CN107129575B - Functional material and its production process and use - Google Patents

Abstract

The invention relates to a novel composite of silica modified by a plurality of organic functional groups, the same composite contains a plurality of sulfydryl, sulfide, thiourea and other functional groups, the functional groups exist in different oligomers, configurations and stereochemical arrays, and the affinity and the selectivity to target metal and specific targets are obviously enhanced. In combination with different structural configurations further improve the ability to bind various forms of targets in actual process streams, product streams, and waste streams, multiple binding mechanisms achieve high levels of purification and selective removal of targets. The use of the compound comprises: product purification, removal of unwanted organic and inorganic compounds (including metals and metal complexes) from product streams, process streams and waste streams, selective removal of target components from a mixture in which multiple components coexist, use as chromatographic media for purification and separation of metals, metal complexes, organic and biological compounds, solid phase extraction, solid phase synthesis, metal ion extraction and biomolecule immobilization.

Description

Functional material and its production process and use

Technical Field

The invention relates to a novel composite (containing a plurality of sulfydryl, sulfide and thiourea groups) of silicon dioxide modified by a plurality of organic functional groups, a production process and application thereof. The material can be used for removing or selectively removing organic/inorganic compounds and metals from products, process streams, waste streams, or as anion and cation exchangers, metal chromatographic materials, solid phase purification or extraction materials, immobilization materials for biomolecules, antimicrobial agents, catalyst supports, hydrophilicity modifiers, flame retardants, antistatic agents, coatings for biomedical devices, controlled release materials, water resistant membranes and coatings, solid phase synthesis materials, and chromatographic materials. The invention also relates to the monomers required for producing the novel products and to a process for preparing these monomers.

Background

The continuous development of new technologies in various industries and market applications has led to increasingly stringent requirements for the purity of chemicals in the industry. For example, the pharmaceutical and biotechnology industries require organic, inorganic impurities to be reduced to lower levels; the electronics industry requires that the concentration of common residual metals (e.g., sodium, magnesium, iron) must be below 1 ppm.

There is a need for cleaner chemical processes to cope with the pressures imposed by society and law on environmental governance and to avoid or reduce the emission of waste, particularly to reduce the residual amounts of toxic metals and chemicals in the environment.

Currently, metals play a crucial role in technological development. Noble metals (such as platinum, rhodium, palladium, ruthenium, iridium, and gold) have limited resources, but are widely used in various industries. With the development of more application fields, it is expected that the available precious metal resources will not meet future demands. Because of their high cost, limited resources and toxicity, a highly efficient technique is sought for recovering and recycling such metals from products, processes, and waste streams. For example, in the petrochemical industry, such metals are recovered from associated products, processes and waste streams of hydroformylation and hydrosilylation reactions.

Metals are widely used in various applications in various industries. These metals are ultimately found in most different forms in different products, processes and waste streams. Specific technologies need to be applied to the formation, use, circulation, production process and waste liquid thereof, so as to realize higher metal recovery rate, improve recycling efficiency and selectivity, and reduce the influence on the environment. For example, in the mining & smelting industry, the treatment of residual metals (copper, nickel, iron) and metal-containing process chemicals (e.g., zinc) is a significant challenge, including the need for a new recovery and reuse technology.

The increasing use of rare earth metals (e.g., scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium) in many areas of industry has resulted in a need for more advanced techniques to more efficiently recover and reuse such metals from products, processes and waste streams.

In the smelting and purification process streams of the mining industry, high value metals (e.g. precious metals) are often present in low ppm concentrations and in other metals, sometimes the latter in significantly higher concentrations. To reduce the large losses of these high value metals, advanced techniques are required a) to remove the desired metals to very low residual concentrations; b) the low-concentration metal is efficiently treated; c) high value metals are selectively removed in the presence of higher concentrations of other metals.

In the mining industry, other metals (e.g. copper, nickel, iron, zinc) also require advanced techniques a) to remove the metal to very low residual concentrations; b) high efficiency in processing various levels of metal concentrations (high to low); c) selectively removing the target metal under the condition that other metals with different concentrations coexist; d) strong adsorption capacity to one or more target metals; e) one or more metals can be captured and recycled, and the technology itself can be reused.

The preparation of high value organic compounds or polymers generally requires a multi-step process and is accompanied by the production of by-products, isomers and impurities. In most cases, such products are to be purified, and in addition, a more efficient purification technique is required to remove a specific range of by-products, isomers and impurities coexisting with the target product. The prior art (e.g. crystallization) will result in substantial loss of product.

One technology currently being developed is that of functionalizing materials, which can be used for product purification, the selective removal of desired components from mixtures or the removal of toxic and/or high value metals or compounds from products, processes and waste streams. A liquid can be flowed through the functionalizing material to selectively remove the desired component. One of the functionalized materials is activated carbon. Depending on the process conditions, the carbon contains multiple oxygenated organic groups on its surface. Although carbon is inexpensive, its disadvantages include: a large loss of product; the removal performance is weak; the final product contains harmful compounds or metals. These disadvantages are caused because the alcohol, phenol, aldehyde and carboxylic acid functional groups on its surface are nonspecific and have poor properties.

Another class of functionalized materials for product purification is organic polymers. The organic polymer support comprises polystyrene and a polyolefin. Only a very limited number of individual functional groups may be attached to these supports, these functional groups including sulfonic acid or amine groups (primarily ion exchange mechanisms). Because of the low affinity of these functional groups for the metals discussed above, high levels of performance are not met with this class of organic polymeric materials. The main disadvantages of organic resins: the inability to attach desired functional groups to the organic polymer support; the functional group loading rate is low. Since only limited chemical manipulations can be performed on such polymers, it is unlikely that a large number of different multifunctional groups can be attached to these organic polymer backbones to achieve the targeted performance levels. In addition, its disadvantages include poor chemical properties, poor thermal stability, swelling and shrinkage in organic solvents. In general, there are severe limitations to the technologies developed for these organic frameworks.

Inorganic polymer systems include silica, alumina and titania, which have been disclosed as functionalizing materials. Inorganic polymeric carriers have several advantages over organic polymeric carriers, including better physical and chemical properties; stronger thermal stability; the regular pore structure on the material makes it easier to access functional groups on the surface; does not swell and is easier to operate.

Examples of simple functionalized inorganic materials: alkylamines and alkylthiols of the silicon, Johnson Matthey, Evonik and Phosphonics S (WO2006/013060, WO 2007/090676). However, a very small range of simple functional groups can only be attached to these frameworks by very limited chemical methods, and the functional group loading of such materials is low. For example, a 1kg loading range of the functionalized material (organic or inorganic framework) is 5-30g, often with actual loading values close to this lower limit.

