CN107129575A - Functionalization material and its production technology and purposes - Google Patents
Functionalization material and its production technology and purposes Download PDFInfo
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- CN107129575A CN107129575A CN201710224578.9A CN201710224578A CN107129575A CN 107129575 A CN107129575 A CN 107129575A CN 201710224578 A CN201710224578 A CN 201710224578A CN 107129575 A CN107129575 A CN 107129575A
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- 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
- C08G77/04—Polysiloxanes
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- 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
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Abstract
Functionalization material and its production technology and purposes, the present invention relates to a kind of new synthetic by multiple organo-functional group improved silicas, same synthetic is containing a large amount of functional groups such as multiple sulfydryls, sulfide and thiourea group, these functional groups exist with different oligomer, configuration, spatial chemistry array, and metal target and the affinity of specific objective are significantly increased with selectivity.The ability being bonded in actual process stream, product stream and waste liquid with various forms of objects is further improved with combining for different structure configuration, a variety of binding mechanisms realize high level purification and selective removal object.The purposes of the compound includes：Product is purified, unwanted organic and inorganic compound (including metal and metal complex) is removed from product stream, technique stream and waste liquid, selectivity removes target component from the mixture that Multiple components coexist, metal, metal complex, organic and biologic artifact are purified and separated as chromatography media, are extracted and biomolecule fixation for SPE, synthesis in solid state, metal ion.
Description
Technical field
(contain multiple sulfydryls, sulfide the present invention relates to the new synthetic of multiple organo-functional group improved silicas
And thiourea group) and its production technology and purposes.The material can be used for removing from product, technique stream, waste liquid or selectivity is gone
Except organic/inorganic compound and metal, or as cation and anion exchange agent, metal chromatographic material, Solid phase cleaned-up or fiber material,
The fixation material of biomolecule, antimicrobial, catalyst carrier, hydrophilic modifier, fire retardant, antistatic additive, biological doctor
Learn coating, controlled-release material, waterproof membrane and the coating, synthesis in solid state material and chromatographic material of device.The invention further relates to produce this
The preparation method of monomer and these monomers needed for class novel product.
Background technology
Continually developing for new technique causes purity requirement of the industry to chemicals more next in major industries and market application
It is stricter.For example, organic and inorganic impurity is down to more low-level by medicine and bio-technology industries requirement；Electronics industry requirement is normal
The concentration for the kish (such as sodium, magnesium, iron) seen have to be lower than 1ppm.
It is currently needed for the chemical technology that more cleans to tackle the pressure that society and law apply environmental improvement, and avoids
Or the discharge of reduction discarded object, particularly reduce the residual quantity of environment Poisoning metal and chemicals.
Currently, metal plays vital effect in development in science and technology.Noble metal (such as platinum, rhodium, palladium, ruthenium, iridium, gold) is provided
Source is limited, is but widely used in all trades and professions.With the exploitation of more application fields, it is contemplated that available Precious Metals Resources are by nothing
Method meets tomorrow requirement.Because this metalloid cost is high, resource-constrained and with toxicity, therefore need to seek a kind of high efficiency technical from
This metalloid is reclaimed and reused in product, technique, waste liquid.For example, in petrochemical industry, from hydroformylation
With the associated products of hydrosilylation reactions, this metalloid is reclaimed in technique and waste liquid.
Metal is widely used in the types of applications field of major industries.These metals are finally most not in different forms
In same product, technique and waste liquid.Particular technology need to be used to its formation, using in, circulation, production process and its waste liquid, from
And higher metal recovery rate is realized, the efficiency and selectivity of recycling are improved, and reduce the influence to environment.For example,
In ＆ smelting industries of digging up mine, the metal (copper, nickel, iron) to residual and process chemical (such as zinc) progress processing containing metal are one
Significant challenge includes, it is therefore desirable to a new recovery and multiplexing technology.
Every profession and trade various fields to rare earth metal (such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,
Thulium, ytterbium, lutetium) use increasingly increase, it is therefore desirable to more advanced technology is more efficiently reclaimed from product, technique and waste liquid lays equal stress on
This metalloid is used again.
In the smelting and purification technique stream of mining industry, high value metals (such as noble metal) generally with low ppm concentration and
Coexisted in other metals, the concentration of the latter is considerably higher sometimes.In order to reduce a large amount of losses of these high value metals, it is necessary to elder generation
The technology a) entered removes required metal to low-down residual concentration；B) metal of efficient process low concentration；C) with compared with
Other metals of high concentration are selectively removed high value metals in the case of coexisting.
In mineral industry, other metals (such as copper, nickel, iron, zinc) are also required to advanced technology a) by metal removal to very
Low residual concentration；B) metal of the various rank concentration (high to low) of efficient process；C) coexisted in other metals of various concentrations
In the case of optionally remove metal target；D) for one or more metal target high adsorption capacities；E) one kind can be captured
Or various metals and reused, and technology is very also reusable in itself.
Prepare high value organic compound or polymer usually requires multi-step process, and can be with accessory substance, isomers
With the generation of impurity.In most cases this kind of product has to be clean, in addition it is also necessary to which a kind of more efficient purification techniques comes
Remove the accessory substance of the particular range coexisted with target product, isomers and impurity.Prior art (as crystallized) will cause product
A large amount of losses.
A kind of current technology developed is functionalization material, and it is purified available for product, the selectivity from mixture
Composition needed for removing removes toxicity and/or high-valency metal or compound from product, technique and waste liquid.Work(can be flowed liquid through
Material can be changed with composition needed for selective removal.One of which functionalization material is activated carbon.According to process conditions, the surface of carbon
It is upper to include multiple oxidation organic groups.Although carbon is cheap, its shortcoming includes：Product largely loses；Removal capacity
It is weak；Hazardous compound or metal are included in final product.Cause alcohol, phenol, aldehyde and carboxylic that these shortcoming reasons are due to its surface
Acid functional group has non-specificity, and performance is weaker.
The another kind of functionalization material purified for product is organic polymer.Organic polymer carrier includes polystyrene
And polyolefin.Only very limited amount of single functional group may be connected on these carriers, and these functional groups include sulfonic acid or amido is (main
To be ion exchange mechanism).Because these functional groups are very low to metal affinity discussed above, therefore using this kind of organic poly-
Compound material can not meet high levels of performance.The major defect of organic resin：Required functional group can not be connected to organic
On polymer support；Functional group's load factor is low.Due to can only perform limited chemical operation on this kind of polymer, therefore less
A large amount of different polyfunctional groups may be connected on these organic polymer main chains to realize target performance level.In addition, it
Shortcoming is also including chemical property is poor, heat endurance is poor, can be swelled and shrink in organic solvent.Generally speaking, have for these
There is serious limitation in the technology of machine frame exploitation.
Inorganic polymer systems include silica, aluminum oxide and titanium oxide, and they are disclosed as functionalization material.
Relative to organic polymer carrier, inorganic polymeric support has some advantages, including physically better and chemical characteristic；It is stronger
Heat endurance；Regular pore structure is made it easier for close to the functional group on surface on material；It will not expand, it is easier to operate.
The case of simple functionalization inorganic material：Silicycle, Johnson Matthey, Evonik and
PhosphonicS (WO2006/013060, WO2007/090676) alkylamine and alkyl hydrosulfide.However, only can be by very
The simple functional group of very little scope is connected on these frameworks by limited chemical method, and functional group's load of this kind of material
It is low.For example, 1 kilogram of functionalization material (organic or inorganic skeleton) loading range is 5-30g, often actual loading value close to this
Lower limit.
