CN105732693B - A kind of bisamide bond distance carbochain organosilan quaternary ammonium compound and its preparation and application - Google Patents
A kind of bisamide bond distance carbochain organosilan quaternary ammonium compound and its preparation and application Download PDFInfo
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- CN105732693B CN105732693B CN201610196253.XA CN201610196253A CN105732693B CN 105732693 B CN105732693 B CN 105732693B CN 201610196253 A CN201610196253 A CN 201610196253A CN 105732693 B CN105732693 B CN 105732693B
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- bisamide
- quaternary ammonium
- carbochain
- ammonium compound
- bond distance
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- 150000003856 quaternary ammonium compounds Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims abstract description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims abstract description 8
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 125000002521 alkyl halide group Chemical group 0.000 claims abstract description 7
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 claims abstract 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl trimethoxysilane Chemical compound 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000499 gel Substances 0.000 claims description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 36
- 239000010457 zeolite Substances 0.000 abstract description 36
- 239000011148 porous material Substances 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000002149 hierarchical pore Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SZLZWPPUNLXJEA-QEGASFHISA-N rescinnamine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)\C=C\C1=CC(OC)=C(OC)C(OC)=C1 SZLZWPPUNLXJEA-QEGASFHISA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of bisamide bond distance carbochain organosilan quaternary ammonium compound and its preparation and application, structural formula of compound are as follows:Wherein, m=1-18 arbitrary integer, n=1-5 arbitrary integer, X‑For Cl‑、Br‑、I‑One of；Preparation: N- methyliminodiacetic acid, fatty amine, I-hydroxybenzotriazole HOBT, carbodiimides EDCI, triethylamine are added in solvent, are then stirred overnight at room temperature, purifies, obtains bisamide chain intermediate；Above-mentioned bisamide chain intermediate and alkylhalide group trimethoxy silane are mixed, reacted, it is cooling, washing to get.Preparation applied to containing mesopore ZSM-5 molecular sieve.Hierarchical zeolite molecular sieve prepared by the present invention can significantly improve the Kong Rong and specific surface area of zeolite molecular sieve, and the carbon atom number by changing double acyl-fatty chains can effectively adjust aperture and the Kong Rong of molecular sieve multistage pore canal.
Description
Technical field
The invention belongs to quaternary ammonium compound and its preparation and application field, in particular to a kind of bisamide bond distance carbochain
Organosilan quaternary ammonium compound and its preparation and application.
Background technique
Zeolite molecular sieve is widely used in petrochemical industry and fine chemistry industry as catalyst, because of its unique adsorbing separation function
The field of engineering technology such as ion exchange, adsorbing separation, environmental protection can be also widely used in.However traditional zeolite molecular sieve is more
For micropore (aperture is less than 2nm), such aperture is difficult to be catalyzed the chemical reaction of macromolecular, and then micro-pore zeolite molecular sieve is big
The application of Journal of Molecular Catalysis field is restricted.Especially less and less in current Global Oil resource, heavy oil content is increasingly in petroleum
More, there is an urgent need to the catalyst of more large aperture to be catalyzed for petrochemical industry.There are also many emerging biological medicines, fining
The chemical reaction that the fields such as work carry out macromolecular is also required to the utilization of new macroporous diameter catalyst.In this context, it develops mesoporous
Molecular sieve or even large pore molecular sieve be particularly important with it is practical.According to international pure and applied chemistry federation (IUPAC)
Classification: be known as poromerics of the aperture less than 2nm, be known as mesoporous material of the aperture 2 to 50nm, aperture is known as greater than 50nm's
Large pore material.
It prepares mesopore molecular sieve usually to need to use template, to develop New Mesoporous Molecular Sieves will develop new type formwork
Agent, surfactant is as common soft template, still or the research emphasis and hot spot of current new type formwork agent.It is preparing
During mesoporous material, the type and property of surfactant have a significant impact to the formation of mesoporous phase, or even can change
The route of synthesis of reaction system.Cationic surfactant is one kind important in surfactant, and hydrophilic radical is positively charged.
And the long chain alkyl ammonium salt of low molecular weight is most common cationic surfactant.But with long chain alkyl ammonium salt type
Cationic surfactant is more single as the mesoporous molecular sieve structure that template synthesizes, and hole wall is relatively thin, point of synthesis
Son sieve hydrothermal stability is poor, and then these problems are exactly that develop novel quaternary cationic surfactant to be solved
Problem.