The existing functionalized inorganic materials have a number of limitations: it is only applicable to a narrow range of simple monofunctional groups; the presence of only one or at most two heteroatoms results in a single binding mechanism, low affinity, low functional group loading, and in practical applications low payload of the target. This is due to a) the starting reagents (silanes) for making these materials are not readily available and are complex to produce; b) limited availability of reagents in the range of chemicals used or modified; c) limited chemistry for silane production; d) cost, based on chemical principles, silane is expensive to manufacture; e) it is difficult to adjust simple functional groups attached to the surface to more complex functional groups, and thus performance cannot be improved.

While functionalized inorganic materials represent some advancement over functionalized organic resins, further improvements are needed to meet current and future technical challenges such as lower residual levels, greater selectivity, higher target loading.

The prior art cannot design or prepare functionalized materials containing required complex functional groups according to actual commercial requirements. Based on the commercial, technical, environmental, social challenges currently and in the future, many market applications require new technologies to meet target performance levels.

In addition, new techniques are needed to selectively remove specific metals from complex mixtures. For example, high concentrations of copper are removed in the presence of multiple metals (zinc, nickel, arsenic). Case (2): the gas produced by ore smelting is purified with water to form an acidic fluid (spent acid liquor) containing various metals including, but not limited to, copper, precious metals, gold, zinc, nickel, lead, arsenic, selenium and antimony, from which copper is then selectively removed.

Other cases are as follows: residual metals in the pharmaceutical compound; metal catalysts in process effluents, such metals being present in different forms and different from the starting form, e.g. different oxidation states, mono-to nanoparticles, polymetallic substances (dissimilated complexes), metals being tightly bound to ligands. Furthermore, each time the production or flow of a pharmaceutical compound may result in differences in the actual composition of all forms of metal mentioned above. In order to meet the target purity of the product or capture metals, the functionalized material must contain specific complex functional groups to specifically bind the target. In addition, these functional groups need to be closely distributed and optimally arranged on the surface of the framework and within the pores to ensure that they can displace the ligand to the target in the liquid and then capture and retain the target. The binding mechanism required for each target may be different and therefore requires that the structure of the functionalized material be easily tuned to achieve the desired level of performance (i.e., low residual level of target), high selectivity and high target loading. In addition, the designed functional material must be resistant to high temperature, physically and chemically stable, highly loaded with functional groups, highly compatible with solvents, highly wettable, non-swellable, and have strong functional group affinity. To improve the cost effectiveness of the materials, it is necessary to ensure that the starting materials are readily available and have readily adjustable chemistry to prepare optimized, high affinity, high selectivity functionalized materials.

Disclosure of Invention

The inventors have successfully discovered a multifunctional compound that possesses all of the above-mentioned target properties and is flexible and simple in manufacturing process. The invention is suitable for a series of applications as follows: inorganic, organic compound and metal scavengers, selective scavengers of targets in complex mixtures, metal chromatography materials, solid phase purification or extraction materials, removal and purification of biological compounds, ion exchange materials, catalyst immobilization supports, immobilization materials of biomolecules (including enzymes), controlled release materials, antimicrobial agents, hydrophilic modifiers, flame retardants, antistatic agents, solid phase synthesis materials and chromatography materials, or monomers of all of the above materials. The first part of the invention provides compounds of formula I:

[(O_2/2)SiXO[SiO_1/2XO]_m]_a[Si(O_4/2)]_b[(O_2/2)SiYO[SiO_1/2YO]_n]_c[(O_2/2)SiZO[SiO_{1/ 2}ZO]_p]_d[VSi(O_3/2)]_e(chemical formula I)

Wherein X is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝F)NHR²Wherein F is O or S or (CH)₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²(ii) a Z is any one of X or Y; s is any integer from 2 to 20; m, n and p are each any integer from 0 to 100, and one of m, n or p is always greater than 0; r²Is hydrogen, straight or branched C_1-22Alkyl radical, C_1-22-alkylaryl, aryl; v is an optionally substituted group selected from C_1-22-alkyl radical、C_1-22Alkyl aryl, C_2-20Alkyl sulfide radical, C_1-12Alkyl radical, C_2-20Alkylene thioether alkyl, C_2-20Alkyl thioether aryl radical, C_2-20-an alkylene thioether aryl group; a. b, c, d, e are integers, and a + c + d: b is in the range of 0.00001 to 100,000, a, b and c/d are always present, and when e is greater than 0, e: the ratio of a + b + c + d is 0.000001 to 100.

By silicon atoms of other groups of formula I, hydrogen, straight or branched C_1-22Alkyl, terminal group R³SiO_1/2Crosslinking agent or chain R_qSi(OR¹)_gO_k/2Wherein one or more of R and R saturate the free valence of the silicate oxygen atom¹Are independently selected from straight chain or branched chain C_1-22Alkyl, aryl and C_1-22Alkyl aryl radical, R³Selected from straight or branched C_1-12Alkyl, k is any integer from 1 to 3, q is any integer from 1 to 2, g is any integer from 0 to 2, and g + k + q is 4, the ratio of the molar ratio to a + b + c + d + e, when end groups, crosslinkers and/or polymer chains are present, being 0-999: 1.

The optionally substituted linear or branched radical being selected from C_1-22Alkyl radical, C_2-22-alkenyl, C_2-22-alkynyl, aryl, C_1-22Alkylaryls, which may each be linear or branched and/or substituted by one or more substituents, but preferably contain only hydrogen and carbon atoms. If present, the substituents may be independently selected from amine, amide, nitro, chloro, fluoro, bromo, nitrile, hydroxy, carboxylic acid ester, sulfide, sulfoxide, sulfone, or C_1-6-alkoxy groups.

Preference is given to compounds of the formula I in which the ratio b: a + c + d is from 10,000 to 0.2; s is any integer from 2 to 4; m and p are each any integer from 0 to 20; n is from 1 to 20; r²Is hydrogen, straight or branched C_1-6-alkyl or aryl.

Particular preference is given to compounds of the formula I in which the ratio b: a + c + d is from 10,000 to 0.2; f is sulfur; s is an integer from 2 to 3; m and p are each any integer from 0 to 10; n isFrom 1 to 10; r²Is hydrogen, straight or branched C_1-4-alkyl or aryl.

In addition, the method for preparing the compound of the chemical formula I is simple and flexible, and the multielement organic functional compound, oligomer and polymer can be prepared from easily obtained starting materials by utilizing a novel chemical method and process. The design can be easily changed by only carrying out a series of reactions in the same reaction vessel and satisfying the functional group complexity required in formula I. The process allows multiple covalent attachment of a range of functional groups to the surface, ensuring longer stability and very low levels of functional group leaching.

The invention also provides a process for the preparation of compounds of formula I. A plurality of different functional groups, different configurations and spatial arrangements in the compound of the general chemical formula I can be easily obtained by novel high-acid-yield catalysis, free radical and substitution reaction, and adjustment of different initial reagents and process conditions.

The present invention aims to provide a convenient, environmentally friendly, industrial scale new process for the preparation of compounds of formula I. The yield, cost, scale and/or purity levels, as well as environmental benefits of this technology are all satisfactory from a commercial perspective compared to the prior art.

