CN106916179A - Functionalization material and its production technology with use - Google Patents

Functionalization material and its production technology with use Download PDF

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CN106916179A
CN106916179A CN201710108305.8A CN201710108305A CN106916179A CN 106916179 A CN106916179 A CN 106916179A CN 201710108305 A CN201710108305 A CN 201710108305A CN 106916179 A CN106916179 A CN 106916179A
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alkyl
integer
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CN106916179B (en
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杨南超
郑文彪
王维
曾威
威尔逊·约翰·罗伯特·豪
高道林
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Suzhou se Xin Xin Mstar Technology Ltd
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Hubei Xinuo Weixin Functional Silicone Materials Co Ltd
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    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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Abstract

The present invention relates to containing the production technology of the functionalization material of acidic-group and its using, the material is used as heterogeneous catalysis, and for removing organic and inorganic compound from product stream, technique stream and waste liquid, also act as cation and anion exchange agent, metal chromatographic material, Solid phase cleaned-up or fiber material, the fixed material of biomolecule, synthesis in solid state material and chromatographic material.

Description

Functionalization material and its production technology with use
The present invention relates to the functionalization material containing acidic-group preparation technology and its use, the material can be used as it is non- Phase catalyst, it may also be used for remove the impurity such as organic and inorganic compound from product stream, technique stream and waste liquid, or as negative and positive Ion-exchanger, metal chromatographic material, it is solid-phase purified or extract material, the fixed material of biomolecule, synthesis in solid state material and Chromatographic material.
In chemical field in the chemical reaction of extensive utilization, heterogeneous catalysis possesses perhaps compared to equal phase reagent and catalyst Many significant advantages.First, the generation of solid and liquid debris in reaction can be largely reduced using heterogeneous catalysis, and Simplification of flowsheet, reduces energy resource consumption, to meet increasingly strict environmental legislation；Furthermore, use heterogeneous catalysis operation Simply, easily can be separated from reaction medium.By contrast, a large amount of additional process are then needed using homogeneous catalyst and is divided From work, and extra discarded object is produced, so needing relative complex process equipment.Additionally, heterogeneous catalysis also has Reusable, selective productive target product, the characteristic that can be applied to continuous production procedure.Therefore, chemical field is to all kinds of The demand of efficient heterogeneous catalysis is growing, including metal complex catalyst, solid acid alkali catalytic agent etc..
The homogeneous catalyst (such as sulfuric acid, hydrofluoric acid and phosphoric acid) used in chemical reaction can produce substantial amounts of noxious waste Thing, need to be further processed to it, and efficient heterogeneous acid catalyst is just for existing and new chemical process opens one Bar new route.Sulfuric acid generally generates ethers byproduct in the esterification reaction, and such as carboxylic acid occurs esterification generation in methyl alcohol Dimethyl ether.These adverse reactions are forced to be needed extra technique and causes the loss of reagent so as to increase cost consumption, and The discarded object that additional technique is produced also increases energy resource consumption.And when using heterogeneous sour, need to only adjust acidity just can reduce pair Reaction, and avoid wasting.
There are many applicable heterogeneous catalysis.Organic polymer and material containing sulfonic acid have many purposes, for example, make For solid acid catalyst removes metal ion, also can purified aqueous solution.The sulfonated polystyrene polymers system of being most commonly based on Into material.Because the key limitation of organic polymer, the physics and chemical property of polystyrene resin have many drawbacks, wrap Include but be not limited to the low and high hydrophobicity of poor chemical stability, heat endurance.In addition, it is easily swollen in organic solvent Swollen and contraction, and useless dark byproduct can be produced in acid catalyzed reaction.And expansion issues will influence the space of reactor Utilization rate, thus reduce yield.Although this kind of side reaction can be avoided by the acidity for adjusting catalyst, due to that can act on In the organic material and limited starting material of this kind of chemical reaction, this is caused to adjust and be difficult to realize.Typically, since polyphenyl second The heat endurance of olefine resin is poor, and it may not apply to more than 80 DEG C, the reaction of any duration, and this just limits generally fitting for they The property used.
