CN101628896A - Alkyl imidazoline quaternary ammonium salt, preparation method and application - Google Patents
Alkyl imidazoline quaternary ammonium salt, preparation method and application Download PDFInfo
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- CN101628896A CN101628896A CN200910305443A CN200910305443A CN101628896A CN 101628896 A CN101628896 A CN 101628896A CN 200910305443 A CN200910305443 A CN 200910305443A CN 200910305443 A CN200910305443 A CN 200910305443A CN 101628896 A CN101628896 A CN 101628896A
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Abstract
The invention relates to an alkyl imidazoline quaternary ammonium salt, a preparation method and application, relating to an imidazoline quaternary ammonium salt, a preparation method and application thereof. The invention solves the problems of poor leaching resistance and high toxicity when using a prior wood preservative. The chemical name of the alkyl imidazoline quaternary ammonium salt is 1-bezyl1-amino ethyl-2-heptyl alkyl imidazoline quaternary ammonium salt. The method comprises steps of synthesizing 1-amino ethyl-2-heptyl imidazoline through a reduced pressure distillation method; and synthesizing 1-amino ethyl-2-heptyl imidazoline with benzyl chloride to produce alkyl imidazoline quaternary ammonium salt under normal pressure. The alkyl imidazoline quaternary ammonium salt is used as the wood preservative. The invention has advantages of simple process, convenient operation and high purity. The produced alkyl imidazoline quaternary ammonium salt has the antibacterial activity equivalent to that of the traditional wood preservative, and has advantages of low toxicity, strong leaching resistance and environmental protection.
Description
Technical field
The present invention relates to a kind of imidazoline quaternary ammonium salt and its production and application.
Background technology
Timber dressing can improve the performances such as antibiotic insect protected of timber, is the important channel of saving timber resources, raising timber utilization rate, increasing the Wood products function.Be undressed 5～6 times the timber work-ing life after the rotproofing.By 2010,, then can save timber 3,600 ten thousand m every year if 10% of usefulness materials such as China's building, finishing and production maintenance are done rotproofing
3, visible wood preservation is very big to the potentiality of saving timber resources, the imbalance between supply and demand of solution timber.
At present, widely used wood preservative comprises ammonia dissolubility cupric chromate (ACC), wood preservative ACQ-C, CA-B (copper azoles) etc., in use has the problem that resistance leachability is poor, toxicity is big, thereby the hazard rating that environment and human body are caused is big.
Summary of the invention
For in use there is the problem that leachability is strong, toxicity is bigger in the wood preservative that solves present use, the invention provides a kind of alkyl imidazoline quaternary ammonium salt and its production and application.That alkyl imidazoline quaternary ammonium salt of the present invention has is efficiently antibacterial, turnover rate is low, the advantage of low toxicity, environmental protection, can be used as wood preservative.
To achieve these goals, the invention discloses a kind of alkyl imidazoline quaternary ammonium salt, its chemical name is 1-benzyl-1-amine ethyl-2-heptyl alkyl imidazoline quaternary ammonium salt, and its structural formula is
In the formula: R is-C
7H
15
Alkyl imidazoline quaternary ammonium salt its preparation method of the present invention is as follows: step 1, synthetic 1-amine ethyl-2-heptyl tetrahydroglyoxaline: the adding mol ratio is 1: 1～1.3 sad and diethylenetriamine in the underpressure distillation bottle, then the underpressure distillation bottle is installed on the rotatory evaporator, be to be mixed under the 150r/min condition evenly in speed of rotation again, it is 145 ℃ in temperature then, vacuum tightness is that 0.074MPa keeps 1h down, pressurize is warming up to 160 ℃ simultaneously, keep 2h, be warming up to 175 ℃ again, boosting to vacuum tightness simultaneously is 0.079MPa, keep 30min, be warming up to 180 ℃ again, boosting to vacuum tightness simultaneously is 0.091MPa, keep 45min, be warming up to 187 ℃ again, boosting to vacuum tightness simultaneously is 0.093MPa, keeps 20min, be warming up to 189 ℃ again, boosting to vacuum tightness simultaneously is 0.1MPa, keeps 1h, cools off under vacuum, the omnidistance time is 5h, obtains 1-amine ethyl-2-heptyl tetrahydroglyoxaline (the clarifying liquid of little Huang); Step 2, synthesis of alkyl imidazoline quaternary ammonium salt: the 1-amine ethyl-2-heptyl tetrahydroglyoxaline of step 1 preparation is joined in the reactor, add benzyl chloride (alkylating reagent) and stirring again, it is 1: 1 that 1-amine ethyl-2-heptyl tetrahydroglyoxaline and benzyl chloride get mol ratio, in temperature is to react 2h under 180 ℃ of conditions, promptly obtains alkyl imidazoline quaternary ammonium salt.
