CN1775792A - Gemini boric acid ester glucose acylamine compound, and its preparing method and use - Google Patents
Gemini boric acid ester glucose acylamine compound, and its preparing method and use Download PDFInfo
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- CN1775792A CN1775792A CN 200510130468 CN200510130468A CN1775792A CN 1775792 A CN1775792 A CN 1775792A CN 200510130468 CN200510130468 CN 200510130468 CN 200510130468 A CN200510130468 A CN 200510130468A CN 1775792 A CN1775792 A CN 1775792A
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Abstract
The invention discloses a method to make bi-boric acid ester glucose amide compound and the application. The invention supplies a method that uses fatty amine -glucose -delta-lactone as raw material to make glucose amide compound then taking esterification reaction with boric acid to make the compound. The invention could be used as the green surface activator and has excellent capability.
Description
Technical field
The present invention relates to a class glycosyl amides, be specifically related to a kind of boric acid ester glucose amides.
Background technology
The boracic tensio-active agent is a kind of novel special surface active agent, because the irreplaceable premium properties of its uniqueness aspect much is widely used in each side such as life and production.Boron is a kind of nontoxic, nuisanceless, has the nonactive element of sterilization, anticorrosion, wear-resistant and flame retardant properties.Therefore, the boracic tensio-active agent has hc-surfactant can't displaced strong point, it is nontoxic, non-corrosiveness, boiling point height, and have flame retardant resistance, bactericidal properties, the additive that can be used for gas dryer, lubricating oil, compressor operating medium, also can be used for the static inhibitor of polyvinyl chloride, polyethylene, polymethyl acrylate, antidrip mist agent, the dispersion agent of various materials and emulsifying agent etc.Boric acid ester is used for additive for ink, has good performance.And it can have good intermiscibility with macromolecular compound, is highly suitable for the static inhibitor of synthetic resins, adds boric acid diacylglycerol mono-laurate and can obtain good antistatic effect in methacrylic resin.
The boracic tensio-active agent generally can be divided into two kinds of oil soluble and water-soluble boron acid esters.Oil-soluble boric acid ester can be divided into several classes such as boric acid ester that mol ratio is 1: 1 type, boric acid ester that mol ratio is 2: 1 types, boric acid diacylglycerol.Mol ratio is boric acid ester or its esters that the boric acid ester of 1: 1 type mainly contains boric acid glycerin three esters, mono-glycerides, generally adopts corresponding alcohols and boric acid direct esterification or transesterify synthetic.Mol ratio is that the boric acid ester of 2: 1 types is organic boron surface promoting agent of a class novel texture, be by 2mol have that vicinal hydroxyl groups adds up to transesterification reaction that boric acid three esters of the low-carbon alcohol of polyvalent alcohol more than 5 and 1mol carry out or/and the direct esterification of 1mol boric acid, make remaining hydroxyl with carboxylic esterification or carry out transesterification reaction with the carboxylicesters of low-carbon alcohol and make then.Also can be disclosed as US3625899, the carboxylicesters of polyvalent alcohol of remaining hydroxyl and boric acid three esters of low-carbon alcohol are exchanged, make and have one in the molecule at least
Group with carboxylic acid bonded surfactant.
US4303445 discloses a kind of method for making of boric acid diacylglycerol, as shown in the formula, at first synthetic DGB, uses DGB and-lipid acid to react with 1: 1 mol ratio again, obtains DGB-MS, i.e. boric acid diacylglycerol mono fatty acid ester.
If lipid acid is excessive in the reaction, will obtain boric acid diacylglycerol dibasic acid esters
The organic boron surface promoting agent of oil soluble is carried out modification just can obtain water-soluble organic boron surface promoting agent, the most frequently used method is exactly the oxyethane that adds certain mole number.A boron atom is wanted corresponding hydroxyl more than six at least, and when the boric acid ester of this polyvalent alcohol and reacting ethylene oxide, used catalyzer is a Lewis acid.