Based on silica, aluminum oxide or titanium dioxide for carrier inorganic polymer catalyst known one section when Between.Active function groups or metal only can be connected to carrier surface by very limited amount of chemical method.One of which method is official Can roll into a ball and carrier surface is only adsorbed onto by physical method, functional group's load factor of such functionalization material is low, applicable solvent Scope is limited, and is using and be easily lost during standing.This is considered as because the surface in functional group and carrier is former Adsorptivity between son is very weak (non-covalent bonding).Comparatively speaking, functional group is connected on carrier by covalent bond will more Firmly.Generally speaking, due to chemical limitation, currently only very limited amount of functional group may be coupled on inorganic carrier, and And, also need to develop new chemical method to realize functional group's load higher.
Heterogeneous acid catalyst is in order to meet cost, performance and the environmental objective of current and future, in addition it is also necessary to capture Great chemistry and synthesis problem.The limitation of acidic functionality synthesis includes：Famine prepares required heterogeneous acid catalyst Ready-made raw material；Ready-made precursor for preparing initiation material is very short；Initiation material is prepared (such as substitution tri-alkoxy silicon Alkane) synthetic method it is very limited；Even if there is ready-made raw material, the chemical method step of solid material needed for preparing is various, multiple It is miscellaneous, and functionalization material low yield, functional group's load factor are low and are difficult to purify.Thus, novel method for synthesizing and suitable need to be developed Initiation material produce required functionalized acidic material.
Alkyl sulfonic acid base is connected to Silica Surface and has been appeared in the newspapers in United States Patent (USP) US 4,552,700 with preparing acid catalyst. The described method for preparing these catalyst is related to multiple chemical steps and middle separation process, high cost, causes some lifes Produce and waste disposal issues.And these methods are also only limited the use of in preparing simple ethyl group and propyl sulfonic acid material.Currently, will The chemical technology that ethylsulfonic acid base is connected on silica gel is also very limited, and a kind of method is to use a well-known method by three Alkoxy silane (RO)3Si(CH2)2SH or (RO)3Si(CH2)3SH is connected to Silica Surface, and subsequent-SH radical oxidations turn into- SO3H groups.But, although certain progress is had been achieved on using oxidants such as hydrogen peroxide, but oxidation reaction is still Right problematic, conversion ratio is low and can produce substantial amounts of discarded object.
Another method has been appeared in the newspapers in BP GB1100531.1, and (CH is aoxidized first in concentrated nitric acid3O)3SiCH2CH2SC (=O) CH3After be connected on silica gel, or first by (CH3O)3SiCH2CH2SC (=O) CH3It is connected on silica gel, Then concentrated nitric acid oxidation is used.Using both approaches, the load factor of functional group is low, and nitric acid oxidation is difficult controlled and exists potential It is dangerous.Further, since having used substantial amounts of nitric acid in these reactions, need to process this kind of dangerous acidic waste with caution after reaction.
The present invention is intended to provide easy, environmentally friendly technique, covalent bonding is prepared in inorganic material using the raw material that is easy to get New sulfonic acid on material (such as silica gel).Separately, the present invention will also describe the use of these new sulfonic acid, and they can serve as heterogeneous catalysis Agent, or for removing unwanted organic and inorganic compound from product stream, technique stream and waste liquid, it is also possible to make negative and positive from Sub- exchanger, metal chromatographic material, Solid phase cleaned-up extract material, biomolecule fixation material, synthesis in solid state material and chromatogram Material.