Existing functionalization inorganic material has many restrictions：It is only applicable to the simple simple function group of narrow range；
One or most two hetero atoms are only existed, causes single binding mechanism, affinity is low, functional group's load is low, and actually should
Pay(useful) load with middle object is low.This is due to that the intitation reagents (silane) for a) manufacturing these materials are difficult to obtain, and production is multiple
It is miscellaneous；B) be used for using or modified chemicals in the range of reagent availability it is limited；C) manufacture silane is chemical limited；D) into
This, based on the principles of chemistry, the manufacture of silane is expensive；E) it is difficult that the simple functional group adhered on surface is adjusted to more complicated work(
Energy group, therefore performance can not be improved.
Although functionalization inorganic material has certain progress compared to functionalization organic resin, need to further it improve with full
The technological challenge of sufficient current and future, such as lower residual volume, stronger selectivity, higher object load capacity.
Prior art can not be for the functionalization material of practical commercial Demand Design or preparation containing required complicated functional group
Material.The business that is faced based on current and future, technology, environment, society's challenge, many markets applications are required for new technology to meet
Target performance level.
Furthermore, it is necessary to which the new choice of technology removes the special metal in complex mixture.For example, various metals (zinc,
Nickel, arsenic) coexist in the case of remove high concentration copper.Case：Ore work method is smelted the gas produced and formed after Water warfare
Acidic fluid containing various metals (including but is not limited to copper, noble metal, gold, zinc, nickel, lead, arsenic, selenium and antimony) (give up by waste acid
Liquid), then therefrom it is selectively removed copper.
Other cases：Kish in medical compounds；Metallic catalyst in process waste liquor, this metalloid is with difference
Form is present and the oxidation state different, such as different from starting form, and unimolecule is to nano particle, and many metallicses (do not assimilate
Complex compound), metal is combined closely with part.In addition, the production of medical compounds or flow may result in above institute each time
The metals of all forms mentioned is actually constituted with difference.In order to meet the aimed purity or capture metal of product, function
Changing material must be containing specific complex function group so as to specific aim combining target thing.In addition, these functional groups need close point
Cloth and optimize the arrangement of in framework surface and hole, so that it is guaranteed that then they can be caught with the part in replacement fluid with object
Obtain and retain object.Each object needs binding mechanism different, it is therefore desirable to which the structure of functionalization material is easy to adjust
It is whole, so that desired performance level (residual level of namely object is low) is realized, high selectivity and the load of high object.This
Outside, the necessary high temperature resistant of the functionalization material of design, physics and chemical stability are strong, and functional group's load is high, and solvent is compatible by force, profit
Wet performance is strong, will not expand and Ju Qiang functional groups affinity.In order to improve the cost efficiency of material, it need to ensure that parent material is
It is readily obtained, and there is the chemical technology easily adjusted to prepare optimization, high-affinity, high selectivity functionalization material.
The content of the invention
Inventor is successfully found that a kind of multi-functional compounds, and it possesses above-mentioned all target properties, and manufacture work
Skill is flexibly simple.The invention is applied to a series of application：The scavenger of inorganic, organic compound and metal, COMPLEX MIXED
The selective clearing agent of object, metal chromatographic material in thing, solid-phase purified or fiber material, the removal of biologic artifact and pure
Change, ion exchange material, catalyst immobilization carrier, the fixation material (including enzyme) of biomolecule, controlled-release material is antimicrobial
Agent, hydrophilic modifier, fire retardant, antistatic additive, synthesis in solid state material and chromatographic material, or above-mentioned all material monomer.
The Part I of the present invention provides chemical formula i compound：
[(O2/2)SiXO[SiO1/2XO]m]a[Si(O4/2)]b[(O2/2)SiYO[SiO1/2YO]n]c[(O2/2)SiZO[SiO1/ 2ZO]p]d[VSi(O3/2)]e(Formula I)
In formula, X is (CH2)sSH；Y is (CH2)sSC3H6NHC (=F) NHR2, wherein F is O or S or (CH2)sSC3H6NHR2
Or (CH2)sSC3H6OR2；Z is any one in X or Y；S is the arbitrary integer from 2 to 20；M, n and p are respectively from 0 to 100
Arbitrary integer, and one in m, n or p be consistently greater than 0；R2It is hydrogen, straight or branched C1-22- alkyl, C1-22- alkylaryl,
Aryl；V is the group that can optionally replace, selected from C1-22- alkyl, C1-22- alkylaryl, aryl, C2-20- alkyl sulfide ether,
C1-12- alkyl, C2-20- alkylen thioether alkyl, C2-20- alkyl thioether aryl, C2-20- alkylen thioether aryl；a、b、c、d、e
It is integer, and a+c+d：B ratio is that 0.00001 to 100,000, a, b and c/d exist all the time, when e is more than 0, e：a+b+
C+d ratio is 0.000001 to 100.
Pass through the silicon atom of other groups, hydrogen, straight or branched C in Formula I1-22Alkyl, end group R3SiO1/2, crosslinking agent
Or chain RqSi(OR1)gOk/2Wherein one or more make the free valency saturation of silicate oxygen atom, wherein R and R1Select respectively
From straight or branched C1-22Alkyl, aryl and C1-22Alkylaryl, R3Selected from straight or branched C1-12Alkyl, k is from 1 to 3
Arbitrary integer, q is the arbitrary integer from 1 to 2, and g is the arbitrary integer from 0 to 2, and meets g+k+q=4, when end group, crosslinking
In the presence of agent and/or polymer chain, its mol ratio and a+b+c+d+e ratio are 0-999:1.
The straight chain base or branched chain group that can optionally replace are selected from C1-22- alkyl, C2-22- alkenyl, C2-22- alkynyl, aryl,
C1-22- alkylaryl can be respectively straight or branched and/or be substituted by one or more substituents, but preferably comprise only
Hydrogen and carbon atom.If substituent, then substituent can be respectively selected from amine, acid amides, nitro, chlorine, fluorine, bromine, nitrile, hydroxyl,
Carboxylic acid, carboxylate, sulfide, sulfoxide, sulfone or C1-6- alkoxy.
It is preferred that following chemical formula i compound, wherein, b:A+c+d ratio is 10,000 to 0.2；S be from 2 to 4 it is any
Integer；M and p are respectively 0 to 20 arbitrary integer；N is from 1 to 20；R2It is hydrogen, straight or branched C1-6- alkyl or aryl.
Particularly preferred following chemical formula i compound, wherein, b:A+c+d ratio is 10,000 to 0.2；F is sulphur；S be from
2 to 3 integer；M and p is respectively the arbitrary integer from 0 to 10；N is from 1 to 10；R2It is hydrogen, straight or branched C1-4- alkyl or
Aryl.
In addition, preparing the method simple and flexible of chemical formula i compound, using new chemical method and technique, it is easy to get
Parent material prepares polynary organic functions compound, oligomer, polymer.Some row steps need to be only carried out in same reactor
Reaction just can easily change design, and meet functional group's complexity needed for Formula I.The technique can be by a series of functional groups
It is multiple to be covalently attached on surface, it is ensured that the stability of longer time and the functional group of extremely low level leach.
Present invention also offers the method for preparing general chemical formula I.Novel high yield acid catalysis, free radical can be passed through
The intitation reagents different with substitution reaction, adjustment and process conditions easily obtain multiple differences in general chemical formula I
Functional group, different configuration and space arrangement.
The present invention is intended to provide convenient, environment-friendly, plant-scale new side for preparing chemical formula i compound
Method.Compared to previous prior art, the technology yield, cost, scale and/or purity level, and environmental benefit is from business perspective
For it is satisfactory.
