CN110479182A - A kind of polyamino Gemini surface active agent and the preparation method and application thereof - Google Patents
A kind of polyamino Gemini surface active agent and the preparation method and application thereof Download PDFInfo
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- CN110479182A CN110479182A CN201910850714.4A CN201910850714A CN110479182A CN 110479182 A CN110479182 A CN 110479182A CN 201910850714 A CN201910850714 A CN 201910850714A CN 110479182 A CN110479182 A CN 110479182A
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- Prior art keywords
- active agent
- surface active
- polyamino
- gemini surface
- reaction
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/04—Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- 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
Abstract
The invention discloses a kind of polyamino Gemini surface active agent and the preparation method and application thereof, which is prepared by following steps: being reacted generation phthalimide with triethylene tetramine first with phthalic anhydride and is protected to primary amine；Then it is reacted using brominated alkanes with secondary amine, by chain alkyl in conjunction with amino；Finally under alkaline condition, calcium phthalate is removed with coprecipitation mode using the difficult dissolving characteristic of calcium salt, then can be obtained polyamino Gemini surface active agent after removing solvent.The Gemini surface active agent not only improves the dispersibility of surfactant in water, while avoiding quaternary ammonium salt product and being easy the problem of being adsorbed in complicated micropore environment, is applied in oily wastewater sterilization processing, has significant effect.
Description
Technical field:
The present invention relates to a kind of Gemini surface active agents, and in particular to a kind of polyamino Gemini surface active agent and its preparation
Method and application.
Background technique:
Traditional quaternary ammonium salt surface active agent class is a kind of common disinfection sanitizer, and sterilization mechanism is typically considered to
It is that negatively charged bacterium surface is adsorbed on by cation head base, changes the permeability of bacteria cell wall；Alkane chain simultaneously
Hydrophobic interaction can occur with the lipoid layer of cell and be inserted, and then lead to desmoenzyme inactivation and protein denaturation.
For cation Gemini surfactant, the positive charge density of the ion head base of molecule increases and two hydrophobic chains enhance and
Cellular lipids layer interaction as a result, thus Gemini surface active agent have good bactericidal activity energy.But cationic gemini
Surfactant easily generates suction-operated in some flow in micro porous media environment and to sterilize since charge characteristic is excessively obvious
Effect is weakened.Therefore, the present invention acts on amido protecting by phthalic anhydride, system using triethylene tetramine as coupler
For a kind of polyamino Gemini surface active agent.
Summary of the invention:
The first aspect of the present invention is designed to provide a kind of polyamino Gemini surface active agent.
The technical scheme adopted by the invention is that:
A kind of polyamino Gemini surface active agent, which is characterized in that there is following molecular structure:
In formula: R is alkyl, carbon atom number 16≤n≤20 in alkyl.
Polyamino Gemini surface active agent of the invention, the surfactant improve amino table by increasing amino amount
Face activating agent is water-soluble, so that surfactant be made to be easy to use in water, and will not excessively significantly affect because of charge characteristic
To the use in complex environment.
The second aspect of the present invention purpose is to provide a kind of preparation method of polyamino Gemini surface active agent, including following
Step: phthalic anhydride and triethylene tetramine are dissolved in toluene solvant, are warming up to 90-100 DEG C, react 5-6h；In obtaining
Mesosome；In ethanol by intermediate dissolution, brominated alkanes are added, are warming up to 70 DEG C, reaction time 2-3h；To the end of reacting
Afterwards, into reaction solution, the reaction was continued for addition calcium hydroxide, obtains target product.
Reaction principle of the invention is as follows:
Primary amine is protected firstly, generating phthalimide with primary amine reaction using phthalic anhydride；Then
It is reacted using brominated alkanes with secondary amine, by chain alkyl in conjunction with amino；Finally under alkaline condition, the indissoluble solution of calcium salt is utilized
Feature removes calcium phthalate with coprecipitation mode, then can be obtained target product after removing solvent.
Reaction equation of the present invention is as follows:
In formula: R is alkyl, carbon atom number 16≤n≤20 in alkyl.
Further, following scheme is taken, better yield can be obtained:
A kind of preparation method of polyamino Gemini surface active agent, which comprises the following steps:
(1) phthalic anhydride and triethylene tetramine are dissolved in toluene solvant, the quality of phthalic anhydride is three
2.0~2.5 times of ethylene tetramine quality, and solutes content control then heats to 90-100 DEG C in 10-15wt%, reacts 5-
6h；
(2) distillation water washing is added in Xiang Shangshu reaction solution, so that product is entered water phase, its water phase is taken using liquid distributing device,
And then remove unreacted phthalic anhydride；By carrying out vacuum distillation operation to aqueous phase solution, and then remove water and not
The triethylene tetramine of reaction, obtained solid are intermediate；
(3) in ethanol by intermediate dissolution, equimolar brominated alkanes, solutes content 10-15%, heating temperature is added
Degree is 70 DEG C, reaction time 2-3h；To after reaction, be added calcium hydroxide into the reaction solution, and calcium hydroxide plus
Entering amount is 0.3 times of solution quality, the reaction was continued 2h；
(4) mixture obtained by step (3) is filtered, takes its liquid and be dried in vacuo, gained waxy solid is mesh
Mark product.
