CN106622016B - A kind of glucosyl group gemini cationic surfactant and its synthetic method - Google Patents

A kind of glucosyl group gemini cationic surfactant and its synthetic method Download PDF

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CN106622016B
CN106622016B CN201710010183.9A CN201710010183A CN106622016B CN 106622016 B CN106622016 B CN 106622016B CN 201710010183 A CN201710010183 A CN 201710010183A CN 106622016 B CN106622016 B CN 106622016B
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cationic surfactant
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glucosyl group
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甘昌胜
李鸿
王珊珊
蔡坤良
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Hefei University of Technology
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    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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Abstract

The invention discloses a kind of glucosyl group gemini cationic surfactant and its synthetic methods.First, the glucosulfone amine that glucose obtains being connected by alkyl chain with alkyl diamine through reductive amination process, the reaction product between epoxychloropropane and chain alkyl dimethyl tertiary amine is reacted again, obtains glucosyl group quaternary ammonium salt type gemini cationic surfactant.Synthesis technology is simple, and equipment requirement is low, is suitble to industrialized production.

Description

A kind of glucosyl group gemini cationic surfactant and its synthetic method
Technical field
The present invention relates to surfactant fields, be exactly a kind of glucosyl group gemini cationic surfactant and Its synthetic method.
Background technology
Surfactant is a kind of functional fine chemicals, and molecular structure includes hydrophobic grouping and hydrophilic ionic Two parts of group or polar group.Surfactant can form micella in the solution, and can oriented attachment on two-phase interface, Interface (surface) tension is reduced, there are the performances such as emulsification, infiltration, dispersion, solubilising, blistering, wetting, decontamination, softness, antistatic, It is widely used in food, cosmetics, articles for washing, medicine, agricultural, oil exploitation, mineral floating and weaving, printing and dyeing, papermaking Equal fields.
Traditional surfactant mostly uses product derived from oil and animal and plant fat.It has swepts the globe in green waves Today, grow to even greater heights to the cry of environmental protection and circular economy, sustainable development, with natural reproducibles such as sugar, amino acid Development of resources production is mild, have no toxic side effect, is environmentally protective, function admirable surfactant has become contemporary trend and research Hot spot.China's starch resource is abundant, utilizes glucidtemns --- and glucose is raw material, develops the surfactant of environment-friendly high-efficiency With very high application value.The more successful glycosyl surfactant active of commercial development at present has alkyl glycosides, glucamide With sugar ester etc., wherein alkyl glycosides is known as the world-class green surfactant of a new generation, and surface tension is low, foaming abundancy is thin Greasy, strong detergency, compatibility are good, and biodegradable thorough, nontoxic non-stimulated, public in American-European multiple companies such as Germany Henkel Department, P&G companies of the U.S. and Seppic companies of France have mass produced, and industrialized production has also been realized in China.
Gemini surface active agent is the amphiphile of a kind of parents' oil base double-hydrophilic.It is single-stranded compared to traditional --- single head (single parent is water base), single tail (single hydrophobic group) surfactant, Gemini surface active agent is joined by a spacer in structure It connects group two monoalkyl chain single head base conventional surfactants are linked together composition with chemical bond.Its structure novel, Usually it is made of three parts：Two hydrophobic chains, two hydrophilic groups and a spacer spacer group, abbreviation m-s-m (s tables Show that connection chain length, m indicate hydrophobic chain length).The unique molecular structure of gemini surfactant makes it have conventional surface work Property the incomparable property of agent, such as extremely low cmc, higher surface-active；Gemini surface active agent also has excellent answer With performance, such as good water-soluble, wetting, blistering, calcium soap dispersibility；Generally there is very low Krafft points, thus have larger Temperature application range.In addition, the Gemini surface active agent of some short chains connection just shows certain dash forward in rather low concentration The rheological behavior (viscoplasticity, gelatification cut thick phenomenon) gone out shows with common surfactant and good cooperates with effect It answers, keeps system performance more remarkable.This all implies that Gemini surface active agent will be that the application field of surfactant is brought New change.Develop the synthesis technology of new structural Gemini surface active agent, the compatibility of raising and conventional surfactants The application field that can, explore Gemini surface active agent is the hot subject of current Gemini surface active agent research and development.