First, the present invention relates to a kind of production technology of the compound of structural formula 1：
[(O3/2)Si(CH2)mS(CH2)nSO3M]a[Si(O4/2)]b[VSi(O3/2)]c[WSi(O3/2)]d(structural formula 1)
Wherein M is hydrogen or transition metal, platinum family or base-metal salt；V is a group for selectivity substitution and is selected from C1-22 Alkyl, C1-22Alkylaryl, C2-20Alkyl hydrosulfide, C2-20Alkyl thioether C3-12Alkyl, C2-20Alkylen thioether C3-12Alkyl, C2-20 Alkyl thioether aryl, C2-20Alkylen thioether aryl；W is a group for selectivity substitution and is taken selected from phenyl, aryl, hydroxyl The C in generation1-10Alkyl；M is 2 to 20 integer；N is 3 to 12 integer；A, b, c, d are integer, and a and b is always In the presence of, and a:The ratio of b is 0.00001 to 100,000, when c or d is more than 0, the ratio of c+d and a+b be 0.00001 to 100,000。
The silicon atom of other groups, hydrogen, straight or branched C in structural formula 11-22Alkyl, end group R3SiO1/2, crosslinking agent or chain Shape RqSi(OR1)gOk/2In one or more make the free valency saturation of silicate oxygen atom, wherein R and R1It is respectively selected from straight chain Or side chain C1-22Alkyl, aryl and C1-22Alkylaryl, k is an integer from 1 to 3, and q is an integer from 1 to 2, and g is From 0 to 2 integer, and meet g+k+q=4, in the presence of end group, crosslinking agent and/or polymer chain, its mol ratio with The ratio of a+b+c is from 0 to 999:Between 1.
The straight chain base or branched chain group of substitution can be optionally selected to be selected from C1-22Alkyl, C2-22Alkenyl, C2-22Alkynyl, aryl, C1-22Alkylaryl, can be respectively straight or branched and/or be substituted by one or more substituents, but preferably only hydrogeneous and carbon Atom.If substituted base, then substitution base can be respectively selected from amino, amide groups, nitro, chlorine, fluorine, bromine, nitrile, hydroxyl, carboxylic Acid, carboxylate, sulfide, sulfoxide, sulfone class or C1-6Alkoxy.
It is preferred that b:The ratio of a is that the compound of structural formula 1 from 10,000 to 0.2, especially m are 2 to 4 and M is the knot of hydrogen The compound of structure formula 1.
The present invention provides a kind of convenience, environment-friendly and large-scale production new technology for the compound of structural formula 1, and shows There is technology to compare, the yield of product, cost, scale and/or purity are satisfied by business demand, and possess environmental benefit.
Present invention has discovered that effectively preparing reagent, functional group, the work of new, high capacity rate required heterogeneous catalysis Skill and reaction condition, another advantage are simple production process, environment-friendly, and the discarded object of generation is few, and has ready-made raw material. Separately, the technique can produce additional functionality, and can change the acidity of sulfonic acid on inorganic carrier (such as silica gel).
Under new technology, first there is substitution reaction in sulfydryl anion, then in a solvent with the precursor containing ring-type sulfonate It is grafted onto inorganic surfaces.The technique includes：
I. in a solvent with the compound (R of structural formula 21O)3Si(CH2)mSM1(wherein M1It is alkali metal or alkaline-earth metal；R1 It is independently chosen from straight or branched C1-12Alkyl, aryl and C1-22Alkylaryl；M is an integer from 2 to 20) and structural formula 3 change Compound (wherein n is an integer from 1 to 10) is contacted, and is reacted 10 minutes to 24 hours at 10-120 DEG C；
Ii. solvent such as alcohols, water and polar solvent and inorganic skeleton (such as silica gel) are added to the reactant mixture of stirring In, continuous heating 1-24 hours at 80-120 DEG C, while slow steam solvent and add the toluene or dimethylbenzene of equivalent to use Make novel solvent so that the ratio between the volume (L) of solvent and the weight (kg) of silica gel is 2-2.4；
Iii. in the compound of structural formula 1, when component C and D presence are that c and d is all higher than 0, by VSi after 1-12 hours (OR1) and WSi (OR1) be added in reactant mixture, wherein V is the group of selectivity substitution and is selected from C1-22Alkyl, C1-22Alkane Base aryl, C2-20Alkyl hydrosulfide, C2-20Alkyl thioether C3-12Alkyl, C2-20Alkylen thioether C3-12Alkyl, C2-20Alkyl thioether virtue Base, C2-20Alkylen thioether aryl；W is the group of selectivity substitution and the C replaced selected from phenyl, aryl, hydroxyl1-10Alkyl, then Continuous heating 1-24 hours at 80-120 DEG C；
Iv. sulfonate is acidified when M is hydrogen in the compound of structural formula 1；
V. solid is filtered or is centrifuged, washed with solvent (such as water or alcohol) and dried.
Preferred reaction temperature (all steps are during above-mentioned the i-th to iv is walked) and reaction time are respectively 100-120 DEG C, 4- 8 hours.Solvent and cleaning solvent in the technique is reusable.