The novel process involves formula II (R)³O)₃The silane or combination of silanes of SiW, wherein W is (CH)₂)_sSC₃H₆NHC(＝O)NHR²、(CH₂)_sSH、(CH₂)_sSC₃H₆NHC(＝S)NHR²、(CH₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²To obtain the compound of formula III [ (R)³O)₂SiWO][SiX(OR³)O]_m][SiY(OR³)O]_n[SiZ(OR³)₁ZO]_p[OWSi(OR³)₂]Corresponding linear and crosslinked siloxanes, wherein W is either X, Y or Z; x is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝F)NHR²Wherein F is O or S or (CH)₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²(ii) a Z is any one of X or Y; r²Is hydrogen, straight or branched C_1-22Alkyl radical, C_1-22-alkylaryl, aryl; r³Selected from straight or branched C_1-22An alkyl group; m, n, p are each any integer from 0 to 100, and one of m, n, or p is always greater than 0.

W is (CH)₂)_sSC₃H₆NHC(＝S)NHR²、(CH₂)_sSC₃H₆NHC(＝O)NHR²、(CH₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²The compounds of the formula II can be prepared by using free-radical initiators with or without solvents (R)³O)₃Si(CH₂)_sSH to an unsaturated carbon-carbon bond, e.g. CH₂CHCH₂NHC(＝S)NHR²、CH₂CHCH₂NHC(＝O)NHR²、CH₂CHCH₂NHR²Or CH₂CHCH₂OR²Is prepared by free radical addition reaction at 20-160 deg.C for 0.5-24 hr. Typical solvents include xylene, toluene, heptane, glycols, ethanol and methanol. Free radical initiators that may be used include, but are not limited to, azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, and t-butyl peroxide.

The compound of the following formula III, wherein X is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝S)NHR²、(CH₂)_sSC₃H₆NHC(＝O)NHR²、(CH₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²(ii) a Z is any one of X or Y and can be prepared by any one of the following methods:

i. the corresponding silane or combination of silanes of formula II is partially polymerized by acid catalysis; or

To W is (CH)₂)_sSH silanes of the formula II are partially polymerized by acid catalysis, followed by the use of free-radical initiators with the unsaturated carbon-carbon bonds (e.g. CH) of the appropriate olefins, with or without solvents₂CHCH₂NHC(＝S)NHR²、CH₂CHCH₂NHR²、CH₂CHCH₂OR²Or CH₂CHCH₂NHC(＝O)NHR²) Free radical addition reaction is carried out, and the reaction is carried out for 0.5 to 24 hours at the temperature of between 20 and 160 ℃. Typical solvents include xylene, toluene, heptane, glycols, ethanol and methanol. Free radical initiators that may be used include, but are not limited to, azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, and t-butyl peroxide.

Strict control of the reaction conditions (including temperature, reaction time, catalyst concentration and acid strength) is critical for partial polymerization reactions that would otherwise result in high molecular weight siloxanes and inefficient synthesis on solid surfaces, in addition to causing large particles of siloxanes to block the pores of the inorganic material. Since the functional group is located in the pores of the material, failure to make good contact will result in poor performance and low loading of the functionalized material.

One of the objectives of the present invention is to provide the reaction conditions and relative molar concentrations for the initial silane partial polymerization reaction. Homogeneous acids of varying acid strength may be used for partial polymerization, including but not limited to methanesulfonic acid, p-toluenesulfonic acid, phosphoric acid, and thioacetic acid. A greater amount of the less acidic acid is required compared to the sulfonic acid. The preferred concentration of alkyl or aryl sulfonic acid is in a molar ratio of 0.001 to 0.01 relative to the silane. The reaction temperature is 70-120 ℃, and the reaction time is 0.5-5 hours. Preferably solvent-free, preferably at a reaction temperature of between 80 and 90 ℃ and preferably for a reaction time of between 0.5 and 1.5 hours.

The length of the chain (integers m, n and p) in formula III can be increased by varying the reaction conditions and reactant ratios in the acid catalyzed partial polymerization reaction. Longer reaction conditions, higher acid strength and higher temperature will result in higher values for the integers m, n and p.

Can be prepared by silica gel and chemical formula II, chemical formula III and (R)¹O)₃The compound of the chemical formula I is obtained by the synthetic reaction of silane in SiV in a solvent, the reaction condition is 20-160 ℃, and the reaction time is 0.5-24 hours. A variety of solvents and solvent combinations may be used in the synthesis reaction, including aliphatic or aromatic hydrocarbons, alcohols, and polar solvents such as dimethylformamide. Generally, preferred solvents are toluene and xylene. The preferred volume (L) to weight (kg) ratio of solvent to silica is between 2.8 and 2.

To achieve the desired selectivity and target loading, the chemical formulas II, III and (R) can be added in the synthesis step¹O)₃Different silane compositions of SiV. Therefore, the process has very strong design flexibility and can prepare functional materials with optimal performance.

Component (R)¹O)₃SiV enables the addition of additional functional groups, improves performance, and allows the hydrophobic-hydrophilic nature of the silica surface around the functional groups to be adjusted, thereby enhancing selective bonding.

After the reaction is finished, the functionalized material of the chemical formula I is obtained by filtration or centrifugation, then washed sufficiently to remove any residual reactants and finally dried. The silica gel materials widely sold on the market are all suitable, the particle size is from nano-sized particles to 5-30mm, meanwhile, the pore size range is very wide, and the preferred pore size range is

Another advantage of this process is the preparation of compounds of formula I with very high functional group loading by a series of reactions (e.g., acid catalyzed partial polymerization, free radical addition and synthesis). Other advantages include: a) the method can be carried out in the same reaction vessel, and the operation steps are simple; b) variations in the design and structure of the compounds of formula I can be readily achieved by varying the reaction conditions of the partially polymerized reaction composition; silanes of formula II and formula III are added in different relative ratios during the synthesis step. Another advantage is that: the efficiency of recovering and reusing the solvent is up to more than 90 percent.

In a further process, the respective mixture of sol-gel, the different compounds of formula II and formula III is reacted with sodium silicate or an alkoxysilane, such as tetraethylorthosilicate, with an acid or base catalyst in a solvent at a temperature of 20 to 160 ℃ for 0.5 to 48 hours. The solid is then triturated, washed to remove any residual reactants and dried to give the compound of formula I. Typical acids and bases used are hydrochloric acid and aqueous ammonia, respectively. Solvents include, but are not limited to, methanol, ethanol, water, and mixtures thereof.

The compounds of formula II and III can be attached to various surfaces using well known methods, either individually or as mixtures (including alkoxysilanes such as tetraethylorthosilicate) to give thin films of formula I.

The compounds of formula I may be linked to the metal complex, e.g. as ligands. The invention further provides compositions comprising metal complexes M (L)_tWherein M is derived from a lanthanide, actinide, main group or transition metal in an oxidation state of 0 to 4, L is one or more optionally substituted ligands and is selected from the group consisting of halide, nitrate, acetate, carboxylate, cyanide, amine, sulphate, carbonyl, imine, alkoxy, triaryl or trialkylphosphine and phenoxy, and t is any integer from 0 to 8, to which metal complex compounds of formula I are attached.

