CN107857861A - A kind of nonionic surfactant and preparation method thereof - Google Patents
A kind of nonionic surfactant and preparation method thereof Download PDFInfo
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- CN107857861A CN107857861A CN201710975264.2A CN201710975264A CN107857861A CN 107857861 A CN107857861 A CN 107857861A CN 201710975264 A CN201710975264 A CN 201710975264A CN 107857861 A CN107857861 A CN 107857861A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
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Abstract
The invention discloses a kind of surfactant, and in particular to a kind of preparation method of nonionic surfactant；Its preparation method：It is included in oil bath heating under nitrogen protective condition, the step such as mixing, solution alternate dropwise addition, rotary evaporation and vacuum drying of ice-water bath.The new non-ionic surfactants of preparation; with characteristics such as nontoxic, without phosphorus, antistatic, low bubbles; preparation technology is simple, simple production process, cost are cheap, it is pollution-free, produced suitable for industrial scale; it can be used as the cleaning of advanced instrument, and can be used as agricultural chemicals, the emulsifying agent of ink, the solubilizer of medicine, suspending agent and anti-coagulants.
Description
Technical field
The present invention relates to surfactant field, and in particular to a kind of synthetic method of nonionic surfactant.
Background technology
Nonionic surfactant is broadly divided into two major classes：One kind is alcohol ether, phenolic ether type, and another kind of is carbohydrate derivative.
Nonionic surfactant does not ionize in water, has promoted nonionic surfactant in some aspects compared with ionic surface
Activating agent is superior, and stability is high in the solution, is not easy to be influenceed by strong electrolyte inorganic salts and acid, alkali, there is good resistance to hard water
The characteristics of ability, low foaming characteristic, therefore it is suitable as special detergent.Because nonionic surfactant has scattered, emulsification, bubble
Foam, wetting, solubilized multiple performance, thus in the cleaning of many space flight articles for use, advanced instrument is clean, has in highly polar unique fabric
Important use.
The application of prior art nonionic surface active agent is more and more extensive, but the synthesis work of this kind of surfactant
Skill also there is course of reaction is complicated, system stability is poor, cost is high, the reaction time is long, yield is not high, environmental pollution, raw material
The utilization rate technical problem for being difficult to overcome such as low, it is impossible to meet the needs of higher in current commercial Application.A kind of so tool of invention
It is very necessary to have that course of reaction is simple, prepares low, the environment-friendly nonionic surface active agent of cost and its preparation technology
's.
The content of the invention
It is an object of the invention to provide the non-ionic surface that a kind of course of reaction is simple, preparation cost is low, environment-friendly
Activating agent.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of preparation method of nonionic surfactant, it comprises the following steps：
1) in 250ml three-necked flasks, according to mol ratio 1:1~10:1, by diethylene glycol two（3- aminopropyls）Ether adds oneself two
Mixed in acid, 120 DEG C of oil bath heating under nitrogen protection under normal pressure, after reacting 2h under 200 ~ 300r/min stirring conditions, in nitrogen
Normal temperature is cooled in air-flow and obtains intermediate 1, adds 30ml ethanol, ultrasound obtains solution 1 to being completely dissolved；
2) according to mol ratio 2:1, HMDI (4,4 dicyclohexyl methyl hydride diisocyanate) is dissolved in respectively with polyetheramine D2000
30ml ethanol, is placed in ice-water bath, under 200 ~ 300r/min stirring conditions, is dripped in ice-water bath into HMDI ethanol solution
Addition polymerization ether amines D2000 ethanol solution, after being added dropwise, obtain solution 2；
3）Under 200 ~ 300r/min stirring conditions, by step 1）Solution 1 and step 2）The alternate dropwise addition of solution 2 to beaker
In, solution 3 is obtained after being added dropwise, solution C is rotated into 0.5h ~ 2h under the conditions of 35 DEG C ~ 60 DEG C removes ethanol, in 60 DEG C of vacuum
Dry 6h and obtain product.
The step 1）In diethylene glycol two（3- aminopropyls）The mol ratio of ether and adipic acid is 9:8-5:4；
The step 1）In ultrasonic time be 0.5h ~ 1h；
The cleaning of nonionic surfactant prepared by the preparation method of described nonionic surfactant a kind of as, instrument
Agent, agricultural chemicals, the emulsifying agent of ink, the solubilizer of medicine, suspending agent and anti-coagulants purposes.
Beneficial effects of the present invention：
The invention provides a kind of new non-ionic surfactants, have the characteristics such as nontoxic, without phosphorus, antistatic, low bubble, prepare
Technique is simple, simple production process, cost are cheap, it is pollution-free, produced suitable for industrial scale, and can be as the cleaning of instrument
Agent, agricultural chemicals, the emulsifying agent of ink, the solubilizer of medicine, the purposes of suspending agent and anti-coagulants.
