycidyl The copolymer of monomer.
As homopolymer, such as, can enumerate the homopolymer of the acrylate with glycidyl, tool There is the homopolymer etc. of the methacrylate of glycidyl.
As copolymer, such as, can enumerate: there is the acrylate monomer of glycidyl and do not have There is the acrylate monomer of glycidyl, not there is the methacrylate monomer of glycidyl Or the copolymer of vi-ny l aromatic monomers, have the methacrylate monomer of glycidyl with not There is the acrylate monomer of glycidyl, not there is the methacrylate list of glycidyl Body or the copolymer etc. of vi-ny l aromatic monomers.It addition, have the height of glycidyl described in as The molecular weight of molecule, it is 8,000～100,000 that mean molecule quantity (weight average molecular weight) is preferably used Macromolecule.
As the macromolecule with glycidyl that epoxide number is 128～600g/ equivalents, such as, As glycidyl acrylate class, the homopolymer (epoxide number of glycidyl acrylate can be enumerated 128g/ equivalent), the homopolymer (epoxide number 142g/ equivalent) of glycidyl methacrylate.Make For copolymer, can enumerate glycidyl methacrylate and cinnamic copolymer (polymerization ratio: Glycidyl methacrylate: during styrene=20:80, epoxide number 544g/ equivalent), methyl Glycidyl acrylate and the copolymer (polymerization ratio: methacrylic acid of methyl methacrylate Ethylene oxidic ester: during methyl methacrylate=20:80, epoxide number 542g/ equivalent) etc..At ring Oxygen value is less than in the range of 600 and demonstrates high adsorption capacity, during due to epoxide number more than 600 Adsorption capacity has the tendency of decline, and therefore, most preferably with epoxide number is less than the tool of 600 scopes There is the macromolecule of glycidyl.
Invention effect
According to the present invention, existing manufacture can be directly utilized by simple method not improveing In the case of equipment, produce that to have high adsorption capacity, chemical-resistant high, can easily add Work becomes the nonwoven cloth-like metal-adsorbing material of diversified form, described simple method through with Lower operation: a) prepare intramolecular have glycidyl high molecular operation, b) mediate have The macromolecule of glycidyl and the polyolefin series fiber mother metal that flowing initial temperature is less than 200 DEG C High molecular operation, c) carry out the operation of non-woven fabrics by meltblown or spun-bond process, d) make nothing Spin the glycidyl of the fiber surface of cloth or make this glycidyl react with hydrogen halides and generate Halo alcohol radical react with the long chain type metal ligand with amino or imino group and introduce metal adsorption The operation of property functional group.The nonwoven cloth-like metal-adsorbing material obtained by the present invention be rich in flexibility, Can be easily processed into be rolled into tubular cylindric form, bonding layered laminate form, Or fold the layered laminate form etc. of (rivel processing), it is possible to produce to have and be suitable to recovery and have The metal adsorption body of the various forms of valency metal and removing heavy metal.It addition, by the present invention The nonwoven cloth-like metal-adsorbing material obtained is due to the most melting adhered between fiber and be not likely to produce fiber Bits are it can also be used to pure water or by the purified treatment of water etc..And then, to being mixed with, there is (+)-2,3-Epoxy-1-propanol After in the high molecular non-woven fabrics of base, introducing has the long chain type metal ligand of amino or imino group, by In reactive amino remaining in long chain type metal ligand molecule or imino group, the amino of this remaining Or imino group by secondary response by further chemical modification, thus make metal adsorption characteristic become Change.
Accompanying drawing explanation
[Fig. 1] illustrates an example of the manufacturing process of the nonwoven cloth-like metal-adsorbing material of the present invention.
[Fig. 2] illustrates that the mixing that embodiment 2 obtains has the acrylic acid series macromolecule of glycidyl The electron micrograph of poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of 30 mass %.
[Fig. 3] illustrates mixed methyl glycidyl acrylate that embodiment 3 obtains and cinnamic Glycidyl methacrylate in the nonwoven cloth-like metal-adsorbing material of copolymer and cinnamic The blending ratio of copolymer and the relation of polluted by copper capacity.
[Fig. 4] illustrates mixed methyl glycidyl acrylate that embodiment 4 obtains and cinnamic Spinning temperature in the nonwoven cloth-like metal-adsorbing material of copolymer and polluted by copper capacity and fibre diameter Relation.
[Fig. 5] illustrates in embodiment 4 and spinning temperature 190 DEG C and obtains during spinning temperature 220 DEG C Mixed methyl glycidyl acrylate and the poly-(ethylene-acetate of cinnamic copolymer 30 mass % Vinyl acetate) electron micrograph of nonwoven cloth-like metal-adsorbing material.Here, a figure is spinning temperature Electron micrograph when spending 190 DEG C, b figure is that ultramicroscope during spinning temperature 220 DEG C shines Sheet.
[Fig. 6] illustrates mixed methyl glycidyl acrylate that embodiment 6 obtains and cinnamic Glycidyl methacrylate in the nonwoven cloth-like metal-adsorbing material of copolymer and cinnamic The blending ratio of copolymer and the relation of polluted by copper capacity.
[Fig. 7] illustrates mixed methyl glycidyl acrylate that embodiment 6 obtains and cinnamic 80% saponification poly-(ethane-acetic acid ethyenyl ester) the nonwoven cloth-like metal-adsorbing material of copolymer 40 mass % Electron micrograph.
Detailed description of the invention
Fig. 1 illustrates an example of the operation of the nonwoven cloth-like metal-adsorbing material manufacturing the present invention.