Another advantage of such technique is that all steps can be carried out in same reactor.
Extensive solvent or different solvents combination may be used to substitution reaction, including alcohols and polar solvent, such as diformazan Base formamide or dimethyl sulfoxide (DMSO) and water.Preferred solvent is alcohols, such as methyl alcohol.
Another advantage of the technique is that the compound of preparation structure formula 2 is very easy, by ready-made (R1O)3Si(CH2)mSH (wherein R1It is independently chosen from straight or branched C1-12Alkyl, aryl and C1-22Alkylaryl, m is an integer from 2 to 20) taking With alkali process in the same solvent that generation reaction is used.Preferred alkali is sodium alkoxide or alcohol sylvite.
Compound (R is used in the coupled reaction with inorganic framework1O)3SiV and (R1O)3SiW provides composite structure formula The 1 compound ([VSi (O of C containing component3/2)]cAnd/or D [WSi (O3/2)]d, wherein c and/or d is more than 0, R1Be independently chosen from straight chain or Side chain C1-12Alkyl, aryl and C1-22Alkylaryl, V is a group for selectivity substitution and is selected from C1-22Alkyl, C1-22Alkyl Aryl, C2-20Alkyl hydrosulfide, C2-20Alkyl thioether C3-12Alkyl, C2-20Alkylen thioether C3-12Alkyl, C2-20Alkyl thioether aryl, C2-20Alkylen thioether aryl；W is a group for selectivity substitution and the C replaced selected from phenyl, aryl, hydroxyl1-10Alkyl) A kind of production method.The component C and D contained in structural formula 1 so that functional group's property of Silica Surface can carry out hydrophobicity With hydrophilic adjustment, so as to improve the efficiency of catalytic reaction, and by the property (polarity is nonpolar) of V and W groups come real Existing this adjustment.For example, non-polar group includes alkyl, aryl, alkyl thioether alkyl, alkyl thioether aryl, hydroxyl alkane Base and hydroxy alkyl thioether alkyl.
M is the compound of structural formula 1 of transition metal, platinum family or base-metal salt, can in a solvent use metal salt treatment knot It is prepared by the sodium salt or sylvite of the respective compound of structure formula 1.For example, processing the product of example 10 with copper sulfate solution, copper is obtained (II) salt.
The compound of structural formula of the present invention 1 has been found to be efficient heterogeneous acid catalyst.This kind of compound can be used to be catalyzed Big quantitative response, especially traditionally with acid catalyzed reaction (such as cyclization), such as contracting of the synthesis, aldehyde and ketone of tetrahydrofuran Close reaction, ketal and aldolisation, alkene dehydration, reset and cracking reaction and isomerization reaction.
In addition to above-mentioned reaction, the compound of structural formula 1 can be additionally used in esterification, the ester exchange of carboxylate and the dehydration of sugar, For example by it is fructose converting be 5 hydroxymethyl furfural.The silica gel framework of the material settling out and the highly acid of sulfonic acid group allow its High conversion is reacted and obtained under all kinds of operating conditions.It is present in the additional functionality in chain or in V and W and can adjust catalyst Acidity.
The sulfoacid compound of structural formula 1 may also be used for catalytic CO and change into unsaturated carbon-carbon bond.
The compound of structural formula 1 optionally can also go the removal of impurity from product stream, technique stream and waste liquid.For example, unnecessary Amine, alkali compounds, metal ion and compound.
Now, the present invention is described in detail with reference to illustrative example of the invention.
Example 1
Sodium methoxide (8mol) and 3- mercaptopropyl trimethoxysilanes (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of PS (9.8mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (6L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (5kg, 147-400 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding diformazan Benzene (10L), then stir the mixture for, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, is filtered and is filled with water Divide washing, the compound of generating structure formula 1 after drying, wherein m and n is hydrogen for 3, M, and c and d are 0.
