CN106866975A - Organic polymer functional group modification silica and its production technology and purposes - Google Patents

Organic polymer functional group modification silica and its production technology and purposes Download PDF

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CN106866975A
CN106866975A CN201710102473.6A CN201710102473A CN106866975A CN 106866975 A CN106866975 A CN 106866975A CN 201710102473 A CN201710102473 A CN 201710102473A CN 106866975 A CN106866975 A CN 106866975A
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integer
alkyl
formula
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aryl
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CN106866975B (en
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威尔逊·约翰·罗伯特·豪
刘大卫
王维
郑文彪
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Suzhou se Xin Xin Mstar Technology Ltd
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Hubei Xinuo Weixin Functional Silicone Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/33—Wastewater or sewage treatment systems using renewable energies using wind energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

Production technology the present invention relates to contain the functionalization material of quaternary ammonium, sulfydryl in same composition is further related in appropriate circumstances, the Multiple Combination of sulfide and thiocarbamide, each functional group is with numerous different oligomers, configuration and stereochemical diversified forms are presented, it is additionally related to its application, such as product purification, or from product stream, unwanted organic and inorganic compound is removed in technique stream and waste liquid includes metal and metal complex, or in multicomponent mixture selective removal target component, or as metal, metal complex, organic and biologic artifact purification with separate chromatography media, or as cation and anion exchange agent, SPE material, synthesis in solid state material, metal ion extracts material and biomolecule fixation material, new component the invention further relates to contain the functionalization material of polyquaternary amine group.

Description

Organic polymer functional group modification silica and its production technology and purposes
Technical field
The present invention relates to containing the new organic polymer functional material and its production technology of anionic group and using, such as it is used as Metal removal or selective metal removal material, or organic and inorganic compound is removed from product stream, technique stream and waste liquid, or As metal chromatographic material, Solid phase cleaned-up or fiber material, biomolecule fixation material, synthesis in solid state material and chromatographic material. The invention further relates to the presoma and its production technology of these new products.
Background technology
, to the pressure of ecological requirements, the requirement to more cleaning procedure is further improved for society and law, and make every effort to avoid or Discarded object is reduced, the residual quantity of toxic metals and compound in environment is especially reduced, is caught metal time in the conceived case Receive and recycle.
Metal plays central role in current technology.For example, including including platinum, rhodium, palladium, ruthenium, iridium and gold These resource-constraineds noble metal, be widely used in numerous different applications of different industries.And, currently find and develop Increasing application is required for using noble metal, and the following demand to noble metal is much larger than its available resources.High valency Lattice, limited resource all force the market to have a kind of efficient technology from product stream, work along with the toxicity of metal, these factors Noble metal is reclaimed in skill stream and waste liquid to realize recycling.Only by taking petrochemical industry as an example (including carbonylation synthesis and Si―H addition reaction it is anti- Should), it is possible to reclaim these metals from its product stream, technique stream and waste liquid.
In numerous different industries, metal is widely used in a variety of applications.Finally, these metals turn into various A part in product stream, technique stream and waste liquid.A kind of technology is needed, by the formation of product, the life for using and processing Cycle manages all these products and its application, production and waste liquid, realizes metal recovery rate higher, recycles efficiency with choosing Selecting property, the influence that reduction is caused to environment.For selectivity, to dig up mine with as a example by smelting industry, the gold for having existed is controlled Belong to and meet with very big challenge if copper, nickel, iron and process chemistry product containing metal (such as zinc).Therefore, a kind of new gold is needed badly Category recycling and reuse technology.
Industry-by-industry use more and more rare earth metal (such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, Dysprosium, holmium, erbium, thulium, ytterbium and lutetium), this is also highlighted market increasing need, and market needs a kind of new more advanced Technology more effectively reclaimed from product stream, technique stream and waste liquid these metals realize recycle.
A recent report (《The key metal of strategic energy technology》(Critical metals in strategic Energy technologies), ISBN 978-92-79-20698-6) to emphasize, special metal is more and more used, and is added The problems being associated with the geographical position of these metals resources so that the supply conditions of metal are more severe, the confession of metal Should shortage by it is potential limitation low-carbon energy technology popularization, such as nuclear energy, solar energy, wind energy, biological energy source, the capture of carbon with storage and Power network industry.14 kinds of key metals have determined that the potential risk that there is short supply, wherein five kinds of high-risk scarcities, i.e. neodymium, dysprosium, Indium, tellurium and gallium.This report also proposes a series of solution simultaneously, including more advanced metal recovery technology, To realize that metal is recycled.
In the smelting and purification technique stream of mining industry, the high value metals (such as noble metal) of extremely low concentration are often golden with other Belong to and deposit, and the latter is in very high concentrations in some cases.To avoid a large amount of losses of high value metals, there is a more preferable skill Art realizes following target：1) required metal is reduced to extremely low concentration；2) extremely low ppm metal concentrations are efficiently acted on；3) with The metal of selective removal high value when other metals of higher concentration coexist.
Other metals of mining industry, such as copper, nickel, iron, zinc are, it is necessary to improved technology：1) it is metal removal is dense to extremely low residual Degree；2) no matter metal concentration height can useful effect；Even if 3) other metal concentrations for coexisting are different, also alternative removal Metal target；4) there is strong absorption affinity to single or multiple metal target；5) the single or multiple metal being not only captured can To recycle, technology is also recycling.
Expensive organic principle or polymer is frequently necessary to multi-stage process production, generally has accessory substance, isomers in product And impurity.In most cases, required product must all be purified, therefore demand to more effective purification techniques is continuously increased, with A series of all of specific accessory substances, isomers and impurity in removal required product.But prior art can cause product as crystallized A large amount of losses.
Functionalization material is developed, and this is component needed for selectively being removed from mixture or from product stream, work One of new and high technology of poisonous and/or high value metal or compound is removed in skill stream and waste liquid.Liquid is flowed through into functionalization Material, target components are to be selectively removed.Activated carbon is exactly a kind of functionalization material, by certain process conditions, activity Some oxygen-containing organic groups are contained on the surface of charcoal, although activated carbon is cheap, there is many shortcomings, due to the key of activated carbon Property is closed to be bonded for non-specific, and the alcohol on its surface, phenol, aldehyde and carboxylic acid functional feature are poor, can lose big volume production Product and unwanted compound or metal cannot be effectively removed in final products to compared with low residual amt.
This functionalization material of functionalization organic polymer can be applied to product purification.Organic polymer backbones (such as polyphenyl Ethene and polyolefin) on can only adhere to several simple single functional groups, such as sulfuric acid or amino group, mainly by ion exchange Mechanism.Regrettably, such functional group is relatively low with the compatibility of above-mentioned associated metal, therefore using possessing organic backbone Current material cannot realize performance requirement higher all the time.These organic resins have two significant limitations, and one cannot be by spy Functional group needed for fixed application is attached on organic polymer backbones, secondly the load of functional group is relatively low.Because can act on Chemical mode on these polymer is limited, is reached using the various different polyfunctional groups of this organic polymer backbones appendix High performance possibility is extremely low.In addition with other limitation, such as chemically and thermally stability is poor, can expand in organic solvent and Shrink.Sum it up, based on these organic backbones, developing required technology has many serious limitation.
Inorganic polymer systems such as silica, aluminum oxide and titanium oxide have also been disclosed as functionalization material.It is poly- with organic Polymer backbone is compared, and inorganic polymer backbone possesses many advantages, and its physics, chemically and thermally stability are higher, surface pore knot Structure definition is good to be more preferably more easy to obtain functional group, need not be expanded before easily operated.
For example, Silicycle companies, the village believe Wan Feng companies (Johnson Matthey), Ying Chuan companies (Evonik) and good fortune The alkylamine and alkyl hydrosulfide of Si Fu Knicks company (PhosphonicS) (WO2006/013060, WO2007/090676) are all It is simple functionalization inorganic material.However, only the few simple functional group of kind can be attached by limited chemical technology It is downloaded on these skeletons.Another limitation of these inorganic polymer materials is functional group relatively low with the load of required target. Load of the per kilogram functionalization material (organic or inorganic skeleton) to object is universal between 5-30g, and often tends to this The more low value of one scope.
