CN106588816A - Gemini quaternary ammonium salt or quaternary ammonium salt compound and preparation method - Google Patents
Gemini quaternary ammonium salt or quaternary ammonium salt compound and preparation method Download PDFInfo
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- CN106588816A CN106588816A CN201510683598.3A CN201510683598A CN106588816A CN 106588816 A CN106588816 A CN 106588816A CN 201510683598 A CN201510683598 A CN 201510683598A CN 106588816 A CN106588816 A CN 106588816A
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- ammonium salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
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- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- 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
- C01B39/42—Type ZSM-12
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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Abstract
The invention relates to gemini quaternary ammonium salt or a quaternary ammonium salt compound and a preparation method. The technical problems that a template existing in the prior art is poor in framework rigidity and poor in guidance quality are mainly solved. According to the technical scheme, gemini quaternary ammonium salt or the quaternary ammonium salt compound is adopted, and the structure is shown as the following structure general formula, wherein R1 is alkyl of C1-C10, R2 is at least one of H, halogen and alkyl of C1-C6, and X is any one of chlorine, bromine, iodine and hydroxyl, and the problem is solved well. Gemini quaternary ammonium salt or the quaternary ammonium salt compound is high in structural rigidity and can serve as a template to be used for synthesis of a zeolite molecular sieve. The general formula is shown in the specification.
Description
Technical field
The present invention relates to a kind of gemini quaternary ammonium salt or quaternary amine alkali cpd and preparation method.
Background technology
Quaternary ammonium salt also known as quarternary ammonium salt, is compound that four hydrogen atoms of ammonium ion are all replaced by alkyl and generated, it is cloudy from
Subbase group mostly is halide anion, and after halide anion is exchanged into hydroxide ion, resulting molecule is referred to as quaternary amine alkali.
Quaternary ammonium salt molecule purposes is enriched, and typically can serve as：Disinfection sanitizer, soft antistatic additive, flocculant, breakdown of emulsion
Agent, drag reducer, thickening agent, anion synergist etc..The quaternary ammonium salt present in nature typically has biological activity, has
A little quaternary ammonium salts can be used for medicinal purpose, phase transfer catalyst in pesticide and chemical reaction etc..Quaternary ammonium salt is cationic surfactant
One big class of agent.With strong sterilization and the mould mothproof performance of suppression.Dodecyl dimethyl benzyl ammonium chloride can be used as acrylon
Levelling agent.Two alkyl in quaternary ammonium molecules of salt are the products of chain alkyl, have good soft effect to various fibers,
Filament expansion can be made soft, appearance looks elegant and smooth, be rich in excellent handle, be a kind of conventional softening agent for fibres.Bromination is double
Octadecyldimethyl ammonium, is not only antibacterial, and all has significant soft effect to cotton, hair, synthetic fabrics.
Octadecyldimethyl hydroxyethyl ammonium nitrate is a kind of fabulous antistatic additive.Quaternary ammonium salt can also make waterproofing agent, retarding agents,
Petroleum demulsifier etc..
Simultaneously the product of quaternary ammonium salt have environmental protection, it is degradable, without the present environmental risks such as APEO, formaldehyde and people
The characteristic of the material of class health.Quaternary ammonium salt is the developing direction of following washing industry surfactant.So exploitation quaternary ammonium salt
Various fine chemical products there is larger market potential and competitiveness.
Additionally, quaternary ammonium salt or quaternary amine base molecule are system with molecular sieve for preparing very important template of a class for during, special construction
Organic amine template plays an important role in Zeolite synthesis, synthesizes the silica-rich zeolite such as ITQ-4 of report in recent years,
ITQ-7, ITQ-12, ITQ-13, ITQ-32, SSZ-26, SSZ-35, SSZ-74 etc., be all by the use of new organic amine as
What template was synthesized.The scientists such as Huo with Gemini type double end quaternary cationicses, by changing two
Side or the length and property of middle alkyl chain, have synthesized SBA-3, MCM-41, MCM-48 under acid or alkalescence condition
Sieve with MCM-50 equimoleculars.
A kind of gemini quaternary ammonium salt or quaternary amine alkali cpd that the present invention is provided has more special structure, and skeleton rigidity is relatively strong,
There is preferable structure directing in Zeolite synthesis.
The content of the invention
One of the technical problem to be solved is that template skeleton poor rigidity, guidance quality present in prior art are poor
Problem, there is provided a kind of new gemini quaternary ammonium salt or quaternary amine alkali cpd.The gemini quaternary ammonium salt or quaternary amine alkali molecular compound bone
Frame rigidity is relatively strong, has preferable structure directing in Zeolite synthesis.
The two of the technical problem to be solved are to provide one of a kind of solution technical problem gemini quaternary ammonium salt or season
The preparation method of amine base compound.
The three of the technical problem to be solved be to provide it is a kind of solve one of the technical problem gemini quaternary ammonium salt or
Application of the quaternary amine alkali cpd in molecular sieve is prepared.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is：A kind of gemini quaternary ammonium salt or quaternary amine alkali chemical combination
Thing, its structure can be represented by following general molecular formula：
Wherein R1For C1～C10Alkyl, R2For H, halogen and C1～C6Alkyl at least one, X is halogen
Any one in ion or hydroxyl.
