CN103012783B - 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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- CN103012783B CN103012783B CN201110284293.7A CN201110284293A CN103012783B CN 103012783 B CN103012783 B CN 103012783B CN 201110284293 A CN201110284293 A CN 201110284293A CN 103012783 B CN103012783 B CN 103012783B
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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. A is oxygen atom or vacancy; R1, R2, and R3 are independently one selected from C6-C8 arylene, C1-C8 straight-chain alkylene, branched-chain alkylene, and a substituent of C1-C8 straight-chain alkylene or branched-chain alkylene; 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 present invention relates to a kind of preparation method of polyquaternium, the product obtained by the method and application thereof.
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.Mono-quaternaries sterilant has that cheap, sterilization speed is fast, sludge stripping ability is strong and the advantage such as the pH value scope of application is wide.The quaternary ammonium salt of biquaternary ammonium salts bactericides mainly Gemini type, this quaternary ammonium salt has the advantages such as surfactivity is high, absorption property is strong, and has special Assembling Behavior and aggregate structure.Though mono-quaternaries sterilant and biquaternary ammonium salts bactericides have certain advantage and are all widely used, but still come with some shortcomings, as toxicity and pungency are comparatively large, chemical stability is undesirable, particularly when macromole anionic compound exists, its fungicidal activity can reduce greatly, even disappears.
Polyquaternium refers to the high molecular polymer containing multiple quaternary ammonium cation in molecule, and its purposes is relatively more extensive, except can be used as sterilant, can also be used 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 preparation method for polyquaternium, comprising: the contact reacts in polar solvent by the compound of structural formula I and the compound of formula II;
Wherein, A is Sauerstoffatom or vacancy; R
1, R
2, R
3be selected from C independently of one another
6-C
8arylidene, C
1-C
8straight-chain alkyl-sub-, branched alkylidene and C
1-C
8straight-chain alkyl-sub-or branched alkylidene hydroxyl substituent in one; X is halogen atom; N is the integer of 0 ~ 5.
X is preferably chlorine atom, bromine atoms or atomic iodine.
The compound of structural formula I is preferably three (2-chloroethyl) phosphoric acid ester (TCEP), three (3-chloropropyl) phosphine oxide, three (the chloro-2-hydroxypropyl of 3-) phosphine oxide, three (3-chloropropyl) phosphoric acid ester or three (2-chloromethyl phenyl) phosphine oxide.
The compound of 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, one or more in Diethylene Glycol, glycerol, acetone, ethylene glycol monomethyl ether, DMF, N-Methyl pyrrolidone, acetonitrile and water.
Temperature of reaction is preferably 20 DEG C ~ 200 DEG C, is more preferably 50 DEG C ~ 120 DEG C.
Reaction times is preferably 4h ~ 60h, is more preferably 8h ~ 30h.
In reaction system, the mol ratio of halogen atom and nitrogen-atoms is preferably 1: 0.75 ~ 1.3, is more preferably 1: 0.8 ~ 1.2, and more preferably 1: 0.9 ~ 1.1.
The present invention also comprises, and after reaction, is separated obtains product by underpressure distillation.
The present invention also can further by recrystallization refined product.
Present invention also offers the product obtained by aforesaid method.
Present invention also offers the application of the said products in sterilant and/or algicide.
Polyquaternium of the present invention has dendritic structure, and this polyquaternium has excellent sterilization algae removal performance, and it both can be used for sterilization algae removal and the pipeline sludge stripping of oil field produced reinjected water or refinery recirculated cooling water, also can be used as 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 illustrate the present invention by the following examples.
Embodiment 1
Polyquaternium is prepared by three (2-chloroethyl) phosphoric acid ester and N,N,N′,N′ tetramethylethylene diamine.
By 28.6g (0.1mol) three (2-chloroethyl) phosphoric acid ester and 17.4g (0.15mol) N; N; N ', N '-Tetramethyl Ethylene Diamine joins in 250ml reaction flask, adds 100g dehydrated alcohol; nitrogen protection; be warmed up to 80 DEG C of reaction 30h, cooling, decompression removing ethanol; the compound EtOH-EtOAc mixed solvent obtained carries out recrystallization, obtains solid 38.4g (productive rate 83.4%).