Existing inorganic functional material only contains the simple single functional group that kind is few, usual only one of which or most Two hetero atoms, there is provided single binding mechanism, the affinity with the object to be removed is low, functional group's load is low, thus to mesh The load effect for marking thing is more low.Because：1) intitation reagents (i.e. silane) for producing these materials are difficult to obtain, because The production of these intitation reagents is extremely complex；2) can use or modification such reagent buying be limited；3) silane is produced Chemical method is limited；4) in view of producing the chemical process that silane is related to, its production cost is high；5) in order to improve performance it is necessary to Turned in the complicated functional group of area load from simple functional group is loaded, but it is extremely difficult.
Although inorganic functional material is a much progress of organic functions resin, in face of choosing for prior art and new technology War (such as the load of more low impurity content, more high selectivity and object), inorganic functional material technology still needs to be obviously improved.
Prior art is not enough to be designed and produced in the commercial base of reality the complicated function multi-functional, high with needed for The required function material of group's load.In face of a variety of challenges of existing and following business, technology, environment and society, only new skill Art can be only achieved different markets with the performance requirement to functionalization material.
Additionally, need badly optionally removing metal from complicated mixture using new technology.For example, have high concentration its Copper removal is removed in the presence of his metal (including zinc, nickel, arsenic and other anion).Illustrated with certain real case, a spent acidic Contain various metals in liquid, purification of water quality including but not limited to is carried out to the gas produced in ore pyrometallurgical processes and is generated Copper, noble metal, gold, zinc, nickel, lead, arsenic, selenium and antimony, it is desirable to the selective removal copper from the acid waste liquid.
Another requirement is removal metal such as copper zinc-nickel iron, or selective removal and is reclaimed from gold mining technique stream Recycle these metals.Metal is main in such fluid exists with anion, metal complex band cryanide ion.Need new skill Art, removes these metal complexs, effectively reclaims and recycle these metals, while providing significant environmental benefit.Therefore, A kind of new anion removal technology is needed, possesses high-affinity and absorption affinity to object, compared to other metals and metal network Compound has selectivity higher to object.
The metallic catalyst in metal residue or process waste liquor in drug products may exist with different forms, Such as different oxidation state, unimolecule, nano particle, various different metal species have different complex compounds or ligand and these gold Species are combined closely.In addition, it is contemplated that the real component of different metal species is changed after various processes.For Metal needed for ensureing the purity of required product or catching, functionalization material must contain complicated particular functional group's combination, Specially it is bonded with object.And, the position arrangement that all functional groups will be mutually adjacent in the hole on skeleton surface, arrangement Realize optimizing, it is ensured that the cooperation base being bonded with object can be replaced under liquid-phase condition, target is caught and retain Thing.Different objects is likely to require different bonding mechanisms, and the structure of functionalization material can will rapidly adapt to different mesh Mark thing, this point is most important, could only in this way realize required performance, realizes the low-residual concentration and functionalization of object The high selectivity of material and the absorption affinity high to object.(heat endurance, physics and chemistry are steady for the stiff stability of functionalization material It is qualitative), the appendix rate high of functional group, extensive compatible, the more preferable wettable to solvent, non-dilatancy and to functional group Easy accessibility is all the factor for having to consider in designing.And the cost benefit of functionalization material is also a key factor, Must be based on the ready-made parent material being easy to get, functionalization material is produced using simple chemical technology, and technique must can be with It is rapid to change to generate required best-of-breed functionality material structure, realize with object high-affinity, be bonded with high selectivity.
The content of the invention
Present invention aim at a kind of new, simple environment-friendly production method is provided, using the starting being readily available Be attached in the inorganic material such as silica for new chosen anion functional group by material.It is another object of the present invention to it Using for removal or selective removal metal from product stream, technique stream and waste liquid, as the clear of inorganic and organic compound Except agent, metal chromatographic material, Solid phase cleaned-up or fiber material, biologic artifact removal and scavenging material, ion exchange material, urge Agent fixation support, biomolecule (such as enzyme) fix material, controlled-release material, antimicrobial, hydrophilic modifier, fire-retardant Agent, antistatic additive, synthesis in solid state material and chromatographic material, or as the presoma of above-mentioned these materials.
First, the present invention relates to the production method of the compound of general formula I：
[(O3/2)Si(CH2)mX]a[Si(O4/2)]b[VSi(O3/2)]c[WSi(O3/2)]d(formula I)
In formula, X is selected from (CH2)3N+(L1)(R6)2CH2CH2CH3)、(CH2)3N+(L1)(R6)2CH2CHCH2Or the chemical combination of formula II Thing；R6It is C1-22Alkyl or aryl；N is an integer from 0 to 100；L1An anion, including but not limited to halide, Nitrate, sulfate, carbonate, phosphate, chromate, potassium permanganate, boron hydride, for boron hydride such as cyano group hydroboration Thing.
V is a selectively substituted group and selected from C1-22Alkyl, C2-20Alkylene, C1-22Alkylaryl or virtue Base；W is (CH2)eZ group, wherein Z are SH, S (CH2)fSH、S(CH2)fNHC (=S) NHR3、NR4R5Or NH [(CH2)2NH]jH, e It is respectively an integer from 2 to 6 with f；J is an integer from 1 to 100；M is an integer from 2 to 12；Wherein R3-5 It is respectively selected from hydrogen, straight or branched C1-12Alkyl, aryl or C1-22Alkylaryl；A, b, c, d are integer, and a+c:The ratio of b Example between 0.00001 to 100, a, b exist all the time, such as c and/or d be more than zero, then the ratio of d and a+b+c between 0.00001 to 100；
By the silicon atom of other groups, hydrogen, straight or branched C in formula I1-22Alkyl, end group R2SiO1/2, crosslinking agent or Chain RqSi(OR1)gOk/2In one or more make the free valency saturation of silicate oxygen atom, wherein R and R1It is respectively selected from straight Chain or side chain C1-12Alkyl, aryl or C1-22Alkylaryl；K is the integer from 1 to 3, and q is the integer from 1 to 2, and g is from 0 to 2 Integer, and meet g+k+q=4, in the presence of end group, crosslinking agent and/or polymer chain, its mol ratio is with a+b+c+d's Ratio is between 0 to 999:1.
Selectively substituted straight or branched group is selected from C1-22Alkyl, C2-22Alkylene, C2-22Alkynyl, aryl, C1-22Alkylaryl, may respectively be straight or branched, and/or may be substituted by one or more substituents, but best Containing only hydrogen atom and carbon atom.In the case of substituted base, these groups can be respectively selected from acid amides, amine, nitro, chloro, fluorine Base, bromo, itrile group, hydroxyl, carboxylic acid, carboxylate, sulfide, sulfoxide, sulfone or C1-6Alkoxy.
It is preferred that X is selected from (CH2)3N+(L1)(R6)2CH2CH2CH3)、(CH2)3N+(L1)(R6)2CH2CHCH2Or the chemical combination of formula II The generalformulaⅰcompound of thing；V is a selectively substituted group and selected from C1-12Alkyl, C2-6Alkylene, aryl；W is Group (CH2)eZ, wherein Z are SH, S (CH2)fSH、S(CH2)fNHC (=S) NHR3、NR4R5Or NH [(CH2)2NH]jH, e and f point It is not an integer from 2 to 3；J is an integer from 1 to 10；M is an integer from 2 to 12；R3-5It is respectively selected from straight Chain or side chain C1-12Alkyl, aryl, C1-22Alkylaryl；R6It is C1-6Alkyl；N is an integer from 0 to 20；L1It is a moon Ion, including but not limited to halide, nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydrides Or for borohydrides such as cyanoborohydride；D is 0；A, b, c are integer and a+c:The ratio of b between 0.00001 to 1, wherein A, b exist all the time.
Particularly preferred X is selected from (CH2)3N+(L1)(R6)2CH2CH2CH3)、(CH2)3N+(L1)(R6)2CH2CHCH2Or formula II The generalformulaⅰcompound of compound；R6It is C1-6Alkyl；N is an integer from 0 to 20；L1It is an anion, including but does not limit In halide, nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydrides or for borohydrides such as cyanogen Base borohydrides；V is a selectively substituted group and selected from C1-6Alkyl, C2-6Alkylene；M be from 2 to 12 one Individual integer；D is 0；A, b, c are integer and a+c:The ratio of b exists all the time between 0.00001 to 1, wherein a, b.