In above-mentioned technical proposal, the X is preferably any one in chlorine, bromine, iodine and hydroxyl.
In above-mentioned technical proposal, R in the quaternary ammonium salt or quaternary amine alkali compound structure1Preferably C1～C4Alkyl；More preferably
For C1～C4Alkyl.
In above-mentioned technical proposal, the R2Preferably H, halogen and C1～C4Alkyl at least one；More preferably
H, halogen and C1～C4Alkyl at least one.
In order to solve the two of above-mentioned technical problem, the technical solution used in the present invention is：The preparation side of gemini quaternary ammonium salt compound
Method, comprises the following steps：
By 1,4- halo dimethylene benzene or 1,4- halo dimethylene substituted benzenes, replace morpholine according to mol ratio 1:(2～5) add
Reactor, in the presence of reaction dissolvent, reacts 4～24 hours at 25～80 DEG C, then filters, filter cake organic solvent washing,
Obtain gemini quaternary ammonium salt compound.
In order to solve the two of above-mentioned technical problem, the technical solution used in the present invention is：The preparation side of Shuangzi quaternary amine alkali cpd
Method, comprises the following steps：
A) by 1,4- halo dimethylene benzene or 1,4- halo dimethylene substituted benzenes, replacement morpholine according to mol ratio 1:(2～5)
Reactor is added, in the presence of reaction dissolvent, is reacted 4～24 hours at 25～80 DEG C, is then filtered, filter cake organic solvent
Washing, obtains gemini quaternary ammonium salt compound.
B) silver oxide powder of 1～3 molar equivalent after will be the quarternary ammonium salt compound obtained in step a) soluble in water, be put into,
React 4～10 hours at 25～50 DEG C, then filter, obtain Shuangzi quaternary amine aqueous slkali.
In above-mentioned technical proposal, the reaction dissolvent preferably is selected from least one in ethanol, acetone；The organic solvent is preferred
At least one from ethyl acetate, ether.
In order to solve the three of above-mentioned technical problem, the technical solution used in the present invention is：Gemini quaternary ammonium salt or quaternary amine alkali chemical combination
Application of the thing in molecular sieve is prepared.
The gemini quaternary ammonium salt or quaternary amine alkali compound structure that the present invention is provided is special, and synthetic method is easy to operate, gained compound
Purity is higher, and yield is preferable.
Using technical scheme, the gemini quaternary ammonium salt for obtaining or quaternary amine alkali cpd are used to prepare molecular sieve, can be with
Synthesis obtains the ZSM-12 molecular sieves of nano-scale particle, achieves preferable technique effect.
Description of the drawings
Fig. 1 obtains sample by embodiment 11H-NMR spectrum.
Below by embodiment, the invention will be further elaborated, but does not therefore limit the scope of the invention.
Specific embodiment
【Embodiment 1】
By 52.8 grams of Isosorbide-5-Nitraes-be dissolved in dibenzyl bromine after 500 milliliters of ethanol, 60.7 grams of N-methylmorpholines are added, 60 DEG C are warming up to,
Stirring 8 hours, stopped reaction are filtered, and filter cake uses 100 milliliters of ethyl acetate, 100 milliliters of ether washing three times to obtain successively
To 90.6 grams of gemini quaternary ammonium salts 1.1H NMR(400MHz,DMSO-D6)δ7.69(s,4H),4.76(s,4H),4.35(s,
2H),3.59-3.53(m,8H),3.61-3.51(m,4H),3.50-3.39(m,2H),3.09(s,6H).
【Embodiment 2】
By 5.96 grams of 2- chloro- Isosorbide-5-Nitrae-be dissolved in dibenzyl bromine after 100 milliliters of ethanol, 8.1 grams of N-methylmorpholines are added, is warming up to
60 DEG C, stir 10 hours, stopped reaction is filtered, filter cake uses 20 milliliters of ethyl acetate successively, 20 milliliters of ether washing three times,
Obtain 9.05 grams of gemini quaternary ammonium salts 2.1H NMR(400MHz,DMSO-D6) δ 7.60 (s, 1H), 7.34 (d, J=7.5Hz,
1H), 7.08 (d, J=7.5Hz, 1H), 4.70 (s, 4H), 4.29 (s, 2H), 3.61-3.50 (m, 8H), 3.60-3.53 (m, 4H),
3.51-3.37(m,2H),3.05(s,6H).
【Embodiment 3】
By 5.28 grams of Isosorbide-5-Nitraes-be dissolved in dibenzyl bromine after 100 milliliters of ethanol, 9.22 grams of N-ethylmorpholines are added, 60 DEG C are warming up to,
Stirring 16 hours, stopped reaction are filtered, and filter cake uses 20 milliliters of ethyl acetate, 20 milliliters of ether washing three times to obtain successively
10.04 gram gemini quaternary ammonium salt 3.1H NMR(400MHz,DMSO-D6)δ7.40(s,1H),4.70(s,4H),4.29(s,
2H), 3.55-3.40 (m, 8H), 3.60-3.53 (m, 4H), 3.51-3.37 (m, 2H), 3.15 (q, J=8.0Hz, 4H), 1.25 (t,
J=8.0Hz, 6H).