Alkyl imidazoline quaternary ammonium salt of the present invention is as wood preservative.
Alkyl imidazoline quaternary ammonium salt of the present invention is the heavy-gravity liquid of reddish-brown.What the present invention used when preparation 1-amine ethyl-2-heptyl tetrahydroglyoxaline is the method for underpressure distillation, and its technology is simple, easy to operate, and dehydrating effect is good under the vacuum, in the reaction process product be difficult for being hydrolyzed, the purity height.The bacteriostasis of the alkyl imidazoline quaternary ammonium salt compound that makes is suitable with traditional wood preservative, and has that low toxicity, resistance leachability are strong, the advantage of environmental protection.
Description of drawings
Fig. 1 is that quality of liquid medicine concentration is that 0.25% embodiment two makes the alkyl imidazoline quaternary ammonium salt soup to whiterot fungi inhibition test photo; Fig. 2 is that quality of liquid medicine concentration is that 0.125% embodiment two makes the alkyl imidazoline quaternary ammonium salt soup to whiterot fungi inhibition test photo; Fig. 3 is that quality of liquid medicine concentration is that 0.0625% embodiment two makes the alkyl imidazoline quaternary ammonium salt soup to whiterot fungi inhibition test photo; Fig. 4 is that quality of liquid medicine concentration is that 0.0313% embodiment two makes the alkyl imidazoline quaternary ammonium salt soup to whiterot fungi inhibition test photo; Fig. 5 be quality of liquid medicine concentration be the 0.25%ACC soup to whiterot fungi inhibition test photo to whiterot fungi; Fig. 6 be quality of liquid medicine concentration be the 0.125%ACC soup to whiterot fungi inhibition test photo to whiterot fungi; Fig. 7 be quality of liquid medicine concentration be the 0.0625%ACC soup to whiterot fungi inhibition test photo to whiterot fungi; Fig. 8 be quality of liquid medicine concentration be the 0.0313%ACC soup to whiterot fungi inhibition test photo to whiterot fungi; Fig. 9 is that quality of liquid medicine concentration is that the 0.25%ACQ-C soup is to whiterot fungi inhibition test photo; Figure 10 be quality of liquid medicine concentration be the 0.125%ACQ-C soup to whiterot fungi inhibition test photo to whiterot fungi; Figure 11 be quality of liquid medicine concentration be the 0.0625%ACQ-C soup to whiterot fungi inhibition test photo to whiterot fungi; Figure 12 be quality of liquid medicine concentration be the 0.0313%ACQ-C soup to whiterot fungi inhibition test photo to whiterot fungi; Figure 13 is that quality of liquid medicine concentration is that 0.25%CA-B is to whiterot fungi; Figure 14 be quality of liquid medicine concentration be the 0.125%CA-B soup to whiterot fungi inhibition test photo to whiterot fungi; Figure 15 be quality of liquid medicine concentration be 0.0625% soup to whiterot fungi inhibition test photo to whiterot fungi; Figure 16 is that quality of liquid medicine concentration is that the 0.0313%CA-B soup is to whiterot fungi inhibition test photo; Figure 17 is that quality of liquid medicine concentration is that 0.25% embodiment two makes the alkyl imidazoline quaternary ammonium salt soup to brown rot fungus inhibition test photo; Figure 18 is that quality of liquid medicine concentration is that 0.125% embodiment two makes the alkyl imidazoline quaternary ammonium salt soup to brown rot fungus inhibition test photo; Figure 19 is that quality of liquid medicine concentration is that 0.0625% embodiment two makes the alkyl imidazoline quaternary ammonium salt soup to brown rot fungus inhibition test photo; Figure 20 is that quality of liquid medicine concentration is that 0.0313% embodiment two makes the alkyl imidazoline quaternary ammonium salt soup to brown rot fungus inhibition test photo; Figure 21 is that quality of liquid medicine concentration is that the 0.25%ACQ-C soup is to brown rot fungus inhibition test photo; Figure 22 is that quality of liquid medicine concentration is that the 0.125%ACQ-C soup is to brown rot fungus inhibition test photo; Figure 23 is that quality of liquid medicine concentration is that the 0.0625%ACQ-C soup is to brown rot fungus inhibition test photo; Figure 23 is that quality of liquid medicine concentration is that the 0.0313%ACQ-C soup is to brown rot fungus inhibition test photo; Figure 25 is that quality of liquid medicine concentration is that the 0.25%CA-B soup is to brown rot fungus inhibition test photo; Figure 26 is that quality of liquid medicine concentration is that the 0.125%CA-B soup is to brown rot fungus inhibition test photo; Figure 27 is that quality of liquid medicine concentration is that the 0.0625%CA-B soup is to brown rot fungus inhibition test photo; Figure 28 is that quality of liquid medicine concentration is that the 0.0313%CA-B soup is to brown rot fungus inhibition test photo; Figure 29 is that the 0.25%ACC soup is to brown rot fungus inhibition test photo; Figure 30 is that quality of liquid medicine concentration is that the 0.125%ACC soup is to brown rot fungus inhibition test photo; Figure 31 is that quality of liquid medicine concentration is that the 0.0625%ACC soup is to brown rot fungus inhibition test photo; Figure 32 is that quality of liquid medicine concentration is that the 0.0313%ACC soup is to brown rot fungus inhibition test photo.
