CN103012784A - Preparation method of polyquaternary ammonium salt, product obtained with method, and application thereof - Google Patents
Preparation method of polyquaternary ammonium salt, product obtained with method, and application thereof Download PDFInfo
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- CN103012784A CN103012784A CN2011102842956A CN201110284295A CN103012784A CN 103012784 A CN103012784 A CN 103012784A CN 2011102842956 A CN2011102842956 A CN 2011102842956A CN 201110284295 A CN201110284295 A CN 201110284295A CN 103012784 A CN103012784 A CN 103012784A
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Abstract
The invention relates to a preparation method of polyquaternary ammonium salt, a product obtained with the method, and an application thereof. The method comprises the steps that: a compound represented by a structural formula I and a compound represented by a structural formula II are subjected to a contact reaction in a polar solvent. X is halogen atom; n is an integer selected from 0-5. The polyquaternary ammonium salt provided by the invention can be used in sterilization and algae eliminating of oilfield-produced reinjection water or refinery circulating cooling water, and can be used in pipeline slime stripping. The polyquaternary ammonium salt can also be used as a crude oil demulsification auxiliary agent.
Description
Technical field
The product and the application thereof that the present invention relates to a kind of preparation method of polyquaternium, obtained by the method.
Background technology
Quaternary ammonium salt bactericide is one of most widely used sterilant, and it can be divided into mono-quaternaries sterilant, biquaternary ammonium salts bactericides and polyquaternium sterilant.The advantages such as that the mono-quaternaries sterilant has is cheap, sterilization speed fast, the foundry loam stripping ability is strong and the pH value scope of application is wide.Biquaternary ammonium salts bactericides mainly is the quaternary ammonium salt of Gemini type, and this quaternary ammonium salt has the advantages such as surfactivity height, absorption property be strong, and has special gathering behavior and aggregate structure.Though mono-quaternaries sterilant and biquaternary ammonium salts bactericides have certain advantage and all are widely used, but still come with some shortcomings, as toxicity and pungency are large, chemical stability is undesirable etc., particularly when the macromole anionic compound exists, its fungicidal activity can reduce greatly, even disappears.
Polyquaternium refers to contain in the molecule high molecular polymer of a plurality of quaternary ammonium cations, and its purposes is more extensive, except can be used as sterilant, and can also be as the amendment of shampoo and the consisting of phase-transferring agent of organic synthesis.Existing polyquaternium all has linear structure, and relevant document has CN101121557, CN1394897 etc.
In sum, though existing mono-quaternaries sterilant and biquaternary ammonium salts bactericides have certain advantage, but still come with some shortcomings.Existing polyquaternium is linear structure, and the polyquaternium with hyperbranched structure has no report.
Summary of the invention
The invention provides a kind of preparation method of polyquaternium, this polyquaternium has dendritic structure.
A kind of preparation method of polyquaternium comprises: with the compound of structural formula I and compound contact reacts in polar solvent of structural formula II;
Wherein, X is halogen atom; N is 0～5 integer.
X is preferably chlorine atom, bromine atoms or iodine atom.
The compound of structural formula II is preferably Tetramethyl Ethylene Diamine, pentamethyl-diethylenetriamine or hexamethyl triethylene tetramine.
Described polar solvent is preferably methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, ethyl acetate, ethylene glycol, in Diethylene Glycol, glycerol, acetone, ethylene glycol monomethyl ether, DMF, N-Methyl pyrrolidone, acetonitrile and the water one or more.
Temperature of reaction is preferably 20 ℃～200 ℃, more preferably 50 ℃～120 ℃.
Reaction times is preferably 4h～60h, more preferably 8h～30h.
In the reaction system, the mol ratio of halogen atom and nitrogen-atoms is preferably 1: 0.75～and 1.3, more preferably 1: 0.8～1.2, more preferably 1: 0.9～1.1.
The present invention also comprises, after the reaction, obtains product by the underpressure distillation separation.
The present invention also can further pass through the recrystallization refined product.
The present invention also provides the product that is obtained by aforesaid method.
The present invention also provides the application of the said products in sterilant and/or algicide.
Polyquaternium of the present invention has dendritic structure, and this polyquaternium has good sterilization algae removal performance, and its sterilization algae removal and pipeline foundry loam that both can be used for oil field produced re-injection water or refinery recirculated cooling water is peeled off, and also can be used as the crude oil demulsification auxiliary agent.