Product
13c NMR analytical results shows, and in raw material N,N,N′,N′ tetramethylethylene diamine, chemical shift is the N-CH of 45.22
3peak disappears, and generates the quaternary ammonium N that chemical shift is 52.38
+-CH
3peak, raw material three (2-chloroethyl) Phosphation displacement study is the C-Cl peak disappearance of 42.34, generates the quaternary ammonium N that chemical shift is 64.37
+-CH
2-peak.
Embodiment 2
Three (3-chloropropyl) phosphine oxide, hexamethyl triethylene tetramine
27.9g (0.1mol) three (3-chloropropyl) phosphine oxide and 17.3g (0.075mol) hexamethyl triethylene tetramine are joined in 250ml reaction flask; add 100g butanols; nitrogen protection; be warmed up to 90 DEG C of reaction 30h; cooling; decompression removing butanols, the compound EtOH-EtOAc mixed solvent obtained carries out recrystallization, obtains solid 37.8g (productive rate 82.7%).
Product
13c NMR analytical results shows, and in raw material hexamethyl triethylene tetramine, chemical shift is the N-CH of 42.51,44.71
3peak disappears, and generates the quaternary ammonium N that chemical shift is 48.99,52.38
+-CH
3peak, raw material three (3-chloropropyl) phosphine oxide chemical shift is the C-Cl peak disappearance of 43.12, generates the quaternary ammonium N that chemical shift is 62.29
+-CH
2-peak.
Embodiment 3
Three (the chloro-2-hydroxypropyl of 3-) phosphine oxide, pentamethyl-diethylenetriamine
By 32.8g (0.1mol) three (the chloro-2-hydroxypropyl of 3-) phosphine oxide; join in 250ml reaction flask with 17.3g (0.1mol) pentamethyl-diethylenetriamine; add 100g dehydrated alcohol; nitrogen protection; be warmed up to 80 DEG C of reaction 250h, cooling, decompression removing ethanol; the compound EtOH-EtOAc mixed solvent obtained carries out recrystallization, obtains solid 43.7g (productive rate 87.2%).
Product
13c NMR analytical results shows, and in raw material pentamethyl-diethylenetriamine, chemical shift is the N-CH of 42.36,44.68
3peak disappears, and generates the quaternary ammonium N that chemical shift is 48.42,52.66
+-CH
3peak, raw material three (the chloro-2-hydroxypropyl of 3-) phosphine oxide chemical shift is the C-Cl peak disappearance of 46.88, generates the quaternary ammonium N that chemical shift is 65.31
+-CH
2-peak.
Embodiment 4
The present embodiment is for illustration of the sterilization of embodiment 1 ~ 3 gained polyquaternium, algae removal effect, and its sterilization, algae removal performance assessment method are as follows.
The dendroid polyquaternium of synthesis 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 reference production department of China PetroChemical Corporation and development division are write.
The method of calculation of sterilizing rate are as follows:
The bacterium number of the blank sample of the sterilizing rate=bacterium number of the bacterium number-survive under the same time of blank sample (under the certain hour)/under certain hour
Above-mentioned method of calculation for the truth of a matter, take into account the impact that extraneous factor is bred bacterial growth with the bacterium number of sample blank under same time, are thus suitable for laboratory thoroughly evaluating sterilant.This experiment adopts aforesaid method to calculate the sterilizing rate of product 6h, 12h, 24h and 36h, and the pharmaceutical quantities added is respectively 40mg/L and 80mg/L, and experimental result is in table 1.
Table 1 test sample is to the killing effect of heterotrophic bacteria
Kill algae assessment of performance
Various algae all contains chlorophyll a, and the content therefore by measuring chlorophyll a just can measure the growth of frustule and the amount of death.Qualification test of the present invention adopts colorimetry, specific as follows:
By cultivation to certain density algae liquid, shake up, accurately measure 50 milliliters, transfer in 150 milliliters of Erlenmeyer flasks, add the algicide to be measured of different concns in each flask, double parallel test, the flask not with algicide does control sample; Bottleneck sterile gauze covers, and puts into algae incubator and cultivates, survey its chlorophyll a every day.