Example 2
Sodium methoxide (8mol) and 3- mercaptopropyl trimethoxysilanes (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of PS (9mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (8L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (6kg, 200-400 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding Dimethylbenzene (12L).Trimethoxy-benzene base silane (1mol) is added, stirred the mixture for, heated cooling after 3h.Water (2L) is added, Sulfuric acid acidifying mixture is used, is filtered and is fully washed with water (12L x4), the compound of generating structure formula 1, wherein m and n after drying It is that 3, M is hydrogen, W is phenyl, and c is 0.
Example 3
Sodium methoxide (8mol) and 3- mercaptopropyl trimethoxysilanes (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of PS (10mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (8L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (6kg, 37-147 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding diformazan Benzene (12L).2- ethoxys trimethoxy silane (1mol) are added, stirred the mixture for, heated cooling after 3h.Water (2L) is added, Sulfuric acid acidifying mixture is used, is filtered and is fully washed with water (12L x4), the compound of generating structure formula 1, wherein m and n after drying It is that 3, M is hydrogen, W is 2- ethoxys, and c is 0.
Example 4
Sodium methoxide (2mol) and 3- mercaptopropyl trimethoxysilanes (2mol) are dissolved in methyl alcohol (1L) and to stir 1 small When, the methyl alcohol (0.3L) that solution then is added dropwise into PS (2.8mol) in 30 minutes at 80 DEG C is molten In liquid.Mixed solution is added into methyl alcohol (2L) after stirring, heating 3h at 100 DEG C, silica gel (1.5kg, 147-400 μ is subsequently added m、), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while plus Enter dimethylbenzene (3L).Hexyl trimethoxy silane (0.25mol) and 2- ethoxys silane (0.1mol) are added, mixture is stirred Mix, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, is filtered and is fully washed with water (12L x 4), dried The compound of generating structure formula 1 afterwards, wherein m and n is hydrogen for 3, M, and V is hexyl, and W is 2- ethoxys.
Example 5
Sodium methoxide (8mol) and 4- mercaptos butyl trimethoxy silane (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of PS (9.6mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (8L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (5kg, 37-147 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding diformazan Benzene (12L), then stir the mixture for, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, water is filtered and use (12L x 4) is fully washed, the compound of generating structure formula 1 after drying, and wherein m is that 3, M is hydrogen for 4, n, and c and d is 0.
Example 6
Sodium methoxide (8mol) and 3- mercaptopropyl trimethoxysilanes (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of Isosorbide-5-Nitrae-butyl sultone (9.6mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (6L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (5kg, 147-400 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding diformazan Benzene (10L), then stir the mixture for, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, is filtered and is filled with water Divide washing, the compound of generating structure formula 1 after drying, wherein m is that 4, M is hydrogen for 3, n, and c and d is 0.
Example 7
Sodium methoxide (8mol) and 2- mercaptos ethyl trimethoxy silane (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of Isosorbide-5-Nitrae-butyl sultone (10mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (6L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (5kg, 147-400 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding diformazan Benzene (10L), then stir the mixture for, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, is filtered and is filled with water Divide washing, the compound of generating structure formula 1 after drying, wherein m is that 4, M is hydrogen for 2, n, and c and d is 0.
Example 8
Sodium methoxide (8mol) and 5- mercaptos amyltrimethoxysilane (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of PS (9.0mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (6L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (5kg, 300-500 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding Dimethylbenzene (10L), then stir the mixture for, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, is filtered and is used in combination Water is fully washed, the compound of generating structure formula 1 after drying, and wherein m is that 3, M is hydrogen for 5, n, and V is 5- sulfydryl amyl groups, and d is 0.
Example 9
Sodium methoxide (8mol) and 7- mercapto heptyl trimethoxy silane (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of Isosorbide-5-Nitrae-butyl sultone (10mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (6L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (5kg, 300-500 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding Dimethylbenzene (10L), then stir the mixture for, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, is filtered and is used in combination Water is fully washed, the compound of generating structure formula 1 after drying, and wherein m is that 4, M is hydrogen for 7, n, and c and d is 0.
