CN102093404A - Method for recovering and treating waste materials in aminosilane preparation - Google Patents
Method for recovering and treating waste materials in aminosilane preparation Download PDFInfo
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- CN102093404A CN102093404A CN2010105300273A CN201010530027A CN102093404A CN 102093404 A CN102093404 A CN 102093404A CN 2010105300273 A CN2010105300273 A CN 2010105300273A CN 201010530027 A CN201010530027 A CN 201010530027A CN 102093404 A CN102093404 A CN 102093404A
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- amine
- aminosilane
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- coupling agent
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Abstract
The invention discloses a method for recovering and treating waste materials in aminosilane preparation. The method comprises the following steps of: metered by weight parts, mixing 40-130 parts of sodium ethylate or potassium ethylate with 100 parts of waste material generated by preparing an aminosilane coupling agent, wherein the waste material in preparing aminosilane comprises amine, amine salt and an aminosilane coupling agent; then recrystallizing at normal temperature or low temperature, filtering or fractionating under normal pressure or by decompressing; and sequentially separating out chloride, ethanol, amine and the aminosilane coupling agents from the obtained product, wherein the chloride is sodium chloride or potassium chloride. In the invention, the ethanol, the sodium chloride or the potassium chloride, the amine and the aminosilane coupling agents which are separated from the system can be recycled. The method has the advantages of simple process, low equipment investment, lower cost and suitability for batch production; and meanwhile, the method improves the utilization ratio of the raw materials, reduces the production cost, does not generate secondary pollution and has obvious social and economic benefits.
Description
Technical field
The invention belongs to the organic chemical industry field, be specifically related to the technological method of a kind of recycling at the waste material of preparation amino silicane coupling agent generation.
Background technology
Amino silicane coupling agent can be divided into α-aminomethyl silane and γ-aminopropyl silane by the difference of chemical structure; The former mainly prepares through alcoholysis and aminolysis by chloromethyl trichlorosilane or chloromethylmethyldichlorsilane, and the reaction formula of the preparation of α-aminomethyl silane is as follows:
R wherein
1And R
2For the H atom or contain a kind of in alkyl, cycloalkyl group and the aryl of C1～C20, R is the alkyl of C1～C4.
The latter (γ-aminopropyl silane) mainly prepares through alcoholysis and aminolysis by chloropropyl trichloro-silane or chloropropyl dimethyl dichlorosilane (DMCS), and the reaction formula of preparation is as follows:
R wherein
1And R
2For the H atom or contain a kind of in alkyl, cycloalkyl group and the aryl of C1～C20, R is the alkyl of C1～C4.
For chloromethyl organoalkoxysilane or chloropropyl organoalkoxysilane fully being reacted and improving productive rate, adopt excessive amine usually, like this, contain more amine salt and unreacted amine in the waste material.In addition, because factors such as preparation technology and purification technique also contain a spot of amino silicane coupling agent in the waste material.The generating principle of amine salt such as following reaction formula:
R wherein
1And R
2For the H atom or contain a kind of in alkyl, cycloalkyl group and the aryl of C1～C20, R is the alkyl of C1～C4.
At present, the yearly capacity of the silane coupling agent of China has reached 50,000 tons, and manufacturing enterprise mainly is distributed in ground such as Jiangsu, Shanghai, Zhejiang, Guangdong, Hubei and Sichuan.Aminosilane is as the principal item of silane coupling agent, comprise aminopropyl triethoxysilane (KH550), N-β-(aminoethyl)-Y-aminopropyl trimethoxysilane (KH792), and anilinomethyl trimethoxy silane (ND73), diethylamine Union carbide A-162 (ND22) and hexanediamine Union carbide A-162 (ND24) etc.The processing waste of amino silicane coupling agent will contaminate environment, harmful to human and animals and plants as if untimely effective processing.Yet domestic production enterprise mostly to buried after the waste material simple process or give recycling station and concentrate burning disposal, not only increases cost but also cause secondary pollution, and can not be effectively with make full use of processing waste.