This novel process is related to Formulae II (R3O)3SiW silane or silane combination is partially polymerized through acid catalysis, wherein, W
It is (CH2)sSC3H6NHC (=O) NHR2、(CH2)sSH、(CH2)sSC3H6NHC (=S) NHR2、(CH2)sSC3H6NHR2Or (CH2)sSC3H6OR2, obtain formula iii [(R3O)2SiWO][SiX(OR3)O]m][SiY(OR3)O]n[SiZ(OR3)1ZO]p[OWSi
(OR3)2] corresponding linear and crosslinking siloxanes, wherein W is any one in X, Y or Z；X is (CH2)sSH；Y is (CH2)sSC3H6NHC (=F) NHR2, wherein F is O or S or (CH2)sSC3H6NHR2Or (CH2)sSC3H6OR2；Z is any one in X or Y
It is individual；R2It is hydrogen, straight or branched C1-22- alkyl, C1-22- alkylaryl, aryl；R3Selected from straight or branched C1-22Alkyl；m、n、p
It is the arbitrary integer from 0 to 100 respectively, and one of them in m, n or p is consistently greater than 0.
W is (CH2)sSC3H6NHC (=S) NHR2、(CH2)sSC3H6NHC (=O) NHR2、(CH2)sSC3H6NHR2Or (CH2)sSC3H6OR2Formulae II compound can be carried out by using radical initiator in the case of having solvent or be solvent-free
(R3O)3Si(CH2)sSH to unsaturated carbon-carbon bond such as CH2CHCH2NHC (=S) NHR2、CH2CHCH2NHC (=O) NHR2、
CH2CHCH2NHR2Or CH2CHCH2OR2Radical Addition prepare, 0.5-24 is reacted at a temperature of 20-160 DEG C small
When.Typical solvent includes dimethylbenzene, toluene, heptane, glycol, ethanol and methanol.Workable radical initiator is included but not
It is limited to azodiisobutyronitrile, benzoyl peroxide, TBHP and tert-butyl peroxide.
Following formula iii compound, wherein X is (CH2)sSH；Y is (CH2)sSC3H6NHC (=S) NHR2、(CH2)sSC3H6NHC (=O) NHR2、(CH2)sSC3H6NHR2Or (CH2)sSC3H6OR2；Z is any one in X or Y, can by with
It is prepared by lower either method：
I. corresponding silane or the silane combination of Formulae II are partially polymerized through acid catalysis；Or
Ii. it is (CH to W2)sThe silane of SH Formulae II is partially polymerized through acid catalysis, then using radical initiator
With unsaturated carbon-carbon bond (such as CH of appropriate alkene in the case of having solvent or be solvent-free2CHCH2NHC (=S) NHR2、
CH2CHCH2NHR2、CH2CHCH2OR2Or CH2CHCH2NHC (=O) NHR2) occur Radical Addition, in 20-160 DEG C of temperature
Degree lower reaction 0.5-24 hours.Typical solvent includes dimethylbenzene, toluene, heptane, glycol, ethanol and methanol.Workable freedom
Base initiator includes but is not limited to azodiisobutyronitrile, benzoyl peroxide, TBHP and tert-butyl peroxide.
Strict control reaction condition (including temperature, reaction time, catalyst concn and sour intensity) is for partially polymerized
Reaction is vital, otherwise can cause the poorly efficient synthesis on the siloxanes and the surface of solids of HMW, in addition, also
The siloxanes of bulky grain can be caused to block the hole of inorganic material.In the hole for being located at material due to functional group, it is impossible to good contact
Functionalization material property will be caused poor, loaded low.
The one of purpose of the present invention is to provide reaction condition and relative molar concentration for the partially polymerized reaction of starting silane.
The homogeneous acid of different acid strengths can be used for partially polymerized, including but not limited to methanesulfonic acid, p-methyl benzenesulfonic acid, phosphoric acid and thio second
Acid., it is necessary to the weaker acid of a greater amount of acidity compared with sulfonic acid.The preferred concentration of alkyl or aryl sulfonic acid is relative to silane
Mol ratio is 0.001 to 0.01.Reaction temperature is 70-120 DEG C, and the reaction time is 0.5-5 hours.It is preferred that it is solvent-free, preferably instead
Temperature is answered between 80-90 DEG C, preferred reaction time is between 0.5-1.5 hours.
Chemical formula can be increased by the reaction condition and reactant ratio that change in acid catalyzed partially polymerized reaction
The length of chain (integer m, n and p) in III.Longer reaction condition, higher acid strength and higher temperature will cause integer m,
N and p value is higher.
Silica gel and Formulae II, formula iii and (R can be passed through1O)3The synthetic reaction of silane in a solvent in SiV is obtained
To chemical formula i compound, reaction condition is 20-160 DEG C, and the reaction time is 0.5-24 hours.Multi-solvents and solvent combination can
For the synthetic reaction, including aliphatic series or aromatic hydrocarbon, alcohol and polar solvent such as dimethylformamide.Generally, it is preferred to solvent be
Toluene and dimethylbenzene.It is preferred that solvent and silica volume (L) and weight (kg) ratio between 2.8-2.
In order to realize required selectivity and targeted loads, Formulae II, formula iii can be added in synthesis step
(R1O)3SiV different silane components.Therefore the design flexibility of the technique is very strong, can prepare optimum performance functionalization material
Material.
Composition (R1O)3SiV makes it possible to add extra functional group, improves performance, and allow two around regulation functional group
The hydrophobic-hydrophilic of silicon oxide surface, so as to strengthen selective bonding.
After reaction terminates, by filtering or being centrifugally separating to obtain Formula I functionalization material, then fully wash to remove
The reactant of any residual, is finally dried.The silica gel material sold extensively on the market is applicable, and grain size is from nano-scale
Grain arrives 5-30mm, meanwhile, pore diameter range is also very wide, and pore diameter range preferably is
Another advantage of this method be by series reaction (such as it is acid catalyzed partially polymerized, free radical addition and
Synthesis) prepare the chemical formula i compound with very high functional group's load.Further advantage includes：A) this method can be same anti-
Answer in container and carry out, and operating procedure is simple；B) can be by the reaction condition of changing section polymerization composition easily
Realize the design of chemical formula i compound and the change of structure；Added in synthesis step different relative ratios Formulae II and
Formula iii silane.Another advantage：The efficiency high of solvent is recycled up to more than 90%.
In further technique, the respective mixture and silicon of the different compounds of collosol and gel, Formulae II and formula iii
Sour sodium or alkoxy silane (such as tetraethyl orthosilicate) are reacted in a solvent with acid or base catalyst, at a temperature of 20-160 DEG C
Reaction 0.5-48 hours.Then solid abrasive, washing are obtained into Formula I to remove the reactant of any residual after drying
Compound.Typical bronsted lowry acids and bases bronsted lowry used is hydrochloric acid and ammoniacal liquor respectively.Solvent includes but is not limited to methanol, ethanol, water and its mixture.
Formulae II and formula iii compound can use known method either individually or as mixture (including alkane
TMOS, such as tetraethyl orthosilicate) it is connected on various surfaces to obtain the film of Formula I.
Chemical formula i compound can be connected with metal complex, such as part.Invention further provides include gold
Belong to complex compound M (L)tChemical formula i compound, wherein M derived from oxidation state for 0 to 4 lanthanide series, actinides, main group
Or transition metal, L be one or more parts that can optionally replace, and selected from halide, nitrate, acetate, carboxylate,
Cyanide, amine, sulfate, carbonyl, imines, alkoxy, triaryl or trialkyl phosphine and phenoxy group, t be from 0 to 8 it is any whole
Number, chemical formula i compound is connected to above-mentioned metal complex.
Chemical formula i compound tool has been widely used.The method of charging is handled the invention provides a kind of, including makes chemistry
Compound of formula I is contacted with charging：
I) one or more compositions of charging are removed, a kind of material without the removal composition is generated；
Ii charging) is flowed through into chemical formula i compound, heterogeneity is separated；
Iii a kind of ionic state in charging) is removed by ion-exchange.