In this embodiment, first, mediating the macromolecule with glycidyl with flowing initial temperature is The polyolefin series fiber mother metal macromolecule of less than 200 DEG C, preparation has as being mixed with of spinning material The high molecular fiber base material macromolecule of glycidyl.Then, this is mixed with have shrink sweet The high molecular fiber base material macromolecule of oil base carries out non-woven fabrics by meltblown or spun-bond process.So After, by the fiber of the gained non-woven fabrics high molecular non-woven fabrics of glycidyl (be mixed with have) The glycidyl that surface exists directly reacts with the long chain type metal ligand with amino or imino group And introduce attractability of metal functional group, or above-mentioned glycidyl and hydrogen halides is made to react generation halogen For alcohol radical, make the halo alcohol radical of this generation again and there is the long chain type metal ligand of amino or imino group React and introduce attractability of metal functional group, thus make nonwoven cloth-like metal-adsorbing material.By this The nonwoven cloth-like metal-adsorbing material of operation manufacture has the high-adsorption-capacity of metallic element and high resistance to Chemicals, and then the nothing with various metal adsorption characteristic can be changing into by chemical modification Spin cloth-like metal-adsorbing material, on this basis, can easily be processed by rivel or reel processing Deng and be processed into various form.
In the present invention, non-woven fabrics is manufactured by meltblown or spun-bond process.These methods use low The thermoplastic resin (predominantly polypropylene, polyethylene etc.) of fusing point, as material resin, can be made Producing by fibre diameter is a few μm～tens of μm, the nonwoven that the fiber of such as 0.5～50 μm is made Cloth.It is a series of that their manufacture method can use cylinder carding machine etc. to pass through in the case of not fibrillation Operation and obtain non-woven fabrics.
Meltblown is by the nozzle that melted thermoplastic resin is arranged after extruder is passed through high temperature Air-flow at a high speed is blown out to trap on screen cloth and manufactures non-woven fabrics.That is, do not implement through spinning work Sequence, fibrillation operation and intertexture operation and the operation of non-woven fabrics, can only be come by 1 step The non-woven fabrics of preparation target.Further, since melting adhered between the fiber of the fiber being spun into, quilt Cooling down, solidify and become non-woven fabrics, therefore manufactured non-woven fabrics has high intensity, the most not It is easily generated Soft flocks.
It addition, spun-bond process is by squeezing melted thermoplastic resin nozzle after being arranged on extruder Go out, spinning, after the fiber of extrusion overlaps on a moving belt, by heating roller will between fiber melted Bonding and produce non-woven fabrics.The non-woven fabrics being made up of continuous print long fibre by the method manufacture, Therefore, non-woven fabrics has high intensity and dimensionally stable method, does not produce Soft flocks.
In general, meltblown is suitable to manufacture the non-woven fabrics of multiple types on a small quantity, and spun-bond process is suitable to system Make volume and lack the non-woven fabrics of kind.
In the present invention, by using these methods, can simultaneously or almost simultaneously carry out spinning and Non-woven fabrics, can be by the fiber detaching of prior spinning, then by the side such as needle point method or water spray Method carries out the operation of the such complexity of non-woven fabricsization and simplifies.It addition, the nothing obtained by these methods Spin cloth to be characterised by, due to the most melting adhered between fiber, do not produce or be not likely to produce fiber Bits.And then, these non-woven fabrics methods are further characterized in that, can will constitute the fiber of non-woven fabrics Make microfibre, it is possible to produce the non-woven fabrics of the roll of continuous print strip.
The macromolecule with glycidyl used in the present invention is preferably enumerated: having can be with ammonia Base or imino group reaction glycidyl vinyl monomer homopolymer or with can be with these The copolymer of the monomer of copolymerization.
As having the vinyl monomer of glycidyl, such as, can enumerate Glycidyl methacrylate sweet Grease, glycidyl acrylate, glycidoxypropyl methyl styrene etc..Can be used these The one kind or two or more of vinyl monomer with glycidyl makes homopolymer, it is also possible to system Become to have the copolymer between the vinyl monomer of glycidyl.
As can with have glycidyl vinyl monomer copolymerization not there is glycidyl Monomer, can enumerate styrene, methacrylate, acrylate, Methacrylamide, propylene Amide etc..
But, when using the many copolymer of the ratio of components of monomer without glycidyl, shrink Glyceryl content reduces as a result, the introduction volume of attractability of metal functional group reduces, and therefore, makes With the copolymer that epoxide number is 128～600g/ equivalents.
During it addition, have the high molecular molecular weight height of glycidyl, become fragility and increase, pinch Conjunction property and the metal-adsorbing material that spinnability reduces and flexibility is low.On the other hand, molecular weight mistake Time low, it is difficult to mediate equably with fiber base material macromolecule.It addition, to using low-molecular-weight When the non-woven fabrics that macromolecule manufactures introduces attractability of metal functional group, according to the condition of use, produce Attractability of metal functional group departs from or the problem of dissolution.Therefore, in the present invention, it is preferred to use flat Average molecular weight (weight average molecular weight) is the macromolecule of 8,000～100,000.
In the present invention, as the fiber with the macromolecule melting mixing spinning with glycidyl Mother metal macromolecule, can enumerate the polyolefin thermoplastic resin that flowing initial temperature is less than 200 DEG C. Typically, since glycidyl is from about 250 DEG C decomposition, therefore, in temperature initial with flowing The melting mixing spinning of the degree fiber base material more than 200 DEG C produces the minimizing of glycidyl or disappears Lose.The fiber base material macromolecule that initial temperature is less than 200 DEG C as flowing, use polyethylene, Polypropylene, poly-(ethane-acetic acid ethyenyl ester), partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) or they Mixture.Wherein, use partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) that saponification degree is high, such as Non-woven fabrics prepared by the saponification degree partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) more than 85% by water or Polar organic solvent is the most swelling, and interfibrous melting adhered a part of disintegrate exists generation and draws Stretch the tendency of the problem that intensity declines.It is therefore preferable that use the partly-hydrolysed of saponification degree less than 85% Poly-(ethane-acetic acid ethyenyl ester).These fiber base material macromolecules are difficult to by general processed solution Acid or alkali corrode, also there is solvent resistance, therefore suitable as be used for preparing chemical-resistant and The fiber base material macromolecule of the nonwoven cloth-like metal-adsorbing material that durability is high.It addition, it is soft having While soft, it is also possible to melting adhered with other macromolecules, therefore it is readily processible to can tackle respectively The rich and varied form of the demand of kind.