Chinese invention patent 03112874.2 discloses the recovery and treatment method of the processing waste of the organo silane coupling agent that contains β-aminoethyl-γ-aminopropyl group, this method is put into processing waste in the reactor with excessive strong alkaline substance, add thermal distillation then, carry out condensation simultaneously and reclaim, reclaim and obtain quadrol; After the quadrol recovery finishes, again with above-mentioned reaction mixture cooling, and add entry and regulate its pH value, make this reaction mixture can carry out effective layering and separate that the organo silane coupling agent that will be positioned at the reaction mixture upper strata with the isolating method of separatory is separated.This method facility investment is less, and technology is simple, and is easy to operate, do not have secondary environmental pollution; But produce moisture in this treatment process, the quadrol of recovery must carry out drying and dewater; And a large amount of water of adding carries out layering in the system, and very easily hydrolysis of silane coupling agent, this measure can't be reclaimed silane coupling agent.
Summary of the invention
The present invention is directed to prior art problems, a kind of novel method that can recycle silane coupling agent and be recovered in other effective constituents of the waste material that produces in the preparation aminosilane is provided.
Purpose of the present invention is achieved through the following technical solutions.
A kind of method that recycles the waste material in the aminosilane preparation may further comprise the steps:
(a), 40-130 part sodium ethylate or potassium ethylate are mixed with 100 parts of preparation waste materials that amino silicane coupling agent produced in mass fraction; The described waste material that contains in the aminosilane preparation contains amine, amine salt and amino silicane coupling agent;
(b) by normal temperature or low temperature recrystallization, filtration or normal pressure or vacuum fractionation, isolate muriate, ethanol, amine and amino silicane coupling agent successively respectively from step (1) products therefrom, described muriate is sodium-chlor or Repone K.
For further realizing the object of the invention, the described muriate of isolating is to filter from step (1) products therefrom by normal temperature and pressure at first to separate.
The described ethanol of isolating is to isolate 77-80 ℃ of fraction by air distillation from step (1) products therefrom.
Fusing point and boiling point according to amine select low temperature crystallization after-filtration or fractionation by distillation to go out amine; The amine that is higher than-20 ℃ for fusing point adopts-20～20 ℃ low temperature recrystallization to separate; The amine that is higher than 100 ℃ for boiling point adopts underpressure distillation to separate; The amine that is lower than 100 ℃ for boiling point adopts air distillation to separate.
Described boiling point is higher than 100 ℃ amine and comprises Di-n-Butyl Amine, di-sec-butylamine, diamylamine, dibenzylamine, diallylamine and octodrine, tert-Octylamine, positive heptyl amice, phenylethylamine, cyclopentamine, normal hexyl Amine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine.
Described amino silicane coupling agent separates by vacuum fractionation.
The present invention
The reaction of sodium ethylate and amine salt:
The reaction of potassium ethylate and amine salt:
R wherein
1And R
2For the H atom or contain a kind of in alkyl, cycloalkyl group and the aryl of C1～C20.
Sodium ethylate or potassium ethylate are as strong alkaline substance, be easy to react with amine salt, and sodium-chlor or the solubleness of Repone K in ethanol that reaction produces are minimum, amine and amino silicane coupling agent can be dissolved in ethanol, normal temperature and pressure filters just can isolate sodium-chlor or Repone K, the two can be used as industrial chemicals and uses, and Repone K also can be used as chemical fertilizer.
Usually, the atmospheric boiling point of amino silicane coupling agent is higher than 120 ℃, is higher than 200 ℃ individually, belongs to heavy cut in system, separates at last.For high boiling amine of low melting point (as Di-n-Butyl Amine) and amino silicane coupling agent system, can adopt vacuum fractionation (rectifying).Because amine and amino silicane coupling agent are at high temperature oxidized easily, hydrolysis takes place in the latter easily, the strict waterproof of whole separation purification process, and high-temperature operation need be led to rare gas element (as nitrogen) protection.Under to the not high situation of reactant purity requirement, can separation of amine and amino silicane coupling agent, directly come into operation.
