CN110354754A - Amide bond quaternary cationics with different the morphology of the aggregate - Google Patents

Amide bond quaternary cationics with different the morphology of the aggregate Download PDF

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Publication number
CN110354754A
CN110354754A CN201910621029.4A CN201910621029A CN110354754A CN 110354754 A CN110354754 A CN 110354754A CN 201910621029 A CN201910621029 A CN 201910621029A CN 110354754 A CN110354754 A CN 110354754A
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China
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morphology
aggregate
amide bond
different
quaternary cationics
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CN201910621029.4A
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Inventor
王丽艳
杨佳
段松言
荆涛
阚伟
赵冰
李云晴
唐丽
刘家庆
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Qiqihar University
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Qiqihar University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Cosmetics (AREA)

Abstract

A kind of amide bond quaternary cationics with different the morphology of the aggregate, it is related to the amide bond quaternary cationics with different the morphology of the aggregate.The problem of it is to solve that existing quaternary cationics critical micelle concentration is high, surface-active is low, and the morphology of the aggregate formed in aqueous solution is single, and application range is limited, the environment such as causes secondary hazards serious not meet environment protection requirement.It is 0.037~0.099mmol/L that amide bond quaternary cationics, which face micellar concentration (CMC), and concentration has rod-shaped micelle → netted micella → vesica → vermiculate glues in 0.3 ~ 10mM.It can be used for sterilizing, the multiple fields such as pharmaceutical carrier, materials synthesis and Biomimetic membrane.