Hierarchical zeolite molecular sieve, duct model are synthesized by template of novel organosilicon quaternary ammonium salt surface active agent
It encloses including micropore and mesoporous or even macropore.This kind of zeolite molecular sieve containing multistage pore canal because have its unique property with it is excellent
Gesture possesses broad application prospect in fields such as catalysis, absorption, separation.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of bisamide bond distance carbochain organosilan quaternary ammonium salt chemical combination
Object and its preparation and application, the present invention, which prepares hierarchical zeolite molecular sieve prepared by the present invention, can significantly improve zeolite molecular sieve
Kong Rong and specific surface area, the carbon atom number by changing bisamide base chain can effectively adjust the hole of molecular sieve multistage pore canal
Diameter and Kong Rong, can also be by changing rubbing for quaternary cationics and the silicon source in zeolite molecular sieve synthesis mother liquid
The pattern that you compare to regulate and control hierarchical zeolite molecular sieve.
A kind of bisamide bond distance carbochain organosilan quaternary ammonium compound of the invention, the structural formula of compound are as follows:
Wherein, m=1-18 arbitrary integer, n=1-5 arbitrary integer, X-For Cl-、Br-、I-One of.
A kind of preparation method of bisamide bond distance carbochain organosilan quaternary ammonium compound of the invention, comprising:
(1) by N- methyliminodiacetic acid, fatty amine, I-hydroxybenzotriazole HOBT, carbodiimides EDCI, triethylamine
It is added in solvent, is then stirred overnight at room temperature, purify, obtain bisamide chain intermediate；Wherein N- methylene imine oxalic acid, fat
Amine, the molar ratio of HOBT, EDCI are 1:2.0-3.0:2.0-2.5:2.0-2.5；
(2) above-mentioned bisamide chain intermediate and alkylhalide group trimethoxy silane are mixed, at 90-130 DEG C, reacts 12-
For 24 hours, it is cooled to room temperature, washs, obtain bisamide bond distance's carbochain organosilan quaternary ammonium compound；Wherein among bisamide chain
The molar ratio of body and alkylhalide group trimethoxy silane is 1:1.0-2.0.
Fatty amine is in the step (1)Wherein any positive integer of m=1-18.
Purification in the step (1) specifically: use saturated sodium bicarbonate, ethyl acetate, with n-hexane weight after ether washing
Crystallization.
Solvent is dimethylformamide or tetrahydrofuran in the step (1).
The molecular formula of alkylhalide group trimethoxy silane in the step (2) are as follows:Wherein X be Cl,
One of Br, I, n=1-5 arbitrary integer.
A kind of application of bisamide bond distance carbochain organosilan quaternary ammonium compound of the invention, it is characterised in that: institute
Preparation of the bisamide bond distance's carbochain organosilan quaternary ammonium compound for containing mesopore ZSM-5 molecular sieve is stated, specifically:
(1) under the conditions of 20-25 DEG C, silicon source, silicon source and water are mixed to homogeneously, then under lasting stirring condition,
Micropore template agent is added, is stirred for homogeneous, obtains the mother liquor of zeolite molecular sieve synthesis, bisamide bond distance carbochain, which is then added, to be had
Machine organosilane quaternary ammonium salt compound, stirring 1-3h mixing, obtains mixed system；Wherein silicon source, silicon source, micropore template agent, double acyls
Amine key Long carbon chain organosilan quaternary ammonium compound, water molar ratio be 1-100:1:20-48:0.01-8:800-5000；
(2) above-mentioned mixed system is subjected to constant temperature stirring, obtains white gels, then carry out crystallization, quenching, filtered, wash
It washs to neutrality, dry, calcining obtains hierarchical zeolite molecular sieve containing mesopore ZSM-5 molecular sieve.
Silicon source is one or more of silicate class, sodium metasilicate crystal, waterglass, silica solution in the step (1)；Aluminium
Source is one or more of sodium metaaluminate, aluminum sulfate, aluminum nitrate, alchlor and aluminium isopropoxide；Micropore template agent is tetramethyl
One of base ammonium bromide, tetraethylammonium bromide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide or
It is several.Speed of agitator is 260-350r/min in the step (1).