The research of Gemini surface active agent starts from the last century 70's.Bunton et al. synthesized one for the first time in 1971 Cationoid type Gemini surface active agent --- the double methyl alkyl ammonium bromides of the bis- dialkyl group of alkyl-α, ω-, until 1991 It is Gemini type surfactant that Mneger etc. gives such Compound nomenclature for the first time, simultaneously synthesizing using rigid radical as linker The double hydrocarbon chain surfactants of double ion head.Condea companies release Ceralution F and Ceralution H two within 2000 The novel Gemini surface active of money, for personal-care supplies industry.In recent years, the research work of Gemini surface active Make mainly with the Zana seminar of French Charles Sadron research institutes, USA New York municipal university Brooklyn institutes Nakatauji groups of Rosen seminar, the Menger seminar of Emory universities of the U.S. and Osaka universities of Japan etc. are representative. It starts late at home, the progress that Zhao Jianxi delivered Gemini type surfactant in 1999 just causes domestic The concern of person.Ikeda work(in 2001 etc. has successively synthesized to be contained in novel double alkyl bi-quaternary ammonium salts, more alkyl multi-quaternary ammonium salts, alkyl chain There is the cationic surfactant of amide groups and ester group；Chen Gong in 2002 etc. synthesized novel parents' oil base a pair of hydrophilic chain sun from Sub- surfactant；Xu Qun in 2004 etc. has synthesized the asymmetric Bis-quaternary Ammonium Salt Surfactant of ester group, and it is domestic not right to open The beginning of title type synthesis of surfactant.Zhao Qiu actors in 2005 etc. have synthesized one sulfuric acid amphoteric surfactants of bi-quaternary ammonium salt Agent；Long richness of Lu in 2006 etc. has synthesized asymmetry quaternary ammonium salt cation asphalt emulsifier, Wei Jun is superfine synthesized it is different hydrophobic The dissymmetric Gemini type surfactant of chain.2 months 2006, Dalian Chemical Research &. Design Inst. newly open one it is completely new Gemini surface active alkyl diphenyl ether disulphonic acid sodium synthesis route, and applied for patent, break alkyl diphenyl ether The situation that the production of sodium disulfonate is monopolized by the U.S. and French company.Liu's equality in 2008 has synthesized that hydrophobic chain is identical, spacer chain The double sodium sulfovinate surfactants of different double alkyl.Auspicious sister-in-law of 2009 annuities etc. synthesizes double type oxalamide ethyl succinate sulphur Sour sodium, gemini surfactant of new generation are constantly emerged in large numbers at home.
With deepening continuously for surfactant research, people combine the characteristic of above-mentioned two classes surfactant, research to open Have issued technology of sugar-based gemini surfactants.Some researchs have shown that such surfactant in food, daily-use chemical industry, industry The numerous areas such as separation, oil, biological medicine, agricultural have a wide range of applications.
Currently, the technology of sugar-based gemini surfactants of report mainly has following a few classes：
(1) Alkyl glycoside dimeric surfactant
Castro etc. has synthesized the glucose fourth glycosides Gemini surface active that interval base is connected by 2 position of glucose hydroxy ester Agent, and have studied such nonionic surfactant interfacial property and interval base connection position, glucosides end group configuration, Every the influence of the type Surfactant of base, it is found that orderly three-dimensional structure is conducive to improve surface-active.
Hongjun ZHU etc., which is reacted with chloro glucosides made from alkyl glycosides (APG) with diethylamine, generates glycosyl tertiary amine, then Quaternization reaction is carried out with glycol dibromide and Shuangzi cationic alkyl glycosides surfactant is made again.Its CMC is 3.16 ×10-3Mol/L, γCMCFor 29.4mN/m, and there is lower Krafft points, hydrophily is preferable.
