CN1978042A

CN1978042A - Tripolymer sufactant and preparing method

Info

Publication number: CN1978042A
Application number: CN200510126038.4A
Authority: CN
Inventors: 陈功; 杨洋; 黄鹏程
Original assignee: Beihang University
Current assignee: Beihang University; Beijing University of Aeronautics and Astronautics
Priority date: 2005-11-30
Filing date: 2005-11-30
Publication date: 2007-06-13
Anticipated expiration: 2025-11-30
Also published as: CN100531883C

Abstract

The present invention relates to a trimer surfactant (TNP) and its preparation method. Said surfactant is made up by using ammonium p-nonylphenoxy-2-hydroxypropyltrimethyl chloride (NPQT) as monomer and coupling trimolecular NPQT. The measurement of critical micelle concentration (CMC) shows that the CMC value of GAP is two magnitude orders lower than NPQT, as compared with dimmer (GNP) of NPQT the CMC value of GAP also is reduced by 20%, so that its surface activity can be obviously raised.

Description

A kind of tripolymer sufactant and preparation method thereof

Technical field

The invention belongs to technical field of surfactant.Be specifically related to the design of tripolymer sufactant 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 its hydrophilic group or near the hydrophilic group place, and 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 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 order of magnitude, critical micelle concentration CMC then will hang down 1-2 the order of magnitude.Therefore, the Gemini surfactant is accepted widely, and becomes surfactant of new generation, about summarizing and studying and reported in numerous documents.

In view of the connection base in the Gemini surfactant molecule has limited the tendency that produces separation between the polar group because of repulsive interaction, it is more tight that it is arranged on the interface, thereby increased the surface-active of surfactant.If two above surfactant monomers, connect by connecting base, then may realize stronger surface-active.Both at home and abroad also seldom about in this respect report.Traditional cationic emulsifier 3-is usually used in weaving, metal, coating, oil, chemical industry, water treatment and material industry to Nonylphenoxy-2-hydroxypropyl trimethyl ammonium chloride (NPQT).According to above-mentioned analysis, purpose of the present invention is the tripolymer sufactant TNP of synthetic NPQT, with the stronger surfactant of obtained performance.

Summary of the invention

As construction unit, designed cation tripolymer sufactant TNP with NPQT, its structural formula is as follows:

The concrete synthetic route of this surfactant is as shown below:

In step (1), nonyl phenol mixes with the ratio of formaldehyde with amount of substance earlier at 2: 1, reacts 4-6h under alkali condition, obtain the phenolic aldehyde dimer, the nonyl phenol of the amount of same substance and formaldehyde continue reaction 4-8h then, whole process is monitored with TLC, and the reaction optimum temperature is 50 ℃-60 ℃.Reaction is used 5%NaHCO respectively after finishing ₃Na is used in solution and saturated common salt water washing ₂SO ₄Drying obtains the light brown transparent oily liquid with chromatographic silica gel post (petrol ether/ethyl acetate) separation.

In step (2), phenolic aldehyde tripolymer, NaOH and isopropyl alcohol mix, and logical nitrogen stirs 1～2h, adds 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (CTA) again, stirs 2～3h, and the entire reaction optimum temperature is 50 ℃-60 ℃.After reaction finished, suction filtration was removed inorganic matter, and with isopropyl alcohol drip washing 2～3 times, merged with filtrate, and distillation removes and desolvates, and separates through silica gel chromatographic column and purifies, and uses acetone recrystallization, and vacuum drying obtains pressed powder TNP.

The critical micelle concentration of this surfactant (CMC) is than low two orders of magnitude of monomer whose NPQT, also reduced closely 20% than corresponding dimer (GNP) surface-active, surface-active significantly improves, and only just can obtain by two-step reaction, synthetic method is simple, and using value is higher.The GNP structural formula is as follows:

The specific embodiment

44g (0.2mol) 4-nonyl phenol is dissolved in 100ml toluene; under nitrogen protection, add 8ml formalin (12.5mol/L) and 2.5g (0.045mol) KOH catalyst, stir 4h at 40～50 ℃; be warmed up to 70～80 ℃ and continue reaction 2h; with chromatographic sheet (TLC) detection reaction terminal point, add 22g (0.1mol) nonyl phenol and 50ml toluene again, 8ml formalin (12.5mol/L); continue reaction 6h; with TLC detection reaction terminal point, stop reaction, use 5%NaHCO ₃Solution washing three times is being washed to neutrality with saturated common salt, uses anhydrous Na ₂SO ₄Drying obtains the light brown transparent oily liquid with chromatographic silica gel post (petrol ether/ethyl acetate) separation, is tripolymer TriNPM, and yield is 53%.