The compounds of formula I have a wide range of uses. The present invention provides a process for treating a feed comprising contacting a compound of formula I:

i) removing one or more components of the feed material to produce a material free of the removed components;

ii) passing the feed stream through a compound of formula I to separate the different components;

iii) removing one ionic state in the feed by ion exchange.

The feed may be a continuous fluid (e.g., a process stream or an intermediate stream), or may be a batch of material for discrete processing. Specific components of such feeds as product streams, waste streams or process streams may be removed. The component to be removed may be an undesired component of the feed and the process results in a feed which, after contacting the feed with a compound of formula I, contains only the desired component, the component to be selectively removed being depleted. The process can be used to remove unwanted target components (e.g., metals) from the feed materials of a pharmaceutical manufacturing process or formulation process, thereby increasing the purity of the pharmaceutical product.

The process may be used to remove desired materials from the feed material which are subsequently processed or analyzed, for example to remove biomolecules such as enzymes, peptides, proteins, endotoxins and nucleic acids from the feed material, and then to further process or analyze the removed components.

The compounds of formula I have high affinity and can remove metals that are tightly bound to ligands, such as metals in highly polar active pharmaceutical ingredients. Noble metals (e.g., palladium, platinum, rhodium, nickel) can be used as catalysts to produce high value, high purity products. These metals are present in different forms after the production process.

A process stream or product containing palladium is treated with any of the products of examples 1-2, 4-8, 14, resulting in complete removal of palladium from the solution. The products of examples 1-2, 4, 6-7, 13 have the same effect on palladium removal for product streams and process streams containing palladium residues from the palladium (0) catalyst. The metal loading is high, and 60-120g of palladium can be removed per kilogram of the functionalized material.

The products of examples 1-2, 4-8, 10-11 were used to treat hydroformylation process streams containing rhodium in various forms, with final residual rhodium concentrations below 1 ppm.

Noble platinum metals are used in a variety of different processes and applications. For example, platinum catalysts are used in hydrosilylation reactions to produce silanes and siloxanes, with platinum always present in the final product, or only low levels of removal can be achieved. Treatment of such products and process streams with compounds of formula I can reduce the level of residual platinum therein to very low levels. Examples include 1-2, 4-6, 8, 11 and 15.

The process and waste streams of the mining industry contain a range of metals, and the metal concentrations to be recovered in the waste streams are generally very low, while the unwanted metal concentrations are relatively high, as is the case: the concentration of noble metals (such as platinum, palladium, rhodium, iridium, ruthenium and gold) in a certain solution is 2-20ppm, and the mixed concentration of iron, copper and zinc is 500-50,000 ppm. The compounds of formula I are very effective in selectively removing certain noble metals. The process achieves high metal loadings, removing 60-120g of noble metal per kg of functionalized material. Examples include 1-2, 4-6, 8, 11 and 15.

The compounds of formula I are very effective in extracting a wide range of cations and anions from a variety of environments. Cations include lanthanides, actinides, main group and transition metals. Anions include arsenate, borate, chromate, permanganate, perchlorate, and perrhenate. For example, the products of examples 1-5, 8-12 and 14-15 were very effective for removing cuprous and cupric ions from various types of solutions. The functionalized material achieved very high copper loadings (100-140 g/kg).

The compounds of formula I can selectively remove a desired target from a complex mixture. Copper is present in the spent acid stream along with other high concentrations of metals (including zinc, nickel, lead, arsenic). Currently there is no efficient technique to selectively separate copper and the value of copper is lost. In addition, careful environmental management is required for such waste liquids. The compounds of formula I can selectively remove copper from these waste acid streams with very high efficiency. For example, for a spent acid stream containing copper (1-8,000ppm), arsenic (1-8,000ppm), zinc (1-2,000ppm), and nickel (200- "1,000 ppm), selective removal and high loading of copper was achieved using the products of examples 8-14. The copper can be recovered and reused, and the functional material can be reused. The process does not use any toxic process chemicals.

The compounds of formula I can be synthesized in solid phase by linking the starting materials. A series of chemical reactions are then performed, with decontamination being accomplished in each step by simply washing the reagents. Finally, the solid phase material releases the desired material.

Alternatively, the compounds of formula I can be used as materials for solid phase extraction to purify the product by selectively retaining the desired product on the functionalizing material and allowing impurities to flow through the functionalizing material. Different solvents were then used to liberate the desired product. The compounds of formula I can further be used as chromatographic separation materials.

Detailed Description

The present invention will now be described in detail with reference to illustrative examples thereof.

Example 1

Allylthiourea (2mol) was added over 30 minutes to a 2L reactor charged with a stirred solution of 3-MPTMS (408.0mL, 2.6mol) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 40 ℃ to give silane a.

Vinyl silane (4mol) was added to thioacetic acid (4.8mol) over 15 minutes at 70 ℃ and the mixture was stirred for 2 hours, during which time t-butyl peroxide (2mL) was added every 10 minutes. Dibutylamine (3mol) was then added and the mixture was slowly heated at 70 ℃ for 1 hour, then cooled to give silane B.

Silica gel (37-147 mu m),

2.2kg) was added to a 20L reactor containing a stirred solution of xylene (4.5L), silane A was added, the reaction mixture was heated at 120 ℃ with stirring for 1 hour, then silane B was added, the reaction mixture was heated with stirring for 5 hours, the solid was filtered after cooling, washed thoroughly with methanol (4 × 5L) and dried to give a composition of formula I wherein X is (CH)₂)₂SH; y is (CH)₂)₃SC₃H₆NHC(＝S)NH₂(ii) a V is (CH)₂)₃SH; m has an average value of 10; n is 0; d is 0.

Example 2

Allylthiourea (2.5mol) was added over 30 minutes to a 2L reactor charged with a 3-MPTMS solution (5.0mol, previously heated with methanesulfonic acid (0.005mol) at 80 ℃ for 2 hours) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was cooled to 40 ℃ and then added to silica gel (147-,

3.4kg) And xylene (7.8L) in a 20L reactor at 120 deg.C for 1 hour, then 3-MPTMS (2.0mol) is added, the reaction mixture is heated and stirred for 5 hours, after cooling the solid is filtered, washed thoroughly with methanol (4 × 5L) and dried to give a composition of formula I, wherein X is (CH)₂)₂SH; v is (CH)₂)₃SH; f is S; m has an average value of 15; n is 0; the average value of p is 5; c is 0.

Example 3

Allyl urea (2.5mol) was added over 30 minutes to a 2L reactor charged with a 3-MPTMS solution (3.0mol, previously heated with methanesulfonic acid (0.001mol) at 70 ℃ for 1 hour) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 80 ℃ and methanesulfonic acid (0.01mol) was added and then heated at 90 ℃ for 1.5 hours, and the solution was added to a silica gel (200-,

1kg) and xylene (2L) at 120 deg.C for 5 hours, cooling and filtering, washing the filtered solid with methanol (4 × 2L) and drying to obtain a composition of formula I, wherein X is (CH)₂)₃SH; v is (CH)₂)₃SH; f is O; m has an average value of 5; n is 0; the average value of p is 5; c is 0.