The metal adsorption volume dependent of the nonwoven cloth-like metal-adsorbing material of the present invention is sweet in having shrink The macromolecule of oil base and the high molecular mixed proportion of fiber base material (mixing ratio) and and glycidyl The introduction volume of the long chain type part with amino or imino group of reaction.There is the height of glycidyl When the blending ratio of molecule is low, the introduction volume of the long chain type part with amino or imino group reduces, As a result, there is the tendency of metal adsorption capacity step-down.Therefore, there is the macromolecule of glycidyl Blending ratio the highest more good, but the high molecular fragility with glycidyl is high, mixed proportion Gao Shi, spinnability declines sometimes.Therefore, the macromolecule with glycidyl is high with fiber base material The mixed proportion of molecule in mass ratio count be preferably 10:90～60:40, more preferably 20:80～ 50:50.
To the attractability of metal functional group being mixed with in the high molecular non-woven fabrics with glycidyl Introducing utilize glycidyl or make this glycidyl react with hydrogen halides and the halohydrin that generates The reaction of base is carried out.The epoxy radicals that glycidyl is had and halo alcohol radical all easily and amino or Imino group reacts.Halo alcohol radical can be described as a kind of reactive derivatives of epoxy radicals.Known have and can make For the various metal-complexing low molecular compounds of attractability of metal functional group, at this metal-complexing In low molecular compound, there is also the compound being prone to react with glycidyl in a large number.But, When such low molecular compound is introduced non-woven fabrics as attractability of metal functional group, owing to coming The short chain of the attractability of metal functional group coming from the strand length of low molecular compound is long, in solution The activity of this attractability of metal functional moieties be extremely limited.Therefore, attractability of metal Functional group reduces with the touch opportunity of metallic element to be caught, and may not necessarily be adsorbed spy rapidly Property.Therefore, in the present invention, the metal ligand of the long chain type with amino or imino group is used. As this long chain type part, polymine, polyallylamine and their part carboxylic first can be enumerated The mixture of any one or they of base compound.
For there is in the high molecular non-woven fabrics of glycidyl introducing attractability of metal to being mixed with First form of the long chain type part with amino or imino group of functional group is chemical formula 1 (changing 1) Polyallylamine shown in shown polymine or chemical formula 2 (changing 2).Wherein, polyethyleneimine Amine, according to the difference of manufacture method, can generate the compound with the structure in nitrogen position branch, have Time commercially available with the form of the mixture containing these branched chain compounds.There is the poly-of branched structure position Aziridine also can react with the glycidyl of fiber surface, it is possible to use such containing having The polyethyleneimine amine blends of the polymine of branched structure.In the present invention, it is used alone poly-second Alkene imines or further mixing have the polymine of branched structure and are used as having amino or Asia The long chain type part of amino uses, and introduces attractability of metal functional group in non-woven fabrics.These polyamine Play the function of the attractability of metal functional group to transition metal, the most also there is conduct The function of anion exchange groups, can not only adsorb the metal oxoanion such as molybdic acid or wolframic acid, and Contribute to ADSORPTION OF GOLD or platinum in acid condition.These polyamine are owing to having substantial amounts of ammonia in intramolecular Base or imino group, therefore can with multiple glycidyls of fiber surface or with by (+)-2,3-Epoxy-1-propanol The halo alcohol radical that base and hydrogen halides react and generate reacts at multiple positions.That is, due to metal adsorption Property functional group with cover fiber base material surface form be introduced into, thus speculate at fiber surface with height Density introduces substantial amounts of metal-complexing functional group.And then, introduced poly-by the form to cover Amine as a result, hydrophobicity based on fiber base material reduce (hydrophilic raisings), can effectively adsorb with Metallic element in recycle-water solution.
Here, n is the integer of more than 2, mean molecule quantity (weight average molecular weight) is less than 3000.
Here, m is the integer of more than 1, mean molecule quantity (weight average molecular weight) be 3,000 with Under.
For there is in the high molecular non-woven fabrics of glycidyl introducing attractability of metal to being mixed with The second form of the long chain type part with amino or imino group of functional group is chemical formula 3 (changing 3) With the polymine by chemical formula 1 (changing 1) shown in chemical formula 4 (changing 4) or chemical formula 2 The nitrogen-atoms of the polyallylamine of (change 2) carries out part carboxy methylation with remaining amino or imino group Form.About the carboxy methylation degree of the carboxymethylated polyamine of part, it is not particularly limited, but necessary Amino during fully residual is used for the glycidyl being incorporated in fiber or imino group.In view of anti- Answering efficiency and introducing rate, carboxy methylation degree is preferably less than 60%.In the present invention, can be used alone The carboxymethylated polyamine of these parts, or carboxymethylated different the gathering of more than two kinds of mixing portion Amine, and then as required, can be used in mixed way as the long chain type part with amino or imino group The polyamine of the first form.The basic metal adsorption characteristic of complete carboxymethylated polyamine and imido Base diethyl acid type part is similar to, but in the case of using the carboxymethylated polyamine of part, exists not By carboxymethylated amino or imino group, the most also having introducing concurrently has as the present invention the first form The characteristic of the metal-adsorbing material of polyamine.And then, the carboxymethylated polyamine of part is in a part There is a large amount of imino group as attractability of metal functional group and aminocarbonyloxymethyl and degree of freedom is high Long chain type, therefore can prepare and form power and absorption than the coordination of iminodiacetic acid (salt) acid type chelating resin The metal-adsorbing material that speed is all excellent.As the carboxymethylated method of part, can be in advance with protecting Protect base and protect a part of amino or imino group, then pass through known method and use carboxy methylation reagent (usually halogenated acetic acids) removes protection group after carboxy methylation, it is also possible to by reducing carboxymethyl The use ratio changing reagent (usually halogenated acetic acids) is reacted.By regulation carboxy methylation Degree, the selectivity to molybdic acid and wolframic acid etc. can be improved.It is explained, makes part carboxylic first In the case of the polyamine reaction of base, there is also amino or the imino group of many, therefore with the present invention The first form similarly, cover fiber so that the multiple glycidyls with fiber surface react female The form on material surface introduces.