Constant temperature stirs in the step (2) are as follows: under the conditions of 20-25 DEG C, speed of agitator 360-450r/min, and mixing time
For 2-3h.Crystallization in the step (2) specifically: in the confined reaction autoclave of the bushing pipe containing polytetrafluoroethylene (PTFE), 140-170
Crystallization 3-96h at DEG C；It is dry are as follows: under the conditions of 80-120 DEG C, dry 10-20h；Calcining is to calcine 10-15h at 400-600 DEG C.
Hierarchical zeolite molecular sieve belongs to MFI type structure Si-Al zeolite in the step (2).
The BET surface area of the hierarchical zeolite molecular sieve is 200~1000m2g-1, the aperture BJH is 2~20nm, hole
Holding is 0.2~1.0cm3g-1。
The present invention relates to serial bisamide bond distance carbochain organosilicone quaternary ammonium salt compounds process for production thereof and applications.Such is changed
Object is closed using serial fatty amine as raw material, bisamide chain intermediate, bisamide chain intermediate are reacted to obtain with N- methylene imine oxalic acid
Target product series bisamide chain organosilicon quaternary ammonium salt is obtained with alkylhalide group trimethoxy silane quaternization reaction.
The present invention prepares the zeolite molecular sieve containing multistage pore canal by new template agent of serial bisamide chain organosilicon quaternary ammonium salt,
Its multistage pore canal includes micropore, mesoporous or even macropore.This hierarchical zeolite molecular sieve has biggish Kong Rong and specific surface
Product, pore-size distribution is uniform, and multistage pore canal can be suitably used for different size of Journal of Molecular Catalysis, adsorb and separate.But also it can pass through
The carbon atom number for changing bisamide bond distance carbochain can effectively adjust aperture and the Kong Rong of molecular sieve multistage pore canal, pass through variation
The molar ratio of silica in quaternary cationics and zeolite molecular sieve synthesis mother liquid regulates and controls multistage pore canal
The pattern of zeolite molecular sieve.
Beneficial effect
Hierarchical zeolite molecular sieve prepared by the present invention can significantly improve the Kong Rong and specific surface area of zeolite molecular sieve, lead to
It crosses and changes the carbon atom number of bisamide bond distance carbochain and can effectively adjust aperture and the Kong Rong of molecular sieve multistage pore canal, it can be with
Regulate and control multistage by the molar ratio of the silicon source in variation quaternary cationics and zeolite molecular sieve synthesis mother liquid
The pattern of duct zeolite molecular sieve；
Zeolite molecular sieve containing multistage pore canal of the invention because have its unique property and advantage, catalysis, absorption,
Separation, biology, medicine and other fields possess broad application prospect.
Detailed description of the invention
Fig. 1 is the XRD diagram for the hierarchical pore MFI structural zeolite molecular sieve that embodiment 4 is prepared；
Fig. 2 is that the nitrogen absorption under low temperature-desorption isothermal for the hierarchical pore MFI structural zeolite molecular sieve that embodiment 4 is prepared is bent
Line；
Fig. 3 is the graph of pore diameter distribution for the hierarchical pore MFI that embodiment 4 is prepared；
Fig. 4 is the scanning electron microscope (SEM) photograph for the hierarchical pore MFI that embodiment 4 is prepared；
Fig. 5 is the transmission electron microscope picture for the hierarchical pore MFI that embodiment 4 is prepared.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
Bisamide chain organosilicone quaternary ammonium salt compound, chemical structural formula are as follows:
Wherein X-For I-, n=3, m=12.
Preparation method: sequentially adding 0.68gN- methyliminodiacetic acid in 150mL three-necked flask, 1.97g tetradecy lamine,
1.225g1- hydroxybenzotriazole (HOBT), 1.773g carbodiimides (EDCI), 1.27mL triethylamine, 100mL DMF room temperature
(25 DEG C) are stirred overnight.50mL saturated sodium bicarbonate solution is poured into three-necked flask reaction solution, there is white solid precipitation, is filtered
White solid is obtained, is washed every time with 20mL DMF solution, washing three times, washs three with 20mL saturated sodium bicarbonate solution later
It is secondary, then washed three times with 20mL ethyl acetate, it finally washed once with 20mL ether, obtained white solid is again with n-hexane weight
Crystallization obtains pure intermediate, is put into the midbody product for drying pure in vacuum drying oven.