The third aspect of the present invention is designed to provide a kind of polyamino Gemini surface active agent at oily wastewater sterilization
Application in reason.Polyamino Gemini surface active agent prepared by the present invention substitutes existing quaternary ammonium salt sterilization as fungicide
Agent is applied to oily wastewater sterilization processing, experiments verify that: to sulfate reducing bacteria in oily wastewater (SRB) and saprophytic bacteria
(TGB) there is good bactericidal effect.
The invention has the following advantages:
The present invention provides a kind of polyamino Gemini surface active agent, contain polyamino base in the Gemini surface active agent
Group not only increases suction-operated of the amino to bacterium surface, promotes the dispersibility of Gemini surface active agent in water, and
It avoids Bis-quaternary Ammonium Surfactants and is easy the problem of being adsorbed in complicated micropore environment.In addition, two long-chains are dredged
Water base group, is conducive to hydrophobic group and hydrophilic group gos deep into the lipoid layer and albumin layer of somatic cells respectively, cause enzyme lose activity and
Protein denaturation.Therefore the Gemini surface active agent has high sterilizing ability, is applied in oily wastewater sterilization processing, has aobvious
The effect of work.
Below by the technical scheme in the embodiment of the invention is clearly and completely described.Obviously, described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without creative efforts belongs to the model that the present invention protects
It encloses.
Detailed description of the invention:
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of gained polyamino Gemini surface active agent in embodiment 1；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of gained polyamino Gemini surface active agent in embodiment 2；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of gained polyamino Gemini surface active agent in embodiment 3.
Specific embodiment:
Embodiment 1:
5g triethylene tetramine, 10g phthalic anhydride are dissolved in 85g toluene.90 DEG C are warming up to, 6h is reacted.Using
Isometric hot water washs gained mixed liquor, its water phase is taken after liquid separation；Then its aqueous phase solution is evaporated under reduced pressure, is obtained
Intermediate.Intermediate 4g, bromohexadecane 6g are taken, ethyl alcohol 90g is configured to solution, and is warming up to 70 DEG C, reacts 2h.Again to it
Middle addition 30g calcium hydroxide after the reaction was continued 3h, filters off solid, is evaporated under reduced pressure to liquid, products obtained therefrom is that target produces
Product, yield 84%.
Target product structure:
In formula: R is alkyl, carbon atom number=16 in alkyl.
Product structure confirmation: the nucleus magnetic hydrogen spectrum of polyamino Gemini surface active agent prepared by embodiment 1 is as shown in Figure 1.
1H NMR (300MHz, DMSO): δ 3.05 (t, 4H), 2.65~2.56 (m, 8H), 2.36 (s, 4H), 1.78 (s,
4H), 1.39~1.23 (m, 56H), 0.89 (m, 6H) ppm.
Embodiment 2:
4g triethylene tetramine, 10g phthalic anhydride are dissolved in 86g toluene.100 DEG C are warming up to, 5h is reacted.Using
Isometric hot water washs gained mixed liquor, its water phase is taken after liquid separation；Then its aqueous phase solution is evaporated under reduced pressure, is obtained
Intermediate.Intermediate 5g, bromo-octadecane 7g are taken, ethyl alcohol 88g is configured to solution, and is warming up to 70 DEG C, reacts 2h.Again to it
Middle addition 30g calcium hydroxide after the reaction was continued 3h, filters off solid, is evaporated under reduced pressure to liquid, products obtained therefrom is that target produces
Product, yield 82%.
Target product structure:
In formula: R is alkyl, carbon atom number=18 in alkyl.
Product structure confirmation: the nucleus magnetic hydrogen spectrum of the polyamino Gemini surface active agent prepared in embodiment 2 is as shown in Figure 2.
1H NMR (300MHz, DMSO): δ 3.03 (t, 4H), 2.63~2.54 (m, 8H), 2.35 (s, 4H), 1.76 (s,
4H), 1.37~1.23 (m, 64H), 0.88 (m, 6H) ppm.