Gao etc. utilizes two kinds of fat during synthesizing dimerization and trimerization type saccharide fatty esters of gallic acid surfactant The esterification of enzymatic glucose methyl glucoside and alpha-brominated tetradecylic acid, then reacted with decanedioic acid, obtain glucose ester group Shuangzi Surfactant.Wherein, the reaction of two kinds of enzymatics all has higher substrate selective.
The glucose such as Wang Jun and dihalo alcohol are under conditions of 80~130 DEG C of temperature, 0.06~0.099MPa of vacuum degree Reaction 2~5 hours obtains dihalo glucosides intermediate, then through quaternization reaction, obtains a kind of work of sugar-based quaternary ammonium salt Shuangzi surface Property agent, its general structure are as follows：
Ren Yanmei is using glucose, ethylene glycol as Material synthesis glucose ethylene glycol glycosides, then using maleic anhydride as linking group With the Shuangzi nonionic surface active agent of lauric acid esterification synthesizing new, the surface tension of the surfactant is 23.60mN/m (20 DEG C), critical micelle concentration are 5.77 × 10-3Mol/L shows good surface-active.
Liu Songbai etc. discloses a kind of preparation method of long-chain fatty alcohol glucose dimeric surfactant：Fatty alcohol is double Subchain, four acetyl glucosamine tri- chloroacetimidates, catalyst are added in organic solvent, are attached reaction；Then it incites somebody to action The product removal acetyl group arrived, obtains target product.
(2) alkyl glucosamine Gemini surface active agent
Ren Longfang etc. discloses a kind of preparation method of siliceous glucose-type Shuangzi nonionic surfactant：By grape The double envelopes of epoxy are added according still further to the ratio of epoxy double-seal head and alkyl glucose amine molar ratio 1: 2 in the obtained alkyl glucose amine of sugar Head makes it be reacted with alkyl glucose amine, and glucose-type Gemini surface active agent is made.
Du Binbin etc. has synthesized the N- alkyl that hydrophobic carbon chain lengths are respectively 8,12,16 by spacer group of aspartic acid Glucose amide Gemini surface active agent.
Yan Shunjie is that raw material is prepared for a series of different chains with glucose and alkylamine (n-octyl amine, lauryl amine, cetylamine) Long glycosyl Shuangzi nonionic surfactant, surface tension are 33.0~38.6mN/m, critical micelle concentration 0.07~ Within the scope of 0.45mmol/L, meanwhile, product has good foaming characteristic and foam stability.
Invention content
The purpose of the present invention is to provide a kind of glucosyl group gemini cationic surfactant and its synthetic methods.
It adopts the following technical scheme that：
A kind of glucosyl group gemini cationic surfactant, it is characterised in that：
The structure of surfactant is as follows：
Wherein, R C8H17、C10H21、C12H25、C14H29、C16H33、C18H37、C18H35, n=2-6.
The glucosyl group gemini cationic surfactant, which is characterized in that the R be C8, C12, C14, One kind in the chain alkyl of C16, C18.
The glucosyl group gemini cationic surfactant, which is characterized in that one kind in preferred following compound：
The preparation method of the glucosyl group gemini cationic surfactant, which is characterized in that include the following steps：
Step 1: the preparation of intermediate alkyl glucosulfone amine：
A, it by alkyl diamine and is equivalent to its 2-2.5 times glucose and is reacted in solvent A glucose imines is made, then Add excessive NaBH45-20h is reacted, the pH to 1~2 of reaction system is adjusted with hydrochloric acid, precipitation is precipitated, filtering obtains alkane Base glucosamine HCL crude product；
Or alkyl diamine is reacted into obtained glucose imines with its 2-2.5 times glucose is equivalent in solvent A, then The method hydrogenated with pressurized catalysis, obtains alkyl glucose amine hydrochlorate crude product；
B, alkyl glucose amine hydrochlorate crude product obtained is stirred at room temperature in excessive alkali and solvent A, is heated up back afterwards 1-3h is flowed, it is cooling, white precipitate is precipitated, suction filtration obtains crude product, washed repeatedly with solvent A, and alkyl glucosulfone amine is made；
The one kind or their mixing of solvent A in methanol, ethyl alcohol, isopropanol, n-butanol, n-amyl alcohol, isoamyl alcohol, water Object；
Step 2: the preparation of glycidyl dimethyl alkyl ammomium chloride：
Chain alkyl dimethyl tertiary amine and epoxychloropropane isothermal reaction 5-8h at 50-55 DEG C in solvent B, then subtract Pressure removes solvent, is cooled to room temperature, with ether washing reaction product, filters out ether under room temperature, obtains glycidyl dimethyl alkyl chloride Change ammonium；
The one kind or their mixture of solvent B in methanol, ethyl alcohol, isopropanol, water.Chain alkyl refer to C8, The chain alkyl of C12, C14, C16 or C18；
Step 3: the preparation of glucosyl group gemini cationic surfactant：
Alkyl glucosulfone amine obtained is dissolved in solvent C, 2-2.5 times of glycidyl dimethyl alkyl chlorination is added dropwise The aqueous solution of ammonium, react 5~8h, through Rotary Evaporators remove solvent C, washed for several times with acetone, obtain glucosyl group Shuangzi sun from Sub- surfactant, solvent C are selected from methanol, ethyl alcohol, isopropanol, n-butanol, isoamyl alcohol, water or their mixture.