Above-mentioned intermediate 0.8g, 3- iodine propyl trimethoxy silicane 0.56g are added in 50mL round-bottomed flask, is slowly heated
To 100 DEG C, 12h is reacted, after reaction, cooled to room temperature is washed repeatedly with n-hexane solvent, obtains above-mentioned bisamide chain
Organosilicone quaternary ammonium salt compound.
Embodiment 2
Bisamide chain organosilicone quaternary ammonium salt compound, chemical structural formula are as follows:
Wherein X-For I-, n=3, m=10.
Preparation method: sequentially adding 0.68gN- methyliminodiacetic acid in 150mL three-necked flask, 1.67g lauryl amine,
1.225g1- hydroxybenzotriazole (HOBT), 1.773g carbodiimides (EDCI), 1.27mL triethylamine, 100mL DMF room temperature
(25 DEG C) are stirred overnight.50mL saturated sodium bicarbonate solution is poured into three-necked flask reaction solution, there is white solid precipitation, is filtered
White solid is obtained, is washed every time with 20mL DMF solution, washing three times, washs three with 20mL saturated sodium bicarbonate solution later
It is secondary, then washed three times with 20mL ethyl acetate, it finally washed once with 20mL ether, obtained white solid is again with n-hexane weight
Crystallization obtains pure intermediate, is put into the midbody product for drying pure in vacuum drying oven.
Above-mentioned intermediate 0.8g, 3- iodine propyl trimethoxy silicane 0.61g are added in 50mL round-bottomed flask, is slowly heated
To 100 DEG C, 12h is reacted, after reaction, cooled to room temperature is washed repeatedly with n-hexane solvent, obtains above-mentioned bisamide chain
Organosilicone quaternary ammonium salt compound.
Embodiment 3
Bisamide chain organosilicone quaternary ammonium salt compound, chemical structural formula are as follows:
Wherein X-For I-, n=3, m=8.
Preparation method: sequentially adding 0.68gN- methyliminodiacetic acid in 150mL three-necked flask, ten amine of 1.47g,
1.225g1 hydroxybenzotriazole (HOBT), 1.773g carbodiimides (EDCI), 1.27mL triethylamine, 100mL DMF room temperature
(25 DEG C) are stirred overnight.50mL saturated sodium bicarbonate solution is poured into three-necked flask reaction solution, there is white solid precipitation, is filtered
White solid is obtained, is washed every time with 20mL DMF solution, washing three times, washs three with 20mL saturated sodium bicarbonate solution later
It is secondary, then washed three times with 20mL ethyl acetate, it finally washed once with 20mL ether, obtained white solid is again with n-hexane weight
Crystallization obtains pure intermediate, is put into the midbody product for drying pure in vacuum drying oven.
Above-mentioned intermediate 0.8g, 3- iodine propyl trimethoxy silicane 0.66g are added in 50mL round-bottomed flask, is slowly heated
To 100 DEG C, 12h is reacted, after reaction, cooled to room temperature is washed repeatedly with n-hexane solvent, obtains above-mentioned bisamide chain
Organosilicone quaternary ammonium salt compound.
Embodiment 4
The synthesis of hierarchical pore MFI structural zeolite molecular sieve: silicon source aluminium isopropoxide (AIP) is added in 250mL three-necked flask
0.08g, water 54.01g, micropore template agent tetrapropylammonium hydroxide (TPAOH, 25%w/w) 4.10g.Mechanical stirring to it is homogeneous (about
Half an hour), silicon source ethyl orthosilicate (TEOS) 4.19g is added, continues to stir to homogeneous (about 1h), then season in example 2 is added dropwise
Ammonium salt 0.35g (0.0005mol) continues stirring two hours, obtains white gels.Gel is put into autoclave in 150 DEG C of crystallization
72h is washed with distilled water suction filtration to neutrality, obtains white solid, be put into 100 DEG C of baking 3h in baking oven, place into horse after crystallization is complete
Not 600 DEG C of calcining 5h in furnace.Up to hierarchical pore MFI structural zeolite molecular sieve, BET surface area 386m2g-1, the aperture BJH is
3.8nm, Kong Rongwei 0.21cm3g-1。
The XRD spectrum of the hierarchical pore MFI structural zeolite molecular sieve is as shown in Figure 1, the crystallinity of ZSM-5 is very as the result is shown
It is good, belong to typical ZSM-5 lattice.