Brief description of the drawings
Fig. 1 is the infrared spectrum of intermediate 1 in embodiment 1（IR）;
Fig. 2 is the infrared spectrum of product A in embodiment 1（IR）;
Fig. 3 is constant-current titration schematic diagram, the oligomer of different change ratios.
Embodiment
Technical scheme is described in detail below in conjunction with specific embodiment, herein schematic implementation of the invention
Example and explanation are used for explaining technical scheme, but not as a limitation of the invention.
Embodiment 1
The preparation method of nonionic surfactant
（1）0.02mol adipic acids and 0.025mol diethylene glycols two are added in 250ml three-necked flasks（3- aminopropyls）Ether,
Mix, 120 DEG C of oil bath under nitrogen protection under normal pressure, 2h is reacted under stirring condition, after reaction terminates, normal temperature is cooled in nitrogen stream and is obtained
To intermediate 1,30ml ethanol is added, ultrasound obtains solution 1 to being completely dissolved.
（2）0.01molHMDI and 0.005mol polyetheramines D2000 are dissolved in 30ml ethanol respectively, is placed in ice-water bath, stirs
Under the conditions of mixing, polyetheramine D2000 ethanol solution is added dropwise into HMDI ethanol solution under ice water bath environment, is added dropwise
Afterwards, solution 2 is obtained.
（3）It is another to take a clean empty beaker, alternate dropwise addition solution 1 and solution 2 thereto under stirring condition, after being added dropwise
Solution 3 is obtained, solution 3 is rotated and removes most of ethanol, 60 DEG C of vacuum drying 6h obtain target product A.
Further confirmed that by Fourier transform infrared, the infrared spectrum of intermediate 1 is as shown in figure 1, wave number in Fig. 1
3499cm-1For N-H stretching vibration absworption peaks on terminal amino group in intermediate 1 and amido link, wave number 1564cm-1For on acid amides
Carbonyl stretches shock absorption peak, wave number 1110cm-1For C-O stretching vibration absworption peaks in ether chain.
Further confirmed that by infrared, product A infrared spectrum is as shown in Fig. 2 wave number 3419cm in Fig. 2-1For in product A
N-H stretching vibration absworption peaks on terminal amino group and amido link, wave number 2930cm-1For C-H stretching vibration absworption peaks of methyl, ripple
Number 1398cm-1For C-H in-plane bending shock absorption spike numbers 1564cm of methyl-1Absorbed for the carbonylic stretching vibration on acid amides
Peak, wave number 1107cm-1For C-O stretching vibration absworption peaks in ether chain.It is possible thereby to judge that experiment has obtained expected product.
Embodiment 2
The preparation method of nonionic surfactant
（1）0.04mol adipic acids and 0.045mol diethylene glycols two are added in 250ml three-necked flasks（3- aminopropyls）Ether,
Mix, 120 DEG C of oil bath under nitrogen protection under normal pressure, 2h is reacted under stirring condition, after reaction terminates, normal temperature is cooled in nitrogen stream and is obtained
To intermediate 2,30ml ethanol is added, ultrasound obtains solution 1 ' to being completely dissolved.
（2）0.01molHMDI and 0.005mol polyetheramines D2000 are dissolved in 30ml ethanol respectively, is placed in ice-water bath, stirs
Under the conditions of mixing, polyetheramine D2000 ethanol solution is added dropwise into HMDI ethanol solution under ice water bath environment, is added dropwise
Afterwards, solution 2 ' is obtained.
（3）It is another to take a clean empty beaker, alternate dropwise addition solution 1 ' and solution 2 ' thereto under stirring condition, it is added dropwise
After obtain solution 3 ', the revolving of solution 3 ' is removed into most of ethanol, 60 DEG C of vacuum drying 6h obtain target product B, obtain sample
Product preserve in drier, under normal temperature and pressure, closed preservation.
Embodiment 3
The preparation method of nonionic surfactant
（1）0.02mol adipic acids and 0.2mol diethylene glycols two are added in 250ml three-necked flasks（3- aminopropyls）Ether, mix
It is even, 120 DEG C of oil bath under nitrogen protection under normal pressure, 2h is reacted under stirring condition.After reaction terminates, normal temperature is cooled in nitrogen stream and is obtained
Intermediate 3, adds 30ml ethanol, and ultrasound obtains solution 1 ' to being completely dissolved '.
（2）0.01molHMDI and 0.005mol polyetheramines D2000 are dissolved in 30ml ethanol respectively, is placed in ice-water bath, stirs
Under the conditions of mixing, polyetheramine D2000 ethanol solution is added dropwise into HMDI ethanol solution under ice water bath environment, is added dropwise
Afterwards, solution 2 ' is obtained '.
（3）It is another to take a clean empty beaker, alternate dropwise addition solution 1 ' ' and solution 2 ' thereto under stirring condition ', drip
Solution 3 ' is obtained after finishing ', by solution 3 ' ' the most of ethanol of revolving removing, 60 DEG C are dried in vacuo 6h and obtain target product C.