Compared with prior art, the present invention has following characteristics:
1. polyquaternium of the present invention has hyperbranched dendritic structure, this polyquaternium good water-soluble, sterilization algae removal is active and surfactivity.
2. the easy biological degradation of polyquaternium of the present invention belongs to environmentally friendly macromolecular cpd.
3. reaction conditions of the present invention is gentle, simple to operate, yield is high, synthetic route is short.
Embodiment
Further specify by the following examples the present invention.
Embodiment 1
Prepare polyquaternium with tetrachloro methylmethane and N,N,N′,N′ tetramethylethylene diamine.
With 21.0g (0.1mol) tetrachloro methylmethane and 23.4g (0.2mol) N; N; N ', N '-Tetramethyl Ethylene Diamine join in the 250ml reaction flask, add the 80g dehydrated alcohol; nitrogen protection; be warmed up to 80 ℃ of reaction 20h, cooling, ethanol is removed in decompression; the compound that obtains mixes recrystallization with ethanol and ethyl acetate, obtains solid 37.4g (productive rate 84.2%).
Product
13C NMR analytical results shows that chemical shift is 45.22 N-CH in the raw material N,N,N′,N′ tetramethylethylene diamine
3The peak disappears, and the generation chemical shift is 52.66 quaternary ammonium N
+-CH
3Peak, the chemical shift of raw material tetrachloro methylmethane are 45.14 C-Cl peak disappearance, and the generation chemical shift is 50.9 quaternary ammonium N
+-CH
2-peak.
Embodiment 2
Prepare polyquaternium with tetrachloro methylmethane and pentamethyl-diethylenetriamine.
38.7g (0.1mol) tetrabromo methylmethane and 23.0g (0.13mol) pentamethyl-diethylenetriamine are joined in the 250ml reaction flask; add 100g ethylene glycol; nitrogen protection; be warmed up to 130 ℃ of reaction 30h; cooling; ethylene glycol is removed in decompression, and the compound that obtains carries out recrystallization with the Ethanol-Acetic Acid acetate mixed solvent, obtains solid 54.6g (productive rate 88.5%).
Product
13C NMR analytical results shows that chemical shift is 42.36,44.68 N-CH in the raw material pentamethyl-diethylenetriamine
3The peak disappears, and the generation chemical shift is 48.88,52.70 quaternary ammonium N
+-CH
3Peak, the chemical shift of raw material tetrachloro methylmethane are 45.14 C-Cl peak disappearance, and the generation chemical shift is 50.93 quaternary ammonium N
+-CH
2-peak.
Embodiment 3
Present embodiment is used for sterilization, the algae removal effect of explanation embodiment 1～2 gained polyquaternium, and its sterilization, algae removal performance assessment method are as follows.
Synthetic dendroid polyquaternium is to the static bactericidal property evaluation of heterotrophic bacteria
Experiment on Microbiology part in " water coolant analysis and experimental technique " book that this experiment is write with reference to production department of China PetroChemical Corporation and development division.
The method of calculation of sterilizing rate are as follows:
Sterilizing rate=(the bacterium number of blank sample under certain hour-survive under the same time bacterium the number)/bacterium number of blank sample under certain hour
The bacterium number of above-mentioned method of calculation blank sample under the same time has been considered the impact of extraneous factor on the bacterial growth breeding, thereby has been suitable for laboratory thoroughly evaluating sterilant as the truth of a matter.This experiment adopts aforesaid method to calculate the sterilizing rate of product 6h, 12h, 24h and 36h, and the pharmaceutical quantities of adding is respectively 40mg/L and 80mg/L, and experimental result sees Table 1.
Table 1 test sample is to the killing effect of heterotrophic bacteria
Kill the algae assessment of performance
Various algae all contain chlorophyll a, therefore just can measure growth and the dead amount of frustule by the content of measuring chlorophyll a.Colorimetry is adopted in qualification test of the present invention, and is specific as follows:
To cultivate certain density algae liquid, and shake up, and accurately measure 50 milliliters, and transfer in 150 milliliters of Erlenmeyer flasks, and add the algicide to be measured of different concns in each flask, the double parallel test is not done control sample with the flask of algicide; Bottleneck covers with sterile gauze, puts into the algae incubator and cultivates, and surveys its chlorophyll a every day.
Culture is shaken up, get the magnesiumcarbonate suspension (it is formulated to add 1g magnesiumcarbonate in the 1000mL distilled water) that an amount of sample adds 0.2～1.0mL.Change in the centrifuge tube, centrifugal 10min (3 500r/min) removes supernatant liquor, collecting cell.