It is an object of the invention to the new technology produced for generalformulaⅰcompound provides convenient, environmental protection, industrial scale, phase Compared with existing science and technology, no matter business very high is provided with terms of yield, cost, scale and/or the purity or in terms of environmental benefit Value.
Compared with homogeneous equivalent, the reagent reacting of functional group on the surface of solids with dissolving in the solution is always notable It is slower, especially it is attached with the silica of functional group.A big advantage of the invention is to be found that effectively produce required new The mixing condition of type ion exchange material, including reagent, functional group, chemical enginnering process and reaction condition, and functional group Load capacity is controllable, target from ready-made functional group the best combination of silica surface tunable somewhat complex design.This hair Bright another big advantage is that have functional group very high to load using the functionalization material of such technique productions.Additionally, technique is simple It is single, environmentally friendly, using ready-made initial compounds and solvent such as water, a little discarded object is only produced, and can be inorganic As being bonded complicated and diversified anionic functional group on silica on surface.
The new method carries out free radical presoma with the unsaturated carbon carbon bond being attached on functionalization material in a solvent Free radical addition.This method includes being contacted with general formula III compounds：
[(O3/2)Si(CH2)hA]a[Si(O4/2)]b[VSi(O3/2)]c[WSi(O3/2)]d(general formula III)
In formula, A is vinyl, and its load is 0.001-4mmol/g；H is an integer from 0 to 10, (CH2CHCH2)2N+(R6)2L1It is placed in solvent, wherein R6It is hydrogen, straight or branched C1-22Alkyl, C1-22Alkylaryl or aryl；L1A moon from Son, including but not limited to halide, nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydrides or For borohydrides such as cyanoborohydride；Regularly added under the conditions of 20-150 DEG C radical initiator react 10 minutes to 48 it is small When, then solid is filtered or is centrifuged, generation generalformulaⅰcompound is dried after being washed using solvent；
Or contacted with general formula IV compounds：
[(O3/2)Si(CH2)hA]a[Si(O4/2)]b(formula IV)
In formula, A is vinyl, and its load is 0.001-4mmol/g；H is an integer from 0 to 10, (CH2CHCH2)2N+(R6)2L1It is placed in solvent, wherein R6It is hydrogen, straight or branched C1-22Alkyl, C1-22Alkylaryl or aryl；L1A moon from Son, including but not limited to halide, nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydrides or For borohydrides such as cyanoborohydride；Regularly added under the conditions of 20-150 DEG C radical initiator react 10 minutes to 48 it is small When, after by solid filter or be centrifuged, using solvent wash after dry generation generalformulaⅰcompound, wherein integer c and d is 0；Then Use VSi (OR1)3Or WSi (OR1)3Or both is processed in a solvent, reacted 10 minutes to 48 under the conditions of 60-150 DEG C Hour, then solid is filtered or is centrifuged, generation generalformulaⅰcompound is dried after being washed using solvent, wherein V and/or W is present.
Typical solvent includes water, dimethylbenzene, toluene, normal heptane, ethylene glycol, ethanol and methyl alcohol.Usable free radical draws Hair agent, including but not limited to azodiisobutyronitrile, benzoyl peroxide, TBHP and tert-butyl peroxide.It is excellent The reaction temperature of choosing and reaction time are 70-120 DEG C, 4-24 hours.
The load on silica of Cautious control reaction condition, such as temperature, reaction time, reagent concentration and functional group, It is most important to generate preferred structure and complex product manufacturing needed for performance to reaction and the generation of subsequent partial polymerization.It is no Then, reaction will produce different bad result, reactionless, only local reaction or adhere to a small amount of high molecular polymer and block nothing The hole of machine material, causes functional group's access relatively low or that material hole is to functional group of load not good, ultimately results in functionalization material Material degraded performance.
It is an object of the invention to provide reaction condition and relative molar concentration, the partial polymerization reaction of preferred control is realized (Integer n), so as to generate required complicated functional group on material, the functionalization material of generation has high-affinity to object, Even and if other metals and compound are present, and can also realize the high selectivity to object, and realize the high capacity of functional group.
(CH2CHCH2)2N+(R6)2L1(wherein R6It is hydrogen, straight or branched C1-22Alkyl, C1-22Alkylaryl or aryl, L1 Chlorine) with general formula III or compound of Formula IV (wherein h is 0 or 1, X are vinyl, functional group load 0.2-4mmol/g) not With under reaction condition, reaction produces surprising result and the relation between chemical constitution and reaction condition.Vinyl functional Group's load is higher, and n values are lower, even if using mandatory condition and Contrast agent concentration.
Reaction condition, reagent and relative concentration are had determined that, to reach required n values.Optimum condition is as follows：Reaction temperature 100-130 DEG C, 1-12 hour of reaction time；Mix reagent and solvent are than the appearance with general formula III or compound of Formula IV weight Anharmonic ratio is 1.8-2.6；Per kilogram general formula III or compound of Formula IV add radical initiator 2-6mL/h.In above-mentioned reaction bar Under part, (the CH of 10-20 molar equivalents is used2CHCH2)2N+(R6)2L1(wherein, R6It is hydrogen, straight or branched C1-22Alkyl, C1-22 Alkylaryl or aryl, L1It is chlorine), generalformulaⅰcompound can be generated, between 0.5-1, the load of vinyl-functional is 2- to n values 4mmol/g.Vinyl-functional is loaded during between 1.5-2mmol/g, and n values are between 1-1.5.Vinyl-functional load between During 0.6-1mmol/g, n values are between 4-6.Vinyl-functional is loaded between 0.2-0.5mmol/g, uses 20-60 molar equivalents (CH2CHCH2)2N+(R6)2L1(wherein R6It is hydrogen, straight or branched C1-22- alkyl, C1-22- alkylaryl or aryl, L1It is Chlorine), then n values are between 6-50.Load and reaction condition by vinyl-functional, can control the length of anionic group chain Degree.
Preferably, reaction temperature is 110-120 DEG C, and the reaction time is 4-8 hour, mix reagent and solvent ratio and formula II The volume to weight ratio of the weight of compound is 2-2.2.
Silica, vinyl trialkyl oxysilane and corresponding silane VSi (OR1)3、WSi(OR1)3, 20-160 DEG C, Grafting reaction is carried out in solvent, is reacted 0.5-24 hours, generate general formula III and compound of Formula IV.Grafting reaction can be used Extensive solvent and solvent mixing, including aliphatic hydrocarbon, aromatic hydrocarbon, alcohols and polar solvent such as dimethylformamide.Preferably Solvent often uses toluene and dimethylbenzene.Solvent is preferably ranged from 2.8-2 with the volume to weight ratio of silica.
To realize preferably selectivity and object load capacity, can be by different silane components VSi (OR1)3And WSi (OR1)3It is added to grafting technique.The technique allows the great flexibility of design, so could the optimal functionalization material of manufacturing property Material.
Component VSi (OR1)3With WSi (OR1)3Also can be by adding an extra functional group, silicon near conversion functional group The hydrophobicity hydrophily on glue surface, enhancing selectivity bonding, improves material property.