Embodiment
Embodiment one: the chemical name name of present embodiment alkyl imidazoline quaternary ammonium salt is called 1-benzyl-1-amine ethyl-2-heptyl alkyl imidazoline quaternary ammonium salt, and structural formula is
In the formula: R is-C
7H
15
The present embodiment alkyl imidazoline quaternary ammonium salt is the heavy-gravity liquid of reddish-brown, and is efficiently antibacterial, turnover rate is low, low toxicity, environmental protection.
Embodiment two: the alkyl imidazoline quaternary ammonium salt preparation method is as follows in the present embodiment: step 1, synthetic 1-amine ethyl-2-heptyl tetrahydroglyoxaline: the adding mol ratio is 1: 1～1.3 sad and diethylenetriamine in the underpressure distillation bottle, then the underpressure distillation bottle is installed on the rotatory evaporator, be to be mixed under the 150r/min condition evenly in speed of rotation again, it is 145 ℃ in temperature then, vacuum tightness is that 0.074MPa keeps 1h down, pressurize is warming up to 160 ℃ simultaneously, keep 2h, be warming up to 175 ℃ again, boosting to vacuum tightness simultaneously is 0.079MPa, keep 30min, be warming up to 180 ℃ again, boosting to vacuum tightness simultaneously is 0.091MPa, keep 45min, be warming up to 187 ℃ again, boosting to vacuum tightness simultaneously is 0.093MPa, keeps 20min, be warming up to 189 ℃ again, boosting to vacuum tightness simultaneously is 0.1MPa, keeps 1h, cools off under vacuum, the omnidistance time is 5h, obtains 1-amine ethyl-2-heptyl tetrahydroglyoxaline (the clarifying liquid of little Huang); Step 2, synthesis of alkyl imidazoline quaternary ammonium salt: the 1-amine ethyl-2-heptyl tetrahydroglyoxaline of step 1 preparation is joined in the reactor, add benzyl chloride (alkylating reagent) and stirring again, it is 1: 1 that 1-amine ethyl-2-heptyl tetrahydroglyoxaline and benzyl chloride get mol ratio, in temperature is to react 2h under 180 ℃ of conditions, promptly obtains alkyl imidazoline quaternary ammonium salt.
The chemical name of the alkyl imidazoline quaternary ammonium salt that present embodiment makes is 1-benzyl-1-amine ethyl-2-heptyl alkyl imidazoline quaternary ammonium salt, and structural formula is
In the formula: R is-C
7H
15, the heavy-gravity liquid of reddish-brown.
The present embodiment step 1 makes 1-amine ethyl-2-heptyl tetrahydroglyoxaline purity height, and purity reaches 95% (quality), and the purity of alkyl imidazoline quaternary ammonium salt reaches 68.96% (quality).
The alkyl imidazoline quaternary ammonium salt that present embodiment is made and bacteriostasis, flow and failure property and the acute toxicity of existing wood preservative compare, and particular content is as follows:
One, bacteriostasis test, particular content is as follows:
A, existing wood preservative are selected ACC (ammonia dissolubility cupric chromate), wood preservative ACQ-C and CA-B (copper azoles) for use.
