CN104437240A - Novel gemini surfactant and synthesis method thereof - Google Patents
Novel gemini surfactant and synthesis method thereof Download PDFInfo
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- CN104437240A CN104437240A CN201410572526.7A CN201410572526A CN104437240A CN 104437240 A CN104437240 A CN 104437240A CN 201410572526 A CN201410572526 A CN 201410572526A CN 104437240 A CN104437240 A CN 104437240A
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- epoxy resin
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Abstract
The invention provides a novel gemini surfactant. A hydrophobic group part of the novel gemini surfactant consists of epoxy chain segments; the structural formula of the polymer is shown in the specification, wherein x, y and z respectively represent an integer from 1 to 5; R represents methyl, ethyl or benzyl; E represents epoxy, and the structure of the epoxy can be represented as the formula in the specification, wherein polyamine can be ethanediamine, diethylene triamine, triethylene tetramine or tetraethylene pentamine; m represents an integer from 1 to 5; the epoxy is E51. Compared with a previous reported gemini surfactant, the surfactant disclosed by the invention has a plurality of hydrophobic groups and a plurality of hydrophilic groups so that the surfactant has more excellent performance than the existing gemini surfactant and has quite good application in the field of fine chemical engineering.
Description
Technical field
The invention belongs to field of fine chemical, specifically a kind of novel gemini surfactants and synthetic method thereof.
Background technology
Surfactant, is described as " industrial monosodium glutamate ", refers to have fixing hydrophilic and oleophilic group, aligns in the surface energy of solution, and can make the material that surface tension significantly declines.Owing to having wetting or anti-stick, emulsification or breakdown of emulsion, foaming or froth breaking and solubilising, dispersion, washing, the series of physical chemical action such as anticorrosion, antistatic, surfactant almost can be applied to all field of fine chemical, becomes class fine chemical product versatile and flexible, broad-spectrum.
Gemini surface active agent refers to by chemical bond by two or more same or almost same surfactant monomer, this amphiphilic composition is linked together formed surfactant at hydrophilic head base or near the hydrophilic head base with spacer group.The special structures shape of Gemini surface active agent it than conventional surfactant, there is more excellent performance.It has multiple hydrophilic group and hydrophobic group, is connected by two parts by spacer group, and spacer group has chemical bond, reduces the electrostatic repulsion forces between bipolarity and the active force between hydrated sheath thereof.Compared with traditional surfactant, double type surfactant has many advantages: become micella ability strong, cmc value is low; The ability being adsorbed on interface exceedes the ability forming micella, reduces capillary efficiency high; Krafft point is low; Good water solubility, and have the excellent hydrotropy and solubilising, contribute to formula Design; With the advantage such as the compatibility of other surfactants is good.
But current Gemini surface active agent concentrates on the surfactant that two hydrophilic groups and two hydrophobic groups are connected mostly.For the surfactant also rare report that more hydrophilic group and hydrophobic group are connected, for above deficiency, we devise the surfactant of multiple hydrophilic groups that a class is hydrophobic group with epoxy resin segment, and its special structure makes it likely well be applied in field of fine chemical.
Summary of the invention
Primary technical problem to be solved by this invention is the deficiency existed for existing background technology, provides containing multiple hydrophilic group and multiple hydrophobic group double type surfactant.This surfactant, for the Gemini surface active agent in the past reported, has multiple hydrophobic group and multiple hydrophilic group, makes it have the performance more excellent than existing Gemini surface active agent, is well applied in field of fine chemical.
The present invention solves the technical scheme that primary technical problem adopts: a kind of novel gemini surfactants, is characterized by, and its hydrophobic group part is formed by epoxy resin segment, and polymer has following general formula:
X, y, z are the integer from 1 to 5, and R is methyl, ethyl or benzyl.
Wherein, E represents epoxy resin, and its structure can be expressed as:
M is the integer from 1 to 5, and epoxy resin is E51.
Second technical problem that the present invention solves is the preparation method of above-mentioned novel gemini surfactants, it is characterized in that comprising the following steps:
The first step, the preparation of epoxy resin polyamines polymer, epoxy resin is added in reactor, add organic solvent dissolution, obtain epoxy resin solution, polyamines is dissolved in certain organic solvent, the polyamines solution of acquisition is added drop-wise in epoxy resin again, dropwise, stir pressure reducing and steaming solvent after 1-2 hour, obtain epoxy resin polyamines polymer;
Second step, the preparation of phosphate Gemini surface active agent, in epoxy resin polyamines polymer, add phosphorous acid and hydrochloric acid, be warming up to 70-80 DEG C, in system, drip 36% formalin, stir after 1-2 hour and cool, there is insoluble matter to separate out, pour out clear liquid, with vigorous stirring, inside system, drip 10% sodium hydroxide solution, system is gradually clarified and is obtained phosphate double sub-surface activator solution.