Example 4

Allylthiourea (2.5mol) was added over 30 minutes to a 2L reactor charged with 3-MPTMS solution (3.0mol) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 90 ℃ and p-toluene sulphonic acid (0.01mol) was added and the mixture was heated with stirring for 1 hour and the solution was added to silica gel (37-74 μm,

4kg) and xylene (8.2L) was stirred at 120 ℃ for 1 hour. 3-MPTMS (2.0mol) was added theretoThe reaction mixture was heated for an additional 5 hours and then cooled and filtered, the filtered solid was washed thoroughly with methanol (4 × 8L) and dried to provide a composition of formula I wherein X is (CH)₂)₃SH; y is (CH)₂)₃SC₃H₆NHC(＝S)NH₂(ii) a m has an average value of 3; c is 0; the average value of d is 6; v is (CH)₂)₃SH。

Example 5

Allylthiourea (2.5mol) was added over 30 minutes to a 2L reactor charged with a stirred solution of 3-MPTMS (408.0mL,2.2mol) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 70 ℃, methanesulfonic acid (0.001mol) was added, then heating and stirring were continued for 0.5 hours, and then the solution was cooled to 40 ℃ to give silane a. Allylthiourea (1.5mol) was added over 30 minutes to a 2L reactor charged with a stirred solution of 3-MPTMS (408.0mL,2.2mol) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 40 ℃ to give silane B. Vinyl silane (2mol) was added to thioacetic acid (3mol) over 15 minutes at 70 ℃ and the mixture was stirred for 2 hours, during which time t-butyl peroxide (1mL) was added every 10 minutes. Dipropylamine (3mol) was then added and the mixture was heated slowly at 70 ℃ for 1 hour and then cooled to give silane C. Silica gel (200-,

5kg) was added to a 20L reactor containing a stirred solution of xylene (10L), silane A, B and C were added, the reaction mixture was heated and stirred at 120 ℃ for 6 hours, the solid was filtered after cooling, washed thoroughly with methanol (4 × 10L) and dried to give a composition of formula I wherein X is (CH) and₂)₂SH; y is (CH)₂)₃SC₃H₆NHC(＝S)NH₂(ii) a m has an average value of 10; the average value of n is 6; f is S; the average value of p is 3; v is (CH)₂)₃SH。

Example 6

At 120 deg.CNext, allylthiourea (2.5mol) was added over 30 minutes to a 2L reactor containing a stirred solution of 3-MPTMS (2.2 mol). Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 100 ℃, methanesulfonic acid (0.01mol) was added, then heating and stirring were continued for 1.5 hours, and then the solution was cooled to 40 ℃ to give silane a. Vinylsilane (2mol) was added to thioacetic acid (3mol) over 15 minutes at 80 ℃ and the mixture was stirred for 3 hours, during which time t-butyl peroxide (2mL) was added every 10 minutes. Morpholine (3mol) was then added and the mixture was heated slowly at 70 ℃ for 1 hour and then cooled to give silane B. Silica gel (147-400 μm),

2.2kg) was added to a 20L reactor containing a stirred solution of xylene (4.5L) silane A, B and phenyltrimethoxysilane (0.2mol) were added and the reaction mixture was heated at 120 deg.C with stirring for 1 hour, the solid was filtered after cooling, washed thoroughly with methanol (4 × 5L) and dried to give a composition of formula I wherein X is (CH) and₂)₂SH; y is (CH)₂)₃SC₃H₆NHC(＝S)NH₂(ii) a V is phenyl; m has an average value of 3; the average value of n is 14; p is 0.

Example 7

Allylthiourea (2.5mol) was added over 30 minutes to a 2L reactor charged with a stirred solution of 3-MPTMS (408.0mL,2.2mol) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 90 ℃, methanesulfonic acid (0.001mol) was added, then heating and stirring were continued for 1.5 hours, and then the solution was cooled to 40 ℃ to give silane a. Allylthiourea (1.5mol) was added over 30 minutes to a 2L reactor charged with a stirred solution of 3-MPTMS (408.0mL,2.2mol) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 70 ℃, methanesulfonic acid (0.001mol) was added, then heating and stirring were continued for 1.5 hours, and then the solution was cooled to 40 ℃ to give silane B. At 80 deg.C, adding ethyl acetateThe alkenylsilane (2mol) was added to thioacetic acid (3.4mol) over 15 minutes and the mixture was stirred for 2 hours, during which time t-butyl peroxide (0.2mL) was added every 10 minutes. Dipropylamine (3mol) was then added and the mixture was heated slowly at 70 ℃ for 1 hour and then cooled to give silane C. Silica gel (200-,

3kg) was added to a 20L reactor containing a stirred solution of xylene (6L), silane A, B and C were added, the reaction mixture was heated and stirred at 120 ℃ for 6 hours, the solid was filtered after cooling, washed thoroughly with methanol (4 × 6L) and dried to give a composition of formula I, wherein X is (CH) and X is (CH) in which₂)₂SH; y is (CH)₂)₃SC₃H₆NHC(＝S)NH₂(ii) a V is (CH)₂)₃SH; m has an average value of 10; the average value of n is 6; the average value of p is 3; f is S; v is (CH)₂)₃SH。

Example 8

Allylthiourea (8.2mol) was added over 30 minutes to a 2L reactor charged with a 3-MPTMS solution (8.0mol, previously heated with methanesulfonic acid (0.05mol) at 80 ℃ for 2 hours) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (2mL) was added every 15 minutes. The solution was then cooled to 40 ℃ and added to silica gel (37-147 μm,

2.2kg) and xylene (4.7L) in a 20L reactor at 120 deg.C for an additional 8 hours, cooling and filtering, washing the filtered solid thoroughly with methanol (4 × 5L) and drying to give a composition of formula I wherein X is (CH)₂)₃SH; v is (CH)₂)₃SH; f is S; m has an average value of 3; p is 0; the average value of n is 5.

Example 9

Allylthiourea (41mol) was added over 30 minutes at 120 ℃ to a solution containing 3-MPTMS (40.0mol, methanesulfonic acid (0.08mol) and 100mL water at 90 ℃ in advanceHot for 2 hours). Heating was continued for 3 hours during which time t-butyl peroxide (10mL) was added every 15 minutes. The solution was then cooled to 40 ℃ and added to silica gel (147-,

14kg) and xylene (30L) at 120 deg.C for 6 hours, filtering the reaction mixture, washing with methanol (4 × 30L) and drying to obtain a composition of formula I, wherein X is (CH)₂)₃SH; v is (CH)₂)₃SH; m has an average value of 3; p is 0; the average value of n is 7.