Description

Amide bond quaternary cationics with different the morphology of the aggregate
Technical field
The present invention relates to surfactant field, in particular to the amide bond quaternary ammonium of different the morphology of the aggregate Cationic surfactants.
Background technique
Traditional quaternary cationics molecular structure is simple, usually contains only a hydrophilic head base and one Hydrophobic alkyl chain belongs to not degradable compound, and not degradable surfactant, which is used for a long time, can cause to aquatile It produces serious influence with Environmental security, wherein zephiran (1227) is common disinfectant, just It is representative one of widely used quaternary cationics, such critical micelle concentration of surfactant (CMC) height, surface-active are low, and long-time service is not big, degradable with drug resistance, dosage, serious to secondary environmental pollution, in water The morphology of the aggregate is single in solution, and application range is limited etc..The quaternary cationics of amide bond refer to structure In a kind of cationic surfactant containing amido bond functional groups, this kind of surfactant not only has conventional surface living Property agent characteristic, under normal circumstances, bronsted lowry acids and bases bronsted lowry catalysis under hydrolysis can occur, therefore, amide bond quaternary ammonium salt sun from Sub- surfactant is easy to be hydrolyzed into the small molecule compound of on-surface-active segment, reduces to the two of environment and water resource etc. Secondary harm.Amido bond is easily formed intermolecular hydrogen bonding, promotes the aggregation of surfactant molecule in aqueous solution, forms not similar shape The aggregation of state expands its application field.The cationic surface with different the morphology of the aggregate is living in aqueous solution for design synthesis Property agent, improves the important research content that its surface-active is the field.
Summary of the invention
That present invention aim to address existing conventional surfactant critical micelle concentrations is high, surface-active is low, in water The morphology of the aggregate formed in solution is single, and application range is limited, serious to environment secondary hazards etc. not meet environmentally protective want The problem of asking, and provide a kind of in aqueous solution with the amide bond quaternary ammonium salt cationic surface-active of different the morphology of the aggregate Agent.A kind of N- alkyl-n,N-Dimethylaniline formyl methyl ammonium chloride, general structure are as follows:
Wherein n is 10~22.
A kind of synthetic method of N- alkyl-n,N-Dimethylaniline formyl methyl chlorination ammonium surfactant, is specifically pressed Following steps are completed:
One, solvent I is added to the container, then presses chloroacetanilide and N, the molar ratio of N- dimethyl alkyl tertiary amine is 1: (1.2~3.0) chloroacetanilide and N, N- dimethyl alkyl tertiary amine is added, is warming up to 70 DEG C~130 DEG C and stirs 4h~12h, Obtain crude product；
Two, by crude product rotary evaporation obtained in step 1, thick lotion is obtained；
Three, thick lotion obtained in step 2 is recrystallized with solvent II, obtains white solid, i.e. N- alkane Base-N, accelerine formyl methyl chlorination ammonium surfactant；
Wherein solvent I is a kind of organic solvent or two kinds of organic mixed solvents in step 1；
Solvent II is one or two kinds of mixtures of ester, alcohol, ketone and alkane in step 3；
The synthesis of a kind of N- alkyl-N of the present invention, accelerine formyl methyl chlorination ammonium surfactant are anti- Answer process as follows:
Wherein n=10~22.
The invention has the advantages that
One, with chloroacetanilide and N in the present invention, N- dimethyl alkyl tertiary amine is a kind of N- alkyl-N of Material synthesis, Accelerine formyl methyl chlorination ammonium surfactant introduces amido bond in molecular structure, there is it in aqueous solution Two critical aggregation concentrations have different the morphology of the aggregate.
Two, using a kind of N- alkyl of one-step synthesis method-n,N-Dimethylaniline formyl methyl chlorination ammonium surfactant, institute It is easy to get with raw material, reaction step is few, and reaction condition is mild, easily controllable, and easy to operate, product is easily isolated, purifies.
Three, a kind of N- alkyl-n,N-Dimethylaniline formyl methyl chlorination ammonium surfactant that the present invention synthesizes, point An amido bond is introduced in minor structure, critical micelle concentration (CMC) is 0.037~0.099mmol/L, critical aggregation concentration It (CAC) is 0.59~1.44mmol/L, it is (critical with traditional cationic surfactant dodecyl benzyl dimethyl ammonium chloride Micellar concentration is 5.8mmol/L) it compares, critical micelle concentration is substantially reduced, surface-active with higher.Can be used for sterilizing, The multiple fields such as pharmaceutical carrier, nano material synthesis and Biomimetic membrane.
Detailed description of the invention
Fig. 1 is N- cetyl-N prepared by embodiment 1, accelerine formyl methyl ammonium chloride (H-AMC-16) γ-logC curve graph；
Fig. 2 is N- cetyl-N prepared by embodiment 1, accelerine formyl methyl ammonium chloride (H-AMC-16) DLS figure；
Fig. 3 is N- cetyl-N prepared by embodiment 1, accelerine formyl methyl ammonium chloride (H-AMC-16) stick The TEM of shape micella schemes；
Fig. 4 is N- cetyl-N prepared by embodiment 1, accelerine formyl methyl ammonium chloride (H-AMC-16) net The TEM of shape structured aggregates schemes；
Fig. 5 is N- cetyl-N prepared by embodiment 1, accelerine formyl methyl ammonium chloride (H-AMC-16) capsule The TEM of bubble schemes；
Fig. 6 is N- cetyl-N prepared by embodiment 1, and accelerine formyl methyl ammonium chloride (H-AMC-16) is compacted The TEM of worm shape structured aggregates schemes.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of N- alkyl-N, accelerine formyl methyl ammonium chloride table Face activating agent, general structure are as follows:Wherein n is 10~22.
Specific embodiment 2: the present embodiment is different from the first embodiment in that n=12,14,16.Other and tool Body embodiment one is identical.
Specific embodiment 3: a kind of N- alkyl-N, accelerine formyl methyl described in specific embodiment one The preparation method of chlorination ammonium surfactant, sequentially includes the following steps:
One, solvent I is added to the container, then presses chloroacetanilide and N, the molar ratio of N- dimethyl alkyl tertiary amine is 1: (1.2~3.0) chloroacetanilide and N, N- dimethyl alkyl tertiary amine is added, is warming up to 70 DEG C~130 DEG C and stirs 4h~12h, Obtain crude product；
Two, by crude product rotary evaporation obtained in step 1, thick lotion is obtained；
Three, thick lotion obtained in step 2 is recrystallized with solvent II, obtains white solid, i.e. N- alkane Base-N, accelerine formyl methyl chlorination ammonium surfactant；
Wherein solvent I is a kind of organic solvent or two kinds of organic mixed solvents in step 1；
Solvent II is one or two kinds of mixtures of ester, alcohol, ketone and ether in step 3；
Specific embodiment 4: present embodiment from unlike specific embodiment three in step 1 solvent I be one kind Organic solvent or two kinds of organic mixed solvents；It is other to be the same as the specific implementation mode 3.
Specific embodiment 5: a kind of present embodiment organic solvent unlike specific embodiment four be acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide；Two kinds of organic mixed solvents be acetonitrile and N,N-dimethylformamide mixed solvent, Acetonitrile and dimethyl sulfoxide mixed solvent, N,N-dimethylformamide and dimethyl sulfoxide mixed solvent；Other and specific implementation Mode four is identical.
Specific embodiment 6: unlike one of present embodiment and specific embodiment three to five in step 1, chlorine The structural formula of antifebrin isIt is other identical as one of specific embodiment three to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment three to six in step 1, chlorine The amount of antifebrin and the volume ratio of solvent I are 1mmol:(1mL~15mL)；Other phases one of with specific embodiment three to six Together.
Specific embodiment 8: unlike one of present embodiment and specific embodiment three to seven in step 3, it is molten Agent II is the mixture of one or more of ester, alcohol, hydrocarbon and ether；It is other identical as one of specific embodiment three to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment three to eight in step 3, it is molten Agent II is ethyl acetate and petroleum ether mixed solvent, ethyl acetate and alcohol mixed solvent, ethyl alcohol and petroleum ether mixed solvent, second Acetoacetic ester and n-hexane mixed solvent, ethyl acetate and methylene chloride mixed solvent, isopropanol and ether mixed solvent, three chloromethanes Alkane and pentane mixed solvent or be acetonitrile and n-hexane mixed solvent.Other phases one of with specific embodiment three to eight Together.
Solvent II is mixed solvent in present embodiment, and in the mixed solvent each component is mixed by any ratio.
Specific embodiment 10: rotation described unlike one of present embodiment and specific embodiment three to nine is steamed Hair operating condition is: revolving speed is 80r/min~180r/min, and bath temperature is 50 DEG C~80 DEG C, other and specific embodiment One of three to nine is identical.
Beneficial effects of the present invention are verified with following embodiment:
Embodiment 1: a kind of N- cetyl-N of the present embodiment, accelerine formyl methyl ammonium chloride surface-active The preparation method of agent, sequentially includes the following steps:
One, 30mL acetonitrile solvent, 1.499g chloroacetanilide, 2.959gN, N- dimethyl are sequentially added into three-necked flask Hexadecylamine stirs 5.5h under conditions of temperature is 75~85 DEG C to get crude product；
Two, crude product is 100r/min in revolving speed, and bath temperature is rotary evaporation under conditions of 60 DEG C, obtains thick cream Body；
Three, using ethyl alcohol and petroleum ether mixed solvent (ethyl alcohol and petroleum ether volume ratio be 5:1), thick lotion is carried out Recrystallization, obtains white solid, as N- cetyl-n,N-Dimethylaniline formyl methyl ammonium chloride.
N- cetyl-N manufactured in the present embodiment, the Fourier infrared spectrum of accelerine formyl methyl ammonium chloride FT-IR data are as follows:
IR(KBr)v/cm-1:3 171cm-1(N-H),3 028cm-1(Ph C-H),2 920cm-1,2 851cm-1(-CH3,- CH2-),1 693cm-1(O=C), 1 596cm-1,1 543cm-1,1 445cm-1(Ph C-C),721cm-1[-(CH2)n-].
N- cetyl-N manufactured in the present embodiment, accelerine formyl methyl ammonium chloride1H-NMR data are such as Under:
1H-NMR(600MHz,CDCl3)δH: 0.87~0.89 (t, 3H, J=6.6Hz ,-CH3), 1.25~1.35 (m, 26H,-(CH2)13-),1.81(br s,2H,-N+-CH2CH2-),3.42(s,6H,-N+-(CH3)2), 3.61~3.63 (t, 2H, J =8.4Hz ,-N+-CH2), 4.88 (s, 2H, O=C-CH2-N+), 7.12~7.14 (t, 1H, J=7.2Hz, PhH), 7.30~ 7.32 (t, 2H, J=7.5Hz, PhH), 7.80 (d, 2H, J=8.4Hz, PhH), 11.73 (s, 1H ,-NH-)
By FT-IR and1H-NMR is to N- cetyl-n,N-Dimethylaniline formyl methyl ammonium chloride, it is known that N- 16 The structural formula of alkyl-N, accelerine formyl methyl ammonium chloride is
Certain density 1 products obtained therefrom N- cetyl-N of embodiment, accelerine formyl first are prepared with ultrapure water Ammonium chloride aqueous solution measures the γ-lgC curve of the aqueous solution using hanging ring method, it is known that N- hexadecane under the conditions of 25 DEG C Base-n,N-Dimethylaniline formyl methyl ammonium chloride critical micelle concentration (cmc) is about 0.09mmol/L, with critical angle micella Conventional surfactant agent N- cetyl N, the N- dimethyl benzyl ammonium chloride of concentration 0.43mmol/L is compared, and critical micell is dense Low 0.34mmol/L is spent, illustrates that the present embodiment product N- cetyl-n,N-Dimethylaniline formyl methyl ammonium chloride has more Low critical micelle concentration and preferable surface-active.
Certain density 1 products obtained therefrom N- cetyl-N of embodiment, accelerine formyl first are prepared with ultrapure water Ammonium chloride aqueous solution, under the conditions of 25 DEG C, using Malvern (ZS-90) laser particle analyzer (helium-neon laser emission wavelength lambda= 632.8nm, angle of scattering are 90 °), DLS measurement is carried out to the target product of various concentration.
Certain density 1 products obtained therefrom N- cetyl-N of embodiment, accelerine formyl first are prepared with ultrapure water Ammonium chloride aqueous solution, under the conditions of 25 DEG C, Salkowski's solution (2%) is used as coloring agent, by sample solution drop on copper mesh, uses Filter paper sucks excessive sample solution, forms it into fluid film, coloring agent is then added dropwise, and sucks excessive coloring agent with filter paper The sample prepared is placed under infrared lamp and dries by solution, carries out TEM test using background stain.