Add 68.5g (0.1mol) tripolymer TriNPM, 13.2g (0.33mol) NaOH and 200ml isopropyl alcohol in there-necked flask, be heated to 50～60 ℃, logical nitrogen stirs 1～2h, slowly add 84g (0.44mol) 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, separate purification through silica gel chromatographic column, use acetone recrystallization, vacuum drying obtains pressed powder TNP.

Following table is depicted as the surface-active of TNP, NQPT and dimer GNP

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

Surfactant	CMC/mmolL ^-1	γCMC/mN m ^-1
Surfactant	CMC/mmolL ^-1	γCMC/mN m ^-1	NQPT GNP TNP	5.10 0.085 0.070	27.5 20.4 31.3

The critical micelle concentration CMC of tripolymer TNP is than little two orders of magnitude of monomer NPQT, than the CMC of dimer GNP also low 20%.This be because molecule to form the curvature of molecule aggregate in the aqueous solution low more, easy more formation micella, the curvature of the formed molecule aggregate of tripolymer TNP can be minimum, the concentration of the middle mutually formation micella of body is also minimum, thereby can infer increase along with the surfactant degree of polymerization, its CMC value reduces.

Above-mentioned three kinds of surfactants are used the asphalt emulsification experiment, and experimental result is as shown in the table

The emulsification test result of traditional cationic surfactant NPQT different amounts

The test sequence number	81	82	83	84	85	86	87	88
The test sequence number	81	82	83	84	85	86	87	88	Surplus (%) bitumen content (%) viscosity C on emulsifying agent consumption (%) sieve ³ ₂₅(s) stable storage degree CH ₅	0.1 7.2 45 13.2 6.89	0.3 6.2 46 13.2 5.46	0.5 5.4 55 14.3 5.36	0.7 3.5 56 14.5 5.30	0.9 2.6 57 14.5 5.26	1.1 1.8 57 14.5 5.23	1.3 1.3 57 14.6 4.25	1.5 1.2 58 14.8 3.96

The emulsification test result of cationic surfactant GNP different amounts

The test sequence number	21	22	23	24	25	26	27	28
The test sequence number	21	22	23	24	25	26	27	28	Surplus (%) bitumen content (%) viscosity C on emulsifying agent consumption (%) sieve ³ ₂₅(s) stable storage degree CH ₅	0.1 0.20 61.4 18.5 3.76	0.3 0.18 61.2 18 2.79	0.5 0.12 60.5 18 2.52	0.7 0.10 61.2 19 2.21	0.9 0.07 61.3 19.5 1.59	1.1 0.05 60.2 20 1.10	1.3 0.02 60.2 20.5 0.56	1.5 0.01 60.2 22 0.20

The emulsification test result of cationic surfactant TNP different amounts

The test sequence number	141	142	143	144	145	146	147	148
The test sequence number	141	142	143	144	145	146	147	148	Emulsifying agent consumption (%)	0.1	0.3	0.5	0.7	0.9	1.1	1.3	1.5
Surplus on the sieve (%)	0.15	0.13	0.09	0.08	0.04	0.02	0.00	0.00	Emulsifying agent consumption (%)	0.1	0.3	0.5	0.7	0.9	1.1	1.3	1.5
Surplus on the sieve (%)	0.15	0.13	0.09	0.08	0.04	0.02	0.00	0.00	Bitumen content (%)	61.2	61.0	60.1	61.3	60.4	60.8	61.2	60.2
Viscosity C ³ ₂₅(s)	18.5	19.5	19.5	20	20.5	21.5	21.5	21.5	Bitumen content (%)	61.2	61.0	60.1	61.3	60.4	60.8	61.2	60.2
Viscosity C ³ ₂₅(s)	18.5	19.5	19.5	20	20.5	21.5	21.5	21.5	Stable storage degree CH ₅	3.10	2.61	2.02	1.38	1.14	0.95	0.25	0.10

But the cationic surfactant structure is to the result of the test (20 ℃) of mixing time influence

Sample	TNP	GTB	GNP	TB	NPQT
Sample	TNP	GTB	GNP	TB	NPQT	Mixing time (s)	210	150	130	40	30

The stability of pitch microballon in solution how, and the δ current potential height of going up the surfactant that adsorbs with its surface is relevant.As seen from the above table, because surfactant TNP has a plurality of hydrophilic groups, when the degree of charge maximum of its emulsified asphalt microballon, the δ current potential is the highest, interaction force maximum between the pitch microballon, the pitch microballon is the most stable in solution, and the mixing time of emulsified asphalt is also the longest.

Claims

1, a kind of cation tripolymer sufactant is characterized in that structure is as follows:

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

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

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