The synthetic method of the surfactant, it is characterised in that：The method of pressurized catalysis hydrogenation described in step 1 Technological parameter be：20-50bar, 30-50 DEG C, 5-10%Pd/C catalysis, 10-24h.
The synthetic method of the surfactant, it is characterised in that：The alkali refers to sodium hydroxide, hydroxide One kind in potassium, sodium methoxide, sodium ethoxide, potassium carbonate.
The synthetic method of the surfactant, it is characterised in that：Long chain alkyl dimethyl in the step two Tertiary amine is octyl dimethyl tertiary amine, decyl dimethyl tertiary amine, Dodecyl Dimethyl Amine, dodecyldimethylamine base uncle Amine, hexadecyldimethyl benzyl ammonium tertiary amine, octadecyldimethyl tertiary amine or octadecylene base dimethyl tertiary amine.
Beneficial effects of the present invention are：
(1) traditional quaternary ammonium salt cationic surfactant has good antistatic, soft, anti-corrosion, sterilization, breast Change, the performances such as dispersion, but be it the shortcomings that quaternary ammonium salt cationic surfactant with stronger skin irritation, and with anion table The compounding effect of face activating agent is very poor.The invention discloses a kind of glucosyl group quaternary ammonium salt type gemini cationic surfactant, Not only had the advantages that being readily biodegradable, is environmental-friendly, being mild non-stimulated for glycosyl surfactant active, but also there is quaternary table The excellent performances such as the antistatic, soft of face activating agent, anti-corrosion, sterilization, emulsification, dispersion, and improve glycosyl cationic surface The compound property of activating agent and anion surfactant.
(2) unique texture of gemini surfactant makes it possess common only single amphiphilic structure surfactant Incomparable property, such as extremely low critical micelle concentration, it is stronger reduce surface tension ability, and preferably application Performance.Sugar-based quaternary ammonium salt Gemini surface active agent is that the glucose of natural reproducible is one kind green Shuangzi surface of Material synthesis Activating agent.Not only there is the glucose hydrophilic group of nonionic in structure, but also there is bi-quaternary ammonium salt hydrophilic group, so having Mildness, the low irritant of nonionic surfactant；The bactericidal properties of cationic surfactant, antistatic property and hard water resistance Property；The synergistic function of energy and anion surfactant compounding not available for also general cationic surfactant； It is a kind of Mobyneb surface-active simultaneously as Gemini surface active agent but also with the excellent properties of Gemini surface active agent Agent has a extensive future.
(3) synthetic method of the present invention is simple, and step is by two reactions in parallel, i.e. reduction amination and quaternization reaction difference Product is obtained, then the two is coupled into target Gemini surface active agent, synthesis technology is simple, and equipment requirement is low, is suitable for work Industry metaplasia is produced.