In the described first step, the organic solvent of dissolved epoxy is C
1~ C
3one or more in alcohol, as preferably, described organic solvent refers to that methyl alcohol or ethanol or both are with the mixture of arbitrary proportion; The ratio of epoxy resin and organic solvent is weight ratio is 2.0: 1-4.0: 1.
In the described first step, polyamines can be ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, preferred ethylenediamine, and the organic solvent dissolving polyamines is C
1~ C
3one or more in alcohol, as preferably, described organic solvent refers to that methyl alcohol or ethanol or both are with the mixture of arbitrary proportion, and the ratio of polyamines and organic solvent is weight ratio is 1.0: 1-2.0: 1.
Described first step by step epoxy resin and the ratio of polyamines be that in epoxy resin, the molal quantity of epoxy is 1: 1.2-1.8 with the ratio of the molal quantity of polyamines, preferably 1: 1.5; Reaction temperature is 30-80 DEG C, preferred 60-80 DEG C.
In described second step, epoxy resin polyamines polymer is first reacted by Mannich, phosphate Gemini surface active agent is obtained again with NaOH neutralization, can first and halogenated acetic acids reaction, obtain carboxylate gemini surfactant with NaOH neutralization again, Bis-quaternary Ammonium Surfactants can be obtained by reacting with alkylating reagent.
The amount of the phosphorous acid in described second step and epoxy resin polyamines polymer is: in phosphorous acid and polyamines, the mol ratio of nitrogen-atoms is 1.1-1.5: 1, preferably 1.2: 1; The mol ratio of formaldehyde and phosphorous acid is 1.2-1.8: 1, preferably 1.5: 1; The mol ratio of hydrochloric acid and phosphorous acid is 1.0-3.0: 1, preferably 2.0: 1; In NaOH and polyamines, the mol ratio of nitrogen-atoms is 1.0: 1.
Reaction temperature in described second step is 60-100 DEG C, preferred 70-80 DEG C.
Compared with prior art, the invention has the advantages that: this surfactant, for the Gemini surface active agent in the past reported, has multiple hydrophobic group and multiple hydrophilic group.Its special structure makes it be expected to well be applied in field of fine chemical.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of embodiment 1 product.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.But protection scope of the present invention is not limited to following embodiment.
Embodiment one
Epoxy resin (E51) 18.8g is added in reactor, add 8mL methyl alcohol to stir, ethylenediamine 8.5mL is dissolved in 6mL methyl alcohol, under room temperature, the methanol solution of ethylenediamine is added drop-wise in epoxy resin, dropwise and be warmed up to 80 DEG C of stirrings after 2 hours, cool to room temperature, pressure reducing and steaming solvent, obtains epoxy resin polyamines polymer.50% phosphorous acid solution 41.8g is added system, adds concentrated hydrochloric acid 40mL.Be warming up to 80 DEG C, drip 36% formalin 28.7mL.Dropwise in 30 minutes.Dropwise rear continuation stirring 2 hours, cooling, has insoluble matter to occur.Pour out supernatant liquor, 10.2g NaOH be dissolved in 91.8mL water, then be added drop-wise in reaction system stir within 2 hours, obtain product.
Embodiment two
Gained double type surfactant 0.2% (mass ratio) and two octyl phenol polyoxyethylene (12) ether 0.1% (mass ratio) compatibility are used for steel surface cleaning.
The mensuration of deoil rate: deoil rate=(wash front test piece quality-wash rear test piece quality)/(washing front test piece quality-test piece quality of not defiling) * 100%
The mensuration of rate of corrosion: rate of corrosion=(wash front test piece quality-wash rear test piece quality)/wash front test piece quality * 100%
Under ultrasonic cleaning condition, use above-mentioned cleaning fluid to clean 30min under (25 ± 1 DEG C), deoil rate can reach 99%, and rate of corrosion is almost nil.
Claims (10)
1. a novel gemini surfactants, is characterized by, and its hydrophobic group part is formed by epoxy resin segment, and the structural formula of this polymer is
Wherein, x, y, z are the integer from 1 to 5, and R is methyl, ethyl or benzyl,
E represents epoxy resin, and its structure can be expressed as:
Polyamines can be ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA,
M is the integer from 1 to 5, and epoxy resin is E51.
2. a preparation method for double type surfactant according to claim 1, is characterized in that comprising the following steps:
1) preparation of epoxy resin polyamines polymer;
2) preparation of double type surfactant.
3. the preparation method of epoxy resin polyamines polymer according to claim 2, is characterized in that: be added to by epoxy resin in reactor, add organic solvent dissolution.Polyamines is dissolved in certain organic solvent, is added drop-wise in epoxy resin, dropwise and stir pressure reducing and steaming solvent after 1-2 hour, obtain epoxy resin polyamines polymer.
4. preparation method according to claim 3, is characterized in that: in described step, the organic solvent of dissolved epoxy is C
1~ C
3one or more in alcohol, as preferably, described organic solvent refers to that methyl alcohol or ethanol or both are with the mixture of arbitrary proportion; The ratio of epoxy resin and organic solvent is weight ratio is 2.0: 1-4.0: 1.