Here, n1 and n2 is the integer of more than 1.
Here, m1 and m2 is the integer of more than 1.
To the attractability of metal functional group being mixed with the high molecular non-woven fabrics with glycidyl Introducing can make to carry out using the following method: containing the long chain type part with amino or imino group Solution in be stirred the method for reaction or spraying containing having the long chain type of amino or imino group Method that the solution of part is carried out, it is being full of containing the long chain type part with amino or imino group Reactive bath technique in the method such as method of dipping.The non-woven fabrics method of the present invention is characterised by permissible It is continuously manufactured by by the roll of long strip type, for the introducing of attractability of metal functional group, makes It is effective by the infusion process in continuous and easily dimmable response time.Such as, infusion process is being used In the case of, by dipping mixing in the solution containing the long chain type part with amino or imino group There is the high molecular non-woven fabrics certain time with glycidyl, be allowed to reaction and carry out.
Amino that long chain type part is had by making long chain type part or imino group and glycidyl Reaction and with the high molecule bonding with glycidyl.Now, due to long chain type part and fiber The glycidyl reaction that surface occurs, thus introduce attractability of metal functional group at fiber surface. Thus, the nonwoven cloth-like metal-adsorbing material that adsorption rate is fast is become.Have to improve to be mixed with The high molecular non-woven fabrics of glycidyl and the reactivity of long chain type part, in advance with hydrogen such as hydrochloric acid Hydracid processes and is mixed with the high molecular non-woven fabrics with glycidyl, it is also possible to by (+)-2,3-Epoxy-1-propanol Base carries out haloalcoholate.The haloalcoholate of glycidyl can use hydrochloric acid or hydrobromic acid as halogen Change hydrogen, carried out by known method, the hydrochloric acid bought with processing ease is preferably used and carries out Chlorohydrination.Such as, as long as impregnating in the aqueous hydrochloric acid solution of 0.05mol/L～1mol/L and being mixed with There are the high molecular non-woven fabrics 10 of glycidyl～30 minutes, chlorohydrination can be carried out.Now, In order to shorten the response time, it is also possible to be heated up to tens of DEG C.Further, since polyolefin macromolecule Hydrophobicity strong, it is possible to reduce be mixed with high molecular non-woven fabrics and the length with glycidyl The response rate of chain part.Therefore, in order to improve reactivity, it is also possible to containing long chain type part Solution in add dioxane or dimethylformamide.But, the dioxane in solution or diformazan When the addition of base Methanamide is too much, the macromolecule with glycidyl may dissolve and dissolution, Therefore, addition preferably suppresses at 20% (volume %) below.The solution dissolving long chain type part can To be aqueous solution, but owing to the high molecular hydrophobicity of polyolefin is strong, it is thus possible to reduce and be mixed with There is the high molecular non-woven fabrics of glycidyl and the response rate of long chain type part.It is therefore preferable that Will not make to have the macromolecule dissolution of glycidyl and the alcoholic solution of dissolution or water-soluble containing alcohol Liquid reacts.Alternatively, it is also possible to heat as required.Due to glycidyl or halo The reaction that alcohol radical introduces long chain type part is relatively rapider, therefore, it can by joining at full long chain type In the impregnated reactive tank of the solution of body, dipping is mixed with the high molecular nonwoven with glycidyl Cloth or be mixed with the height with the halo alcohol radical making glycidyl react in a large number and to generate with hydrogen halides The non-woven fabrics of molecule and introduce long chain type part.Certainly, the introducing operation of this long chain type part is permissible Use continuous way, step any one.Reacted non-woven fabrics remains unreacted shrink Glyceryl or halo alcohol radical, but with alkali or acid treatment, glycidyl or halo alcohol radical are changed into Hydroxyl, it is also possible to reduce based on the high molecular hydrophobicity of fiber base material further.
In the present invention, with being formed to be mixed with, there is the high score of glycidyl due to long chain type part The glycidyl reaction that the fiber surface of the non-woven fabrics of son exists, thus introduce gold at fiber surface Belong to adsorptivity functional group.But, a part has the macromolecule of glycidyl and is ingested fiber In, high molecular whole glycidyls with glycidyl of mixing not necessarily exist in fibre Dimension table face.It is thus impossible to all having introducing long chain type part in the macromolecule of glycidyl. The amount of the glycidyl being present in fiber surface and can react and the high score with glycidyl Son all relies on fibre diameter to the high molecular combined amount of fiber base material.Fibre diameter is the thinnest, often single The fiber surface area (specific surface area) of position weight increases as a result, per unit weight reactive The amount of glycidyl increases, and can improve the metal adsorption amount of per unit weight.In this respect, exist In the present invention, preferential use that can to manufacture by fibre diameter be a few μm～tens of μm, such as 0.5～ The meltblown of the non-woven fabrics that the fiber of 50 μm is made or spun-bond process.