Embodiment 3:
5g triethylene tetramine, 10g phthalic anhydride are dissolved in 85g toluene.100 DEG C are warming up to, 6h is reacted.Using
Isometric hot water washs gained mixed liquor, its water phase is taken after liquid separation；Then its aqueous phase solution is evaporated under reduced pressure, is obtained
Intermediate.It takes intermediate 6g, bromo eicosane 9g, ethyl alcohol 85g to be configured to solution, and be warming up to 70 DEG C, reacts 2h.Again to it
Middle addition 30g calcium hydroxide after the reaction was continued 2h, filters off solid, is evaporated under reduced pressure to liquid, products obtained therefrom is that target produces
Product, yield 83%.
Target product structure:
In formula: R is alkyl, carbon atom number=20 in alkyl.
Product structure confirmation: the nucleus magnetic hydrogen spectrum of the polyamino Gemini surface active agent prepared in embodiment 3 is as shown in Figure 3.
1H NMR (300MHz, DMSO): δ 3.01 (t, 4H), 2.61~2.52 (m, 8H), 2.34 (s, 4H), 1.75 (s,
4H), 1.35~1.21 (m, 72H), 0.87 (m, 6H) ppm.
Application Example:
According to People's Republic of China's petroleum gas standard SY/T5329-2012 " clastic rock reservoir water water quality indicator
And analysis method ", using the sample of secondary iterative method testing example 2 to the bactericidal effect of oily wastewater.Liquid in test bottle
Blackening has black precipitate, that is, indicates sulfate reducing bacteria (SRB)；Liquid is by red flavescence or muddy i.e. table in test bottle
Show that (TGB) containing saprophytic bacteria, the sample bactericidal effect of Statistics Implementation example 2 are as shown in table 1.
The sample Evaluation of Germicidal Efficacy result of table 1, embodiment 2
As shown in table 1: Gemini surface active agent prepared by embodiment 2 is to sulfate reducing bacteria in oily wastewater (SRB)
There is good bactericidal effect with saprophytic bacteria (TGB).
Analysis: contain polyamino group in polyamino Gemini surface active agent prepared by above-described embodiment, enhance ammonia
Suction-operated of the base to bacterium surface improves the dispersibility of Gemini surface active agent in water, in addition, two long-chains are dredged
Water base group, is conducive to hydrophobic group and hydrophilic group gos deep into the lipoid layer and albumin layer of somatic cells respectively, cause enzyme lose activity and
Protein denaturation, therefore the Gemini surface active agent has high sterilizing ability, applies in oil-contaminated water of oil field bacterial treatment, has
There is significant effect.
Claims (4)
1. a kind of polyamino Gemini surface active agent, which is characterized in that have following molecular structure:
In formula: R is alkyl, carbon atom number 16≤n≤20 in alkyl.
2. the preparation method of polyamino Gemini surface active agent described in a kind of claim 1, which is characterized in that including following step
It is rapid: phthalic anhydride and triethylene tetramine being dissolved in toluene solvant, are warming up to 90-100 DEG C, reacts 5-6h；It obtains intermediate
Body；In ethanol by intermediate dissolution, brominated alkanes are added, are warming up to 70 DEG C, reaction time 2-3h；To after reaction,
Calcium hydroxide is added into reaction solution, and the reaction was continued, obtains target product.
3. a kind of preparation method of polyamino Gemini surface active agent according to claim 2, which is characterized in that including following
Step:
(1) phthalic anhydride and triethylene tetramine are dissolved in toluene solvant, the quality of phthalic anhydride is triethylene
2.0~2.5 times of tetramine quality, and solutes content control then heats to 90-100 DEG C in 10-15wt%, reacts 5-6h；
(2) distillation water washing is added in Xiang Shangshu reaction solution, so that product is entered water phase, its water phase is taken using liquid distributing device, in turn
Remove unreacted phthalic anhydride；By carrying out vacuum distillation operation to aqueous phase solution, and then remove water and unreacted
Triethylene tetramine, obtained solid is intermediate；
(3) in ethanol by intermediate dissolution, equimolar brominated alkanes, solutes content 10-15% are added, warming temperature is
70 DEG C, reaction time 2-3h；To which calcium hydroxide, and the additional amount of calcium hydroxide after reaction, are added into the reaction solution
It is 0.3 times of solution quality, the reaction was continued 2h；
(4) mixture obtained by step (3) is filtered, takes its liquid and is dried in vacuo, gained waxy solid is that target produces
Product.
4. application of the polyamino Gemini surface active agent in oily wastewater sterilization processing described in a kind of claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021047139A1 (en) * | 2019-09-10 | 2021-03-18 | 肯特催化材料股份有限公司 | Polyamino surfactant, preparation method therefor and use thereof |
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Application publication date: 20191122 |