B, to be tried bacterial classification be whiterot fungi [Coriolus (Coriolus versicolor)], brown rot fungus [gloeophyllum trabeum (Gloeophyllum trabeum)];
It is 1% sanitas soup that c, alkyl imidazoline quaternary ammonium salt, ACC, wood preservative ACQ-C and CA-B that present embodiment is made prepare mass concentration respectively, and with above-mentioned whiterot fungi and brown rot fungus respectively configuration concentration be 1 * 0
6CFU/mL is tried bacterium suspension;
D, 2 times of dilution methods of employing, with being tried bacterium suspension dilution sanitas soup, dilute 7 times, make medicine (referring to alkyl imidazoline quaternary ammonium salt, ACC, wood preservative ACQ-C and CA-B that present embodiment makes) mass concentration have certain gradient, promptly 0.5%, 0.25%, 0.125%, 0.0625%, 0.0313%, 0.0156%, 0.0078%; Be 30min the action time of its Chinese traditional medicine and bacterium suspension;
E, substratum and culture dish sterilization;
F, with the dilution soup pour culture dish into, seal, put into the fixed temperature and humidity incubator.28 ℃ of incubator temperature, humidity 75%～85%.According to the bacterial classification difference, whiterot fungi is cultivated 7d, and brown rot fungus is cultivated 3d.Take out culture dish, observe the colony growth situation, the result is referring to table 1, and is that 0.25%, 0.125%, 0.0625% and 0.0313% colony growth situation is taken pictures to sanitas quality of liquid medicine concentration, as Fig. 1-shown in Figure 32.
Table 1: to whiterot fungi and brown rot fungus inhibition test comparison sheet as a result
Annotate :-expression does not have bacterium colony; + expression has colony growth; ++ the expression bacterium colony increases; +++expression bacterium colony raised growth.
Two, the flow and failure property test is carried out according to forestry industry standard " wood preservative is to rot fungi toxicity test chamber test method " LY/T 1283-1998, and the sanitas quality of liquid medicine concentration that this test is adopted is 10%; Sample in the test after sanitas is handled after fully gas is done, is placed on the sample of same group of maintenance dose on the stainless steel rack in the 600ml beaker, pushes down with the glass briquetting, adds the ratio adding distilled water of 50ml distilled water in every sample.Beaker is placed in the vacuum drier, is evacuated to vacuum tightness 90kPa, keep 30min.Eliminate vacuum, under atmospheric pressure keep 24h, remove the water in the beaker, with the water recently distilled replacement of equivalent.Afterwards, repeat aforesaid operations, amount to 14d every 24h; Test-results is as shown in table 2.
Table 2: leaching test comparative result table
| Wood preservative | Drug loading (kg/m 3) | Turnover rate (%) |
| The alkyl imidazoline quaternary ammonium salt that present embodiment makes | ??57.75 | ??10.05 |
| ??ACQ-C | ??54.75 | ??20.43 |
| ??CA-B | ??57.94 | ??17.23 |
| ??ACC | ??53.79 | ??7.57 |
Three, acute toxicity test:
A, carry out according to " State Standard of the People's Republic of China's water quality material is to fresh-water fishes (zebra fish) determination of acute toxicity method " (GB/T 13267-91).
B, with reference to poisonous substance: K
2Cr
2O7.
Toxic limit medium dose (the LC of c, medicine
50) and the LC of the calculating medicine of safe concentration
50Value is according to the mortality ratio of the zebra fish relation curve to liquor strength, adopts the estimation of straight line interpolation method and draws.Safe concentration (c) is calculated according to formula:
c＝(48LC
50×0.3)/(24LC
50/48LC
50)
2
Table 3 wood preservative is to the acute toxicity comparative result table of zebra fish
As can be seen, the bacteriostasis of the alkyl imidazoline quaternary ammonium salt that present embodiment makes and wood preservative ACQ-C and CA-B (copper azoles) are suitable, and are better than ACC from table 1, table 2 and table 3; Its toxicity is less, and resistance leachability is better than wood preservative ACQ-C and CA-B (copper azoles), and over-all properties is higher.
Embodiment three: what present embodiment and embodiment two were different is: sad and mol ratio diethylenetriamine is 1: 1.1～1.2 in the step 1.Other step and parameter are identical with embodiment one.
Embodiment four: present embodiment embodiment one described alkyl imidazoline quaternary ammonium salt is as the application of wood preservative.