Charging can be continuous fluid (such as technique stream or intermediate flow), or can be for a collection of of discrete processes
Material.It can remove as the specific composition in product stream, waste liquid or this kind of charging of technique stream.The composition being removed can be into
Unwanted composition in material, and the charging that the technique is obtained after charging is contacted with chemical formula i compound is only containing required
Composition, the composition that need to be selectively removed has exhausted.The technique can be used for the charging for removing medicine manufacturing process or process for preparation
Unwanted target component (such as metal) in material, so as to improve the purity of drug products.
The technique can be used for removing required material from charging, and then it is processed or analyzed, such as from entering
Remove biomolecule in material, such as enzyme, peptide, protein, endotoxin and nucleic acid, then to remove composition is further processed
Or analysis.
Chemical formula i compound has high-affinity, can remove the metal combined closely with part, such as in highly polar activity
Metal in drug ingedient.Noble metal (such as palladium, platinum, rhodium, nickel) can be used as catalyst, to prepare the product of high value high-purity.
These metals exist in different forms after production procedure.
Contain the technique stream or product of palladium using example 1-2,4-8,14 any product treatment, as a result the palladium in solution
It is removed completely.For product stream and technique stream containing the palladium residue from palladium (0) catalyst, example 1-2,4,6-7,13
Product have same effect for the removal of palladium.The load of metal is high, and every kilogram of functionalization material can remove 60-120g palladiums.
Contain the hydroformylation process stream of diversified forms rhodium using example 1-2,4-8,10-11 product treatment, finally
The concentration of remaining rhodium is less than 1ppm.
Noble metal platinum is used in all kinds of different techniques and application.For example, using platinum catalysis in hydrosilylation reactions
Always there is platinum in agent, or can only realize low-level removal to produce in silane and siloxanes, end product.Use Formula I chemical combination
The level of wherein residual platinum can be down to extremely low level by this product of thing processing and technique stream.Example includes 1-2, the and of 4-6,8,11
15。
A series of metal concentration to be recycled in metals, usual waste liquid is included in the technique stream and waste stream of mining industry very
It is low, without metal concentration it is relatively much higher, case：Noble metal (such as platinum, palladium, rhodium, iridium, ruthenium and gold) is dense in certain solution
Spend for 2-20ppm, the melting concn of iron copper zinc is 500-50,000ppm.Chemical formula i compound is being selectively removed your specific gold
It is highly effective in terms of category.The technique realizes high metal load, and every kilogram of functionalised materials can remove 60-120g noble metals.It is real
Example includes 1-2,4-6,8,11 and 15.
Chemical formula i compound effectively extracts large-scale cation and anion from various environment.Cation
Including lanthanide series, actinides, main group and transition metal.Anion include arsenate, borate, chromate, permanganate,
Perchlorate and perrhenate.For example, example 1-5,8-12 and 14-15 product from all kinds of solution for removing cuprous and copper
Ion is highly effective.The functionalization material obtains very high copper load capacity (100-140g/kg).
Target needed for chemical formula i compound is optionally removed from complex mixture.There is copper in spent acid stream, simultaneously
There are other high concentration metals (including zinc, nickel, lead, arsenic).Effective technology is currently had no to be optionally sequestered copper, and loss
The value of copper.In addition, for this kind of waste liquid, also needing to carry out careful environmental management.Chemical formula i compound can be useless from these
Copper is optionally removed with very high efficiency in acid stream.For example, to containing copper (1-8,000ppm), arsenic (1-8,000ppm),
Certain spent acid stream of zinc (1-2,000ppm) and nickel (200-1,000ppm), selective removal is realized using example 8-14 product
With the high capacity of copper.Copper can be recycled, and functionalization material can also be reused.The technique is without using any toxicity
Process chemical.
Chemical formula i compound can realize synthesis in solid state by connecting parent material.Then series of chemical is carried out,
Purification is completed by simply washing reagent in each step.Finally, solid phase material discharges required material.
In addition, chemical formula i compound can be used as the material of solid phase extractions, required product is retained in by function by selectivity
Change on material, and allow impurity to flow through functionalization material to purify product.Then required product is discharged using different solvents.
Chemical formula i compound can also be further used as chromatographic separation material.
Embodiment
Now, the present invention is described in detail with reference to the illustrative example of the present invention.
Example 1
Under the conditions of 120 DEG C, allylthiourea (2mol) was added equipped with 3-MPTMS agitating solutions in 30 minutes
In the 2L reactors of (408.0mL, 2.6mol).Continue to heat 3 hours, during which added tert-butyl peroxide every 15 minutes
(1mL).Then solution is cooled to 40 DEG C, obtains silane A.
At 70 DEG C, vinyl silanes (4mol) were added in 15 minutes in thioacetic acid (4.8mol), will be mixed
Thing is stirred 2 hours, during which adds tert-butyl peroxide (2mL) every 10 minutes.Then dibutyl amine (3mol) is added, will be mixed
Thing is slowly heated 1 hour at 70 DEG C, is then cooled down, and obtains silane B.
By silica gel (37-147 μm,2.2kg) add the 20L equipped with dimethylbenzene agitating solution (4.5L) anti-
Answer in kettle.Add silane A, by reactant mixture at 120 DEG C heating stirring 1 hour.Then silane B is added, reaction is mixed
Thing is stirred under heating 5 hours.Cooled and filtered solid, is fully washed and dried with methanol (4 × 5L), obtain the one of Formula I
Composition is planted, wherein X is (CH2)2SH；Y is (CH2)3SC3H6NHC (=S) NH2；V is (CH2)3SH；M average value is 10；N=
0；D=0.
Example 2
Under the conditions of 120 DEG C, allylthiourea (2.5mol) was added in 30 minutes equipped with 3-MPTMS solution
In the 2L reactors of (5.0mol is heated 2 hours at 80 DEG C with pyrovinic acid (0.005mol) in advance).Continue to heat 3 hours,
Period added tert-butyl peroxide (1mL) every 15 minutes.Solution is cooled to 40 DEG C, then this solution is added to and is equipped with
Stirring mixture silica gel (147-400 μm,3.4kg) and in the 20L reactors of dimethylbenzene (7.8L), 120
Continue heating stirring at DEG C 1 hour.Then 3-MPTMS (2.0mol) is added, reactant mixture is stirred under heating 5 hours.It is cold
But filter solid is crossed afterwards, is fully washed and dried with methanol (4 × 5L), a kind of composition of chemical formula I is obtained, and wherein X is (CH2)2SH；V is (CH2)3SH；F is S；M average value is 15；N=0；P average value is 5；C=0.
Example 3
Under the conditions of 120 DEG C, pi-allyl urea (2.5mol) was added in 30 minutes equipped with 3-MPTMS solution
In the 2L reactors of (3.0mol is heated 1 hour at 70 DEG C with pyrovinic acid (0.001mol) in advance).Continue to heat 3 hours,
Period added tert-butyl peroxide (1mL) every 15 minutes.Then solution is cooled to 80 DEG C, adds pyrovinic acid
(0.01mol), is then heated 1.5 hours under the conditions of 90 DEG C, and this solution is added to equipped with stirring mixture silica gel (200-
500μm、1kg) and in the 10L reactors of dimethylbenzene (2L), continue heating stirring at 120 DEG C cooled after 5 hours
Filter.Solid after filtering is fully washed and dried with methanol (4 × 2L), a kind of composition of chemical formula I is obtained, wherein X is
(CH2)3SH；V is (CH2)3SH；F is O；M average value is 5；N=0；P average value is 5；C=0.