Culture is shaken up, gets the magnesiumcarbonate suspension (adding 1g magnesium carbonate in 1000mL distilled water to form) that appropriate amount of sample adds 0.2 ~ 1.0mL.Proceed in centrifuge tube, centrifugal 10min (3500r/min), remove supernatant liquor, collecting cell.
By the cell collected, proceed to homogenizer or mortar, add the acetone soln (distilled water that the acetone of 9 parts of volumes adds a volume is formulated) of 2 ~ 3mL 90%, at room temperature grind 3min.
Extracting solution is proceeded in graduated tool plug centrifuge tube, homogenizer or mortar is washed with the acetone soln of about 1mL 90%, and washings is poured in above-mentioned centrifuge tube, repetition like this 1 ~ 2 time, last constant volume is 10mL, centrifugal 3min (3500 ~ 4000r/min), leave standstill 1 ~ 2min, above operation all needs in the dark to carry out.
Getting supernatant liquid, is the cuvette of 1cm measures them respectively optical density(OD) at 750nm, 669nm, 645nm, 630nm wavelength place with optical path.For the error that minimizing reagent and operation cause, get the supernatant liquor (without culture) prepared by said process, as the blank regulating zero point during colorimetric estimation.In addition, for making 0.2 < OD663 < 1, the cuvette of different optical path should be selected or control extent of dilution.Absorption peak is there is respectively in chlorophyll a, b and c at 663nm, 645nm, 630nm wavelength place.The OD recorded at 750nm place is for correcting turbidity.Therefore when calculating their content, reply OD first corrects, and namely deducts OD750 respectively:
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 formula, Ca, Cb, Cc are respectively the content of extracting solution Determination of Chlorophyll a, b, c, g/L; OD645, OD630 and OD663 are the OD after correction.
The content of unit volume culture Determination of Chlorophyll a is:
Content=(Ca × extracting liquid volume)/filtration culture volume of chlorophyll a
Test-results is in table 2.
Table 2 test sample is to the algae removal effect of grid algae (Chlorophyta)
Control sample chlorofucine a=7.872
Claims (10)
1. the preparation method of a polyquaternium, comprise: the contact reacts in polar solvent by the compound of structural formula I and the compound of formula II, temperature of reaction is 20 DEG C ~ 200 DEG C, and the reaction times is 4h ~ 60h, and the mol ratio of halogen atom and nitrogen-atoms is 1: 0.75 ~ 1.3;
Wherein, A is Sauerstoffatom or vacancy; R
1, R
2, R
3be selected from C independently of one another
6-C
8arylidene, C
1-C
8straight-chain alkyl-sub-, branched alkylidene and C
1-C
8straight-chain alkyl-sub-or branched alkylidene hydroxyl substituent in one; X is halogen atom; N is the integer of 0 ~ 5.
2. in accordance with the method for claim 1, it is characterized in that, X is chlorine atom, bromine atoms or atomic iodine.
3. in accordance with the method for claim 1, it is characterized in that, the compound of structural formula I is three (2-chloroethyl) phosphoric acid ester, three (3-chloropropyl) phosphine oxide, three (the chloro-2-hydroxypropyl of 3-) phosphine oxide, three (3-chloropropyl) phosphoric acid ester or three (2-chloromethyl phenyl) phosphine oxide.
4. 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, one or more in Diethylene Glycol, glycerol, acetone, ethylene glycol monomethyl ether, DMF, N-Methyl pyrrolidone, acetonitrile and water.
5. in accordance with the method for claim 1, it is characterized in that, temperature of reaction is 50 DEG C ~ 120 DEG C.
6. in accordance with the method for claim 1, it is characterized in that, in reaction system, the mol ratio of halogen atom and nitrogen-atoms is 1: 0.8 ~ 1.2.
7. in accordance with the method for claim 6, it is characterized in that, in reaction system, the mol ratio of halogen atom and nitrogen-atoms is 1: 0.9 ~ 1.1.
8. in accordance with the method for claim 1, it is characterized in that, after reaction, be separated by underpressure distillation and obtain product.
9. according to the product that the arbitrary described method of claim 1 ~ 8 obtains.
10. the application of product according to claim 9 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 |
-
2011
- 2011-09-22 CN CN201110284293.7A patent/CN103012783B/en active Active
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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