At the end of reaction, by the functionalization material of formula I by filtering or centrifugation, fully wash, remove it is any residual Dried after remaining reactant.This process may apply to extensive commercial silica gel, and particle diameter and distribution are from nano particle to 5- 30 millimeters, can also be applied to extensive known pore size.It is preferred that aperture between
The present invention also provides the new compound of general formula I：
In formula, X is selected from (CH2)3N+(L1)(R6)2CH2CH2CH3)、(CH2)3N+(L1)(R6)2CH2CHCH2Or the chemical combination of formula II Thing；R6It is C1-22Alkyl or aryl；N is an integer from 0 to 100；L1An anion, including but not limited to halide, Nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydrides or for borohydrides such as cyano group hydrogen boronation Thing；
V is a selectively substituted group and selected from C1-22Alkyl, C2-20Alkylene, C1-22Alkylaryl or virtue Base；W is group (CH2)eZ, wherein Z are SH, S (CH2)fSH、S(CH2)fNHC (=S) NHR3、NR4R5Or NH [(CH2)2NH]jH, e An integer from 2 to 6 is respectively with f；J is an integer from 1 to 100；M is an integer from 2 to 12；Wherein R3-5 It is respectively selected from hydrogen, straight or branched C1-12Alkyl, aryl and C1-22Alkylaryl；A, b, c, d are integer, and a+c:The ratio of b Example between 0.00001 to 100, a, b exist all the time, when c and/or d be more than zero when d and a+b+c ratio between 0.00001 to 100。
The silicon atom of other groups, hydrogen, straight or branched C in formula I1-22Alkyl, end group R2SiO1/2, crosslinking agent or chain RqSi(OR1)gOk/2In one or more make the free valency saturation of silicate oxygen atom, wherein, R and R1Be respectively selected from straight chain or Side chain C1-12Alkyl, aryl and C1-22Alkylaryl；K is the integer from 1 to 3, and q is the integer from 1 to 2, g be from 0 to 2 it is whole Number, and meet g+k+q=4, in the presence of end group, crosslinking agent and/or polymer chain, the ratio of its mol ratio and a+b+c+d Between 0 to 999:1.
Particularly preferred X is selected from (CH2)3N+(L1)(R6)2CH2CH2CH3)、(CH2)3N+(L1)(R6)2CH2CHCH2Or formula II The generalformulaⅰcompound of compound；R6It is C1-6Alkyl, n is the arbitrary integer between 0 and 50；V is one and is selectively substituted Group and be selected from C1-6Alkyl, C2-8Alkylidene；W is group (CH2)eZ, wherein Z are SH, S (CH2)fSH、S(CH2)fNHC (= S)NHR3, wherein e and f is respectively the arbitrary integer between 2 to 6；M is the arbitrary integer between 2 to 6；Wherein R3It is respectively selected from hydrogen, straight Chain or side chain C1-12Alkyl, aryl；A, b, c, d are integer, and a+c:, between 0.00001 to 100, a, b are all the time for the ratio of b In the presence of when c and/or d is more than 0, the ratio of d and a+b+c is between 0.00001 to 100.
The compound of formula I has many applications.The present invention provides a kind of feed processing, including charging is changed with formula I Compound is contacted：
I) one or more components are removed from charging, to generate a kind of material without the removal composition；
Ii) one or more components of selective removal from charging, to recycle the removal component；
Iii a kind of ionic species) is removed from charging with ion-exchange process.
Charging can be continuous fluid, such as technique stream or intermediate flow, also can batch carry out discrete processes.Charging, such as produces Product stream, waste liquid or technique stream, the alternative removal component therein after treatment.Removed is probably unwanted in feeding Component, after being contacted with generalformulaⅰcompound, unwanted component is selectively removed in charging, obtains required composition.Illustrate Bright, this method can be used to remove unwanted object in charging from certain pharmaceutical production or technique, such as different metal species, To improve medicine purity.
This method can remove required species from charging, to carry out subsequent treatment or analysis, such as by biomolecule (such as Enzyme, peptide, albumen, endotoxin and nucleic acid) removed from charging, removed component is further processed or analyzes.
Generalformulaⅰcompound possesses required high-affinity, and to remove the metal combined closely with particular ligand, such as polarity is lived Part in property drug ingedient.The noble metals such as palladium, platinum, rhodium and nickel are often used as catalyst, what manufacture had high requirements to purity At the end of a large amount of difference high-value products, manufacturing process, these metals exist with many different forms, such as present example 4- Product in 8.
The technique stream or product stream of the palladium being bonded with product, knot are included using any product treatment of present example 4-8 Fruit shows that the palladium in solution is removed completely.The residue of product stream and technique stream from palladium (0) catalyst containing palladium, using this The product of invention example 7 and 8 is processed, and also has same removal effect.Realize that higher metal is loaded, per kilogram functionalization material The palladium of material absorption 60-120g.
In the technique stream of hydroformylation reaction contain different rhodium species, through the product treatment of present example 7-8 after, The residual content of rhodium is less than 1ppm.The rhodium catalyst waste liquid of acetic acid technique through present example 1-4 or 9-20 product treatment Effectively remove rhodium.
Noble metal platinum is used for numerous different techniques and application.For example, platinum catalyst is generated for hydrosilylation Silane and silicone, but it is unalterable, either platinum is stayed in the product, or only realize a small amount of removal.Use the chemical combination of formula I The such product stream of thing treatment and technique stream, as a result show that the content of platinum in these fluids is very low, such as present example 7 and 8.
The technique stream and waste liquid of mining industry contain a series of different metal, need the metal concentration for reclaiming very low in waste liquid Metal concentration without reclaiming is especially high, for example, noble metal such as platinum, palladium, rhodium, iridium, ruthenium and gold in certain solution Combined concentration is 2-20ppm, and iron, copper, zinc concentration are 500-50000ppm.Generalformulaⅰcompound selectivity efficient is removed Required noble metal, realizes metal adsorption higher, and the noble metal amount of per kilogram functionalization material absorption reaches 60-120g, such as originally The product of invention example 5-8.
Generalformulaⅰcompound various anion of high efficiency extraction from various environment, including lanthanide series metal, actinide metals, main group Metal and transition metal, each metal exist with anionic form.Anion includes arsenate, borate, chromate, permanganic acid Salt, perchlorate, platinate, perrhenate and gold anion complex such as cyanide.
For example, the product of present example 1-4 and 9-20 efficiently remove gold cyanide, chromate, copper cyanide and Arsenate, and realize that higher metal is loaded.
Gold mining and smelting industry produce many technique streams and waste liquid, wherein metal to exist in the form of anion, such as contain There are the various lean solutions of copper, zinc, iron, lead, gold and other metals.A kind of effective technology is needed to remove, recycle this A little metals, and effective environment solution is provided, manage these metals and free cyanide.Using the functional group high of formula I Load compound, present example 1-3 and 9-20 are efficiently eliminated in copper, zinc, iron, lead and such Gold Mining Industry fluid Stream free cyanide.
Generalformulaⅰcompound can optionally remove the required object in complex mixture.The acid waste liquid of certain cupric In have other metals (including zinc, nickel, lead, arsenic) of very high concentration, can be optionally sequestered there is presently no effective technology Copper, thus waste the value of a large amount of copper.Additionally, also environmental management must be carried out to such discarded object with caution.Present example The generalformulaⅰcompound of 4-8 optionally efficiently can remove copper removal from these acid waste liquids.For example, containing in certain acid waste liquid Copper (1-8,000ppm), arsenic (1-8,000ppm), zinc (1-2,000ppm) and nickel (200-1,000ppm), waste liquid injection is contained There is the cylinder of the product of present example 7 or 8, realize the optionally removal and high capacity of copper.Adsorbed copper can be by Reclaim and reuse, functionalization material is also reusable.And poisonous process chemical is not used in technique.
Generalformulaⅰcompound can also be used for synthesis in solid state, and parent material is adhered to first, then can carry out a series of chemistry anti- Should, being eluted using simple reagent per single step reaction can easily realize purification, and material requested is finally disengaged from solid phase.
Additionally, generalformulaⅰcompound is alternatively arranged as SPE material, required product is functionalized material selectivity and retains net Change, and impurity then circulating function material, then discharge required product using different dicyandiamide solutions.Generalformulaⅰcompound is also There is other application, be such as used as chromatographic separation material.
Specific embodiment
With reference now to illustrative example of the invention, describe the present invention in detail.
Example 1
In 200L reactors add silica gel (37-147 μm,20kg) with dimethylbenzene (42L), at 120 DEG C Stirring mixing, adds vinyltrimethoxy silane (16mol), and reactant mixture is heated and 5h is stirred.Cooled and filtered Solid, is fully washed (4x50L) with water, and a kind of component of formula IV is generated after drying, and wherein A is vinyl, and its functional group bears Load rate is 0.74mmol/g, and integer h, c, d are 0.A part of solid (11.8kg) is added to diallyldimethylammonium chloride Agitating solution (140mol, 60% aqueous solution) in, 7h are heated at 120 DEG C after the mixture of generation stirring 1h, period is per 15min Add TBHP (5mL).By liquid removal after cooling, solid adds water after (100L) stirs 30min and filters.Again to solid More water (100L) are added in body, is filtered after stirring the mixture for 30min.This process repeats 3 times and dries generation formula I afterwards A kind of component, wherein X is formula II, and the n in formula II is 6；R6It is methyl；M is 3；V is vinyl, and integer d is 0.