The metal adsorption characteristic of the nonwoven cloth-like metal-adsorbing material of the present invention depends on to be mixed with to be had The long chain type metal with amino or imino group introduced in the high molecular non-woven fabrics of glycidyl The metal adsorption characteristic of part.But, divide at the long chain type metal ligand with amino or imino group In son, carrying out the most remaining reactive amino, imino group after the introducing of non-woven fabrics is reacted. By introducing further functional group by secondary response in this amino or imino group, (chemistry is repaiied Decorations), thus it is possible to vary metal adsorption characteristic.Introduce in non-woven fabrics as having amino or imino group After the polymine of the first form of long chain type part or polyallylamine, known side can be passed through Method uses carboxy methylation reagent (generally using halogenated acetic acids) to carry out carboxy methylation.Thus, it is possible to Change into iminodiacetic acid or ethylenediaminetetraacetic acid such aminocarboxylic acid type metal ligand.This is anti- The carboxymethylated polyamine of part should be also apply be applicable to, by utilizing secondary response to carry out carboxy methylation, The metal adsorption characteristic closer to aminocarboxylic acid type metal ligand can be changed into.It addition, make phosphine When acid and formaldehyde react under hydrochloric acid acidity, phosphine methyl can be introduced in amino or imino group, can To improve the selectivity to terres rares.And then, by anti-with acetic anhydride in non-water system organic solvent Answer and amino or imino group are carried out N-acetylation, can improve gold and the selectivity of platinum.It addition, In the case of needs improve ion-exchange capacity, by known method in the basic conditions by halogen Substituted alkyl compound is incorporated in amino or imino group, forms quaternary ammonium group.Certainly, these are anti- Should be implemented in the carboxymethylated polyamine of part, thus can prepare that to have characteristic different many The nonwoven cloth-like metal-adsorbing material of individual metal ligand.Except having the long chain type of amino or imino group Beyond the secondary response of metal ligand, by the shrink of the remaining after introducing long chain type metal ligand Glyceryl introduces amino, carboxyl, sulfonic group isoiony functional group and low molecule type part, The metal adsorption characteristic of nonwoven cloth-like metal-adsorbing material can also be improved.
Below, by embodiment, the present invention is described, but the present invention is not by any limit of these embodiments System.
Embodiment 1
(1) there is the macromolecule of glycidyl and the kneading of polyethylene
Will as the high molecular Low Density Polyethylene of polyolefin series fiber mother metal (Japan's polyethylene society system, LH902, flow initial temperature: 107 DEG C) 7.0kg and to have the acrylic acid series of glycidyl high Molecule (You society system, マ プ Le Off G-0150M, weight average molecular weight: 8,000～10,000, Epoxide number: 310g/ equivalent) 3.0kg puts into biaxial kneader (toshiba machine by conventional method Society's system, TEM26SS) in, mediate at 200 DEG C, obtaining mixing by comminutor, to have shrink sweet The polyethylene pellet of acrylic acid series macromolecule 30 mass % of oil base.
(2) melt spinning
The pellet obtained in above-mentioned (1) is dried 24 hours at 50 DEG C, as raw material, Use device for melt blowing, spinning temperature 190 DEG C, gas flow temperature 200 DEG C, air velocity 155m/sec, Under conditions of nozzle bore 0.4mm, carry out melt-spraying spinning, obtain mass area ratio 65g/m2's Mixing has the polyethylene nonwoven of acrylic acid series macromolecule 30 mass % of glycidyl.
(3) introducing of attractability of metal functional group
The mixing obtained in above-mentioned (2) is had acrylic acid series macromolecule 30 matter of glycidyl The polyethylene nonwoven cutting device of amount % is cut into the square of the about 50mm length of side, will be 40 DEG C of guarantors In the aqueous isopropanol of five hexamine (Wako Pure Chemical Industries, Ltd.'s system) containing 20 mass % of temperature Impregnate 20 minutes, introduce five hexamine.After reaction, with pure water, obtain introducing five second The nonwoven cloth-like metal-adsorbing material of alkene hexamine.The nonwoven cloth-like metal-adsorbing material dipping that will obtain In the copper-bath (pH5.5) of 0.5mol/L, absorbing copper.Measure with atom absorption photometric Determining the decrement of copper in copper-bath, obtain polluted by copper amount, result is 0.52mmol Cu/g. The nitric acid being used for the nonwoven cloth-like metal-adsorbing material 3mol/L of this mensuration is washed, makes absorption Copper depart from after, be immersed in the nitric acid of 1mol/L 50 hours.After dipping, fully wash, logical Cross method similar to the above and again obtain polluted by copper amount.Metal adsorption amount after hydrogen nitrate dipping washing For 0.50mmol Cu/g, confirm that the performance in strongly acidic solution does not decline.It addition, with aobvious Micro mirror observe be impregnated with nonwoven cloth-like metal-adsorbing material aqueous solution of nitric acid and dipping after water Wash water, does not observe chopped fiber and fibre plate, it is judged that do not produce Soft flocks.
Embodiment 2
In embodiment 1 (1) and (2), (polyolefin series fiber is female to replace Low Density Polyethylene Material macromolecule), use poly-(ethane-acetic acid ethyenyl ester) (three wells-Du Pont-poly-chemical company system, Evaflex EV420, flow initial temperature: 84 DEG C), in addition, use identical condition, Make poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of mixing acrylic acid series macromolecule 30 mass %.That is, At spinning temperature 190 DEG C, gas flow temperature 200 DEG C, air velocity 155m/sec, nozzle bore 0.4mm Under conditions of, carry out the melt-spraying spinning of conventional method, obtain mass area ratio 65g/m2Mixing There is poly-(ethane-acetic acid ethyenyl ester) nothing of acrylic acid series macromolecule 30 mass % of glycidyl Spin cloth.The mixing obtained has the poly-(ethylene of acrylic acid series macromolecule 30 mass % of glycidyl -vinyl acetate) non-woven fabrics electron micrograph as shown in Figure 2.Have to the mixing made Poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of acrylic acid series macromolecule 30 mass % of glycidyl In introduce five hexamine (Wako Pure Chemical Industries, Ltd.'s system) by the method as embodiment 1 (3), Prepare nonwoven cloth-like metal-adsorbing material.Polluted by copper amount is 0.73mmol Cu/g.It addition, confirm Performance after impregnating 50 hours in 3mol/L nitric acid does not decline, and does not the most observe Soft flocks.