Example 10

Allylthiourea (88mol) was added over 30 minutes to a 50L reactor charged with a 3-MPTMS solution (80.0mol, previously heated at 90 ℃ for 2 hours with methanesulfonic acid (0.8mol) and 100mL water) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (20mL) was added every 15 minutes. The solution was then cooled to 40 ℃ and added to silica gel (147-,

30kg) and xylene (60L) at 120 ℃ for 6 hours, then cooling, filtering and washing thoroughly with methanol (4 × 60L) and drying to give a composition of formula I wherein X is (CH)₂)₃SH; f is S; m has an average value of 5; p is 0; the average value of n is 8.

Example 11

Allylthiourea (88mol) was added over 30 minutes to a 50L reactor charged with a 3-MPTMS solution (80.0mol, previously heated at 90 ℃ for 2 hours with methanesulfonic acid (2mol) and 100mL water) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (20mL) was added every 15 minutes. The solution was then cooled to 40 ℃ and added to silica gel (147-,

30kg) and xylene (60L) at 120 ℃ for 6 hours, then cooling, filtering and washing thoroughly with methanol (4 × 60L) and drying to give a composition of formula I wherein X is (CH)₂)₃SH; f is S; m has an average value of 5; p is 0; the average value of n is 8.

Example 12

Allylthiourea (1.1mol) was added over 30 minutes to a 2L reactor charged with a 3-MPTMS solution (1.0mol, previously heated at 90 ℃ for 2 hours with methanesulfonic acid (0.02mol) and 1mL water) at 120 ℃. Heating was continued for 3 hours during which time t-butyl peroxide (0.2mL) was added every 15 minutes. The solution was then cooled to 40 ℃ and added to a stirred mixture of tetraethylorthosilicate (6mol) dissolved in methanol (3L) and 1M HCl (0.4L). The mixture was heated at 80 ℃ until glass formation occurred as a result of methanol evaporation. Grinding the obtained glass, stirring and filtering in refluxing methanol, and drying to obtain a compound of formula I, wherein X is (CH)₂)₃SH; f is S; m has an average value of 5; p is 0; the average value of n is 8.

Example 13

Allylthiourea (1.1mol) was added over 30 minutes to a 2L reactor charged with a stirred solution of 3-MPTMS (1.0mol, previously heated at 90 ℃ for 2 hours with methanesulfonic acid (0.02mol) and water (1 mL)) at 120 ℃. Further heating was carried out for 3 hours, during which t-butyl peroxide (0.2mL) was added every 15 minutes. The solution was then cooled to 40 ℃ and then added to a stirred mixture of tetraethoxysilane (8mol) dissolved in methanol (3L) and 1M HCl (0.4L). The mixture was heated at 80 ℃ until glass formation occurred as a result of methanol evaporation. Grinding the obtained glass, filtering under stirring in refluxing methanol, and drying to obtain a compound of formula I, wherein X is (CH)₂)₃SH; f is S; m has an average value of 5; p is 0; n has an average value of 8).

Example 14

Allylthiourea (1.1mol) was added to a stirred solution containing 3-MPTMS (1.0 mol) at 120 ℃ over 30 minutesPreviously heated at 90 ℃ for 2 hours in a 2L reactor with methanesulfonic acid (0.02mol) and water (1 mL). Further heating was carried out for 3 hours, during which t-butyl peroxide (0.2mL) was added every 15 minutes. The solution was then cooled to 40 ℃ and then added with stirring and dissolved in 3M HCl (3L) sodium silicate (8 mol). The mixture was heated at 80 ℃ until glass formation. Grinding the obtained glass, stirring and filtering in refluxing deionized water, and drying to obtain a compound of formula I, wherein X is (CH)₂)₃SH; f is S; m has an average value of 5; p is 0; the average value of n is 8.

Example 15

Allylamine (2.5mol) was added over 30 minutes to a 2L reactor charged with a stirred solution of 3-MPTMS (3.0mol, heated at 70 ℃ for 1 hour with methanesulfonic acid (0.001 mol)) at 120 ℃. Further heating was carried out for 3 hours, during which t-butyl peroxide (1mL) was added every 15 minutes. The solution was then cooled to 80 ℃, methanesulfonic acid (0.01mol) was added, and the solution was then heated at 90 ℃ for 1.5 hours. This solution was added to a solution containing xylene (2L) and silica gel (200-,

1kg) of a 10L reactor with stirring of the mixture, heating at 120 ℃ for 5 hours with stirring and then cooling and filtering, the filtered solid is washed thoroughly with methanol (4 × 2L) and dried to give a composition of formula I wherein X is (CH)₂)₃SH; y is (CH)₂)₃SC₃H₆NH₂(ii) a V is (CH)₂)₃SH; m has an average value of 5; n is 0; the average value of p is 5; c is 0.

Example 16

Allyl butyl ether (2.5mol) was added over 30 minutes to a 2L reactor charged with a stirred solution of 3-MPTMS (3.0mol, heated at 70 ℃ for 1 hour with methanesulfonic acid (0.001 mol)) at 120 ℃. Further heating was carried out for 3 hours, during which t-butyl peroxide (1mL) was added every 15 minutes. The solution was cooled to 80 ℃, methanesulfonic acid (0.01mol) was added and heated at 90 ℃ for 1.5 hours. The solution was added to a reaction vessel containing xylene (2L) and silica gel (200-,

1kg) in a 10L reactor with stirring of the mixture, heating at 120 deg.C for 5 hours and then cooling and filtering, washing the filtered solid thoroughly with methanol (4 × 2L), and drying to obtain a composition of formula I wherein X is (CH)₂)₃SH; y is (CH)₂)₃SC₃H₆OC₄H₉(ii) a V is (CH)₂)₃SH; m has an average value of 5; n is 0; the average value of p is 5; c is 0.

Example 17

The product of example 1 (0.05g) was added to a sample (6mL) of a product stream containing 205ppm iridium, the iridium in the stream being derived from the iridium chloride used. The mixture was stirred at 30 ℃ for 1 hour and then filtered, and analysis of the filtrate showed that iridium had been removed. Examples 2, 4-7 and 12-14 have the same effect in this test.

Example 18

The product of example 2 (0.03g) was added to a sample (10mL) of a product stream containing 55ppm of iridium derived from the carbonyl chloride bis (triphenylphosphonium) iridium (I) catalyst used. The mixture was stirred at 60 ℃ for 6 hours and then filtered, and analysis of the filtrate showed that iridium had been removed. Examples 4-7 have the same effect in this test.

Example 19

The product of example 1 (0.03g) was added to a sample (3mL) of a process stream containing 150ppm rhodium, the rhodium in the process stream being derived from triphenylphosphine rhodium (I) chloride, the Wilkinson catalyst used. The mixture was stirred at room temperature for 8 hours and then filtered, and analysis of the filtrate showed that rhodium had been removed. Examples 4-7 and 9-11 have the same effect in this test.