Example 2
In 200L reactors add silica gel (300-500 μm,20kg) with dimethylbenzene (42L), at 120 DEG C Stirring mixing, adds vinyltrimethoxy silane (20mol), and reactant mixture is heated and 5h is stirred.Cooled and filtered Solid, is fully washed (4x50L) with water, and a kind of component of formula IV is generated after drying, and wherein A is vinyl, and its functional group bears Load rate is 0.92mmol/g, and integer h, c, d are 0.A part of solid (14kg) is added to diallyldimethylammonium chloride In agitating solution (150mol, 60% aqueous solution), 7h is heated at 120 DEG C after the mixture stirring 1h of generation, period adds per 15min Enter TBHP (5mL).By liquid removal after cooling, solid adds water after (100L) stirs 30min and filters.Again to solid It is middle to add more water (100L), filtered after stirring the mixture for 30min.This process repeats 3 times and dries generation formula I afterwards A kind of component, wherein X are formulas II, and the average value of n is 5.5 in formula II；M is 4；R6It is methyl；Integer c and d are 0.
Embodiment 3
In 200L reactors add silica gel (147-300 μm,20kg) with dimethylbenzene (42L), at 120 DEG C Stirring mixing, adds vinyltrimethoxy silane (20mol), and reactant mixture is heated and 5h is stirred.Cooled and filtered Solid, is fully washed (4x50L) with water, and a kind of component of general formula III is generated after drying, and wherein A is vinyl, and its functional group bears Load rate is 0.92mmol/g；V is phenyl；H, d are 0.A part of solid (14kg) is added to diallyldimethylammonium chloride Agitating solution (180mol, 60% aqueous solution) in, heat 75h at 130 DEG C after the mixture of generation stirring 1h, period is every 15min adds TBHP (5mL).By liquid removal after cooling, solid adds water after (100L) stirs 30min and filters. Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process repeats 3 times and dries life afterwards Into a kind of component of formula I, wherein X is formula II, and the average value of n is 5 in formula II；R6It is methyl；V is phenyl；M is 3；It is whole Number d is 0.
Example 4
In 200L reactors add silica gel (147-300 μm,20kg) with dimethylbenzene (42L), at 120 DEG C Stirring mixing, adds vinyltrimethoxy silane (20mol), and reactant mixture is heated and 5h is stirred.Cooled and filtered Solid, is fully washed (4x50L) with water, and a kind of component of general formula III is generated after drying, and wherein A is vinyl, and its functional group bears Load rate is 0.92mmol/g；V is phenyl；H, d are 0.A part of solid (14kg) is added to diallyldimethylammonium chloride Agitating solution (180mol, 60% aqueous solution) in, 5h are heated at 130 DEG C after the mixture of generation stirring 1h, period is per 15min Add TBHP (5mL).By liquid removal after cooling, solid adds water after (100L) stirs 30min and filters.Again to solid More water (100L) are added in body, is filtered after stirring the mixture for 30min.This process repeats 3 times and dries generation formula I afterwards A kind of component, wherein X is formula II, and the average value of n is 5 in formula II；R6It is methyl；V is phenyl；M is 3；Integer d is 0. Product is added in dimethylbenzene (30L), 3- mercaptopropyl trimethoxysilanes (2mol) is added after stirring 1h, the mixture is existed Stirred at 120 DEG C, heat 6h, wash 4 times (using 30L water washings every time) after cooling with water, while stirring, then dries generation logical A kind of component of formula I, wherein X is formula II, and the average value of n is 4.2 in publicity 2；R6It is methyl；V is phenyl；W is 3- mercaptos third Base；M is 3.
Example 5
In 50L reactors add silica gel (147-300 μm,5kg) with dimethylbenzene (12L), stirred at 120 DEG C Mixing is mixed, vinyltrimethoxy silane (2mol) is added, reactant mixture is heated and 5h is stirred.Cooled and filtered is consolidated Body, is fully washed (4x50L) with water, and a kind of component of formula IV is generated after drying, and wherein A is vinyl, the load of its functional group Rate is 0.4mmol/g；H, c, d are 0.Solid is added to agitating solution (20mol, 60% of diallyldimethylammonium chloride The aqueous solution) in, 5h is heated at 130 DEG C after the mixture stirring 1h of generation, period adds TBHP per 15min (5mL).By liquid removal after cooling, solid adds water after (30L) stirs 30min and filters.Again to adding more water in solid (30L), filters after stirring the mixture for 30min.This process repeats 3 times and dries a kind of component for generating formula I, wherein X afterwards It is formula II, the average value of n is 5 in formula II；R6It is methyl；M is 3；Integer c and d are 0.Product is added to dimethylbenzene In (12L), 3- mercaptopropyl trimethoxysilanes (6mol) is added after stirring 1h, the mixture is stirred at 120 DEG C, is heated 6h, is washed with water 4 times after cooling, and 30L water washings are used every time, while stirring, then dries a kind of component of generation formula I, Wherein X is formula II, and the average value of n is 5.4 in publicity 2；R6It is methyl；W is 3- mercapto propyl group；M is 3；C is 0.
Example 6
In 200L reactors add silica gel (300-500 μm,20kg) with dimethylbenzene (42L), at 120 DEG C Stirring mixing, adds vinyltrimethoxy silane (16mol), phenyltrimethoxysila,e (1mol), is additionally added pi-allyl The product of thiocarbamide (1.8mol) and 3- mercaptopropyl trimethoxysilanes (1.5mol) after 120 DEG C of reaction 3h, by reactant mixture Heat and stir 5h.Cooled and filtered solid, is fully washed (4x50L) with water, and a kind of component of general formula III is generated after drying, Wherein A is vinyl, and its functional group's load factor is 0.76mmol/g；V is phenyl；W is 3- (3- thiocarbamide propyl group thioether) propyl group；h It is 0.A part of solid (14kg) is added to the agitating solution (200mol, 60% aqueous solution) of diallyldimethylammonium chloride In, 5h is heated at 130 DEG C after the mixture stirring 1h of generation, period adds TBHP (5mL) per 15min.Cooling Afterwards by liquid removal, solid adds water after (100L) stirs 30min and filters.Again to more water (100L) are added in solid, will be mixed Filtered after compound stirring 30min.This process repeats 3 times and dries a kind of component for generating formula I afterwards, and wherein X is formula II, leads to The average value of n is 4.5 in formula II；R6It is methyl；V is phenyl；W is 3- (3- thiocarbamide propyl group thioether) propyl group；M is 3.
Example 7
In 50L reactors add silica gel (147-300 μm,5kg) with dimethylbenzene (12L), stirred at 120 DEG C Mixing is mixed, vinyltrimethoxy silane (2mol) is added, reactant mixture is heated and 5h is stirred.Cooled and filtered is consolidated Body, is fully washed (4x50L) with water, and a kind of component of formula IV is generated after drying, and wherein A is vinyl, the load of its functional group Rate is 0.4mmol/g；H, c, d are 0.Solid is added to agitating solution (20mol, 60% of diallyldimethylammonium chloride The aqueous solution) in, 5h is heated at 130 DEG C after the mixture stirring 1h of generation, period adds TBHP per 15min (5mL).By liquid removal after cooling, solid adds water after (30L) stirs 30min and filters.Again to adding more water in solid (30L), filters after stirring the mixture for 30min.This process repeats 3 times and dries a kind of component for generating formula I, wherein X afterwards It is formula II, the average value of n is 5 in formula II；R6It is methyl；M is 3；Integer c and d are 0.Product is added to dimethylbenzene In (12L), after stirring 1h, allylthiourea (7mol) and 3- mercaptopropyl trimethoxysilanes (6mol) are added in 125 DEG C of reactions The product obtained after 3h, the mixture is stirred at 120 DEG C, 6h is heated, and is washed with methyl alcohol 4 times after cooling, and 30L is used every time Methyl alcohol is washed, while stirring, then dries a kind of component of generation formula I, wherein X is formula II, the average value of n in publicity 2 It is 4.2；R6It is methyl；W is 3- (3- thiocarbamide propyl group thioether) propyl group；M is 3；C is 0.