Embodiment 3
By method similarly to Example 2, research has the high molecular mixing of glycidyl The impact of ratio.Polyolefin series fiber mother metal macromolecule is set as poly-(ethylene similarly to Example 2 -vinyl acetate), have glycidyl macromolecule use glycidyl methacrylate and Cinnamic copolymer (You society system, マ プ Le Off G-0250S, weight average molecular weight: 20,000, Epoxide number: 310g/ equivalent).Spinning condition is same as in Example 2.There is the height of glycidyl The blending ratio of molecule is set as 30 mass %, 40 mass %, 50 mass % and 60 mass %.In system Poly-(the ethylene-acetate second being mixed with glycidyl methacrylate and cinnamic copolymer made Alkene ester) in non-woven fabrics, use the method with embodiment 1 (3) as, introducing TEPA (with Wako Pure Chemical Industries society system), prepare nonwoven cloth-like metal-adsorbing material.Result is shown in Fig. 3.By accompanying drawing Understanding, by improving blending ratio, metal adsorption capacity increases, and is 60 mass % at blending ratio Time, obtain the metal adsorption capacity (polluted by copper capacity) of 1.32mmol Cu/g.But, mixing Ratio and metal adsorption capacity the most linearly proportionate relationship, it was observed that blending ratio is in 50 mass % Time above, polluted by copper capacity substantially reaches the tendency of steady state value.
Comparative example 1
Use fiber base material same as in Example 3 and there is the macromolecule of glycidyl, with Under conditions of embodiment 3 is identical, carry out being mixed with glycidyl methacrylate and cinnamic The making of the non-woven fabrics of copolymer 70 mass %.For blending ratio 70 mass %, although also Energy spinning, but interfibrous melting adhered degree is low, can not get having the uniform of sufficient intensity Non-woven fabrics.It is mixed with glycidyl methacrylate and cinnamic copolymer 70 matter to this In poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of amount %, attempt using as embodiment 1 (3) Method introduces TEPA (Wako Pure Chemical Industries, Ltd.'s system).Molten at the TEPA of 20 mass % Several minutes after dipping in liquid, a part for fiber is loose out, after the response time (20 points) terminates, Cannot mention as non-woven fabrics.
Embodiment 4
Result based on embodiment 3, the impact of research spinning temperature.Same as in Example 3, will The blending ratio of glycidyl methacrylate and cinnamic copolymer is set to 30 mass %, fine Dimension mother metal macromolecule is same as in Example 2, uses poly-(ethane-acetic acid ethyenyl ester).In spinning condition, Spinning temperature is set as 190 DEG C, 200 DEG C, 210 DEG C and 220 DEG C.For remaining condition, spinning Gas flow temperature 200 DEG C, air velocity 155m/sec during silk temperature 190 DEG C, during spinning temperature 200 DEG C Gas flow temperature 210 DEG C, air velocity 162m/sec, gas flow temperature 220 DEG C during spinning temperature 210 DEG C, Air velocity 168m/sec, gas flow temperature 230 DEG C, air velocity during spinning temperature 220 DEG C 175m/sec, carries out melt-spraying spinning, obtains mixed methyl propylene under conditions of nozzle bore 0.4mm Poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of acid glycidyl ester-styrol copolymer 30 mass %. To the mixed methyl glycidyl acrylate of making and gathering of cinnamic copolymer 30 mass % In (ethane-acetic acid ethyenyl ester) non-woven fabrics, use the method as embodiment 1 (3), introduce TEPA (Wako Pure Chemical Industries, Ltd.'s system), prepares nonwoven cloth-like metal-adsorbing material.Result is such as Shown in Fig. 4.From accompanying drawing, by improving spinning temperature, metal adsorption capacity increases, and obtains It is 1.22mmol Cu/g at spinning temperature 210 DEG C, is 1.32mmol at spinning temperature 220 DEG C The metal adsorption capacity of Cu/g.But, spinning temperature and metal adsorption capacity the most linearly ratio Relation, it was observed that spinning temperature is the tendency of this metal adsorption capacity substantial constant more than 210 DEG C. Mixed methyl glycidyl acrylate during spinning temperature 190 DEG C and during spinning temperature 220 DEG C and The ultramicroscope of poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of cinnamic copolymer 30 mass % Photo is as shown in Figure 5.Side's fibre diameter that spinning temperature is high is thin, as shown in Figure 5 b, and spinning temperature The fibre diameter spending 220 DEG C is about 15 μm.
Embodiment 5
As polyolefin series fiber mother metal macromolecule, the partly-hydrolysed poly-(second using saponification degree to be 80% Alkene-vinyl acetate) (Dong Cao company system, メ Le セ Application H6822, flow initial temperature: 105 DEG C), Similarly to Example 1, by the acrylic acid with glycidyl that blending ratio is 30 mass % It is that macromolecule is mediated together, under conditions of similarly to Example 2, carries out melt-spraying spinning, mixed Close the 80% partly-hydrolysed poly-(second having acrylic acid series macromolecule 30 mass % with glycidyl Alkene-vinyl acetate) non-woven fabrics.The acrylic acid series that being mixed with of making has glycidyl is high 80% partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of molecule 30 mass % is at 0.1mol/L Aqueous hydrochloric acid solution in impregnate 30 minutes (40 DEG C), after glycidyl is changed into chloropharin base, The method of reference example 1 (3), carboxymethylated five hexamine of introducing portion.Part carboxylic first Five hexamine of base are prepared via a method which: containing 40 mass % five hexamine (with Wako Pure Chemical Industries society system) 1mol/L sodium hydroxide solution in, add sodium monochloroacetate so that five The proportioning (mol ratio of relative nitrogen) of hexamine and sodium monochloroacetate (Wako Pure Chemical Industries, Ltd.'s system) For 1:0.6, react at 40 DEG C and prepare for 4 hours.Carboxymethylated five second of part that will obtain Alkene hexamine solution pure water is diluted to 2 times, makes to be mixed with third of the glycidyl with chlorohydrination 80% partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics leaching of olefin(e) acid system macromolecule 30 mass % Stain, reacts 20 minutes at 40 DEG C.In reaction, it was observed that fiber is some swelling, but after reaction, It is mixed with 80% partly-hydrolysed gathering of acrylic acid series macromolecule 30 mass % with glycidyl The mechanical strength of (ethane-acetic acid ethyenyl ester) nonwoven cloth-like metal-adsorbing material does not reduce.It is mixed with Have glycidyl acrylic acid series macromolecule 30 mass % 80% partly-hydrolysed poly-(ethylene- Vinyl acetate) the metal adsorption capacity (polluted by copper capacity) of nonwoven cloth-like metal-adsorbing material is 0.48mmol Cu/g。