Claims (4)

1. a kind of amide bond quaternary cationics with different the morphology of the aggregate.
2. a kind of amide bond quaternary ammonium salt cationic surface-active with different the morphology of the aggregate according to claim 1 Agent, it is characterised in that carbon chain lengths 12,14,16.
3. a kind of amide bond quaternary ammonium salt cationic surface-active with different the morphology of the aggregate according to claim 1 Agent, it is characterised in that there are two aggregate concentrations to exist in aqueous solution for it.
4. a kind of amide bond quaternary ammonium salt cationic surface-active with different the morphology of the aggregate according to claim 1 Agent, it is characterised in that it is in aqueous solution when concentration increases to 10mM from 0.3mM, and the morphology of the aggregate changes are as follows: rod-shaped micelle → netted micella → vesica → vermiculate glues.
CN201910621029.4A 2019-07-10 2019-07-10 Amide bond quaternary cationics with different the morphology of the aggregate Pending CN110354754A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101111473A (en) * 2004-12-06 2008-01-23 迪士曼药品和化学品有限公司 Preparation of a quaternary ammonium hydroxide and use thereof for the preparation of q quaternary ammonium salt
WO2011052601A1 (en) * 2009-10-26 2011-05-05 独立行政法人産業技術総合研究所 Ionic organic compound, production method therefor, and carbon nanotube dispersant comprising said ionic organic compound
CN104226188A (en) * 2014-10-11 2014-12-24 齐齐哈尔大学 Quaternary ammonium salt cationic surface active agent and preparation method thereof
CN105906572A (en) * 2016-05-13 2016-08-31 齐齐哈尔大学 Synthesis method for pyrimidine derivative quaternary ammonium salt cationic surfactant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101111473A (en) * 2004-12-06 2008-01-23 迪士曼药品和化学品有限公司 Preparation of a quaternary ammonium hydroxide and use thereof for the preparation of q quaternary ammonium salt
WO2011052601A1 (en) * 2009-10-26 2011-05-05 独立行政法人産業技術総合研究所 Ionic organic compound, production method therefor, and carbon nanotube dispersant comprising said ionic organic compound
CN104226188A (en) * 2014-10-11 2014-12-24 齐齐哈尔大学 Quaternary ammonium salt cationic surface active agent and preparation method thereof
CN105906572A (en) * 2016-05-13 2016-08-31 齐齐哈尔大学 Synthesis method for pyrimidine derivative quaternary ammonium salt cationic surfactant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIANYOU HE ET AL: ""The Effects of Amide Bonds and Aromatic Rings on the Surface Properties and Antimicrobial Activity of Cationic Surfactants"", 《JOURNAL OF SURFANTANTS AND DETERGENTS》 *

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