Example 8
In 200L reactors add silica gel (300-500 μm,17kg) with dimethylbenzene (36L), at 120 DEG C Stirring mixing, adds vinyltrimethoxy silane (8mol), adds allylthiourea (18mol) and 3- mercapto propyl group trimethoxies Product of the base silane (15mol) after 125 DEG C of reaction 3h, reactant mixture is heated and 5h is stirred.Cooled and filtered solid, uses Water is fully washed (4x50L), and a kind of component of general formula III is generated after drying, and wherein A is vinyl, and its functional group's load factor is 0.4mmol/g；W is 3- (3- thiocarbamide propyl group thioether) propyl group；H is 0.Solid is added to stirring for diallyldimethylammonium chloride Mix in solution (150mol, 60% aqueous solution), 5h is heated at 130 DEG C after the mixture stirring 1h of generation, period adds per 15min TBHP (5mL).By liquid removal after cooling, solid adds water after (100L) stirs 30min and filters.Again in solid More water (100L) are added, is filtered after stirring the mixture for 30min.This process repeats 3 times and dries the one of generation formula I afterwards Component is planted, wherein X is formula II, and the average value of n is 6 in formula II；R6It is methyl；W is 3- (3- thiocarbamide propyl group thioether) propyl group； M is that 3, c is 0.
Example 9
The material (12kg, wherein A are vinyl, and its functional group's load factor is 2.6mmol/g) of formula IV is added into diene In the agitating solution (200mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 130 DEG C after the mixture stirring 1h that will be generated Heating 7h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 0.7 in formula II；R6It is first Base；V is vinyl；M is 3；Integer d is 0.
Example 10
The material (6kg, wherein A are vinyl, and its functional group's load factor is 4mmol/g) of formula IV is added into diallyl In the agitating solution (100mol, 60% aqueous solution) of alkyl dimethyl ammonium chloride, in 120 DEG C of heating after the mixture stirring 1h that will be generated 7h, period adds TBHP (3mL) per 15min.By liquid removal after cooling, add water (50L) stirring in solid Filtered after 30min.Again to more water (50L) are added in solid, filtered after stirring the mixture for 30min.This process repeats 3 It is secondary, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 0.3 in formula II；R6It is methyl；V It is vinyl；M is 3；Integer d is 0.
Example 11
The material (6kg, wherein A are vinyl, and its functional group's load factor is 3.3mmol/g) of formula IV is added into two allyls In the agitating solution (100mol, 60% aqueous solution) of base alkyl dimethyl ammonium chloride, add at 120 DEG C after the mixture stirring 1h that will be generated Hot 7h, period adds TBHP (3mL) per 15min.By liquid removal after cooling, add water (50L) stirring in solid Filtered after 30min.Again to more water (50L) are added in solid, filtered after stirring the mixture for 30min.This process repeats 3 It is secondary, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 0.5 in formula II；R6It is methyl；V It is vinyl；M is 3；Integer d is 0.
Example 12
The material (12kg, wherein A are vinyl, and its functional group's load factor is 1.2mmol/g) of formula IV is added into diene In the agitating solution (200mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 130 DEG C after the mixture stirring 1h that will be generated Heating 7h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 2 in formula II；R6It is methyl；V It is vinyl；M is 3；Integer d is 0.
Example 13
The material (12kg, wherein A are vinyl, and its functional group's load factor is 1.2mmol/g) of formula IV is added into diene In the agitating solution (200mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 130 DEG C after the mixture stirring 1h that will be generated Heating 7h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 1.2 in publicity 2；R6It is methyl； V is vinyl；M is 3；Integer d is 0.
Example 14
The material (12kg, wherein A are vinyl, and its functional group's load factor is 1.8mmol/g) of formula IV is added into diene In the agitating solution (200mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 120 DEG C after the mixture stirring 1h that will be generated Heating 7h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 1.0 in publicity 2；R6It is ethyl； V is vinyl；M is 3；Integer d is 0.
Example 15
The material (12kg, wherein A are vinyl, and its functional group's load factor is 0.5mmol/g) of formula IV is added into diene In the agitating solution (170mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 110 DEG C after the mixture stirring 1h that will be generated Heating 8h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 14 in publicity 2；R6It is methyl；m It is 3；Integer c and d are 0.
Example 16
The material (24kg, wherein A are vinyl, and its functional group's load factor is 0.2mmol/g) of formula IV is added into diene In the agitating solution (160mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 130 DEG C after the mixture stirring 1h that will be generated Heating 6h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 44 in publicity 2；R6It is methyl；m It is 3；Integer c and d are 0.
Example 17
The material (24kg, wherein A are vinyl, and its functional group's load factor is 0.4mmol/g) of formula IV is added into diene In the agitating solution (300mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 125 DEG C after the mixture stirring 1h that will be generated Heating 8h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 19 in publicity 2；R6It is methyl；m It is 3；Integer c and d are 0.
Example 18
The material (10kg, wherein A are vinyl, and its functional group's load factor is 0.8mmol/g) of formula IV is added into diene In the agitating solution (160mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 125 DEG C after the mixture stirring 1h that will be generated Heating 8h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 5 in publicity 2；R6It is ethyl；m It is 3；Integer c and d are 0.
Example 19
The material (24kg, wherein A are vinyl, and its functional group's load factor is 1mmol/g) of formula IV is added into two allyls In the agitating solution (400mol, 60% aqueous solution) of base alkyl dimethyl ammonium chloride, add at 125 DEG C after the mixture stirring 1h that will be generated Hot 8h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, add water (100L) stirring in solid Filtered after 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is repeated 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 3 in publicity 2；R6It is methyl；M is 3；Integer c and d are 0.
Example 20
The material (14kg, wherein A are vinyl, and its functional group's load factor is 0.72mmol/g) of formula IV is added into diene In the agitating solution (180mol, 60% aqueous solution) of diallyidimethylammonium chloride, at 110 DEG C after the mixture stirring 1h that will be generated Heating 5h, period adds TBHP (5mL) per 15min.By liquid removal after cooling, added water in solid (100L) stir Filtered after mixing 30min.Again to more water (100L) are added in solid, filtered after stirring the mixture for 30min.This process is weighed again It is multiple 3 times, a kind of component of formula I is generated after drying, wherein X is formula II, and the average value of n is 4 in publicity 2；R6It is methyl；m It is 3；Integer c and d are 0.
Example 21
The product (0.05g) for taking example 5 is added in certain the product stream sample (6mL) containing iridium (205ppm), in the fluid Iridium be derived from iridous chloride in the catalyst 1M HCl that use.Filtered after this mixture is stirred into 4h at 30 DEG C.Analysis is aobvious Show that the iridium in filtrate has been completely removed.Example 1,4,6 and 13-20 have effect same in this experiment.
Example 22
The product (0.03g) for taking example 7 is added in certain the product stream sample (10mL) containing iridium (55ppm), in the fluid Iridium be derived from double (triphenylphosphine) iridium (I) of the catalyst chlorocarbonyl that uses.Filtered after this mixture is stirred into 6h at 60 DEG C.Point Iridium in analysis display filtrate has been completely removed.Example 8,11 and 15-18 have same effect in this experiment.
Example 23
The product (0.03g) for taking example 6 is added in certain technique stream sample (3mL) of rhodium-containing (150ppm), in the fluid Rhodium be derived from rhodium (III) in the catalyst 1M HCl that use.Filtered after this mixture is stirred into 4h at 30 DEG C.Analysis display Rhodium in filtrate has been completely removed.Example 1-5,7-8 and 13-20 have same effect in this experiment.
Example 24
The product (0.03g) for taking example 8 is added in certain technique stream sample (3mL) of rhodium-containing (240ppm), in the fluid Rhodium be derived from catalyst acetyl acetone dicarbonyl rhodium (I) that uses.Filtered after this mixture is stirred into 12h at ambient temperature. Analysis display rhodium has been removed.