Embodiment 4
The preparation method of nonionic surfactant
（1）0.02mol adipic acids and 0.02mol diethylene glycols two are added in 250ml three-necked flasks（3- aminopropyls）Ether, mix
It is even, 120 DEG C of oil bath under nitrogen protection under normal pressure, 2h is reacted under stirring condition, after reaction terminates, normal temperature is cooled in nitrogen stream and is obtained
Intermediate 4, adds 30ml ethanol, and ultrasound obtains solution 1 ' to being completely dissolved ' '.
（2）0.01molHMDI and 0.005mol polyetheramines D2000 are dissolved in 30ml ethanol respectively, is placed in ice-water bath, stirs
Under the conditions of mixing, polyetheramine D2000 ethanol solution is added dropwise into HMDI ethanol solution under ice water bath environment, is added dropwise
Afterwards, solution 2 ' is obtained ' '.
（3）It is another to take a clean empty beaker, alternate dropwise addition solution 1 ' ' ' and solution 2 ' thereto under stirring condition ' ', dropwise addition
After obtain solution 3 ' ' ', by solution 3 ' ' ' revolving remove most of ethanol, 60 DEG C of vacuum drying 6h obtain target product D.
The surface tension of nonionic surfactant prepared by embodiment 1-4 is similar to similar surfactant, has nothing
The characteristics such as malicious, without phosphorus, antistatic, low bubble, preparation technology is simple, simple production process, cost are cheap, it is pollution-free, suitable for work
Industry large-scale production, it can be used as the cleaning of advanced instrument, and can be as agricultural chemicals, the emulsifying agent of ink, the solubilizer of medicine, suspending
Agent and anti-coagulants.
Claims (4)
1. a kind of preparation method of nonionic surfactant, comprises the following steps：
It is 1 according to mol ratio in 250ml three-necked flasks:1~10:1, by diethylene glycol two（3- aminopropyls）Ether adds oneself two
Mixed in acid, 120 DEG C of oil bath heating under nitrogen protection under normal pressure, after reacting 2h under 200 ~ 300r/min stirring conditions, in nitrogen
Normal temperature is cooled in air-flow and obtains intermediate 1, adds 30ml ethanol, ultrasound obtains solution 1 to being completely dissolved；
According to mol ratio 2:1, HMDI (4,4 dicyclohexyl methyl hydride diisocyanate) and polyetheramine D2000 are dissolved in 30ml respectively
Ethanol, it is placed in ice-water bath, under 200 ~ 300r/min stirring conditions, is added dropwise and gathers into HMDI ethanol solution in ice-water bath
Ether amines D2000 ethanol solution, after being added dropwise, obtain solution 2；
3）Under 200 ~ 300r/min stirring conditions, by step 1）Solution 1 and step 2）The alternate dropwise addition of solution 2 to beaker
In, solution 3 is obtained after being added dropwise, solution 3 is rotated into 0.5h ~ 2h under the conditions of 35 DEG C ~ 60 DEG C removes ethanol, in 60 DEG C of vacuum
Dry 6h and obtain product.
A kind of 2. preparation method of nonionic surfactant according to claim 1, it is characterised in that：The step 1）
In diethylene glycol two（3- aminopropyls）The mol ratio of ether and adipic acid is 9:8~5:4.
A kind of 3. preparation method of nonionic surfactant according to claim 1, it is characterised in that：The step 1）
In ultrasonic time be 0.5h ~ 1h.
4. nonionic surfactant prepared by a kind of preparation method of nonionic surfactant according to claim 1
As, the solubilizer of the emulsifying agent of the cleaning agent of instrument, agricultural chemicals, ink, medicine, suspending agent and anti-coagulants purposes.
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| CN201710975264.2A CN107857861A (en) | 2017-10-19 | 2017-10-19 | A kind of nonionic surfactant and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840936A (en) * | 2017-11-19 | 2018-03-27 | 哈尔滨师范大学 | A kind of antistatic bio-based nonionic surfactant and preparation method thereof |
| CN114773563A (en) * | 2022-04-12 | 2022-07-22 | 武汉纺织大学 | Organic silicon modified polymeric nonionic surfactant and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840936A (en) * | 2017-11-19 | 2018-03-27 | 哈尔滨师范大学 | A kind of antistatic bio-based nonionic surfactant and preparation method thereof |
| CN114773563A (en) * | 2022-04-12 | 2022-07-22 | 武汉纺织大学 | Organic silicon modified polymeric nonionic surfactant and preparation method thereof |
| CN114773563B (en) * | 2022-04-12 | 2023-07-25 | 武汉纺织大学 | Organosilicon modified multimeric nonionic surfactant and preparation method thereof |
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Application publication date: 20180330 |