CN104645874A - Rosin-based choline quaternary ammonium salt surfactant and preparation method thereof - Google Patents
Rosin-based choline quaternary ammonium salt surfactant and preparation method thereof Download PDFInfo
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- CN104645874A CN104645874A CN201510060144.0A CN201510060144A CN104645874A CN 104645874 A CN104645874 A CN 104645874A CN 201510060144 A CN201510060144 A CN 201510060144A CN 104645874 A CN104645874 A CN 104645874A
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- rosin
- choline
- ammonium salt
- quaternary ammonium
- abietyl
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Abstract
The invention discloses a rosin-based choline quaternary ammonium salt surfactant and a preparation method thereof. With dehydroabietic acid, dehydroabietic acid maleate, ofacrylpimaric acid and maleopimaric acid, serving as derivatives of rosin, as raw materials, one-step reaction is carried out on the raw materials and choline to generate the quaternary ammonium salt surfactant. The invention also discloses a preparation method of the rosin-based choline quaternary ammonium salt surfactant. The preparation method comprises the following step: with the derivatives of the rosin and the choline as the raw materials, carrying out acid-base neutralization at room temperature in one step to prepare the rosin-based choline quaternary ammonium salt surfactant. The prepared rosin-based choline quaternary ammonium salt surfactant has the critical micellar concentration to be 1.87-12mmol/L and the range of surface tension to be 35.2-43.7mN/m, is very low in Krafft point (below 0 DEG C) and high in HLB (larger than 18), can be used for the aspects of an emulsifier, a detergent and the like, is a novel green surfactant, has good antibacterial activity to staphylococcus epidermidis with the minimum inhibitory concentration reaching 2mg/L and can be used as a bacteriostatic agent for the staphylococcus epidermidis.
Description
Technical field
The present invention relates to a kind of surfactant and preparation method thereof, particularly relate to a kind of abietyl choline quaternary surfactant and preparation method thereof.
Background technology
Quaternary surfactant with positive charge, for the usual textile with negative surface charge, metal, glass,
Its adsorption capacity such as plastics, mineral, animal or human soma than anion and nonionic strong.Due to the sorptive power that it is strong, easily form lipophile film on the substrate surface, low-fiber coefficient of friction can be fallen significantly, be widely used as the waterproofing agent of textile, softening agent, antistatic additive, dye fixing etc.Quaternary amine surfactant has stronger sterilizing effect in addition, is widely used as medical disinfectant.Compared with the surfactant be not optionally substituted by a hydroxyl group with similar structures, between the surfactant molecule of hydroxyl, can hydrogen bond be formed, promote surfactant adsorption and gathering, demonstrate better surface property.Research shows that the CMC of hydroxyl methylene connection base Gemini surface active than corresponding containing methylene connection base Gemini surface active is low more than 3 times, thus improves dispersiveness and the washing performance of surfactant.
Rosin is a kind of abundant natural reproducible resource, and its main component is tricyclic diterpene unitary resin acid, main containing the luxuriant and rich with fragrance skeleton of three-membered ring hydrogenation and a carboxyl in its structure, has the character of amphiphile, amphiphilic molecule.Be that the novel surfactant of Material synthesis had both solved the crisis that there is lack of raw materials, price is high with rosin, meet again the requirement of surfactant " greenization ".Choline is the indispensable nutrients of human body, plays an important role to some human body physiological function.Choline is at the hydroxide being chemically (beta-hydroxyethyl) trimethyl ammonia, and it is ionic compound, has good water-soluble and biological degradability.Choline is separated in 1894 by Streker first from pig's bile, and 1962 is choline by definite designation, has now become additive conventional in human food.
Summary of the invention
The invention provides a kind of abietyl choline quaternary surfactant and preparation method thereof.This surfactant is raw material with rosin derivative, and raw material is cheap and easy to get, and preparation technology is simple, and product is biodegradable.The surfactant of preparation has good some surface active property, can be used for the aspect such as emulsifying agent, washing agent.
The present invention adopts following technical scheme: a kind of abietyl choline quaternary surfactant, and its general structure is as follows:
In formula, R is any one in Dehydroabietic acid, dehydroabietylamine maleic, rosin acrylic acid base, maleopimaric acid base.
A kind of preparation method of abietyl choline quaternary surfactant, step is: rosin derivative carboxyl and choline are dissolved in ethanol by amount of substance (1:1-1.3), 1:1 can be selected, 1:1.1,1:1.2,1:1.3, at room temperature single step reaction 8-12 h, can select 8 h, 9 h, 10 h, 11 h, 12 h.Reaction terminates rear steaming except ethanol, crude product with appropriate ethanol/ether (1:80-120) can selection percentage 1:80,1:90,1:100,1:110,1:120 mixed solvent recrystallization twice, last freeze drying 24-48 h, can select 24 h, 30 h, 36 h, 42 h, 48 h.
Abietyl choline quaternary surfactant, critical micelle concentration is 1.87-12mmol/L; Capillary scope, at 35.2-43.7 mN/m, has extremely low Krafft point (less than 0 DEG C) and higher HLB value (being greater than 18).