Example 10
Sodium methoxide (8mol) and 3- mercaptopropyl trimethoxysilanes (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of PS (9.5mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (8L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (6kg, 200-400 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding Dimethylbenzene (12L), then stir the mixture for, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, is filtered and is used in combination Water (12L x 4) is fully washed, the compound of generating structure formula 1 after drying, and wherein m and n is sodium for 3, M, and W is phenyl, and c is 0.
Example 11
Sodium methoxide (8mol) and 3- mercaptopropyl trimethoxysilanes (8mol) are dissolved in methyl alcohol (3L) and to stir 1 small When, then solution be added dropwise to methyl alcohol (1L) solution of PS (10mol) at 80 DEG C in 30 minutes In.Mixed solution is added into methyl alcohol (6L) at 100 DEG C after stirring, heating 3h, be subsequently added silica gel (5kg, 147-400 μm,), mixture is stirred at 120 DEG C, 2h is heated.Methyl alcohol is slowly steamed in ensuing 2h, while adding diformazan Benzene (10L), then stir the mixture for, heat cooling after 3h.Water (2L) is added, sulfuric acid acidifying mixture is used, is filtered and is filled with water Divide washing, the compound of generating structure formula 1 after drying, wherein m and n is potassium for 3, M, c and d is 0.
Example 12
The compound (0.5kg) that example 10 is obtained is added in copper-bath (1M), the mixture stirring that will be generated Filtered after 2h.Product is cleaned (4x2L) with water, the compound of generating structure formula 1 after drying, wherein m and n is copper for 3, M, and W is benzene Base, c is 0.
Example 13
The compound (0.5kg) that example 11 is obtained is added in cobalt chloride solution (1M), the mixture stirring that will be generated Filtered after 2h.Product is cleaned (4x2L) with water, the compound of generating structure formula 1 after drying, wherein m and n is cobalt, c and d for 3, M It is 0.
Example 14
The compound (0.5kg) that example 11 is obtained is added in silver nitrate solution (1M), the mixture stirring that will be generated Filtered after 2h.Product is cleaned (4x2L) with water, the compound of generating structure formula 1 after drying, wherein m and n is that 3, M is silver, c and d It is 0.
Example 15
The compound (3.0g) that 1,4- dihydroxy butane (180.0g, 2mol) and example 1 are obtained is stirred under 120 DEG C of oil baths Heating is mixed, tetrahydrofuran and water are distilled from reactant mixture.Again to being dropwisely added 1,4- dihydroxies in reactant mixture Base butane, generates more tetrahydrofurans and water.The compound that example 2-9 is obtained has same effect.
Example 16
At reduced pressure conditions, maleic acid (116.0g, 1mol), 2-Ethylhexyl Alcohol (390.0g, 3mol) and example 5 are obtained Compound (3.0g) stirred under 120 DEG C of oil baths, heated.Mixture is cooled down after 12h, catalyst is recovered by filtration.Removed After the alcohol of amount, the purity of analysis display diester is 98%.The compound that example 2 and 6-9 are obtained also has same effect.
Example 17
At reduced pressure conditions, maleic acid (116.0g, 1mol), 2-Ethylhexyl Alcohol (390.0g, 3mol) and example 1 are filtered Catalyst (3.0g) afterwards is stirred under 120 DEG C of oil baths, heated.Mixture is cooled down after 12h, catalyst is recovered by filtration.Remove After excessive alcohol, the purity of analysis display diester is 98%.
Example 18
Under nitrogen atmosphere, the chemical combination for octadecenic acid (126.0g, 0.45mol), glycerine (24.0g) and example 7 being obtained Thing (1.5g) is stirred under 140-150 DEG C of oil bath, heated.Mixture is cooled down after 12h, filters out solid catalyst.Product point Analysis display hydroxyl value is less than 0.1.This reaction is repeated, using the catalyst washed after filtering and through methyl alcohol, close yield is obtained.
Example 19
The compound that sad (46.2g, 0.3mol), trimethylolpropane (13.8g, 0.1mol) and example 8 are obtained (0.1g, 0.1wt%) is stirred under 140 DEG C of oil baths, heating.It is after 24h that mixture cooling, filtering post analysis display alcohols is complete It is converted into diester (12%) and three esters (88%).The compound that example 1-4 and 7 is obtained also has same effect.