Nitrogen absorption under low temperature-desorption isothermal curve is as shown in Fig. 2, bright when relative pressure is greater than 0.4MPa as the result is shown
Explict occurrence hysteresis loop illustrates there are a large amount of irregular mesoporous generations.
BJH graph of pore diameter distribution is as shown in Figure 3, it is seen that aperture is mainly distributed on 4nm, is macropore range.
The convex-concave that the scanning electron microscope and transmission electron microscope of Fig. 4, Fig. 5 are clearly visible sample surfaces rises and falls, from transmission electron microscope side
The crystalline structure on surface can be observed in edge.
Embodiment 5
The synthesis of hierarchical pore MFI structural zeolite molecular sieve: silicon source aluminium isopropoxide (AIP) is added in 250mL three-necked flask
0.08g, water 54.64g, micropore template agent tetrapropylammonium hydroxide (TPAOH, 25%w/w) 4.09g.Mechanical stirring to it is homogeneous (about
Half an hour), silicon source ethyl orthosilicate (TEOS) 4.18g is added, continues to stir to homogeneous (about 1h), then season in example 1 is added dropwise
Ammonium salt 0.36g (0.0005mol) continues stirring two hours, obtains white gels.Gel is put into autoclave in 150 DEG C of crystallization
72h is washed with distilled water suction filtration to neutrality, obtains white solid, be put into 100 DEG C of baking 3h in baking oven, place into horse after crystallization is complete
Not 600 DEG C of calcining 5h in furnace.Up to hierarchical pore MFI structural zeolite molecular sieve, BET surface area 392m2g-1, the aperture BJH is
3.81nm, Kong Rongwei 0.25cm3g-1。
The x-ray diffraction pattern of product has the feature of Fig. 1；Nitrogen absorption under low temperature-desorption isothermal curve has the feature of Fig. 2；
Pore-size distribution has the feature of Fig. 3；Stereoscan photograph has the feature of Fig. 4；Transmission electron microscope photo has the feature of Fig. 5.
Embodiment 6
The synthesis of hierarchical pore MFI structural zeolite molecular sieve: silicon source aluminium isopropoxide (AIP) is added in 250mL three-necked flask
0.08g, water 54.64g, micropore template agent tetrapropylammonium hydroxide (TPAOH, 25%w/w) 4.08g.Mechanical stirring to it is homogeneous (about
Half an hour), silicon source ethyl orthosilicate (TEOS) 4.18g is added, continues to stir to homogeneous (about 1h), then season in example 3 is added dropwise
Ammonium salt 0.41g (0.0005mol) continues stirring two hours, obtains white gels.Gel is put into autoclave in 150 DEG C of crystallization
72h is washed with distilled water suction filtration to neutrality, obtains white solid, be put into 100 DEG C of baking 3h in baking oven, place into horse after crystallization is complete
Not 600 DEG C of calcining 5h in furnace.Up to hierarchical pore MFI structural zeolite molecular sieve, BET surface area 397m2g-1, the aperture BJH is
3.93nm, Kong Rongwei 0.21cm3g-1。
Embodiment 7
The synthesis of hierarchical pore MFI structural zeolite molecular sieve: silicon source aluminium isopropoxide (AIP) is added in 250mL three-necked flask
0.08g, water 54.64g, micropore template agent tetrapropylammonium hydroxide (TPAOH, 25%w/w) 4.08g.Mechanical stirring to it is homogeneous (about
Half an hour), silicon source ethyl orthosilicate (TEOS) 4.18g is added, continues to stir to homogeneous (about 1h), then season in example 3 is added dropwise
Ammonium salt 0.8g (0.001mol) continues stirring two hours, obtains white gels.Gel is put into autoclave in 150 DEG C of crystallization
72h is washed with distilled water suction filtration to neutrality, obtains white solid, be put into 100 DEG C of baking 3h in baking oven, place into horse after crystallization is complete
Not 600 DEG C of calcining 5h in furnace.Up to hierarchical pore MFI structural zeolite molecular sieve, BET surface area 454m2g-1, the aperture BJH is
2.9nm, Kong Rongwei 0.34cm3g-1。
The x-ray diffraction pattern of product has the feature of Fig. 1；Nitrogen absorption under low temperature-desorption isothermal curve has the feature of Fig. 2；
Pore-size distribution has the feature of Fig. 3；Stereoscan photograph has the feature of Fig. 4；Transmission electron microscope photo has the feature of Fig. 5.