The described alkyl imidazoline quaternary ammonium salt of present embodiment is a kind of waterborne-type preservation.The method that adopts vacuum to impregnate during use is to the not influence of following process of timber.Mass concentration during use is 2%.
Claims (4)
1. alkyl imidazoline quaternary ammonium salt, the chemical name that it is characterized in that alkyl imidazoline quaternary ammonium salt is 1-benzyl-1-amine ethyl-2-heptyl alkyl imidazoline quaternary ammonium salt, its chemical structural formula is
In the formula: R is-C7H15.
2. the preparation method of alkyl imidazoline quaternary ammonium salt as claimed in claim 1, the preparation method who it is characterized in that alkyl imidazoline quaternary ammonium salt is undertaken by following step: step 1, synthetic 1-amine ethyl-2-heptyl tetrahydroglyoxaline: the adding mol ratio is 1: 1～1.3 sad and diethylenetriamine in the underpressure distillation bottle, then the underpressure distillation bottle is installed on the rotatory evaporator, be to be mixed under the 150r/min condition evenly in speed of rotation again, it is 145 ℃ in temperature then, vacuum tightness is that 0.074MPa keeps 1h down, pressurize is warming up to 160 ℃ simultaneously, keep 2h, be warming up to 175 ℃ again, boosting to vacuum tightness simultaneously is 0.079MPa, keeps 30min, be warming up to 180 ℃ again, boosting to vacuum tightness simultaneously is 0.091MPa, keeps 45min, is warming up to 187 ℃ again, boosting to vacuum tightness simultaneously is 0.093MPa, keep 20min, be warming up to 189 ℃ again, boosting to vacuum tightness simultaneously is 0.1MPa, keep 1h, cool off under vacuum, the omnidistance time is 5h, obtains 1-amine ethyl-2-heptyl tetrahydroglyoxaline; Step 2, synthesis of alkyl imidazoline quaternary ammonium salt: the 1-amine ethyl-2-heptyl tetrahydroglyoxaline of step 1 preparation is joined in the reactor, add benzyl chloride and stirring again, it is 1: 1 that 1-amine ethyl-2-heptyl tetrahydroglyoxaline and benzyl chloride get mol ratio, in temperature is to react 2h under 180 ℃ of conditions, promptly obtains alkyl imidazoline quaternary ammonium salt.
3. the preparation method of alkyl imidazoline quaternary ammonium salt according to claim 2 is characterized in that sad and mol ratio diethylenetriamine is 1: 1.1～1.2 in the step 1.
4. the application of alkyl imidazoline quaternary ammonium salt as claimed in claim 1; It is characterized in that alkyl imidazoline quaternary ammonium salt is as wood preservative.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239836A (en) * | 2010-05-11 | 2011-11-16 | 中国林业科学研究院木材工业研究所 | Tetrafluoroborate hyamine wood anticorrosion insect prevention agent, preparation method and application thereof |
| WO2012170026A1 (en) * | 2011-06-09 | 2012-12-13 | Empire Technology Development Llc | Pre-treatment for preservation of wood |
| CN116410725A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Corrosion inhibition type foam discharging agent for gas field, preparation method and application |
| CN117946561A (en) * | 2024-03-26 | 2024-04-30 | 安徽海螺制剂工程技术有限公司 | Preparation method of hydrolyzed polymaleic anhydride betaine for scale and corrosion inhibitor |
-
2009
- 2009-08-10 CN CN2009103054430A patent/CN101628896B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239836A (en) * | 2010-05-11 | 2011-11-16 | 中国林业科学研究院木材工业研究所 | Tetrafluoroborate hyamine wood anticorrosion insect prevention agent, preparation method and application thereof |
| CN102239836B (en) * | 2010-05-11 | 2014-07-09 | 中国林业科学研究院木材工业研究所 | Tetrafluoroborate hyamine wood anticorrosion insect prevention agent, preparation method and application thereof |
| WO2012170026A1 (en) * | 2011-06-09 | 2012-12-13 | Empire Technology Development Llc | Pre-treatment for preservation of wood |
| CN116410725A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Corrosion inhibition type foam discharging agent for gas field, preparation method and application |
| CN117946561A (en) * | 2024-03-26 | 2024-04-30 | 安徽海螺制剂工程技术有限公司 | Preparation method of hydrolyzed polymaleic anhydride betaine for scale and corrosion inhibitor |
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