Example 20

The product of example 7 (0.03g) was added to a sample (3mL) of a process stream containing 240ppm of rhodium, the rhodium in the process stream being derived from the rhodium (I) dicarbonylacetylacetonate catalyst used. The mixture was stirred at room temperature for 12 hours and then filtered, and analysis of the filtrate showed that rhodium had been removed. Examples 1-2, 4-6 and 12-14 have the same effect in this test.

Example 21

The product of example 5 (0.01g) was added to a sample (3mL) of a product stream containing 60ppm of palladium, the rhodium in the product stream being derived from the catalyst used, palladium acetate. The mixture was stirred at 30 ℃ for 30 minutes and then filtered, and analysis of the filtrate showed that palladium had been removed. Examples 1-2, 4, 6-8 and 14 have the same effect in this test.

Example 22

The product of example 6 (0.03g) was added to a sample (3mL) of a product stream containing 120ppm of palladium, the palladium in the product stream being derived from the catalyst tetrakistriphenylphosphine palladium (0) used. The mixture was stirred at 50 ℃ for 2 hours and then filtered and analysis showed that the palladium had been removed.

Example 23

The product of example 7 (0.03g) was added to a sample of a product stream (2mL) containing 200ppm palladium, the palladium in the product stream being derived from the catalyst tris (dibenzylideneacetone) dipalladium (0) used. The mixture was stirred at 60 ℃ for 6 hours and then filtered, and analysis of the filtrate showed that palladium had been removed. Examples 1-2, 4 and 13 have the same effect in this test.

Example 24

The product of example 2 (0.04g) was added to a sample of a process stream (15mL) containing 50ppm of platinum, the platinum in the process stream being derived from the catalyst chloroplatinic acid used. The mixture was stirred at 80 ℃ for 6 hours and then filtered, and analysis of the filtrate showed that platinum had been removed. Examples 1, 4-6 and 15 have the same effect in this test.

Example 25

The product of example 5 (100g) was loaded into an adsorption column through which a silane waste process stream (20L) containing 40ppm platinum was passed at 50 ℃. Analysis of the treated fluid showed a residual content of platinum below 1 ppm.

Example 26

The product of example 6 (100g) was loaded into an adsorption column through which a certain hydroformylation process effluent containing 300ppm rhodium was passed at 80 ℃. Analysis of the treated stream indicated that the remaining rhodium content was below 1 ppm.

Example 27

The product of example 12 (0.04g) was added to a sample of a process stream containing 50ppm ruthenium (4mL) derived from the used grubbs catalyst phenylmethylenebis (tricyclohexylphosphine) dichlororuthenium. The mixture was stirred at 30 ℃ for 6 hours and then filtered. Analysis of the filtrate showed that ruthenium had been removed.

Example 28

The product of example 6 (100g) was charged into a fixed bed, and a solution (30L) containing zinc-iron total concentration of 10,000ppm, 4ppm of platinum, 4ppm of palladium, 3ppm of ruthenium and 1.5ppm of rhodium was passed through the fixed bed at a flow rate of 0.3L/h. Palladium (99%), platinum (99%), ruthenium (60%) and rhodium (90%) were selectively removed from the solution. Examples 1-2 and 4-5 were also effective in this experiment.

Example 29

The product of example 4 (0.2g) was added to a sample of a process stream (40 mL) containing 60ppm copper, the copper in the process stream being derived from the copper (I) catalyst used. The mixture was stirred slowly at room temperature for 2 hours and then filtered. Analysis of the filtrate showed that copper had been removed. Examples 8-11 were also effective in this experiment.

Example 30

A process effluent containing 6000ppm copper was treated with the product of example 8 (2.0 g). The copper loading of the product of example 8 was 120 g/kg. Similar test results are as follows: the copper loading of the product of example 9 was 105 g/kg; the copper loading of the product of example 10 was 150 g/kg; the copper loading of the product of example 11 was 134 g/kg.

Example 31

A certain acidic waste stream having a pH of 1.7 and containing 2,000ppm copper, 700ppm zinc, 200pmm nickel and 6,800ppm arsenic was treated with the product of example 8 (2.0 g). The copper in the waste stream is selectively removed while the zinc, nickel and arsenic remain in the waste stream.

Example 32

The product of example 9 (50g) was loaded into an adsorption column and an acidic waste solution having a pH of 1.7 and containing 2,000ppm copper, 700ppm zinc, 200pmm nickel and 6,800ppm arsenic was passed to the column with a retention time of 15-18 mL/min. Copper is selectively removed while zinc, nickel, arsenic and other metals in the waste stream remain in the waste stream.

Example 33

The product of example 10 (50g) was loaded into an adsorption column and an acidic waste solution having a pH of 1.7 and containing 6,000ppm copper, 1000ppm zinc, 200pmm nickel and 5,500ppm arsenic was passed through the column with a retention time of 15-18 mL/min. Copper is selectively removed while zinc, nickel, arsenic and other metals in the waste stream remain in the waste stream.

Claims (14)

1. A compound of formula I:

[(O_2/2)SiXO[SiO_1/2XO]_m]_a[Si(O_4/2)]_b[(O_2/2)SiYO[SiO_1/2YO]_n]_c[(O_2/2)SiZO[SiO_1/2ZO]_p]_d[VSi(O_3/2)]_e(chemical formula I)

Wherein X is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝F)NHR²Wherein F is O, S, (CH)₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²Z is X or Y; s is an integer from 2 to 20; m, n and p are each an integer from 0 to 100, and one of m, n or p is always greater than 0; r²Is hydrogen, straight or branched C_1-22Alkyl radical, C_1-22-alkylaryl, aryl; v is selected from C_1-22Alkyl radical, C_1-22Alkyl aryl, C_2-20Alkyl sulfide radical, C_1-12Alkyl radical, C_2-20Alkylene thioether alkyl, C_2-20Alkyl thioether aryl radical, C_2-20-an alkylene thioether aryl group; a. b, c, d and e are integers, and a + c + d: b is in the range of 0.00001 to 100000, a, b and c/d are always present, and when e is greater than 0, e: the ratio of a + b + c + d is 0.000001 to 100;

by one or more silicon atoms, hydrogen, straight or branched C of other groups in formula I_1-22Alkyl, terminal group R³SiO_1/2Crosslinking agent or chain R_qSi(OR¹)_gO_k/2Wherein one or more of R and R saturate the free valence of the silicate oxygen atom¹Are independently selected from straight chain or branched chain C_1-12Alkyl, aryl and C_1-22Alkyl aryl radical, R³Selected from straight or branched C_1-12Alkyl, k is any integer from 1 to 3, q is any integer from 1 to 2, g is any integer from 0 to 2, and g + k + q is 4, the ratio of the molar ratio to a + b + c, when end groups, cross-linking agents and/or polymer chains are present, being from 0 to 999: 1.