(4) sugar-based quaternary ammonium salt cationic surfactant not only has the mild non-stimulated, environment of glycosyl surfactant active Friendly, the advantages of being readily biodegradable, also have the antistatic, soft of quaternary ammonium salt cationic surfactant, anti-corrosion, sterilization, emulsification, The excellent performances such as dispersion, and can have synergistic function with the compounding of anion surfactant.It is also equipped with simultaneously The excellent properties of Gemini surface active agent such as further increase surface-active, reduce critical micelle concentration, are a kind of Mobynebs Surfactant can be widely applied to the industries such as daily-use chemical industry, weaving, papermaking, oil, pesticide and mining, have wide answer Use foreground.
Specific implementation mode
Embodiment 1
Step (1)
The synthesis of N, N- glucosulfone base ethylenediamine
In 250mL three-neck flasks, 10g glucose (56mmol), 1.68g ethylenediamines (28mmol) and 120mL first is added Reaction 12h is stirred at room temperature in alcohol.Then, in ice-water bath, 2.3g (61mmol) sodium borohydride is added, reaction 4-6h is stirred at room temperature. 2N hydrochloric acid is added dropwise into reaction solution to pH1~2, white solid is precipitated.It filters, 50mL isopropanols are added in filter cake and sodium hydroxide is molten Liquid, until system pH=9 or so, is stirred at room temperature temperature rising reflux 2h after 8h, it is cooling, it filters, obtains product N, N- glucosulfone base second two Amine.1H-NMR(DMSO-d6,ppm):δ2.38(m,8H),3.40(m,12H),3.53(m,10H).13C-NMR(DMSO-d6, ppm):49.2,50.9,63.7,70.7,70.9,71.2,71.6.
Step (2)
The preparation of glycidyl dimethyl dodecyl ammonium chlorides
In three-neck flask, 8.2g (38.4mmol) Dodecyl Dimethyl Amines are added and 50mL isopropanols -20mL is gone The mixed solvent of ionized water is warming up to 50~55 DEG C.3.8g (40.8mmol) epoxychloropropane is slowly added dropwise under stirring, constant temperature is anti- Answer 5h.Then solvent is removed under reduced pressure, is cooled to room temperature, with ether washing reaction product, with remove unreacted epoxychloropropane and Tertiary amine.Ether is filtered out under room temperature, obtains product.1H-NMR(D2O-d6,ppm):0.97(t,3H),1.24(m,20H),2.78(m, 2H),3.22-3.43(m,11H).
Step (3)
The preparation of N, N- glucosulfone base-two (2- hydroxyl -3- dodecyl dimethyls quaternary ammonium group) propyl-ethylenediamine
In three-neck flask, 7.8gN, N- glucosulfone base ethylenediamines (20mmol), 80ml water-isopropanol mixing is added Solvent (1：1) it is used as reaction medium, is warming up to 55 DEG C, is added dropwise and contains 12.3g (40mmol) glycidyl dimethyl dodecyl base The aqueous solution (concentration 50%) of ammonium chloride drips off in 1h.Isothermal reaction 6h.After stopping reaction, it is cooled to room temperature, is filtered to remove insoluble Object concentrates filtrate on a rotary evaporator.Then, concentrate is instilled to the acetone of excessive 4~6 times of volumes under magnetic agitation In, there are a large amount of white precipitates to be precipitated.It stands, to be precipitated that completely rear suction filtration is precipitated, filter cake acetone recrystallization obtains product.1H- NMR(CD3OD,ppm):0.97(t,6H),1.24(m,40H),2.38(m,8H),2.42(m,4H),3.40(m,20H),3.53- 3.71(m,12H),3.95(m,4H).
Embodiment 2,
Step (1)
The synthesis of N, N- glucosulfone base ethylenediamine；
With (1) the step of embodiment 1
Step (2)
The preparation of glycidyl dimethyl hexadecyl ammonium chloride
In three-neck flask, 5.3g (19.7mmol) hexadecyldimethyl benzyl ammonium tertiary amines and 50mL isopropanols is added, is warming up to 50~55 DEG C.1.94g (21mmol) epoxychloropropane, isothermal reaction 7h are slowly added dropwise under stirring.Then solvent is removed under reduced pressure, it is cold To room temperature, with ether washing reaction product, to remove unreacted epoxychloropropane and tertiary amine.Ether is filtered out under room temperature, must be produced Object.1H-NMR(D2O-d6,ppm):0.97(t,3H),1.25(m,28H),2.76(m,2H),3.20-3.41(m,11H).