Example 20
The compound (1.0g) that 2,3- dimethyl -2,3- butanediols (60.0g, 0.5mol) and example 9 are obtained is at 120 DEG C Lower stirring, heating 2h.Reaction flask connects small-sized fractionating column and is used for distilling, obtain colourless 3,3- dimethyl that yield is 86%- 2- butanone liquid (51.0g) (boiling point measured value is 106 DEG C with literature value).It is anti-that the compound obtained with example 1 and 5 repeats this Should, obtain the ketone of same yield.After reaction terminates, a number of Pinacol is added, repeat to react Also same effect is obtained.
Example 21
The compound (2.0g) that 2,3- biacetyl monoximes (200.0g, 1.98mol) and example 1 are obtained adds at 120 DEG C Heat.Reaction rapidly, obtains a number of acetic acid and acetonitrile after continuous heating 10h.
Example 22
Obtained to acetophenone (48.0g, 0.4mol), ethylene glycol (60mL), example 5 is added in Dien Stark condenser Compound (2.0g) and toluene (300mL), flow back 4h.By reactant mixture cooling, filter and wash with water (3x200mL), use Magnesium sulfate is dried.Concentrate, obtain 1- methyl isophthalic acids-phenyl -1,3- dioxolane solids that yield is 93%.With in example 4 and 6-9 The compound for obtaining repeats this reaction, obtains the ketal of same yield.
Example 23
The compound (0.3g) that 1- phenyl-1-propanols (16.0g, 0.12mol) and example 9 are obtained adds toluene (40mL) In, 75 DEG C are stirred, heat 5h under nitrogen atmosphere.Ether (50mL) is added, mixture is filtered, catalyst is removed.In room temperature, bear Pressure, concentrates organic detergent liquid, obtains colorless oil Beta-methyl styrene, and conversion ratio is 93%.The catalyst that will be filtrated to get It is added in toluene (40mL) with 1- phenyl-1-propanols (16.0g), repeats same course of reaction, obtains colorless oil β-first Base styrene, conversion ratio is 92%.
Example 24
Compound (1.0g), 18 diluted acids (282.0g, 0.91mol) and ethanol (500mL) mixing that will be obtained in example 1 It is stirred at reflux 10h.Cooled and filtered falls solid, and oily ethyl oleate of the purity more than 99% is obtained after solution concentration.Use example The compound obtained in 3-6 and 9 repeats this reaction, obtains the esters of same yield.
Example 25
Compound (5.0g), ethyl oleate (155.0g, 0.5mol) and amylalcohol (300mL) mixing that will be obtained in example 7 It is stirred at reflux 6h.Cooled and filtered falls catalyst, and oily oleic acid penta of the conversion ratio more than 97% is obtained after reactant mixture concentration Ester.
Example 26
Fructose (4.5g, 0.027mol) is dissolved in water (11mL), with methylisobutylketone, 2- butanol (7:3rd, 30mL) and The compound (0.5g) obtained in example 1 is stirred at 130 DEG C, heats 2h, and the 5- that conversion ratio is 85% is progressively obtained after separation Hydroxymethylfurfural.
Example 27
The product (4.0g) that to be obtained in example 10 and containing Cu2+After the aqueous phase solution of (124ppm, 1L) mixes 30min Filtering, analysis filtrate is showed more than 99% Cu2+It is removed.
Example 28
The product (4.0g) that to be obtained in example 10 and containing Co2+(124ppm, 1L) solution is filtered after mixing 30min, Analysis filtrate is showed more than 99% Co2+It is removed.