2. A compound according to claim 1 and wherein X in formula I is (CH)₂)_sSH, Y are (CH)₂)_sSC₃H₆NHC(＝S)NHR²Z is X or Y, s is any integer from 2 to 4, m, n and p are each any integer from 0 to 20 and one of m, n or p is always greater than 0, R²Is hydrogen, straight or branched C_1-6-alkyl, V is selected from C_1-6Alkyl, aryl, C_2-20-an alkyl sulfide group, a, b, c, d, e are integers and a + c + d: b is in the range of 0.00001 to 100,000, a, b and c/d are always present, and when e is greater than 0, e: the ratio of a + b + c + d is 0.000001 to 100;

by one or more silicon atoms, hydrogen, straight or branched C of other groups in formula I_1-22Alkyl, terminal group R³SiO_1/2Crosslinking agent or chain R_qSi(OR¹)_gO_k/2Wherein one or more of R and R saturate the free valence of the silicate oxygen atom¹Are independently selected from straight chain or branched chain C_1-6Alkyl, aryl and C_1-22Alkyl aryl radical, R³Selected from straight or branched C_1-6Alkyl, k is any integer from 1 to 3, q is any integer from 1 to 2, g is any integer from 0 to 2, and g + k + q is 4, the ratio of the molar ratio to a + b + c, when end groups, cross-linking agents and/or polymer chains are present, being from 0 to 999: 1.

3. A process for producing a compound of formula I as claimed in claim 1, by combining various compounds OR combinations of compounds of formula III and/OR formula II in a solvent with an inorganic material OR surface, adding VSi (OR)¹)₃Reacting at 20-160 deg.c for 0.5-4 hr; the solvent is selected from aliphatic or aromatic hydrocarbons or a combination of an alcohol and a polar solvent;

the chemical formula III is [ (R)³O)₂SiWO][SiX(OR³)O]_m][SiY(OR³)O]_n[SiZ(OR³)₁ZO]_p[OWSi(OR³)₂]The chemical formula II is (R)³O)₃SiW; wherein W is any one of X, Y, Z; x is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝S)NHR²(ii) a Z is any one of X or Y; s is any integer from 2 to 4; r²Is hydrogen, straight or branched C_1-6Alkyl radical, C_1-22-alkylaryl, aryl; r³Selected from straight or branched C_1-6An alkyl group; m, n and p are each any integer from 0 to 20, and one or more of m, n or p is always greater than 0.

4. A compound of formula III:

[(R³O)₂SiWO][SiX(OR³)O]_m][SiY(OR³)O]_n[SiZ(OR³)₁ZO]_p[OWSi(OR³)₂](chemical formula III) wherein W is any one of X, Y, Z; x is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝F)NHR²Wherein F is O, S, (CH)₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²(ii) a Z is any one of X or Y; s is any integer from 2 to 20; r²Is hydrogen, straight or branched C_1-12Alkyl radical, C_1-22-alkylaryl, aryl; r³Selected from straight or branched C_1-12An alkyl group; m, n and p are each integers from 0 to 100, and one of m, n or p is always greater than 0.

5. A compound of formula III:

[(R³O)₂SiWO][SiX(OR³)O]_m][SiY(OR³)O]_n[SiZ(OR³)₁ZO]_p[OWSi(OR³)₂](chemical formula III) wherein W is any one of X, Y, Z; x is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝S)NHR²(ii) a Z is any one of X or Y; s is any integer from 2 to 4; r²Is hydrogen, straight or branched C_1-6Alkyl radical, C_1-22-alkylaryl, aryl; r³Selected from straight or branched C_1-6An alkyl group; m, n and p are each any integer from 0 to 20, and one or more of m, n or p is always greater than 0.

6. A process for the manufacture of a compound of formula III as claimed in claim 5 wherein W is any one of X, Y, Z; x is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝F)NHR²Wherein F is O, S, (CH)₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²(ii) a Z is any one of X or Y; the preparation method comprises the following steps:

i. chemical formula II (R)³O)₃SiW corresponding silanes and silane combinations are partially polymerized by acid catalysis, wherein W is (CH)₂)_sSC₃H₆NHC(＝S)NHR²、(CH₂)_sSC₃H₆NHC(＝O)NHR²、(CH₂)_sSH、(CH₂)_sSC₃H₆NHR²Or (CH)₂)_sSC₃H₆OR²Wherein s is any integer from 2 to 20; r²Is hydrogen, straight or branched C_1-12Alkyl radical, C_1-22-alkylaryl, aryl; r³Selected from straight or branched C_1-12An alkyl group; using a non-aqueous acid selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid, phosphoric acid, thioacetic acid, in a molar ratio of acid to silane of 0.001 to 0.01, reactingThe temperature is 70-120 ℃, and the reaction time is 0.5-5 hours; or

Acid catalyzed partial polymerization of a silane of formula II, wherein W is (CH)₂)_sSH, followed by the use of a free radical initiator with unsaturated carbon-carbon bonds of a suitable olefin, selected from CH, in the presence or absence of a solvent₂CHCH₂NHC(＝S)NHR²、CH₂CHCH₂NHR²、CH₂CHCH₂OR²Or CH₂CHCH₂NHC(＝O)NHR²Free radical addition reaction is carried out, and the reaction lasts for 0.5 to 24 hours at the temperature of between 20 and 160 ℃; the solvent is xylene, toluene, heptane, glycol, ethanol, methanol; free radical initiators that may be used include, but are not limited to, azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide (CH)₃)₃COOH, tert-butyl peroxide (CH)₃)₃COOC(CH₃)₃。

7. A method of manufacturing a compound of formula III according to claim 6, wherein W in formula III is any one of X, Y, Z; x is (CH)₂)_sSH; y is (CH)₂)_sSC₃H₆NHC(＝S)NHR²(ii) a Z is any one of X or Y; s is any integer from 2 to 4; r²Is hydrogen, straight or branched C_1-6Alkyl radical, C_1-22-alkylaryl, aryl; r³Selected from straight or branched C_1-6-an alkyl group.

8. A feed treatment process comprising contacting with a compound according to any one of claims 1 to 2:

i) removing one or more components of the feed material to produce a material free of the removed components;

ii) selectively removing one or more components of the feed material, thereby recycling the removed components; or

iii) removing one ionic state in the feed by ion exchange.

9. A compound according to any one of claims 1 to 2 for use as a functionalised material in the removal, selective removal or reduction of desirable or undesirable organic, inorganic or biological compounds from a liquid feed.

10. A compound according to any one of claims 1 to 2 for use as a functionalised material in the removal, selective removal or reduction of precious, rare earth and transition metals from reaction mixtures, process streams, product streams, waste or waste streams, or in the removal, selective removal or reduction of such metals bound or bound to other organic compounds.

11. A compound according to any one of claims 1 to 2 for use as a functionalised material in the selective removal of copper from an acidic waste stream.

12. A compound according to any one of claims 1 to 2 for use as a functionalised material in the selective removal of metals from acidic waste streams.

13. A compound according to any one of claims 1 to 2 for use as an anion or cation exchanger.

14. A compound according to any one of claims 1 to 2 for use in the separation or purification of organic, biological or inorganic molecules from gaseous, liquid, solid environments.