Step (3)
The preparation of N, N- glucosulfone base-two (2- hydroxyl -3- hexadecyldimethyl benzyl ammoniums quaternary ammonium group) propyl-ethylenediamine
In 250mL three-neck flasks, 7.8g N, N- glucosulfone base ethylenediamines (20mmol), 60ml water-isopropyl is added Alcohol mixed solvent (1：1.5) it is used as reaction medium, is warming up to 55 DEG C, is added dropwise and contains 14.5g (40mmol) glycidyl dimethyl The aqueous solution (concentration 50%) of cetyl chloride ammonium drips off in 1h.Isothermal reaction 8h.After stopping reaction, it is cooled to room temperature, filters Insoluble matter is removed, filtrate is concentrated on a rotary evaporator.Then, concentrate is instilled into excessive 4~6 times of volumes under magnetic agitation Acetone in, there are a large amount of white precipitates to be precipitated.It stands, to be precipitated that completely rear suction filtration is precipitated, filter cake acetone recrystallization must produce Object.1H-NMR(CD3OD,ppm):0.97(t,6H),1.22-1.28(m,56H),2.39(m,8H),2.44(m,4H),3.41(m, 20H),3.56-3.81(m,12H),3.98(m,4H).
The product of the step of Examples 1 and 2 (1) can also be obtained by catalytic hydrogenation：Glucose, alkyl diamine exist In methanol solution containing 5%Pd/C compressive reaction for 24 hours, 40bar, 40 DEG C.Reaction product is recrystallized with methanol/water.
Embodiment 3
Step (1)
The synthesis of N, N- glucosulfone base butanediamine
In 250mL three-neck flasks, 10g (56mmol) glucose, 2.47g (28mmol) butanediamine and 130mL first is added Reaction 15h is stirred at room temperature in alcohol.Then, in ice-water bath, 2.3g (61mmol) sodium borohydride is added, reaction 4-6h is stirred at room temperature. 2N hydrochloric acid is added dropwise into reaction solution to pH1~2, white solid is precipitated.It filtering, slightly excessive sodium ethoxide and ethyl alcohol is added in filter cake, Temperature rising reflux 2h after 10h is stirred at room temperature, it is cooling, it filters, obtains product N, N- glucosulfone base butanediamine.1H-NMR(DMSO-d6, ppm):1.26(m,4H),2.36(m,8H),3.39(m,12H),3.51(m,8H).13C-NMR(DMSO-d6,ppm):29.3, 49.5,51.2,63.9,70.8,71.0,71.3,71.9.
Step (2)
The preparation of glycidyl dimethyl dodecyl ammonium chlorides
With 1 step of embodiment (2)
Step (3)
The preparation of N, N- glucosulfone base-two (2- hydroxyl -3- dodecyl dimethyls quaternary ammonium group) propyl-butanediamine
In three-neck flask, it is mixed that 8.33g N, N- glucosulfone base butanediamine (20mmol), 60ml water-isopropanol is added Bonding solvent (1：2) it is used as reaction medium, is warming up to 50 DEG C, is added dropwise and contains 12.3g (40mmol) glycidyl dimethyl dodecyl The aqueous solution (concentration 50%) of ammonium chloride drips off in 1h.Isothermal reaction 6h.After stopping reaction, it is cooled to room temperature, is filtered to remove not Molten object concentrates filtrate on a rotary evaporator.Then, concentrate is instilled the third of excessive 8~10 times of volumes under magnetic agitation In ketone, there are a large amount of white precipitates to be precipitated.It stands, to be precipitated that completely rear suction filtration is precipitated, filter cake acetone recrystallization obtains product.1H- NMR(CD3OD,ppm):0.96(t,6H),1.23-1.28(m,44H),2.40(m,8H),2.43(m,4H),3.43(m,20H), 3.56-3.75(m,12H),3.95(m,4H).