Example 4
Under the conditions of 120 DEG C, allylthiourea (2.5mol) was added in 30 minutes equipped with 3-MPTMS solution
In the 2L reactors of (3.0mol).Continue to heat 3 hours, during which added tert-butyl peroxide (1mL) every 15 minutes.Then
Solution is cooled to 90 DEG C, p-methyl benzenesulfonic acid (0.01mol) is added, then proceedes to heating stirring 1 hour, this solution is added to
Equipped with stirring mixture silica gel (37-74 μm,4kg) and in the 20L reactors of dimethylbenzene (8.2L), 120
Continue heating stirring at DEG C 1 hour.3-MPTMS (2.0mol) is added, this reactant mixture is continued to cool down after heating 5 hours
Filtering.Solid after filtering is fully washed and dried with methanol (4 × 8L), a kind of composition of chemical formula I, wherein X is obtained
For (CH2)3SH；Y is (CH2)3SC3H6NHC (=S) NH2；M average value is 3；C is 0；D average value is 6；V is (CH2)3SH。
Example 5
Under the conditions of 120 DEG C, allylthiourea (2.5mol) was added in 30 minutes equipped with 3-MPTMS agitating solutions
In the 2L reactors of (408.0mL, 2.2mol).Continue to heat 3 hours, during which added tert-butyl peroxide every 15 minutes
(1mL).Then solution is cooled to 70 DEG C, adds pyrovinic acid (0.001mol), then proceed to heating stirring 0.5 hour, so
Solution is cooled to 40 DEG C afterwards, silane A is obtained.At 120 DEG C, allylthiourea (1.5mol) was added to dress in 30 minutes
In the 2L reactors for having 3-MPTMS agitating solutions (408.0mL, 2.2mol).Continue to heat 3 hours, during which added every 15 minutes
Enter tert-butyl peroxide (1mL).Then solution is cooled to 40 DEG C, obtains silane B.At 70 DEG C, by vinyl silanes
(2mol) was added in 15 minutes in thioacetic acid (3mol), is stirred the mixture for 2 hours, was during which added uncle every 10 minutes
Butylperoxide (1mL).Then di-n-propylamine (3mol) is added, mixture is slowly heated 1 hour, Ran Houleng at 70 DEG C
But, silane C is obtained.By silica gel (200-500 μm,5kg) it is added to equipped with dimethylbenzene agitating solution (10L)
In 20L reactors.Add silane A, B and C, by reactant mixture at 120 DEG C heating stirring 6 hours.Cooled and filtered solid,
Fully washed and dried with methanol (4 × 10L), obtain a kind of composition of Formula I, wherein X is (CH2)2SH；Y is (CH2)3SC3H6NHC (=S) NH2；M average value is 10；N average value is 6；F is S；P average value is 3；V is (CH2)3SH。
Example 6
Under the conditions of 120 DEG C, allylthiourea (2.5mol) was added in 30 minutes equipped with 3-MPTMS agitating solutions
In the 2L reactors of (2.2mol).Continue to heat 3 hours, during which added tert-butyl peroxide (1mL) every 15 minutes.Then
Solution is cooled to 100 DEG C, pyrovinic acid (0.01mol) is added, then proceedes to heating stirring 1.5 hours, it is then that solution is cold
But to 40 DEG C, silane A is obtained.At 80 DEG C, vinyl silanes (2mol) were added to thioacetic acid (3mol) in 15 minutes
In, this mixture is stirred 3 hours, during which tert-butyl peroxide (2mL) was added every 10 minutes.Then morpholine is added
(3mol), this mixture is slowly heated 1 hour at 70 DEG C, then cools down, obtains silane B.By silica gel (147-400 μm,2.2kg) it is added in the 20L reactors equipped with dimethylbenzene agitating solution (4.5L).Add silane A, B and benzene
Base trimethoxy silane (0.2mol), by reactant mixture at 120 DEG C heating stirring 1 hour.Cooled and filtered solid, uses first
Alcohol (4 × 5L) is fully washed and dried, and obtains a kind of composition of Formula I, and wherein X is (CH2)2SH；Y is (CH2)3SC3H6NHC (=S) NH2；V is phenyl；M average value is 3；N average value is 14；P is 0.
Example 7
Under the conditions of 120 DEG C, allylthiourea (2.5mol) was added in 30 minutes equipped with 3-MPTMS agitating solutions
In the 2L reactors of (408.0mL, 2.2mol).Continue to heat 3 hours, during which added tert-butyl peroxide every 15 minutes
(1mL).Then solution is cooled to 90 DEG C, adds pyrovinic acid (0.001mol), then proceed to heating stirring 1.5 hours, so
Solution is cooled to 40 DEG C afterwards, silane A is obtained.Under the conditions of 120 DEG C, allylthiourea (1.5mol) was added in 30 minutes
Into the 2L reactors equipped with 3-MPTMS agitating solutions (408.0mL, 2.2mol).Continue to heat 3 hours, during which every 15 points
Clock adds tert-butyl peroxide (1mL).Then solution is cooled to 70 DEG C, adds pyrovinic acid (0.001mol), Ran Houji
Continuous heating stirring 1.5 hours, is then cooled to 40 DEG C by solution, obtains silane B.Under the conditions of 80 DEG C, by vinyl silanes
(2mol) was added in 15 minutes in thioacetic acid (3.4mol), is stirred the mixture for 2 hours, was during which added every 10 minutes
Tert-butyl peroxide (0.2mL).Then di-n-propylamine (3mol) is added, mixture 1 hour is slowly heated at 70 DEG C, then
Cooling, obtains silane C.By silica gel (200-400 μm,3kg) it is added to equipped with dimethylbenzene agitating solution (6L)
20L reactors in.Add silane A, B and C, by reactant mixture at 120 DEG C heating stirring 6 hours.Cooled and filtered is consolidated
Body, is fully washed and dried with methanol (4 × 6L), obtains a kind of composition of chemical formula I, and wherein X is (CH2)2SH；Y is
(CH2)3SC3H6NHC (=S) NH2；V is (CH2)3SH；M average value is 10；N average value is 6；P average value is 3；F is
S；V is (CH2)3SH。
Example 8
Under the conditions of 120 DEG C, allylthiourea (8.2mol) was added in 30 minutes equipped with 3-MPTMS solution
In the 2L reactors of (8.0mol is heated 2 hours at 80 DEG C with pyrovinic acid (0.05mol) in advance).Continue to heat 3 hours,
Period added tert-butyl peroxide (2mL) every 15 minutes.Then solution is cooled to 40 DEG C, this solution is added to and is equipped with
Silica gel (37-147 μm,2.2kg) stirred with dimethylbenzene (4.7L) in the 20L reactors of mixture, at 120 DEG C
Lower continuation heating stirring cold filtration after 8 hours.Solid after filtering is fully washed and dried with methanol (4 × 5L), is obtained
A kind of composition of chemical formula I, wherein X is (CH2)3SH；V is (CH2)3SH；F=S；M average value is 3；P=0；N's is averaged
Value is 5.
Example 9
Under the conditions of 120 DEG C, allylthiourea (41mol) was added in 30 minutes equipped with 3-MPTMS solution
In the reactor of (40.0mol, methylate sulfonic acid (0.08mol) and 100mL water are heated 2 hours at 90 DEG C in advance).Continue to add
Heat 3 hours, during which added tert-butyl peroxide (10mL) every 15 minutes.Then solution is cooled to 40 DEG C, by this solution
Be added to equipped with silica gel (147-400 μm,14kg) stirred with dimethylbenzene (30L) in the reactor of mixture,
Continue heating stirring at 120 DEG C 6 hours, after then reactant mixture is filtered, washed and dried with methanol (4 × 30L), obtained
To a kind of composition of chemical formula I, wherein X is (CH2)3SH；V is (CH2)3SH；M average value is 3；P=0；N average value
It is 7.