Example 25
The product (0.01g) for taking example 5 is added in certain the product stream sample (3mL) containing palladium (60ppm), in the fluid Palladium is derived from the catalyst acetic acid palladium for using.Filtered after this mixture is stirred into 30min at 30 DEG C.Palladium in analysis display filtrate It has been completely removed.Example 7-8 has same effect in this experiment.
Example 26
The product (0.03g) for taking example 7 is added in certain the product stream sample (3mL) containing palladium (120ppm), in the fluid Palladium be derived from the catalyst tetrakis triphenylphosphine palladium (0) that uses.Filtered after this mixture is stirred into 2h at 50 DEG C.Analysis display Palladium in filtrate has been removed.
Example 27
The product (0.03g) for taking example 7 is added in certain the product stream sample (2mL) containing palladium (200ppm), in the fluid Palladium be derived from three (dibenzalacetone) two palladium (0) catalyst for using.Filtered after this mixture is stirred into 6h at 60 DEG C.Point Palladium in analysis display filtrate has been removed.Example 5 and 8 has same effect in this experiment.
Example 28
The product (0.04g) for taking example 2 is added in certain technique stream sample (15mL) of platiniferous (50ppm), in the fluid Platinum be derived from the catalyst chloroplatinic acid that uses.Filtered after this mixture is stirred into 6h at 80 DEG C.Platinum in analysis display filtrate It has been removed.Example 1,3-20 has same effect in this experiment.
Example 29
Certain silane process waste liquid (20L) of platiniferous in acid solution (40ppm) is produced at 20 DEG C by containing example 16 The pillar of product (100g).The residual content of the fluid display platinum after analyzing and processing is less than 1ppm.Example 2 and 17 has in this experiment Same effect.
Example 30
Certain prepares the hydroformylation process waste liquid of the Process Production rhodium-containing (300ppm) of acetic acid, by the waste liquid (5L) 80 By the pillar filled with the product of example 1 (100g) at DEG C.The residual content of the solution display rhodium after analyzing and processing is less than 1ppm. Example 13-20 has same effect in this experiment.
Example 31
The product (0.04g) for taking example 7 is added in certain technique stream sample (4mL) containing ruthenium (50ppm), in the fluid Ruthenium is derived from and uses Grubbs catalyst, double (tricyclohexyl phosphine) benzal ruthenium (IV) dichloride.Mistake after stirring 6h at 30 DEG C Filter mixture.Analysis filtrate shows that ruthenium has been removed.
Example 32
Zinc-iron (melting concn 10,000ppm), platinum (4ppm), palladium (4ppm), ruthenium (3ppm) and rhodium (1.5ppm) will be contained 30L acid solutions with 0.3L/h flow velocitys by the fixed bed filled with the product of example 7 (100g).99% in these noble metals Platinum, 99% palladium, 60% ruthenium and 80% rhodium optionally removed from the solution.Example 1-2,5-6 and 15-17 exist It is also effective in this experiment.
Example 33
Take example 8 product (0.05g) add cupric (60ppm) certain technique stream sample in, the copper source in the technique stream From copper (I) catalyst for using.Filtered after mixture to be gently mixed 2h at room temperature.Analysis filtrate shows that copper has been removed.It is real 4-7 is also effective in this experiment for example.
Example 34
Use certain process waste liquor of product (2.0g) Treatment of Copper (II) (6,000ppm) of example 5.By mixture in room Filtered after 2h is gently mixed under temperature.Analysis filtrate shows that copper has been removed.
Example 35
Processed using the product (2.0g) of example 8 and contain copper (2,000ppm), zinc (700ppm), nickel (200ppm) and arsenic The pH of (6,800ppm) is 1.7 certain acid waste liquid.Copper is optionally removed from the fluid, leave zinc, nickel, arsenic and other Metal.Example 4-7 is also effective in this experiment.
Example 36
By certain acid that the pH containing copper (2,000ppm), zinc (700ppm), nickel (200ppm) and arsenic (6,800ppm) is 1.7 Property waste liquid by the pillar filled with the product of example 9 (50g), retain 15-18mL/min.Copper is by the selectivity from the acid waste liquid Ground removal, leaves zinc, nickel, arsenic and other metals.
Example 37
PH by cupric (3,000ppm), zinc (700ppm), lead (40ppm) and iron (300ppm) is 11.7 certain gold essence Refining stream is by filled with the product of example 9 (50g), retaining the pillar of 15-18mL/min.Copper, zinc, lead and iron are from the fluid Remove.
Example 38
By certain high-sulfur cyanogen that the pH containing copper (1500ppm), zinc (300ppm), lead (30ppm) and iron (50ppm) is 11.2 The poor gold solution gold refining liquid of compound retains 15-18mL/min by the pillar filled with the product of example 16 (50g).Copper, zinc, Lead and iron are to be removed from the fluid.
Example 39
To contain copper (2,000ppm), zinc (700ppm), lead (40ppm), iron (100ppm) and free cyanide with acid The pH of certain gold refined waste liquid of (200ppm) is adjusted to 10, then by the waste liquid by the post filled with the product of example 9 (50g) Son, retains 15-18mL/min.Copper, zinc, lead, iron and cyanide are to be removed from the fluid.
Example 40
Certain gold refined waste liquid that pH containing copper (60ppm) and zinc (40ppm) is 10 is produced by filled with example 19 The pillar of product (50g), retains 15-18mL/min.Copper and zinc are to be removed from the fluid.
Example 41
Will be containing copper (50ppm), zinc (20ppm) and free cyanide (35ppm), certain gold refined waste liquid that pH is 11 By the pillar filled with the product of example 18 (50g), 15-18mL/min is retained.Copper, zinc and cyanide are from the fluid Remove.
Example 42
To pass through to contain from embodiment 18 with the flow velocity of 15-18mL/min containing the waste stream of chromate (150ppm) The pillar of 50g products.Result shows to remove chromate from this waste stream.
Example 43
Certain process stream containing bromide (500ppm) is crossed into the pillar filled with the product of example 17 (50g), 15- is retained 18mL/min.Bromide is to be removed from the fluid.
Example 44
The product (20g) of example 16 is added in certain acid process stream (10mL) after being processed with excess of sodium carbonate, stirs 1h.Stream Body is neutralized.

Claims (14)

1. a kind of method for producing the compound of general formula I：
[(O3/2)Si(CH2)mX]a[Si(O4/2)]b[VSi(O3/2)]c[WSi(O3/2)]d(formula I)
In formula：
X is selected from (CH2)3N+(L1)(R6)2CH2CH2CH3)、(CH2)3N+(L1)(R6)2CH2CHCH2Or the compound of formula II；R6It is Hydrogen, C1-22Alkyl or aryl；N is an integer from 0 to 100；L1It is an anion, including but not limited to halide, nitric acid Salt, sulfate, carbonate, phosphate, chromate, permanganate, borohydrides, for borohydrides such as cyanoborohydride；
V is a selectively substituted group, selected from C1-22Alkyl, C2-20Alkylene, C1-22Alkylaryl or aryl；W is Group (CH2)eZ, wherein Z are SH, S (CH2)fSH、S(CH2)fNHC (=S) NHR3、NR4R5Or NH [(CH2)2NH]jH, e and f point It is not an integer from 2 to 6；J is an integer from 1 to 100；M is an integer from 2 to 12；Wherein R3-5Select respectively From hydrogen, straight or branched C1-12Alkyl, aryl or C1-22Alkylaryl；A, b, c, d are integer, and a+c:The ratio of b between 0.00001 to 100, a, b exist all the time, and such as c and/or d is more than zero, then the ratio of d and a+b+c is between 0.00001 to 100；
By the silicon atom of other groups, hydrogen, straight or branched C in formula I1-22Alkyl, end group R2SiO1/2, crosslinking agent or chain RqSi(OR1)gOk/2In one or more make the free valency saturation of silicate oxygen atom, wherein R and R1Be respectively selected from straight chain or Side chain C1-12Alkyl, aryl or C1-22Alkylaryl；K is an integer from 1 to 3, and q is an integer from 1 to 2, and g is from 0 To 2 integer, and meet g+k+q=4, in the presence of end group, crosslinking agent and/or polymer chain, its mol ratio and a+b The ratio of+c+d is between 0 to 999:1；
This method includes：
Contacted with general formula III compounds,
[(O3/2)Si(CH2)hA]a[Si(O4/2)]b[VSi(O3/2)]c[WSi(O3/2)]d(general formula III)
In formula, A is vinyl, and its load is 0.001 to 4mmol/g；H is an integer from 0 to 10；10-100 moles is worked as (the CH of amount2CHCH2)2N+(R6)2L1It is placed in solvent, wherein R6It is hydrogen, straight or branched C1-22Alkyl, C1-22Alkylaryl or Aryl；Regularly added under the conditions of 20-150 DEG C radical initiator react 10 minutes to 48 hours, then by solid filtering or Centrifugation, dries generation generalformulaⅰcompound after being washed using solvent；Or contacted with general formula IV compounds,
[(O3/2)Si(CH2)hA]a[Si(O4/2)]b(formula IV)
In formula, A is vinyl, and its load is 0.001 to 4mmol/g；H is an integer from 0 to 10；10-100 moles is worked as (the CH of amount2CHCH2)2N+(R6)2L1It is placed in solvent, radical initiator is regularly added under the conditions of 20-150 DEG C and reacts 10 points Clock to 48 hours, after by solid filter or be centrifuged, use solvent wash after dry generation generalformulaⅰcompound, wherein integer c and d It is 0；Then use VSi (OR1)3Or WSi (OR1)3Or both is processed in a solvent, 10 are reacted under the conditions of 60-150 DEG C Solid, to 48 hours, is then filtered or is centrifuged by minute, is used solvent to be dried after washing and is generated generalformulaⅰcompound, wherein V and W Exist.