Abietyl choline quaternary surfactant raw material is from natural products, and easily biological-degradable is a kind of surfactant of green.
The present invention obtains following technique effect:
1. the present invention adopts rosin derivative to be raw material, carries out modification to the carboxyl in rosin, synthesizes a kind of abietyl choline quaternary surfactant, and preparation technology is simple, and biological degradability is good, improves the added value of rosin.
2. this abietyl choline quaternary surfactant has good surface-active, and critical micelle concentration is 1.87-12mmol/L; Capillary scope is at 35.2-43.7mN/m; Krafft is lower than 0 DEG C; HLB value is greater than 18, can be used as the aspect such as emulsifying agent, washing agent, is a kind of novel green surfactant.
3. this abietyl choline quaternary ammonium salt has good inhibitory action to MRSE, can be used as bacteriostatic agent.
Detailed description of the invention
Embodiment 1
Take dehydroabietic acid that mol ratio is 1:1.1 respectively and choline is poured in there-necked flask, take ethanol as solvent, react 12h under room temperature, reaction terminates rear steaming except ethanol, crude product appropriate ethanol/ether (1:120) mixed solvent recrystallization twice, obtains solid after freeze drying 48 h.
Embodiment 2
Synthesis technique is similar to embodiment 1, and dehydroabietic acid rosin acrylic acid replaces, and the mol ratio of rosin acrylic acid and choline is 1:2.2.
Embodiment 3
IR is carried out to rosin choline quaternary ammonium salt,
1h NMR and
13c NMR structural characterization, dehydroabietic acid choline quaternary ammonium salt (I
1) spectroscopic data: IR (cm
-1): 3249 (-OH), 2929,2869 (-CH
2,-CH
3), 1566 (-COO
-);
1h NMR:(CDCl
3, δ, 300MHz), 7.13 (d, 1H, Ar-H), 6.94 (d, 1H, Ar-H), 6.81 (s, 1H, Ar-H), 3.99 (s, 2H ,-
ch
2-OH), 3.57 (s, 2H, N
+(CH
3)
3-
ch
2-), 3.22 (s, 9H ,-N
+(CH
3)
3), 2.81 (d, 2H ,-CH
2-), 2.76 (s, 1H ,-CH (CH
3)
2), 2.23 (d, 1H ,-CH), 1.87 ~ 1.36 (m, 8H ,-CH
2-), 1.20 ~ 1.04 (m, 12H ,-CH
3).
13c NMR:(CDCl
3, δ, 300MHz), 184.04 (1C ,-C=O), 148.10,145.12,135.08,126.60,124.01,123.46 (6C, C=C-), 68.30 (1C ,-CH
2), 64.87 (1C ,-CH
2), 55.90 ~ 54.32 (3C ,-CH
3), 48.09 (1C ,-CH), 45.54 (1C ,-C-), 24.84,23.97,23.95,21.60 (4C ,-CH
3), 38.60,37.80,30.23,19.18,17.91 (5C ,-CH
2).
Embodiment 4
The some surface active property of abietyl choline quaternary surfactant measures, the important parameter of surfactant properties during surface tension, surfactant dissolves is mixed with certain density solution by this research in deionized water, and progressively dilute, adopt hanging slice method its surface tension of sequentially determining at 25 DEG C, make γ-lgc curve, try to achieve the γ under critical micelle concentration CMC value and critical micelle concentration by point of inflexion on a curve
cMC.
Get 40 mL mass fractions be 0.1% product water solution pour in the tool plug graduated cylinder of 100 mL, add 40 mL atoleines again, first upper and lower thermal agitation 5 times, after leaving standstill 1 min, vibrate 5 times up and down again, according to said method repeat 5 times, when last vibration stops, accurate recording separates the time needed for 10 mL water.
Take 0.2 g surfactant product to be measured, add 20 ml diox-benzene (90:4 volume ratio) solution and make it dissolve, then be titrated to obviously muddy appearance with distilled water, record the milliliter number V of distilled water used, be then calculated as follows HLB value:
HLB=23.64lgV-10.16
the surface-active of table 1 abietyl choline surfactant
Embodiment 5
Adopt dull and stereotyped doubling dilution, measure the minimum inhibitory concentration (MIC) of compound.Test strain chooses pathogenic bacteria MRSE.Rosin choline quaternary surfactant I
1, II
1, III
1, IV
116 are respectively to MRSE minimum inhibitory concentration, 16,2,2 mg/L.
Claims (4)
1. an abietyl choline quaternary surfactant, its general structure is as follows:
In formula, R is rosin derivative, Dehydroabietic acid (
), dehydroabietylamine maleic (
), rosin acrylic acid base (
), maleopimaric acid base (
) in any one.
2. the preparation method of the abietyl choline quaternary surfactant as described in right 1, it is characterized in that, rosin derivative carboxyl and choline are pressed amount of substance (1:1-1.3) and are dissolved in ethanol, next step reaction of room temperature 8-12 h, reaction terminates rear steaming except ethanol, abietyl choline quaternary surfactant is obtained after crude product ethanol/ether (1:80-120) mixed solvent recrystallization twice, freeze drying 24-48 h.