5. preparation method according to claim 3, is characterized in that: in described step, polyamines can be ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, preferred ethylenediamine; The organic solvent dissolving polyamines is C
1~ C
3one or more in alcohol, as preferably, described organic solvent refers to that methyl alcohol or ethanol or both are with the mixture of arbitrary proportion; The ratio of polyamines and organic solvent is weight ratio is 1.0: 1-2.0: 1.
6. preparation method according to claim 3, is characterized in that: described step epoxy resin and the ratio of polyamines are that in epoxy resin, the molal quantity of epoxy is 1: 1.2-1.8 with the ratio of the molal quantity of polyamines, preferably 1: 1.5; Reaction temperature is 30-80 DEG C, preferred 60-80 DEG C.
7. the preparation of epoxy resin polyamines polymer according to claim 2, it is characterized in that: epoxy resin polyamines polymer is first reacted by Mannich, phosphate Gemini surface active agent is obtained again with NaOH neutralization, can first and halogenated acetic acids reaction, obtain carboxylate gemini surfactant with NaOH neutralization again, Bis-quaternary Ammonium Surfactants can be obtained by reacting with alkylating reagent.
8. the preparation of phosphate Gemini surface active agent according to claim 7, it is characterized in that: epoxy resin polyamines polymer, phosphorous acid and formaldehyde are under hydrochloric acid catalysis, stir cooling after 1-2 hour at a certain temperature, separate out insoluble matter, then in insoluble matter, drip 10% sodium hydroxide solution obtain phosphate double sub-surface activator solution.
9. preparation method according to claim 8, is characterized in that: in phosphorous acid and polyamines, the mol ratio of nitrogen-atoms is 1.1-1.5: 1, preferably 1.2: 1; The mol ratio of formaldehyde and phosphorous acid is 1.2-1.8: 1, preferably 1.5: 1.The amount of hydrochloric acid and the amount of phosphoric acid are mol ratio is 1.0-3.0: 1, preferably 2.0: 1, and in described NaOH and polyamines, the mol ratio of nitrogen-atoms is 1.0: 1.
10. preparation method according to claim 8, is characterized in that: described step epoxy resin polyamines polymer, the temperature of phosphorous acid and formolite reaction is 60-100 DEG C, preferred 70-80 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774391A (en) * | 2021-08-12 | 2021-12-10 | 上海新阳半导体材料股份有限公司 | Application of post-chemical mechanical polishing cleaning solution |
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| US5944650A (en) * | 1997-10-29 | 1999-08-31 | Xerox Corporation | Surfactants |
| CN101628214A (en) * | 2009-07-25 | 2010-01-20 | 大连理工大学 | Acrylamide polymerizable emulsifier with cations and non-ions and preparation method thereof |
| CN101745340A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Cationic asphalt emulsifier and preparation method and application thereof |
| CN103497311A (en) * | 2013-09-18 | 2014-01-08 | 中国水利水电第八工程局有限公司 | Expoxy resin polyamine curing agent and waterborne epoxy curing agent emulsion |
| CN103755923A (en) * | 2013-12-26 | 2014-04-30 | 江苏苏博特新材料股份有限公司 | Low-temperature-cured aliphatic amide polyamine epoxy resin curing agent and preparation method thereof |
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2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5944650A (en) * | 1997-10-29 | 1999-08-31 | Xerox Corporation | Surfactants |
| CN101745340A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Cationic asphalt emulsifier and preparation method and application thereof |
| CN101628214A (en) * | 2009-07-25 | 2010-01-20 | 大连理工大学 | Acrylamide polymerizable emulsifier with cations and non-ions and preparation method thereof |
| CN103497311A (en) * | 2013-09-18 | 2014-01-08 | 中国水利水电第八工程局有限公司 | Expoxy resin polyamine curing agent and waterborne epoxy curing agent emulsion |
| CN103755923A (en) * | 2013-12-26 | 2014-04-30 | 江苏苏博特新材料股份有限公司 | Low-temperature-cured aliphatic amide polyamine epoxy resin curing agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774391A (en) * | 2021-08-12 | 2021-12-10 | 上海新阳半导体材料股份有限公司 | Application of post-chemical mechanical polishing cleaning solution |
| CN113774391B (en) * | 2021-08-12 | 2023-08-04 | 上海新阳半导体材料股份有限公司 | Application of cleaning liquid after chemical mechanical polishing |
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Effective date of registration: 20200511 Address after: Room 2206, floor 19, building 601, wangjingyuan, Chaoyang District, Beijing 100000 Patentee after: Beijing Yingu Rainbow Technology Co., Ltd Address before: Box 29, Ningbo University, No. 818, Fenghua Road, Jiangbei District, Ningbo City, Zhejiang Province Patentee before: Ningbo University |