With respect to prior art, the present invention has following advantage:
(1) present method is separated amine and the amino coupling agent purify out and can be utilized again, can improve the utilization ratio of amine and the output of amino silicane coupling agent, makes full use of starting material, reduces the production cost of amino silicane coupling agent;
(2) ethanol of Chan Shenging, sodium-chlor or Repone K can be used as the industrial chemicals use, and Repone K also can be used as potash fertilizer, makes a silk purse out of a sow's ear.
(3) present method and technology are simple, are easy to control, and cost is lower, and does not produce secondary pollution, and application limit is little, are fit to suitability for industrialized production, can solve trouble and worry for silane coupling agent manufacturing enterprise.
Embodiment
Below in conjunction with embodiment the present invention is done detailed explanation, but embodiments of the present invention are not limited thereto.
Embodiment 1
Get 100 and restrain the waste material (containing have an appointment 75% diethyl amine salt, 20% diethylamine, 5% diethylamine Union carbide A-162) that is equipped with the generation of diethylamine Union carbide A-162, be put in the flask, add 46 gram sodium ethylates, after fully stirring, normal temperature and pressure filters, and isolates sodium-chlor.Filtrate is carried out the normal pressure fractionation, and the fraction of collecting 77-80 ℃ is an ethanol, and the fraction of collecting 54-57 ℃ is a diethylamine; Raffinate is the diethylamine Union carbide A-162.
At present, this type of waste material adopts buried or burning disposal after alkali (NaOH or the unslaked lime) simple process usually, both can't recycle the effective ingredient in the waste material, causes second environmental pollution again.And the method for alkaline purification waste material can generate moisture, can make silane coupling agent generation hydrolysis; After need dewatering, the amine that generates just can reuse.
Embodiment 2
Get 100 and restrain to be equipped with the waste material that anilinomethyl trimethoxy silane produces (containing 80% the aniline salt of having an appointment, 15% aniline, 5% anilinomethyl trimethoxy silane), be put in the flask, add 85 gram potassium ethylates, after fully stirring, normal temperature and pressure filters, and isolates Repone K.Filtrate is carried out air distillation, and the fraction of collecting 77-80 ℃ is an ethanol, and residual solution filters to isolate aniline at-10～-8 ℃ of following recrystallizations; Raffinate is an anilinomethyl trimethoxy silane.
Embodiment 3
Getting 100 restrain to be equipped with the waste material that N-β-(aminoethyl)-Y-aminopropyl trimethoxysilane produces and (to contain 70% the ethylenediamine salt of having an appointment, 20% quadrol, 10% N-β-(aminoethyl)-Y-aminopropyl trimethoxysilane), be put in the flask, add 72 gram sodium ethylates, after fully stirring, normal temperature and pressure filters, and isolates sodium-chlor.Filtrate is carried out air distillation, and the fraction of collecting 77-80 ℃ is an ethanol, and residual solution filters to isolate quadrol at 6～8 ℃ of following recrystallizations; Raffinate is N-β-(aminoethyl)-Y-aminopropyl trimethoxysilane.
Embodiment 4
Getting 100 restrain to be equipped with the waste material that N-β-(aminoethyl)-Y-aminopropyl methyldiethoxysilane produces and (to contain 80% the ethylenediamine salt of having an appointment, 15% quadrol, 5% N-β-(aminoethyl)-Y-aminopropyl methyldiethoxysilane), be put in the flask, add 102 gram potassium ethylates, after fully stirring, normal temperature and pressure filters, and isolates Repone K.Filtrate is carried out air distillation, and the fraction of collecting 77-80 ℃ is an ethanol, and residual solution filters to isolate quadrol at 6～8 ℃ of following recrystallizations; Raffinate is N-β-(aminoethyl)-Y-aminopropyl methyldiethoxysilane.
Embodiment 5
Get 100 and restrain to be equipped with the waste material that the hexanediamine Union carbide A-162 produces (containing 85% the hexanediamine salt of having an appointment, 10% hexanediamine, 5% hexanediamine Union carbide A-162), be put in the flask, add 62 gram sodium ethylates, after fully stirring, normal temperature and pressure filters, and isolates sodium-chlor.Filtrate is carried out air distillation, and the fraction of collecting 77-80 ℃ is an ethanol, and residual solution filters to isolate hexanediamine at 15～20 ℃ of following recrystallizations, and raffinate is the hexanediamine Union carbide A-162.