【Embodiment 4】
139.9 grams of gemini quaternary ammonium salts 1 are dissolved in 300 milliliters of distilled water, 104.3 grams of silver oxide powders, room temperature is added
Stopped reaction after stirring 6 hours, sand core funnel are filtered, with 50 milliliters of distilled water wash filtering residues, merging filtrate.Rubbed with 0.1
That/liter hydrochloric acid standard solution titration concentration, obtains the aqueous solution of Shuangzi quaternary amine alkali 4, and liquid quality fraction is 19.6%wt.
【Embodiment 5】
By 0.021 gram of sodium metaaluminate, 0.29 gram of sodium hydroxide, the Ludox of 1,6.15 gram 40% of 1.46 grams of gemini quaternary ammonium salts with
And 10.8 grams of water mix homogeneously, said mixture is moved in 170 DEG C of crystallization 100 hours in reactor, reaction terminate after Jing
Cross washing, be dried after, Jing XRD are accredited as the molecular sieve with ZSM-12 structures.
Claims (10)
1. a kind of gemini quaternary ammonium salt or quaternary amine alkali cpd, its structure below formula are represented：
Wherein R1For C1～C10Alkyl, R2For H, halogen and C1～C6Alkyl at least one, X is halogen
Any one in ion or hydroxyl.
2. gemini quaternary ammonium salt according to claim 1 or quaternary amine alkali cpd, it is characterised in that the R1For C1～C4
Alkyl.
3. gemini quaternary ammonium salt according to claim 2 or quaternary amine alkali cpd, it is characterised in that the R1For C1～C4
Alkyl.
4. gemini quaternary ammonium salt according to claim 1 or quaternary amine alkali cpd, it is characterised in that R2For H, halogen with
And C1～C4Alkyl at least one.
5. gemini quaternary ammonium salt according to claim 1 or quaternary amine alkali cpd, it is characterised in that R2For H, halogen with
And C1～C4Alkyl at least one.
6. the preparation method of gemini quaternary ammonium salt compound according to claim 1, comprises the following steps：
By 1,4- halo dimethylene benzene or 1,4- halo dimethylene substituted benzenes, replace morpholine according to mol ratio 1:(2～5) add
Reactor, in the presence of reaction dissolvent, reacts 4～24 hours at 25～80 DEG C, then filters, and filter cake is washed with organic solvent
Wash, obtain gemini quaternary ammonium salt compound.
7. the preparation method of gemini quaternary ammonium salt compound according to claim 6, it is characterised in that the reaction is molten
At least one of the agent in ethanol, acetone.
8. the preparation method of gemini quaternary ammonium salt compound according to claim 6, it is characterised in that described organic molten
At least one of the agent in ethyl acetate, ether.
9. the preparation method of Shuangzi quaternary amine alkali molecular compound according to claim 1, it is characterised in that will by right
After asking the 6 gemini quaternary ammonium salt compounds for obtaining soluble in water, the silver oxide powder of 1～3 molar equivalent is put into, at 25～50 DEG C
Reaction 4～10 hours, then filters, obtains Shuangzi quaternary amine aqueous slkali.
10. the application of gemini quaternary ammonium salt or quaternary amine alkali cpd in molecular sieve is prepared described in a kind of Claims 1 to 5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665541A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The synthetic method of low silica-alumina ratio ZSM-12 type zeolite molecular sieve |
| CN109665544A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method |
| CN109665543A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453000A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Synthetic method of biquaternary ammonium salt |
| CN103626200A (en) * | 2013-11-21 | 2014-03-12 | 太原理工大学 | Preparation method of hydrogen type EUO (europium oxide) type molecular sieve |
-
2015
- 2015-10-20 CN CN201510683598.3A patent/CN106588816B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453000A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Synthetic method of biquaternary ammonium salt |
| CN103626200A (en) * | 2013-11-21 | 2014-03-12 | 太原理工大学 | Preparation method of hydrogen type EUO (europium oxide) type molecular sieve |
Non-Patent Citations (2)
| Title |
|---|
| J. G. BLACKMAN ET AL.: "Assessment of depressor activity and mydriatic activity of hexamethonium analogues", 《BRIT. J. PHARMACOL.》 * |
| STN REGISTRY: "RN101831-45-2, RN101858-15-5", 《STN REGISTRY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665541A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The synthetic method of low silica-alumina ratio ZSM-12 type zeolite molecular sieve |
| CN109665544A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method |
| CN109665543A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method |
| CN109665541B (en) * | 2017-10-17 | 2022-04-01 | 中国石油化工股份有限公司 | Synthesis method of ZSM-12 type zeolite molecular sieve with low silica-alumina ratio |
| CN109665543B (en) * | 2017-10-17 | 2022-04-05 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
| CN109665544B (en) * | 2017-10-17 | 2022-05-27 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
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