Example 10
Under the conditions of 120 DEG C, allylthiourea (88mol) was added in 30 minutes equipped with 3-MPTMS solution
In the 50L reactors of (80.0mol, methylate sulfonic acid (0.8mol) and 100mL water are heated 2 hours at 90 DEG C in advance).Continue
Heating 3 hours, during which added tert-butyl peroxide (20mL) every 15 minutes.Then solution is cooled to 40 DEG C, this is molten
Liquid be added to equipped with silica gel (147-400 μm,The 200L reactions of mixture 30kg) are stirred with dimethylbenzene (60L)
In kettle, then reactant mixture is cooled down, filtered and fully washed with methanol (4 × 60L) by heating stirring 6 hours at 120 DEG C
And dry, a kind of composition of chemical formula I is obtained, wherein X is (CH2)3SH；F=S；M average value is 5；P=0；N's is averaged
Value is 8.
Example 11
Under the conditions of 120 DEG C, allylthiourea (88mol) was added in 30 minutes equipped with 3-MPTMS solution
In the 50L reactors of (80.0mol, methylate sulfonic acid (2mol) and 100mL water are heated 2 hours at 90 DEG C in advance).Continue to add
Heat 3 hours, during which added tert-butyl peroxide (20mL) every 15 minutes.Then solution is cooled to 40 DEG C, by this solution
Be added to equipped with silica gel (147-400 μm,The 200L reactors of mixture 30kg) are stirred with dimethylbenzene (60L)
In, then reactant mixture is cooled down, filtered and fully washed simultaneously with methanol (4 × 60L) by heating stirring 6 hours at 120 DEG C
Dry, obtain a kind of composition of chemical formula I, wherein X is (CH2)3SH；F=S；M average value is 5；P=0；N average value
It is 8.
Example 12
Under the conditions of 120 DEG C, allylthiourea (1.1mol) was added in 30 minutes equipped with 3-MPTMS solution
In the 2L reactors of (1.0mol, methylate sulfonic acid (0.02mol) and 1mL water are heated 2 hours at 90 DEG C in advance).Continue to heat
3 hours, during which added tert-butyl peroxide (0.2mL) every 15 minutes.Then solution is cooled to 40 DEG C, this solution is added
Enter into the stirring mixture for the tetraethyl orthosilicate (6mol) being dissolved in methanol (3L) and 1M HCl (0.4L).This is mixed
Compound is heated at 80 DEG C until methanol volatilization has glass to be formed.By obtained glass grinding, then stirred in the methanol of backflow
Filtering is mixed, a kind of compound of chemical formula I is obtained after drying, wherein X is (CH2)3SH；F=S；M average value is 5；P=0；n
Average value be 8.
Example 13
Under the conditions of 120 DEG C, allylthiourea (1.1mol) was added in 30 minutes equipped with 3-MPTMS agitating solutions
In the 2L reactors of (1.0mol adds methanesulfonic acid (0.02mol) and water (1mL) to heat 2 hours at 90 DEG C in advance).Further plus
Heat 3 hours, during which added tert-butyl peroxide (0.2mL) every 15 minutes.Then solution is cooled to 40 DEG C, then added
To be dissolved in methanol (3L) and with the stirring mixture of 1M HCl (0.4L) tetraethoxysilane (8mol).By this mixture
Heated at 80 DEG C until methanol volatilization has glass to be formed.By after obtained glass grinding in the methanol of backflow agitation and filtration,
A kind of compound of Formula I is obtained after drying, wherein X is (CH2)3SH；F=S；M average values are 5；P is 0；N average values are
8)。
Example 14
Under the conditions of 120 DEG C, allylthiourea (1.1mol) was added in 30 minutes equipped with 3-MPTMS agitating solutions
In the 2L reactors of (1.0mol adds methanesulfonic acid (0.02mol) and water (1mL) to heat 2 hours at 90 DEG C in advance).Further plus
Heat 3 hours, during which added tert-butyl peroxide (0.2mL) every 15 minutes.Then solution is cooled to 40 DEG C, then added
Stir and be dissolved in 3M HCl (3L) sodium metasilicate (8mol).This mixture is heated at 80 DEG C until glass is formed.Will
After obtained glass grinding in the deionized water of backflow agitation and filtration, a kind of compound of Formula I is obtained after drying, wherein
X is (CH2)3SH；F=S；M average value is 5；P is 0；N average value is 8.
Example 15
Under the conditions of 120 DEG C, allyl amine (2.5mol) was added in 30 minutes equipped with 3-MPTMS agitating solutions
In the 2L reactors of (3.0mol adds methanesulfonic acid (0.001mol) to heat 1 hour under the conditions of 70 DEG C).Further heat 3 hours,
Period added tert-butyl peroxide (1mL) every 15 minutes.Then solution is cooled to 80 DEG C, adds methanesulfonic acid
(0.01mol), then heats solution 1.5 hours under the conditions of 90 DEG C.This solution is added to equipped with dimethylbenzene (2L) and silicon
Glue (200-500 μm,1kg) in the 10L reactors of stirring mixture, heating stirring is after 5 hours under the conditions of 120 DEG C
Cold filtration.The solid of filtering fully washs (4 × 2L) with methanol, and a kind of composition of Formula I is obtained after drying, wherein, X
It is (CH2)3SH；Y is (CH2)3SC3H6NH2；V is (CH2)3SH；M average value is 5；N is 0；P average value is 5；C is 0.
Example 16
Under the conditions of 120 DEG C, pi-allyl butyl ether (2.5mol) was added in 30 minutes equipped with 3-MPTMS agitating solutions
In the 2L reactors of (3.0mol adds methanesulfonic acid (0.001mol) to heat 1 hour under the conditions of 70 DEG C).Further heat 3 hours,
Period added tert-butyl peroxide (1mL) every 15 minutes.Solution is cooled to 80 DEG C, methanesulfonic acid (0.01mol) is added simultaneously
Heated 1.5 hours under the conditions of 90 DEG C.By solution be added to equipped with dimethylbenzene (2L) and silica gel (200-500 μm,
1kg) in the 10L reactors of stirring mixture, cold filtration after being heated 5 hours under the conditions of 120 DEG C.The solid methanol of filtering
(4 × 2L) is fully washed, and a kind of composition of Formula I is obtained after drying, wherein, X is (CH2)3SH；Y is (CH2)3SC3H6OC4H9；V is (CH2)3SH；M average value is 5；N is 0；P average value is 5；C is 0.
Example 17
The product (0.05g) of example 1 is added in certain product stream sample (6mL) of the iridium containing 205ppm, in the product stream
Iridium be derived from the iridium chloride that uses.Filtered after mixture is stirred 1 hour under the conditions of 30 DEG C, analysis filtrate shows that iridium is gone
Remove.Example 2,4-7 and 12-14 have same effect in this experiment.
Example 18
The product (0.03g) of example 2 is added in certain product stream sample (10mL) of the iridium containing 55ppm, in the product stream
Iridium be derived from double (triphenyl phosphorus base) iridium (I) of catalyst carbonyl chlorine used.After mixture is stirred 6 hours under the conditions of 60 DEG C
Filtering, analysis filtrate shows that iridium has been removed.Example 4-7 has same effect in this experiment.
Example 19
The product (0.03g) of example 1 is added in certain technique stream sample (3mL) of the rhodium containing 150ppm, in the technique stream
Rhodium be derived from Wilkinson catalyst triphenylphosphine radium chloride (I) used.Mistake after 8 hours is stirred at room temperature in mixture
Filter, analysis filtrate shows that rhodium has been removed.Example 4-7 and 9-11 have same effect in this experiment.