Comparative example 2
In embodiment 5, as fiber base material macromolecule, replace the partly-hydrolysed poly-(second of saponification degree 80% Alkene-vinyl acetate), partly-hydrolysed poly-(the ethane-acetic acid ethyenyl ester) (east using saponification degree to be 90% Cao company system, メ Le セ Application H6960, flowing initial temperature: 118 DEG C), in other conditions and reality Execute example 5 identical under conditions of, make be mixed with the acrylic acid series macromolecule 30 with glycidyl 90% partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of quality %.Then, use and implement The method that example 5 is same, to being mixed with acrylic acid series macromolecule 30 mass % with glycidyl 90% partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics in introducing portion carboxymethylated five Hexamine.It is mixed with 90% of acrylic acid series macromolecule 30 mass % with glycidyl Poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics dividing saponification is carboxymethylated in introducing chlorohydrination and part During five hexamine, it was observed that fiber the most swelling.At carboxymethylated five hexamine of part Introducing reaction in, a part for fiber is loose out.After reaction, although can be as nonwoven cloth-like It is raised, but finds that mechanical strength is decreased obviously, can easily tear.Be mixed with have shrink sweet 90% partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) of acrylic acid series macromolecule 30 mass % of oil base Metal adsorption capacity (polluted by copper capacity) ratio of non-woven fabrics is mixed with the propylene with glycidyl Acid is that 80% partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics of macromolecule 30 mass % omits Low, for 0.44mmol Cu/g.
Embodiment 6
Result based on embodiment 5, uses partly-hydrolysed poly-(the ethylene-acetate second of saponification degree 80% Alkene ester), research has the impact of the high molecular blending ratio of glycidyl.As having shrink Glyceryl macromolecule, same as in Example 3, use glycidyl methacrylate and benzene second The copolymer of alkene.The high molecular blending ratio with glycidyl is set to 20 mass %, 30 matter Amount % and 40 mass %.Spinning condition is at spinning temperature 160 DEG C, gas flow temperature 200 DEG C, gas Carry out melt-spraying spinning under Flow Velocity 155m/sec, nozzle bore 0.4mm, obtain mass area ratio For 65g/m2Be mixed with the partly-hydrolysed of glycidyl methacrylate and cinnamic copolymer Poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics.
To the mixed methyl glycidyl acrylate made and cinnamic copolymer partly-hydrolysed In poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics, with the method as embodiment 1 (3), introduce Four hexamine (with Wako Pure Chemical Industries system), prepare nonwoven cloth-like metal-adsorbing material.Result such as figure Shown in 6.From accompanying drawing, by improving blending ratio, metal adsorption capacity (polluted by copper capacity) Increase, under the blending ratio of 40 mass %, obtain the metal adsorption capacity of 0.67mmol Cu/g. Although this metal adsorption Capacity Ratio uses non-saponification poly-(ethane-acetic acid ethyenyl ester) of embodiment 3 It is low, even with partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) that saponification degree is 80%, it is also possible to Obtain the nonwoven cloth-like metal-adsorbing material with sufficient metal adsorption ability.In the present embodiment The mixed methyl glycidyl acrylate that arrives and cinnamic copolymer 40 mass % partly-hydrolysed The electron micrograph of poly-(ethane-acetic acid ethyenyl ester) non-woven fabrics is as shown in Figure 7.
Embodiment 7
In embodiment 1 (1), polyolefin series fiber mother metal macromolecule is changed to polypropylene (day This Port リ プ ロ society system, ノ バ テ ッ Network PP SA3A, flow initial temperature: 176 DEG C), use There is the acrylic acid series macromolecule of glycidyl, obtain being mixed with the propylene with glycidyl Acid is the polypropylene granules of macromolecule 30 mass %.Spinning condition is at spinning temperature 220 DEG C, gas Carry out melt-blown under conditions of stream temperature 230 DEG C, air velocity 175m/sec, nozzle bore 0.4mm Spinning, makes the polypropylene being mixed with acrylic acid series macromolecule 30 mass % with glycidyl Non-woven fabrics.Four ethylene five are introduced with the method as embodiment 1 (3) in the non-woven fabrics obtained Amine (Wako Pure Chemical Industries, Ltd.'s system), prepares nonwoven cloth-like metal-adsorbing material.It is mixed with and there is shrink Metal adsorption capacity (the copper of the polypropylene non-woven fabric of glyceryl acrylic acid series macromolecule 30 mass % Adsorption capacity) it is 0.49mmol Cu/g, with being mixed with of embodiment 1, there is glycidyl The situation of the polyethylene nonwoven of acrylic acid series macromolecule 30 mass % is essentially identical.
Comparative example 3
As polyolefin series fiber mother metal macromolecule, use polymethylpentene (Mitsui Chemicals society system, TPX DX845, flow initial temperature: 239 DEG C), as having the macromolecule of glycidyl, with Embodiment 1 is identical, uses the acrylic acid series macromolecule with glycidyl, attempts making mixing There is the polymethylpentene non-woven fabrics of acrylic acid series macromolecule 30 mass % with glycidyl.Will Mediate temperature and be set as 260 DEG C, use the method as embodiment 1 (1), be mixed with There is the polymethylpentene pellet of acrylic acid series macromolecule 30 mass % of glycidyl.Obtain The xanthochromia of pellet is notable, and the high molecular decomposition of acrylic acid series with glycidyl is carried out terrifically, Both do not had the spinnability can not non-woven fabrics.