2. a kind of method according to claim 1, wherein, the A of general formula III or IV is vinyl, and its load is arrived for 0.01 4mmol/g；V is a selectively substituted group and selected from C1-6Alkyl, C2-8Alkylene, aryl；W is (CH2)eZ bases Group, wherein Z is SH, S (CH2)fNHC (=S) NHR3、NR4R5Or NH [(CH2)2NH]jH, wherein e and f be respectively from 2 to 3 one Individual integer；J is an integer from 1 to 20；M is an integer from 2 to 6；Wherein R3-5It is respectively selected from hydrogen, straight or branched C1-12Alkyl, aryl or C1-22Alkylaryl；R6It is straight or branched C1-12Alkyl.
3. a kind of method according to claim 1, wherein, the A of general formula III or IV is vinyl, and its load is arrived for 0.01 2.0mmol/g；V is a selectively substituted group and selected from C1-6Alkyl, C2-8Alkylene, aryl；M is from 2 to 6 Integer；R6It is straight or branched C1-12Alkyl.
4. a kind of method according to claim 1, wherein, the A of general formula III or IV is vinyl, and its load is arrived for 0.01 1.2mmol/g；V is a selectively substituted group, selected from C1-6Alkyl, C2-6Alkylene, aryl；M is from 2 to 6 Integer；R6It is straight or branched C1-4Alkyl.
5. a kind of method according to Claims 1-4, its solvent for using is water, dimethylbenzene, toluene, normal heptane, second two Alcohol, ethanol or methyl alcohol；Reaction temperature be 80-150 DEG C, addition radical initiator for example azodiisobutyronitrile, benzoyl peroxide, TBHP and tert-butyl peroxide, react 30 minutes to 8 hours.
6. the composition of general formula I：
[(O3/2)Si(CH2)mX]a[Si(O4/2)]b[VSi(O3/2)]c[WSi(O3/2)]d(formula I)
In formula, X is selected from (CH2)3N+(L1)(R6)2CH2CH2CH3)、(CH2)3N+(L1)(R6)2CH2CHCH2Or the compound of formula II； R6It is a C1-22Alkyl or aryl；N is an integer from 0 to 100；L1It is an anion, including but not limited to halogenation Thing, nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydrides or for borohydrides such as cyano group hydrogen boron Compound；
V is a selectively substituted group and selected from C1-22Alkyl, C2-20Alkylene, C1-22Alkylaryl or aryl；W It is group (CH2)eZ, wherein Z are SH, S (CH2)fSH、S(CH2)fNHC (=S) NHR3、NR4R5Or NH [(CH2)2NH]jH, e and f Respectively from 2 to 6 an integer；J is an integer from 1 to 100；M is an integer from 2 to 12；Wherein R3-5Respectively Selected from hydrogen, straight or branched C1-12Alkyl, aryl or C1-22Alkylaryl；A, b, c, d are integer, and a+c:The ratio of b is situated between In 0.00001 to 100, a, b exist all the time, and the ratio of d and a+b+c is between 0.00001 to 100 if c and/or d is more than 0；
By the silicon atom of other groups, hydrogen, straight or branched C in formula I1-22Alkyl, end group R2SiO1/2, crosslinking agent or chain RqSi(OR1)gOk/2In one or more make the free valency saturation of silicate oxygen atom, wherein, R and R1Be respectively selected from straight chain or Side chain C1-12Alkyl, aryl or C1-22Alkylaryl；K is the integer from 1 to 3, and q is the integer from 1 to 2, g be from 0 to 2 it is whole Number, and meet g+k+q=4, in the presence of end group, crosslinking agent and/or polymer chain, the ratio of its mol ratio and a+b+c+d Between 0 to 999:1.
7. compound according to claim 6, wherein, X is selected from (CH2)3N+(L1)(R6)2CH2CH2CH3)、(CH2)3N+(L1) (R6)2CH2CHCH2Or the compound of formula II；R6It is a C1-6Alkyl；N is the integer from 0 to 50；V be one selectively by Substituted group and selected from C1-6Alkyl, C2-8Alkylene；W is (CH2)eZ group, wherein Z are SH, S (CH2)fSH、S(CH2)fNHC (=S) NHR3, e and f is respectively an integer from 2 to 6；M is an integer from 2 to 12；Wherein R3Selected from hydrogen, straight chain or Side chain C1-12Alkyl or aryl；A, b, c, d are integer, and a+c:Between 0.00001 to 100, a, b are deposited the ratio of b all the time , as c and/or d be more than 0 if d and a+b+c ratio between 0.00001 to 100.
8. a kind of feed processing, comprising with the compound according to claim 6 or claim 7 any claim Contact, or charging is contacted with the compound of the method generation according to any claim in claim 1 to 5：
I. one or more components are removed from charging, to generate a kind of material without the removal component；
Ii. one or more components of selective removal from charging, to recycle the removal component；
Iii. a kind of ionic species is removed from charging with ion-exchange process.
9. a kind of compound according to any claim in claim 6 to 7, or one kind is according to claim 1 to 5 The compound of the method generation described in middle any claim, as a kind of functionalization material, for being removed from liquid feedstock Or selective removal is unwanted organic and inorganic or biologic artifact or reduces its content.
10. a kind of compound according to any claim in claim 6 to 7, or one kind according to claim 1 to The compound of the method generation in 5 described in any claim, as a kind of functionalization material, for removing, selective removal Or reduce in reactant mixture, technique stream, product stream, waste liquid or waste water or being bonded or combine with other organic compounds Noble metal such as platinum, palladium, rhodium, iridium, gold, ruthenium, rhenium, rare earth metal or transition metal such as copper, zinc, nickel.
A kind of 11. compounds according to any claim in claim 6 to 7, or one kind according to claim 1 to The compound of the method generation in 5 described in any claim, as a kind of functionalization material, for being selected from acid waste liquid Property removes copper removal.
A kind of 12. compounds according to any claim in claim 6 to 7, or one kind according to claim 1 to The compound of the method generation in 5 described in any claim, as a kind of functionalization material, for from gold ore stream and smelting Removal and selective removal metal and cyanide in fluid.
A kind of 13. compounds according to any claim in claim 6 to 7, or one kind according to claim 1 to The compound of the method generation in 5 described in any claim, as cation or anionite, for product stream, work Skill stream and waste liquid.
A kind of 14. compounds according to any claim in claim 6 to 7, or one kind according to claim 1 to The compound of the method generation in 5 described in any claim, has for being purified from gas, liquid and solid environment or being separated Machine, biology or inorganic molecule.
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