Example 20
The product (0.03g) of example 7 is added in certain technique stream sample (3mL) of the rhodium containing 240ppm, in the technique stream
Rhodium be derived from catalyst dicarbonyl rhodium acetylacetonate (I) used.Mixture was stirred at room temperature after 12 hours and filtered, analysis
Filtrate shows that rhodium has been removed.Example 1-2,4-6 and 12-14 have same effect in this experiment.
Example 21
The product (0.01g) of example 5 is added in certain product stream sample (3mL) of the palladium containing 60ppm, in the product stream
Rhodium is derived from catalyst acetic acid palladium used.Filtered after mixture is stirred 30 minutes under the conditions of 30 DEG C, analysis filtrate shows palladium
It has been removed.There is same effect example 1-2,4,6-8 and 14 in this experiment.
Example 22
The product (0.03g) of example 6 is added in certain product stream sample (3mL) of the palladium containing 120ppm, in the product stream
Palladium be derived from catalyst tetra-triphenylphosphine palladium (0) used.Filtered after mixture is stirred 2 hours under the conditions of 50 DEG C, analysis
Display palladium has been removed.
Example 23
The product (0.03g) of example 7 is added in certain product stream sample (2mL) containing 200ppm palladiums, the product stream
In palladium be derived from the palladium (0) of catalyst three (dibenzalacetone) two used.After mixture is stirred 6 hours under the conditions of 60 DEG C
Filtering, analysis filtrate shows that palladium has been removed.There is same effect example 1-2,4 and 13 in this experiment.
Example 24
The product (0.04g) of example 2 is added in certain technique stream sample (15mL) of the platinum containing 50ppm, in the technique stream
Platinum be derived from catalyst chloroplatinic acid used.Filtered after mixture is stirred 6 hours under the conditions of 80 DEG C, analysis filtrate shows platinum
It has been removed.There is same effect example 1,4-6 and 15 in this experiment.
Example 25
The product (100g) of example 5 is fitted into adsorption column, under the conditions of 50 DEG C, certain silane containing 40ppm platinum given up
Technique stream (20L) flows through the adsorption column.Fluid after analyzing and processing shows that the remaining content of platinum is less than 1ppm.
Example 26
The product (100g) of example 6 is fitted into adsorption column, under the conditions of 80 DEG C, by certain hydrogenation first containing 300ppm rhodiums
Acylation process waste liquid flows through the adsorption column.Fluid after analyzing and processing shows that the remaining content of rhodium is less than 1ppm.
Example 27
The product (0.04g) of example 12 is added in certain technique stream sample (4mL) of the ruthenium containing 50ppm, in the technique stream
Ruthenium be derived from double (thricyclohexyl phosphorus) ruthenous chlorides of Ge Labu catalyst phenylmethylene used.By mixture in 30 DEG C of conditions
Lower stirring is filtered after 6 hours.Analysis filtrate shows that ruthenium has been removed.
Example 28
The product (100g) of example 6 is loaded into fixed bed, zinc-iron total concentration 10,000ppm, 4ppm platinum, 4ppm will be contained
Certain solution (30L) of palladium, 3ppm rutheniums and 1.5ppm rhodiums flows through the fixed bed with 0.3L/h flow velocity.Optionally gone from solution
Except palladium (99%), platinum (99%), ruthenium (60%) and rhodium (90%).Example 1-2 and 4-5 is also effective in this experiment.
Example 29
The product (0.2g) of example 4 is added in certain technique stream sample (40mL's) of the copper containing 60ppm, in the technique stream
Copper be derived from certain copper (I) catalyst used.Mixture was slowly stirred at a room temperature after 2 hours and filtered.Analysis filtrate shows
Copper has been removed.Example 8-11 is also effective in this experiment.
Example 30
Certain process waste liquor of the copper containing 6000ppm is handled using the product (2.0g) of example 8.The product of example 8 is born to copper
Carrying capacity is 120g/kg.Similar result of the test is as follows：The product of example 9 is 105g/kg to the load capacity of copper；The product of example 10
Load capacity to copper is 150g/kg；The product of example 11 is 134g/kg to the load capacity of copper.
Example 31
PH is handled for 1.7 and copper containing 2,000ppm, 700ppm zinc, 200pmm nickel and 6 using the product (2.0g) of example 8,
Certain acid waste liquid of 800ppm arsenic.Copper in the waste liquid is selectively removed and zinc, nickel and arsenic are retained in waste liquid.
Example 32
The product (50g) of example 9 is fitted into adsorption column, by pH be 1.7 and containing 2,000ppm copper, 700ppm zinc,
Certain acid waste liquid of 200pmm nickel and 6,800ppm arsenic is passed through pillar, and retention time is 15-18mL/min.Copper is selectively removed
And the zinc, nickel, arsenic and other metals in waste liquid are retained in waste liquid.
Example 33
The product (50g) of example 10 is fitted into adsorption column, by pH be 1.7, containing 6,000ppm copper, 1000ppm zinc,
Certain acid waste liquid of 200pmm nickel and 5,500ppm arsenic is passed through pillar, and retention time is 15-18mL/min.Copper is selectively removed
And the zinc, nickel, arsenic and other metals in waste liquid are retained in waste liquid.
Claims (14)
1. a kind of method for producing following chemical formula i compound：
[(O2/2)SiXO[SiO1/2XO]m]a[Si(O4/2)]b[(O2/2)SiYO[SiO1/2YO]n]c[(O2/2)SiZO[SiO1/2ZO]p]d
[VSi(O3/2)]e(Formula I)
In formula, X is (CH2)sSH；Y is (CH2)sSC3H6NHC (=F) NHR2, wherein F is O, S, (CH2)sSC3H6NHR2Or (CH2)sSC3H6OR2, Z is X or Y；S is 2 to 20 integer；M, n and p be respectively 0 to 100 an integer, and m, n or p in wherein one
It is individual to be consistently greater than 0；R2It is hydrogen, straight or branched C1-22- alkyl, C1-22- alkylaryl, aryl；V is the group optionally replaced,
Selected from C1-22- alkyl, C1-22- alkylaryl, aryl, C2-20- alkyl sulfide ether, C1-12Alkyl, C2-20- alkylen thioether alkyl,
C2-20- alkyl thioether aryl, C2-20- alkylen thioether aryl；A, b, c, d and e are integers, and a+c+d：B ratio is
0.00001 to 100000, a, b and c/d exist all the time, when e is more than 0, e：A+b+c+d ratio is 0.000001 to 100；
Pass through one or more silicon atoms of other groups, hydrogen, straight or branched C in Formula I1-22Alkyl, end group R3SiO1/2、
Crosslinking agent or chain RqSi(OR1)gOk/2Wherein one or more make the free valency saturation of silicate oxygen atom, wherein R and R1
It is respectively selected from straight or branched C1-12Alkyl, aryl and C1-22Alkylaryl, R3Selected from straight or branched C1-12Alkyl, k be from
1 to 3 arbitrary integer, q is the arbitrary integer from 1 to 2, and g is the arbitrary integer from 0 to 2, and meets g+k+q=4, works as end
In the presence of base, crosslinking agent and/or polymer chain, its mol ratio and a+b+c ratio are from 0 to 999:Between 1.