Embodiment 6
Get 100 waste materials that restrain to be equipped with two positive amine Union carbide A-162s generations (containing 70% the Di-n-Butyl Amine salt of having an appointment, 20% Di-n-Butyl Amine, 10% two positive amine Union carbide A-162s), be put in the flask, add 40 gram potassium ethylates, after fully stirring, normal temperature and pressure filters, and isolates Repone K.Filtrate is carried out air distillation, and the fraction of collecting 77-80 ℃ is an ethanol, and surplus liquid carries out underpressure distillation, and 62-64 ℃ fraction is a Di-n-Butyl Amine under the collection 5mmHg, and raffinate is the Di-n-Butyl Amine Union carbide A-162.
Claims (6)
1. method that recycles the waste material in the aminosilane preparation is characterized in that may further comprise the steps:
(a), 40-130 part sodium ethylate or potassium ethylate are mixed with 100 parts of preparation waste materials that amino silicane coupling agent produced in mass fraction; The described waste material that contains in the aminosilane preparation contains amine, amine salt and amino silicane coupling agent;
(b) by normal temperature or low temperature recrystallization, filtration or normal pressure or vacuum fractionation, isolate muriate, ethanol, amine and amino silicane coupling agent successively respectively from step (1) products therefrom, described muriate is sodium-chlor or Repone K.
2. the method for the waste material in the recycling aminosilane preparation according to claim 1 is characterized in that: the described muriate of isolating is to filter from step (1) products therefrom by normal temperature and pressure at first to separate.
3. the method for the waste material in the recycling aminosilane preparation according to claim 1, it is characterized in that: the described ethanol of isolating is to isolate 77-80 ℃ of fraction by air distillation from step (1) products therefrom.
4. the method for the waste material in the recycling aminosilane preparation according to claim 1 is characterized in that: fusing point and boiling point according to amine select low temperature crystallization after-filtration or fractionation by distillation to go out amine; The amine that is higher than-20 ℃ for fusing point adopts-20～20 ℃ low temperature recrystallization to separate; The amine that is higher than 100 ℃ for boiling point adopts underpressure distillation to separate; The amine that is lower than 100 ℃ for boiling point adopts air distillation to separate.
5. the method for the waste material in the recycling aminosilane according to claim 1 preparation is characterized in that: described boiling point is higher than 100 ℃ amine and comprises Di-n-Butyl Amine, di-sec-butylamine, diamylamine, dibenzylamine, diallylamine and octodrine, tert-Octylamine, positive heptyl amice, phenylethylamine, cyclopentamine, normal hexyl Amine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine.
6. the method for the waste material in the recycling aminosilane preparation according to claim 1, it is characterized in that: described amino silicane coupling agent separates by vacuum fractionation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880875A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Preparation method for sand-consolidation coupling agent |
| CN107778325A (en) * | 2016-08-29 | 2018-03-09 | 张家港市国泰华荣化工新材料有限公司 | The preparation method of N [3 (trimethoxy silicon substrate) propyl group] n-butylamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6673954B1 (en) * | 2003-02-19 | 2004-01-06 | General Electric Company | Process for the preparation of N-silylorganocarbamates |
| CN101423528A (en) * | 2007-11-02 | 2009-05-06 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing mercaptoalkyl alkoxy silane |
-
2010
- 2010-10-29 CN CN2010105300273A patent/CN102093404B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6673954B1 (en) * | 2003-02-19 | 2004-01-06 | General Electric Company | Process for the preparation of N-silylorganocarbamates |
| CN101423528A (en) * | 2007-11-02 | 2009-05-06 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing mercaptoalkyl alkoxy silane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880875A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Preparation method for sand-consolidation coupling agent |
| CN107778325A (en) * | 2016-08-29 | 2018-03-09 | 张家港市国泰华荣化工新材料有限公司 | The preparation method of N [3 (trimethoxy silicon substrate) propyl group] n-butylamine |
| CN107778325B (en) * | 2016-08-29 | 2021-03-30 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of N- [3- (trimethoxysilyl) propyl ] N-butylamine |
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