Claims (10)
1. a kind of bisamide bond distance carbochain organosilan quaternary ammonium compound, it is characterised in that: the structural formula of compound are as follows:
Wherein, m=1-18 arbitrary integer, n=1-5 arbitrary integer, one of X- Cl-, Br-, I-.
2. a kind of preparation method of bisamide bond distance carbochain organosilan quaternary ammonium compound as described in claim 1, packet
It includes:
(1) N- methylene imine oxalic acid, fatty amine, I-hydroxybenzotriazole HOBT, carbodiimides EDCI, triethylamine are added
It in solvent, is then stirred overnight at room temperature, purifies, obtain bisamide chain intermediate；Wherein N- methylene imine oxalic acid, fatty amine,
The molar ratio of HOBT, EDCI are 1:2.0-3.0:2.0-2.5:2.0-2.5；
(2) above-mentioned bisamide chain intermediate and alkylhalide group trimethoxy silane are mixed, at 90-130 DEG C, reacts 12-24h, it is cold
But to room temperature, washing obtains bisamide bond distance's carbochain organosilan quaternary ammonium compound；Wherein bisamide chain intermediate and halogen
The molar ratio of alkyl trimethoxysilane is 1:1.0-2.0.
3. a kind of preparation method of bisamide bond distance carbochain organosilan quaternary ammonium compound according to claim 2,
It is characterized by: fatty amine is in the step (1)Wherein m=1-18's is any just whole
Number.
4. a kind of preparation method of bisamide bond distance carbochain organosilan quaternary ammonium compound according to claim 2,
It is characterized by: purification in the step (1) specifically: use saturated sodium bicarbonate, ethyl acetate uses n-hexane after ether washing
Recrystallization.
5. a kind of preparation method of bisamide bond distance carbochain organosilan quaternary ammonium compound according to claim 2,
It is characterized by: solvent is dimethylformamide or tetrahydrofuran in the step (1).
6. a kind of preparation method of bisamide bond distance carbochain organosilan quaternary ammonium compound according to claim 2,
It is characterized by: in the step (2) alkylhalide group trimethoxy silane molecular formula are as follows:Wherein X
For one of Cl, Br, I, n=1-5 arbitrary integer.
7. a kind of application of bisamide bond distance carbochain organosilan quaternary ammonium compound as described in claim 1, feature
Be: the bisamide bond distance carbochain organosilan quaternary ammonium compound is used for the preparation of containing mesopore ZSM-5 molecular sieve, specifically
Are as follows:
(1) under the conditions of 20-25 DEG C, silicon source, silicon source and water is mixed, micropore template agent is then added, stirred, double acyls are added
Amine key Long carbon chain organosilan quaternary ammonium compound, is stirred, obtains mixed system；Wherein silicon source, silicon source, micropore template
Agent, bisamide bond distance's carbochain organosilan quaternary ammonium compound, water molar ratio be 1-100:1:20-48:0.01-8:800-
5000；
(2) above-mentioned mixed system is subjected to constant temperature stirring, obtains white gels, then carry out crystallization, quenching, filtered, washing is extremely
Neutrality, dry, calcining obtains containing mesopore ZSM-5 molecular sieve.
8. a kind of application of bisamide bond distance carbochain organosilan quaternary ammonium compound according to claim 7, special
Sign is: silicon source is one or more of silicate class, sodium metasilicate crystal, waterglass, silica solution in the step (1)；Aluminium
Source is one or more of sodium metaaluminate, aluminum sulfate, aluminum nitrate, alchlor and aluminium isopropoxide；Micropore template agent is tetramethyl
One of base ammonium bromide, tetraethylammonium bromide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide or
It is several.
9. a kind of application of bisamide bond distance carbochain organosilan quaternary ammonium compound according to claim 7, special
Sign is: constant temperature stirs in the step (2) are as follows: under the conditions of 20-25 DEG C, speed of agitator 360-450r/min, and mixing time
For 2-3h.
10. a kind of application of bisamide bond distance carbochain organosilan quaternary ammonium compound according to claim 7, special
Sign is: crystallization in the step (2) specifically: in the confined reaction autoclave of the bushing pipe containing polytetrafluoroethylene (PTFE), 140-170
Crystallization 3-96h at DEG C；It is dry are as follows: under the conditions of 80-120 DEG C, dry 10-20h；Calcining is to calcine 10-15h at 400-600 DEG C.
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