Claims (10)

1. a kind of method for producing the compound of following structural 1：
[(O3/2)Si(CH2)mS(CH2)nSO3M]a[Si(O4/2)]b[VSi(O3/2)]c[WSi(O3/2)]d
In formula, M is hydrogen, transition metal, platinum family or base-metal salt；V is one can optionally select the group of substitution and selected from C1-22 Alkyl, C1-22Alkylaryl, C2-20Alkylthiol groups, C2-20Alkyl thioether C3-12Alkyl, C2-20Alkylen thioether C3-12Alkyl, C2-20Thioether aryl, C2-20Alkylen thioether aryl；W be one can optionally select substitution group and be selected from phenyl, aryl, The C of hydroxyl substitution1-10Alkyl；M is an integer from 2 to 20；N is an integer from 3 to 12；A, b, c, d are integer, And a:The ratio of b is that, from 0.00001 to 100,000, a and b exists always, when c or d is more than zero, the ratio of c+d and a+b It is from 0.00001 to 100,000；The silicon atom of other groups, hydrogen, straight or branched C in structural formula 11-22Alkyl, end group R3SiO1/2, crosslinking agent or chain RqSi(OR1)gOk/2Wherein one or more make the free valency saturation of silicate oxygen atom, its Middle R and R1It is respectively selected from straight or branched C1-22Alkyl, aryl and C1-22Alkylaryl, k is an integer from 1 to 3, q be from 1 to 2 integer, g is an integer from 0 to 2, and meets g+k+q=4, when end group, crosslinking agent and/or polymer In the presence of chain, the ratio of its mol ratio and a+b+c+d is 0 to 999:1；
This method includes：
I. in a solvent with the compound (R of structural formula 21O)3Si(CH2)mSM1Contacted with the compound of structural formula 3, in 10-
Reaction 10 minutes to 24 hours in 120 DEG C of temperature ranges；
Structural formula 3
R in structural formula 21It is independently chosen from straight or branched C1-12Alkyl, aryl and C1-22Alkylaryl, M1It is alkali metal or alkaline earth gold Category, m is an integer from 2 to 20；
N is an integer from 1 to 10 in structural formula 3；
Ii. solvent such as alcohols, water and polar solvent and inorganic skeleton are added in the reactant mixture of stirring, at 80-120 DEG C Lower continuous heating 1-24 hours, while slowly being steamed solvent and adding the toluene or dimethylbenzene of equivalent so that in units of L Ratio between solvent volume and the silica gel weight in units of kg is as 2-2.4；
Iii. as component C [VSi (O3/2)]cWith D [WSi (O3/2)]dWhen presence is that c and d is all higher than 0, by VSi after 1-12 hours (OR1) and WSi (OR1) be added in reactant mixture, continuous heating 1-24 hours at 80-120 DEG C；
Iv. the compound of structural formula 1 that M is hydrogen is acidified；
V. solid is filtered or is centrifuged, washed with solvent, the compound of structural formula 1 is obtained after drying.
2. a kind of method according to claim 1, the reaction of its i-th to iv steps carries out 2 to 12 at 80-120 DEG C Hour, the compound of generating structure formula 1.
3. a kind of method according to foregoing any claim, wherein, the integer c and d of structural formula 1 are zero, by structure The silicon atom of other groups, hydrogen, straight or branched C in formula 11-6One or more in alkyl make the freedom of silicate oxygen atom Valency saturation.
4. a kind of method for carrying out acid catalyzed reaction or heterogeneous catalytic reaction, comprising one or more reactants in reaction with The compound contact of the method manufacture according to any claim in claims 1 to 3.
5. a kind of method according to claim 4, be alkylated, be polymerized, being acylated, isomerization, esterification, transesterification, ether Change, ketalization, carbonylation is carbon monoxide and unsaturated compound addition or rearrangement reaction, this method is included will be according to right It is required that the product of the method generation in 1 to 3 described in any claim is used as catalyst.
6. the compound that a kind of method according to any claim in claims 1 to 3 is produced, as acid catalyst or Heterogeneous catalysis.
7. a kind of purposes as heterogeneous catalysis according to claim 6, for being alkylated, being polymerized, be acylated, isomery Change, be esterified, transesterification, etherificate, ketalization, carbonylation are carbon monoxide and unsaturated compound addition or rearrangement reaction.
8. the compound that a kind of method according to any claim in claims 1 to 3 is produced, as functionalization material Unwanted organic and inorganic or biologic artifact is removed or reduced from liquid feedstock.
9. the compound that a kind of method according to any claim in claims 1 to 3 is generated, as cation or the moon Ion-exchanger.
10. the compound that a kind of method according to any claim in claims 1 to 3 is generated, for purifying or dividing From biomolecule, such as enzyme, polypeptide, protein and nucleic acid.
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