With the cell of collecting, change homogenizer or mortar over to, add the acetone soln (it is formulated that the acetone of 9 parts of volumes adds the distilled water of a volume) of 2～3mL 90%, at room temperature grind 3min.
Extracting solution is changed in the graduated tool plug centrifuge tube, wash homogenizer or mortar with the acetone soln of about 1mL 90%, and washings poured in the above-mentioned centrifuge tube, so repeat 1～2 time, last constant volume is 10mL, centrifugal 3min (3500～4000r/min), leave standstill 1～2min, more than operation all need in the dark be carried out.
Get supernatant liquid, with optical path be the cuvette of 1cm at 750nm, 669nm, 645nm, 630nm wavelength place measures respectively their optical density(OD).The error that causes for reducing reagent and operation is got the supernatant liquor (without culture) by the said process preparation, the blank of regulating zero point during as colorimetric estimation.In addition, for making 0.2＜OD663＜1, should select cuvette or the control extent of dilution of different optical paths.Chlorophyll a,b and c be respectively at 663nm, 645nm, and there is absorption peak in 630nm wavelength place.The OD that records at the 750nm place is used for proofreading and correct turbidity.So reply OD proofreaies and correct first when calculating their content, namely deducts respectively OD750:
Ca＝11.64(OD663)-2.16(OD645)+0.1(OD630)
Cb＝20.91(OD645)-3.90(OD663)-3.66(OD630)
Cc＝54.22(OD630)-14.81(OD645)-5.33(OD663)
In the formula, Ca, Cb, Cc are respectively the content of extracting solution Determination of Chlorophyll a, b, c, the g/L of unit; OD645, OD630 and OD663 are the OD after the correction.
The content of unit volume culture Determination of Chlorophyll a is:
The content of chlorophyll a=(Ca * extracting liquid volume)/filtration culture volume
Test-results sees Table 2.
Table 2 test sample is to the algae removal effect of grid algae (Chlorophyta)
Control sample chlorofucine a=7.872
Claims (12)
1. the preparation method of a polyquaternium comprises: with the compound of structural formula I and compound contact reacts in polar solvent of structural formula II;
Wherein, X is halogen atom; N is 0～5 integer.
2. in accordance with the method for claim 1, it is characterized in that X is chlorine atom, bromine atoms or iodine atom.
3. in accordance with the method for claim 1, it is characterized in that, described polar solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, ethyl acetate, ethylene glycol, in Diethylene Glycol, glycerol, acetone, ethylene glycol monomethyl ether, DMF, N-Methyl pyrrolidone, acetonitrile and the water one or more.
4. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 20 ℃～200 ℃.
5. in accordance with the method for claim 4, it is characterized in that temperature of reaction is 50 ℃～120 ℃.
6. in accordance with the method for claim 1, it is characterized in that the reaction times is 4h～60h.
7. in accordance with the method for claim 1, it is characterized in that in the reaction system, the mol ratio of halogen atom and nitrogen-atoms is 1: 0.75～1.3.
8. in accordance with the method for claim 7, it is characterized in that, in the reaction system, the mol ratio of halogen atom and nitrogen-atoms 1: 0.8～1.2.
9. in accordance with the method for claim 8, it is characterized in that, in the reaction system, the mol ratio of halogen atom and nitrogen-atoms is preferably 1: 0.9～and 1.1.
10. in accordance with the method for claim 1, it is characterized in that, after the reaction, obtain product by the underpressure distillation separation.
11. the product by arbitrary described method acquisition in the claim 1～10.
12. the application of the described product of claim 11 in sterilant and/or algicide.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4349646A (en) * | 1980-01-31 | 1982-09-14 | Research Foundation Of State University Of New York | Water insoluble disinfectant composition |
| CN1394897A (en) * | 2002-08-21 | 2003-02-05 | 清华大学 | Superbranched polyquaternary ammonium salt and its preparation method |
| CN101856600A (en) * | 2010-06-25 | 2010-10-13 | 西北大学 | Amphoteric ionic Gemini surfactant and synthetic method thereof |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4349646A (en) * | 1980-01-31 | 1982-09-14 | Research Foundation Of State University Of New York | Water insoluble disinfectant composition |
| CN1394897A (en) * | 2002-08-21 | 2003-02-05 | 清华大学 | Superbranched polyquaternary ammonium salt and its preparation method |
| CN101856600A (en) * | 2010-06-25 | 2010-10-13 | 西北大学 | Amphoteric ionic Gemini surfactant and synthetic method thereof |
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