Embodiment 4
Step (1)
The preparation of N, N- glucosulfone base butanediamine：With 3 step of embodiment (1)
Step (2)
The preparation of glycidyl dimethyl hexadecyl ammonium chloride：With 2 step of embodiment (2)
Step (3)
The preparation of N, N- glucosulfone base-two (2- hydroxyl -3- hexadecyldimethyl benzyl ammoniums quaternary ammonium group) propyl-butanediamine
In three-neck flask, 8.33g N, N- glucosulfone base butanediamine (20mmol), 60ml isopropanols is added, is warming up to 55 DEG C, the aqueous solution (concentration 50%) containing 14.5g (40mmol) glycidyl dimethyl hexadecyl ammonium chloride is added dropwise, in 1h It drips off.Isothermal reaction 7h.After stopping reaction, it is cooled to room temperature, is filtered to remove insoluble matter, filtrate is concentrated on a rotary evaporator. Then, concentrate is instilled in the acetone of excessive 8~10 times of volumes under magnetic agitation, there are a large amount of white precipitates to be precipitated.It stands, waits for Precipitation filters afterwards completely, and filter cake is washed 2~3 times with acetone, is drained.Vacuum drying, obtains product.1H-NMR(CD3OD, ppm):0.98(t,6H),1.22-1.29(m,60H),2.38(m,8H),2.45(m,4H),3.45(m,20H),3.53-3.80 (m,12H),3.95(m,4H).
Data test：
Surface-active is tested
Using Pulling escape, the surface tension (γ) of the sample aqueous solution of various concentration is measured at 20 DEG C, passes through γ-lgc's Relation curve, corresponding concentration is critical micelle concentration cmc at inflection point, and corresponding surface tension is at this concentration γcmc.It is determined by experiment, glucosyl group gemini quaternary ammonium salt cationic surfactant made from embodiment 1-4 is all in the present invention With excellent surface-active.N, N- glucosulfone base-two (2- hydroxyl -3- dodecyl dimethyls quaternary ammonium group) propyl-second two The cmc and γ of aminecmcRespectively 2.15 × 10-4mol/L,27.2mN/m；(2- hydroxyl -3- the hexadecanes of N, N- glucosulfone base-two Base dimethyl quaternary ammonium base) propyl-ethylenediamine cmc and γcmcRespectively 3.52 × 10-5mol/L,24.6mN/m；Bis- grape of N, N- The cmc and γ of glycosyl-two (2- hydroxyl -3- dodecyl dimethyls quaternary ammonium group) propyl-butanediaminecmcRespectively 4.36 × 10- 5mol/L,25.8mN/m；N, N- glucosulfone base-two (2- hydroxyl -3- hexadecyldimethyl benzyl ammoniums quaternary ammonium group) propyl-butanediamine Cmc and γcmcRespectively 1.48 × 10-5mol/L、22.3mN/m。
The compounding stability test of glucosyl group gemini quaternary ammonium salt cationic surfactant and anion surfactant
Pass through (2- hydroxyl -3- the dimethyls of surfactant N, N- glucosulfone base-two to different mixing proportion Base quaternary ammonium group) propyl-ethylenediamine and the light transmittance of anionic (K12) mixed solution grind Study carefully, to investigate the stability of compound system.Experiment is with traditional cation surfactant cetyl trimethylammonium bromide (CTAB) it compares.It is 0: 1,0.2: 1,0.4: 1,0.6: 1,0.8: 1,1: 1 to prepare molar ratio respectively, 2: 1 and 1: 0 solution, Oscillation makes it be uniformly mixed, and stands at room temperature for 24 hours, saturating at 700nm with ultraviolet-uisible spectrophotometer detection solution Light rate, to judge the stability of solution.The result shows that the light transmittance of the mixed solution only at 0.6: 1~1: 1 is relatively low (about 50% or so), N in the case of remaining, N- glucosulfones base-two (2- hydroxyl -3- dodecyl dimethyls quaternary ammonium group) propyl - The light transmittance of the mixed solution of ethylenediamine and K12 is all higher than 90%, shows good compound property.And CTAB and K12 is answered With poor performance.Other glucosyl group gemini quaternary ammonium salt cationic surfactants are answered with anion surfactant K12's It is also fine with performance.Show that this kind of glucosyl group gemini cationic surfactant can live with other types surfaces such as anion Property agent be used in compounding, be applied to various product develop.