3. abietyl choline quaternary surfactant according to claim 1, is characterized in that, critical micelle concentration is 1.87-12 mmol/L; Capillary scope, at 35.2-43.7 mN/m, has extremely low Krafft point (less than 0 DEG C) and higher HLB value (being greater than 18).
4. abietyl choline quaternary surfactant according to claim 1, is 2 mg/L to the staphylococcic minimum inhibitory concentration of epidermis, can be used as bacteriostatic agent.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413577A (en) * | 2015-11-16 | 2016-03-23 | 江南大学 | Viscous and elastic solution constructed by rosin-based amino acid surfactant |
| CN107311882A (en) * | 2017-06-16 | 2017-11-03 | 江南大学 | A kind of Dehydroabietic acid dipeptides surfactant and its performance |
| CN108441350A (en) * | 2018-03-23 | 2018-08-24 | 浙江工业大学 | A kind of kitchen cleaning agent and preparation method thereof based on bio-based compounds |
| CN109052416A (en) * | 2018-08-13 | 2018-12-21 | 江西农业大学 | A kind of orderly ultra-microporous material of stratiform and its synthetic method |
| CN110776551A (en) * | 2019-11-29 | 2020-02-11 | 中国林业科学研究院林产化学工业研究所 | Polymerizable rosin quaternary ammonium salt bactericide, preparation method thereof and polymerized rosin quaternary ammonium salt bactericide prepared from polymerizable rosin quaternary ammonium salt bactericide |
| CN110845526A (en) * | 2019-11-29 | 2020-02-28 | 中国林业科学研究院林产化学工业研究所 | Rosin quaternary ammonium salt antibacterial coating compound based on modified non-woven fabric, and preparation method and application thereof |
| CN113185448A (en) * | 2021-04-27 | 2021-07-30 | 华侨大学 | Rosin-based zwitterionic surfactant and preparation method and application thereof |
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| US3201386A (en) * | 1964-08-25 | 1965-08-17 | Bristol Banyu Res Inst Ltd | Coumermycin and salts thereof |
| CN101260051A (en) * | 2008-04-24 | 2008-09-10 | 中国科学院过程工程研究所 | Biodegradable choline-like ionic liquid |
| CN103304534A (en) * | 2013-06-05 | 2013-09-18 | 中国林业科学研究院林产化学工业研究所 | Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof |
-
2015
- 2015-02-05 CN CN201510060144.0A patent/CN104645874B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3201386A (en) * | 1964-08-25 | 1965-08-17 | Bristol Banyu Res Inst Ltd | Coumermycin and salts thereof |
| CN101260051A (en) * | 2008-04-24 | 2008-09-10 | 中国科学院过程工程研究所 | Biodegradable choline-like ionic liquid |
| CN103304534A (en) * | 2013-06-05 | 2013-09-18 | 中国林业科学研究院林产化学工业研究所 | Preparation method of rosinyl cyclic carbonate and quaternary ammonium salt antibacterial derivative thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413577A (en) * | 2015-11-16 | 2016-03-23 | 江南大学 | Viscous and elastic solution constructed by rosin-based amino acid surfactant |
| CN107311882A (en) * | 2017-06-16 | 2017-11-03 | 江南大学 | A kind of Dehydroabietic acid dipeptides surfactant and its performance |
| CN108441350A (en) * | 2018-03-23 | 2018-08-24 | 浙江工业大学 | A kind of kitchen cleaning agent and preparation method thereof based on bio-based compounds |
| CN109052416A (en) * | 2018-08-13 | 2018-12-21 | 江西农业大学 | A kind of orderly ultra-microporous material of stratiform and its synthetic method |
| CN109052416B (en) * | 2018-08-13 | 2021-05-11 | 江西农业大学 | Layered ordered ultramicropore material and synthesis method thereof |
| CN110776551A (en) * | 2019-11-29 | 2020-02-11 | 中国林业科学研究院林产化学工业研究所 | Polymerizable rosin quaternary ammonium salt bactericide, preparation method thereof and polymerized rosin quaternary ammonium salt bactericide prepared from polymerizable rosin quaternary ammonium salt bactericide |
| CN110845526A (en) * | 2019-11-29 | 2020-02-28 | 中国林业科学研究院林产化学工业研究所 | Rosin quaternary ammonium salt antibacterial coating compound based on modified non-woven fabric, and preparation method and application thereof |
| CN110845526B (en) * | 2019-11-29 | 2022-05-27 | 中国林业科学研究院林产化学工业研究所 | Rosin quaternary ammonium salt antibacterial coating compound based on modified non-woven fabric, and preparation method and application thereof |
| CN113185448A (en) * | 2021-04-27 | 2021-07-30 | 华侨大学 | Rosin-based zwitterionic surfactant and preparation method and application thereof |
| CN113185448B (en) * | 2021-04-27 | 2023-05-26 | 华侨大学 | Rosin-based amphoteric ion surfactant, and preparation method and application thereof |
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