The result observing embodiment 1 to embodiment 7 understands, and embodiment 1 to embodiment 7 obtains Nonwoven cloth-like metal-adsorbing material is respectively provided with high metal adsorption capacity, carries out embodiment 1 (3) institute After the hydrogen nitrate dipping test shown, the most do not observe the reduction of metal adsorption capacity.It addition, at nitre In acid dip test, the aqueous solution of nitric acid that carries out making nonwoven cloth-like metal-adsorbing material impregnate and The microscope of the washing water after dipping is observed, and the arbitrary nonwoven cloth-like metal obtained in each embodiment is inhaled Enclosure material does not the most observe the generation of chopped fiber and fibre plate, does not the most produce Soft flocks.
Industrial applicability
According to the present invention it is possible to by easy method, directly utilize existing system not improveing In the case of manufacturing apparatus, produce have high adsorption capacity, chemical-resistant high, can be easily Being processed into the nonwoven cloth-like metal-adsorbing material of diversified form, the method for described simplicity is passed through Following operation: a) prepare intramolecular and there is the high molecular operation of glycidyl, b) will have The macromolecule of glycidyl and the polyolefin series fiber mother metal that flowing initial temperature is less than 200 DEG C Operation that macromolecule carries out mediating, c) by meltblown or spun-bond process carry out non-woven fabrics operation, D) make the glycidyl of the fiber surface of non-woven fabrics or make this glycidyl anti-with hydrogen halides Should and the halo alcohol radical generated and the long chain type metal ligand with amino or imino group react with introducing The operation of attractability of metal functional group.The cloth-like metal-adsorbing material that spins obtained by the present invention is rich in soft Soft, can be easily processed into reel cylindric form, bonding layered laminate form, Or fold the layered laminate form etc. of (rivel processing), it is possible to produce to have and be suitable for there is valency The metal adsorption body of various form that metal recovery and heavy metal remove.It addition, by the present invention Between the fiber spinning cloth-like metal-adsorbing material obtained the most melting adhered, therefore have sufficiently Intensity, and it is not likely to produce Soft flocks it can also be used to pure water or by the purified treatment of water etc..And then, Be introduced into non-woven fabrics the amino in the long chain type metal ligand of amino or imino group with remaining or Imino group is chemically modified by secondary response, thus can change metal adsorption characteristic.

Claims (5)

1. nonwoven cloth-like metal-adsorbing material, manufactures by the following method, and described method includes: will Epoxide number is that the macromolecule with glycidyl of 128～600g/ equivalents is with flowing initial temperature Less than 200 DEG C selected from polyethylene, polypropylene, poly-(ethane-acetic acid ethyenyl ester), saponification degree 85% Polyolefin in following partly-hydrolysed poly-(ethane-acetic acid ethyenyl ester) and their mixture is fine Dimension mother metal macromolecule is high molecular with polyolefin series fiber mother metal with the macromolecule with glycidyl Blending ratio is calculated as 10:90～60:40 in mass ratio and carries out melting mixing, by meltblown or spin Bonding makes non-woven fabrics, then make non-woven fabrics fiber surface glycidyl with have amino or The long chain type metal ligand of imino group reacts to introduce attractability of metal functional group, or makes this shrink Glyceryl react with hydrogen halides and change into halo alcohol radical after again with the long-chain with amino or imino group Type metal ligand reacts and introduces attractability of metal functional group.
2. the nonwoven cloth-like metal-adsorbing material described in claim 1, it is characterised in that there is contracting The glyceryl macromolecule of water is selected from having the acrylate of glycidyl or having glycidyl Methacrylate in the homopolymer of monomer, or above-mentioned monomer is sweet with selected from not having shrink The acrylate of oil base, the methacrylate without glycidyl or vi-ny l aromatic monomers In the copolymer of monomer, and the molecular weight of these homopolymer or copolymer presses Weight-average molecular gauge It is 8,000～100,000.
3. the nonwoven cloth-like metal-adsorbing material described in claim 1, it is characterised in that there is ammonia The long chain type metal ligand of base or imino group is selected from polymine, polyallylamine, their portion Divide the polymer in carboxymethyl compound and mixture thereof or polymeric blends.
4. the manufacture method of nonwoven cloth-like metal-adsorbing material, it is characterised in that be by epoxide number The macromolecule with glycidyl of 128～600g/ equivalents with flowing initial temperature be 200 DEG C with Under selected from polyethylene, polypropylene, poly-(ethane-acetic acid ethyenyl ester), the portion of saponification degree less than 85% Divide the polyolefin series fiber mother metal in saponification poly-(ethane-acetic acid ethyenyl ester) and their mixture high Molecule is to have macromolecule and the high molecular blending ratio of polyolefin series fiber mother metal of glycidyl It is calculated as 10:90～60:40 in mass ratio and carries out melting mixing, made by meltblown or spun-bond process After non-woven fabrics, make the glycidyl of the fiber surface of non-woven fabrics and the length with amino or imino group Chain metal ligand reacts to introduce attractability of metal functional group, or makes this glycidyl and halogen Change hydrogen reaction and after changing into halo alcohol radical again with the long chain type metal ligand with amino or imino group React and introduce attractability of metal functional group, thus manufacture nonwoven cloth-like metal-adsorbing material, its In,
As having the long chain type metal ligand of amino or imino group, use selected from polymine, Polymer in polyallylamine, their part carboxymethyl compound and mixture thereof or polymer mixed Thing.
5. the manufacture method of the nonwoven cloth-like metal-adsorbing material described in claim 4, its feature exists In, as having the macromolecule of glycidyl, use selected from the acrylic acid with glycidyl Ester or the homopolymer of the monomer during there is the methacrylate of glycidyl, or above-mentioned monomer With selected from not having the acrylate of glycidyl, not there is the methacrylic acid of glycidyl The copolymer of the monomer in ester or vi-ny l aromatic monomers, and these homopolymer or copolymer point Son amount is calculated as 8,000～100,000 by weight average molecular weight.
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