CN100531882C

CN100531882C - Gemini surfactant and preparing method thereof

Info

Publication number: CN100531882C
Application number: CNB200510126037XA
Authority: CN
Inventors: 陈功; 杨洋; 黄鹏程
Original assignee: Beihang University
Current assignee: Beihang University
Priority date: 2005-11-30
Filing date: 2005-11-30
Publication date: 2009-08-26
Anticipated expiration: 2025-11-30
Also published as: CN1978041A

Abstract

The present invention relates to a dimeric surfactant (GAP) and its preparation method. Said surfactant is obtained by using ammonium p-nonylphenoxy-2-hydroxypropyltrimethyl chloride (NPQT) as monomer and coupling dimeric NPQT. The measurement of critical micelle concentration (CMC) shows that the CMC value of GAP is two magnitude orders lower than NPQT, so that its surface activity is obviously raised.

Description

A kind of Gemini surface active agent and preparation method thereof

Technical field

The invention belongs to technical field of surfactant.Be specifically related to the design of Gemini surface active agent and preparation method's research.

Background technology

Shuangzi (Gemini) surfactant is meant and contains two hydrophilic groups and two hydrophobic groups in the molecule at least, at its hydrophilic group or near the hydrophilic group place, the compound that by chemical bond two two parent bondings is got up to form by spacer group (spacer or claim to isolate base).In the Gemini surfactant molecule, two (or a plurality of) hydrophilic groups rely on the connection base to connect by chemical bond, are combined closely in two surfactant structure unit.This structure has increased the hydrophobic effect of hydrocarbon chain on the one hand, and the trend that hydrophobic grouping is escaped in the aqueous solution increases; Chemical bond has limited the tendency that produces separation between the polar group because of repulsive interaction on the other hand, and it is more tight that it is arranged on the interface, thereby has increased the surface-active of surfactant.The surfactant water base with having structure single parent's oil base roughly the same and single parent compared, and the Gemini surfactant is easier arranges and form aggregation on aqueous solution surface in the aqueous solution, and it reduces the C of surface tension efficient ₂₀Value, low 2-3 orders of magnitude, critical micelle concentration CMC then will hang down 1-2 orders of magnitude.Therefore, the Gemini surfactant is accepted widely, and becomes surfactant of new generation, about summarizing and studying and reported in numerous documents.

The Gemini surfactant is roughly summarized, and can be divided into anionic, cationic, nonionic and mixed type.Wherein, about the anionic type Gemini surface active agent report at most, and other Gemini surfactant report is less relatively.It with the nonyl phenol the synthetic traditional cationic emulsifier 3 of base-, be usually used in weaving, metal, coating, oil, chemical industry, water treatment and material industry to Nonylphenoxy-2-hydroxypropyl trimethyl ammonium chloride NPQT.But produce the tendency of separation between the NPQT polar group because of repulsive interaction, it is not tight that it is arranged on the interface, thereby reduced the surface-active of surfactant, having limited its scope of application, is the relevant report of the synthetic Gemini surfactant molecule of construction unit with NPQT and yet there are no document.Therefore, it is raw material that the present invention is intended to the nonyl phenol, as construction unit, adopts different spacer groups with NPQT, and synthetic a series of cation Gemini surfactants are to improve its surface-active.

Summary of the invention

As construction unit, designed cation Gemini surfactant GAP with NPQT, structural formula is as follows:

R comprises alkyl, ester group or ether chain for connecting base.

This surfactant obtains two molecule NPQT couplings by connecting basic R, and concrete synthetic route is as shown below:

CTA:3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.

Whole process is made of two-step reaction, in the step (1), nonyl phenol, NaOH and isopropyl alcohol are mixed, under 40 ℃ of-90 ℃ of conditions, react 2-3h with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (CTA), 50 ℃-60 ℃ of optimum temperatures, suction filtration is removed inorganic matter, and uses isopropyl alcohol drip washing, merges with filtrate, distillation removes and desolvates, be recrystallized with acetone, vacuum drying obtains light yellow solid powder (NPQT).

In the step (2), directly be raw material with NPQT, under anhydrous low temperature highly basic NaH conditioning, and action of coupling agents, obtain required product.The reaction optimum temperature is a room temperature, and used coupling agent BrRBr comprises: methylene bromide, Bromofume, dibromopropane, dibromobutane, dibromo pentane, m-dibromobenzene, paradibromobenzene, to bromobenzene ether or oxalyl bromine.

The critical micelle concentration of this Gemini surfactant (CMC) is than low two orders of magnitude of monomer whose NPQT, and surface-active is significantly improved, and can directly obtain by the NPQT coupling, and synthetic method is simple, and using value is higher.

The specific embodiment

Add 22g (0.1mol) to nonyl phenol, 4.4g (0.11mol) NaOH and 50ml isopropyl alcohol in there-necked flask, be heated to 50 ℃～60 ℃, logical nitrogen stirs 1～2h, slowly add 21g (0.11mol) 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, stir 2～3h, be chilled to room temperature, suction filtration is removed inorganic matter, and with isopropyl alcohol drip washing 2～3 times, merge with filtrate, distillation removes and desolvates, and is recrystallized with acetone, vacuum drying obtains light yellow solid powder NPQT.

In there-necked flask, add anhydrous glycol dimethyl ether 50ml and 7.5g (0.02mol) NPQT, cool to below 10 ℃, slowly add 0.22mol60%NaH (with absolute ether drip washing oil removing) several times, after the bubble complete obiteration, add 0.12mol methylene bromide ethylene glycol dimethyl ether solution, stirring at room 2～3h monitors course of reaction with HPLC, and reaction finishes, be chilled to room temperature, suction filtration is removed inorganic matter, and with isopropyl alcohol drip washing 2～3 times, merges with filtrate, distillation removes and desolvates, be recrystallized with butanone, vacuum drying obtains pressed powder GAP ₁After the same method, with 1, the 2-Bromofume can obtain GAP ₂With 1, the 3-dibromopropane can obtain GAP ₃With 1, the 4-dibromobutane can obtain GAP ₄Can obtain GAPC with oxalyl chloride.

Following table is the surface-active contrast of different Gemini cationic surfactants and NPQT,

The surface-active (25 ℃) of different cationic surfactants

As seen from the above table, the CMC value of GAP is than low 2 orders of magnitude of NPQT, and surface-active is significantly increased.

Claims

1, a kind of cation Gemini surfactant is characterized in that, structure is as follows:

R comprises alkyl, ester group or ether chain for connecting base.

2, the preparation method of the described surfactant of claim 1 is characterized in that, divides following two steps:

CTA:3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.

3, the preparation method of the described surfactant of claim 2 is characterized in that: in the step (1), reaction temperature is 50 ℃-60 ℃.

4, the preparation method of the described surfactant of claim 2 is characterized in that: in the step (2), reaction temperature is a room temperature.

5, the preparation method of the described surfactant of claim 2 is characterized in that: used coupling agent BrRBr comprises: methylene bromide, Bromofume, dibromopropane, dibromobutane, dibromo pentane, m-dibromobenzene, paradibromobenzene, to bromobenzene ether or oxalyl bromine.