Claims (7)

1. a kind of glucosyl group gemini cationic surfactant, it is characterised in that：
The structure of surfactant is as follows：
Wherein, R C8H17、C10H21、C12H25、C14H29、C16H33、C18H37、C18H35, n=2-6.
2. glucosyl group gemini cationic surfactant as described in claim 1, which is characterized in that the R be C8, One kind in the chain alkyl of C12, C14, C16, C18.
3. glucosyl group gemini cationic surfactant as described in claim 1, which is characterized in that preferred following compound In one kind：
4. a kind of preparation method of glucosyl group gemini cationic surfactant as described in claim 1, which is characterized in that Include the following steps：
Step 1: the preparation of intermediate alkyl glucosulfone amine：
A, alkyl diamine and the glucose for the amount for being equivalent to its 2-2.5 times of substance are reacted in solvent A and glucose imines are made, Then excessive NaBH is added45-20h is reacted, the pH to 1~2 of reaction system is adjusted with hydrochloric acid, precipitation is precipitated, filtering obtains To alkyl glucose amine hydrochlorate crude product；
Or the glucose of alkyl diamine and the amount for being equivalent to its 2-2.5 times of substance is reacted in solvent A, glucose Asia is made Amine, then with pressurized catalysis hydrogenate method, obtain alkyl glucose amine hydrochlorate crude product；
B, alkyl glucose amine hydrochlorate crude product obtained is stirred at room temperature in excessive alkali and solvent A, rear temperature rising reflux 1- 3h, it is cooling, white precipitate is precipitated, suction filtration obtains crude product, washed repeatedly with solvent A, and alkyl glucosulfone amine is made；
The one kind or their mixture of solvent A in methanol, ethyl alcohol, isopropanol, n-butanol, n-amyl alcohol, isoamyl alcohol, water；
Step 2: the preparation of glycidyl dimethyl alkyl ammomium chloride：
Chain alkyl dimethyl tertiary amine and epoxychloropropane isothermal reaction 5-8h at 50-55 DEG C in solvent B, then decompression remove Solvent is removed, room temperature is cooled to, with ether washing reaction product, ether is filtered out under room temperature, obtains glycidyl dimethyl alkyl ammomium chloride；
The one kind or their mixture of solvent B in methanol, ethyl alcohol, isopropanol, water, chain alkyl refer to C8, C12, The chain alkyl of C14, C16 or C18；
Step 3: the preparation of glucosyl group gemini cationic surfactant：
Alkyl glucosulfone amine obtained is dissolved in solvent C, the glycidyl dimethyl alkyl of the amount of 2-2.5 times of substance is added dropwise The aqueous solution of ammonium chloride reacts 5~8h, removes solvent C through Rotary Evaporators, is washed for several times with acetone, obtain glucosyl group Shuangzi Cationic surfactant, solvent C are selected from methanol, ethyl alcohol, isopropanol, n-butanol, isoamyl alcohol, water or their mixture.
5. the preparation method of glucosyl group gemini cationic surfactant according to claim 4, it is characterised in that：Step The technological parameter of method of pressurized catalysis hydrogenation described in rapid one is：20-50bar, 30-50 DEG C, 5-10%Pd/C catalysis, 10- 24h。
6. the preparation method of glucosyl group gemini cationic surfactant according to claim 4, it is characterised in that：Institute The alkali stated refers to one kind in sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium carbonate.
7. the preparation method of glucosyl group gemini cationic surfactant according to claim 4, it is characterised in that：Institute Chain alkyl dimethyl tertiary amine in the step of stating two is octyl dimethyl tertiary amine, Dodecyl Dimethyl Amine, the tetradecane Base dimethyl tertiary amine, hexadecyldimethyl benzyl ammonium tertiary amine or octadecyldimethyl tertiary amine.
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