2. a kind of composition according to claim 1, and X in Formula I is (CH2)sSH, Y are (CH2)sSC3H6NHC
(=S) NHR2, Z is X or Y, s are arbitrary integers from 2 to 4, m, n and p be respectively 0 to 20 arbitrary integer and m, n or p wherein
One of be consistently greater than 0, R2It is hydrogen, straight or branched C1-6- alkyl, V is the group optionally replaced and is selected from C1-6- alkyl, virtue
Base, C2-20- alkyl sulfide ether, a, b, c, d, e are integer and a+c+d：B ratio is 0.00001 to 100,000, a, b and c/
D exists all the time, when e is more than 0, e：A+b+c+d ratio is 0.000001 to 100；
Pass through one or more silicon atoms of other groups, hydrogen, straight or branched C in Formula I1-22Alkyl, end group R3SiO1/2、
Crosslinking agent or chain RqSi(OR1)gOk/2Wherein one or more make the free valency saturation of silicate oxygen atom, wherein R and R1
It is respectively selected from straight or branched C1-6Alkyl, aryl and C1-22Alkylaryl, R3Selected from straight or branched C1-6Alkyl, k is from 1
To 3 arbitrary integer, q is the arbitrary integer from 1 to 2, and g is the arbitrary integer from 0 to 2, and meets g+k+q=4, works as end
In the presence of base, crosslinking agent and/or polymer chain, its mol ratio and a+b+c ratio are from 0 to 999:Between 1.
3. formula iii is [(R3O)2SiWO][SiX(OR3)O]m][SiY(OR3)O]n[SiZ(OR3)1ZO]p[OWSi(OR3)2]
A kind of compound, in formula, W is any one in X, Y, Z；X is (CH2)sSH；Y is (CH2)sSC3H6NHC (=F) NHR2,
Wherein F is O, S, (CH2)sSC3H6NHR2Or (CH2)sSC3H6OR2；Z is any one in X or Y；S be from 2 to 20 it is any
Integer；R2It is hydrogen, straight or branched C1-12- alkyl, C1-22- alkylaryl, aryl；R3Selected from straight or branched C1-12Alkyl；m、n
It is respectively 0 to 100 integer with p, and one of them in m, n or p is consistently greater than 0.
4. formula iii is [(R3O)2SiWO][SiX(OR3)O]m][SiY(OR3)O]n[SiZ(OR3)1ZO]p[OWSi(OR3)2]
A kind of compound, in formula, W is any one in X, Y, Z；X is (CH2)sSH；Y is (CH2)sSC3H6NHC (=S) NHR2；Z
It is any one in X or Y；S is the arbitrary integer from 2 to 4；R2It is hydrogen, straight or branched C1-6- alkyl, C1-22- alkyl virtue
Base, aryl；R3Selected from straight or branched C1-6Alkyl；M, n and p are respectively the arbitrary integer from 0 to 20, and m, n or p are therein
It is one or more to be consistently greater than 0.
5. a kind of method for manufacturing formula iii compound, wherein, W is any one in X, Y, Z；X is (CH2)sSH；Y is
(CH2)sSC3H6NHC (=F) NHR2, wherein F is O, S, (CH2)sSC3H6NHR2Or (CH2)sSC3H6OR2；Z is any in X or Y
One；Preparation method is as follows：
I. Formulae II (R3O)3The corresponding silane of SiW and silane combination are partially polymerized through acid catalysis, wherein, W is (CH2)sSC3H6NHC (=S) NHR2、(CH2)sSC3H6NHC (=O) NHR2、(CH2)sSH、(CH2)sSC3H6NHR2Or (CH2)sSC3H6OR2,
Wherein s is the arbitrary integer from 2 to 20；R2It is hydrogen, straight or branched C1-12- alkyl, C1-22- alkylaryl, aryl；R3It is selected from
Straight or branched C1-12Alkyl；Use non-aqueous acid, including but not limited to methanesulfonic acid, p-methyl benzenesulfonic acid, phosphoric acid, thioacetic acid, acid
Mol ratio relative to silane is 0.001 to 0.01, and reaction temperature is 70-120 DEG C, and the reaction time is 0.5-5 hours；Or
Ii. the silane of Formulae II is partially polymerized through acid catalysis, and W is (CH in formula2)sSH, is then being had using radical initiator
Solvent or solvent-free situation and unsaturated carbon-carbon bond (such as CH of appropriate alkene2CHCH2NHC (=S) NHR2、
CH2CHCH2NHR2、CH2CHCH2OR2Or CH2CHCH2NHC (=O) NHR2) occur Radical Addition, in 20-160 DEG C of temperature
Degree lower reaction 0.5-24 hours；Common solvent has dimethylbenzene, toluene, heptane, glycol, ethanol, methanol；Workable free radical
Initiator includes but is not limited to azodiisobutyronitrile, benzoyl peroxide, TBHP, tert-butyl peroxide.
6. a kind of method according to claim 5, wherein, the W in formula iii is any one in X, Y, Z；X is
(CH2)sSH；Y is (CH2)sSC3H6NHC (=S) NHR2；Z is any one in X or Y；S is the arbitrary integer from 2 to 4；R2It is
Hydrogen, straight or branched C1-6- alkyl, C1-22- alkylaryl, aryl；R3Selected from straight or branched C1-6- alkyl.
7. a kind of method for generating chemical formula i compound, in a solvent by the various chemical combination of formula iii and/or Formulae II
Thing or the combination combination inorganic material of compound or surface, fit situation addition VSi (OR1)3, reacted at a temperature of 20-160 DEG C
0.5-4 hours；Optional solvent or solvent combination scope are very wide, including aliphatic series or aromatic hydrocarbon, alcohol and polar solvent such as dimethyl
Formamide and water.
8. a kind of feed processing, including contacted with the compound according to any claim in claim 1 to 2：
I) one or more compositions in charging are removed, a kind of material without the removal composition is generated；
Ii) one or more compositions in selective removal charging, so as to reuse the composition of the removal；Or
Iii a kind of ionic state in charging) is removed by ion-exchange.
9. a kind of compound according to any claim in claim 1 to 2, as functionalization material from liquid feedstock
Middle removal, selective removal reduce required or unwanted organic and inorganic or biologic artifact.
10. a kind of compound according to any one of claim 1 to 2 claim, as functionalization material from reaction
Removed in mixture, technique stream, product stream, waste liquid or waste water, selective removal or reduce noble metal such as platinum, palladium, rhodium iraurite ruthenium rhenium,
Rare earth metal and transition metal such as copper zinc-nickel, or removal, selective removal or reduction are bonded or tied with other organic compounds
The above-mentioned metal closed.
11. a kind of compound according to any claim in claim 1 to 2, as functionalization material from spent acidic
Copper removal is optionally removed in liquid.
12. a kind of compound according to any claim in claim 1 to 2, as functionalization material from spent acidic
Metal is optionally removed in liquid.
13. a kind of compound according to any claim in claim 1 to 2, as anions and canons exchanger.
14. a kind of compound according to any claim in claim 1 to 2, for from gas, liquid, solid ring
Isolated or purified is organic, biological in border or inorganic molecule.
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| CN107930601A (en) * | 2017-11-02 | 2018-04-20 | 苏州硒诺唯新新材料科技有限公司 | The new component of the new organically-modified silica gel material of poly and its use |
| CN109261224A (en) * | 2018-09-03 | 2019-01-25 | 苏州硒诺唯新新材料科技有限公司 | Functionalized silicon glue material and its production technology and use |
| CN109401364A (en) * | 2018-11-27 | 2019-03-01 | 湖北硒诺唯新功能化硅胶材料有限公司 | Functionalized silicon glue material and its production technology and use |
| CN110527097A (en) * | 2018-05-23 | 2019-12-03 | 王萌萌 | The novel synthetic and its production technology and purposes of improved silica |
| CN111992056A (en) * | 2020-07-08 | 2020-11-27 | 广东工业大学 | Functional magnetic-based dynamic membrane system and implementation method thereof |
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