The general formula of water-soluble organic boron surface work-property agent is as follows:
X in the formula, X ', Y, Y ' can for
-H，-CH
3，-C
2H
5，H-(OCH
2CH
2)
k-O，
Or
With the natural reproducible resource is the green surfactant of raw material synthetic methyl glucamine (NAGA) as novel gentleness, and NAGA has many outstanding advantages.The synthetic method of N-methyl glucamine generally comprises three steps:
1) glucose and long-chain amine (N-alkylamine) carry out addition condensation reaction, generate Schiff's base (being the dehydrating condensation product of aldehydes or ketones carbonyl and amine)
The used amine of addition reaction is difference with the difference of the application target of N-alkyl glucose amine, as the U.S. Pat 5334764 disclosed R bases that are used for the synthetic usefulness of tensio-active agent H, CH is arranged
3, CH
2CH
2OH, CH
3OCH
2CH
2CH
2And C
12H
25Or the like.Except glucose, maltose, syrup etc. all can be used as the used sugared source of reaction.
2) the Schiff's base hydrogenation generates N-alkyl glucose amine, U.S. Pat 5334764, and US5380891, US5777165 disclose the catalyzer of the use of this class hydrogenation reaction, and as Ni, Pt, Pd, Fe, Cu and W etc., catalyzer commonly used is a nickel.Nickel both can be particle nickel, also can be nickel-loaded or Raney's nickel, and practical application mainly is a Raney's nickel, reactive behavior height not only, and be easy to remove by filter.
Except above-mentioned operational path, US519463 discloses a kind of method of directly reacting in the mixed solution of amine and catalyzer that sugar is added.But because during sugaring, reaction system under high pressure, the container of sugaring needs high pressure resistant, inconvenient operation.Simultaneously, this method only is fit to anhydrous organic solvent reaction system.Therefore, the main at present route that adopts first addition back end hydrogenation.
3) the N-methyl glucamine is synthetic, be with N-alkyl glucose amine and lipid acid, fatty acid ester, fatty acid anhydride or grease are raw material, carry out amidate action, product is of low quality when making raw material with lipid acid, fatty acid methyl ester (WO96/33967) commonly used, the lipid acid lactone of hydroxyl (is seen Laughlin R G, FuY C, et al.The Physical Science of N-Dodecanoyl-N-methylglucamine andIts Aqueous Mixtures.NOVEL SURFACTANTS.Chapter 8.Marrel Dekker, 1998) and grease be raw material.
During reaction, can be divided into two kinds of solvent-laden reaction system and solvent-free systems by the composition of reaction system.US5194639 discloses the hydroxyl organic solvent that adds in reaction system, as methyl alcohol, ethanol, propyl alcohol and propylene glycol etc., the most frequently used is the mixture of methyl alcohol and propylene glycol or methyl alcohol and propylene glycol, with the dissolving that helps glucosamine and with the mixing of fatty acid ester.US5380891 discloses the method for reacting in the presence of solvent-free, is warmed up to 130～140 ℃ and makes the glucosamine fusing, forms liquid/liquid mixture with fatty acid ester.Because the polarity difference of glucosamine and fatty acid ester is bigger, both do not dissolve each other, and the lipophilicity when fatty acid ester is very strong especially, and is all the more so as grease, Witconol 2301 and the methyl stearate etc. of Oleum Cocois or higher carbon number.Need to add consisting of phase-transferring agent or emulsifying agent, to promote the mixing of two kinds of liquid.Consisting of phase-transferring agent that this method is selected for use or emulsifying agent are nonionogenic tensides, as fatty alcohol-polyoxyethylene ether, and alkyl glycoside (APG) and glucosamine, add-on is 1～10% of a glucosamine quality.
As novel green surfactant, the glycosyl amide surfactants has many outstanding advantages: used main raw material starch of (1) NAGA building-up reactions and grease derivative are renewable resources, have realized the greenization of raw material; Single-minded, efficient, green catalyzer and the solvent of many employings improved the selectivity of reaction, realized the greenization of reaction; (2) NAGA is a kind of nonionogenic tenside, can reduce the pungency of cleaning product, and to the skin gentleness, and biological degradability can reach 98-99%, realized the greenization of product; (3) be used for washing composition and can improve consistency with environment, can improve the transparency of detergent product, play solubilizing agent, wettability is given prominence to; (4) have very high surfactivity under the micelle-forming concentration reaching: detersive power is stronger than alkyl polyglycoside (APG), belongs to above the average; Foam is fine and smooth and stablize, and is better than ethoxylized fatty alcohol, near anion surfactant.Amido linkage has good acidproof, alkaline-resisting, resistance toheat in addition, makes it have a wide range of applications in fields such as weaving, food, industrial separation and biological medicines.
The boracic tensio-active agent is because its good surfactivity has received increasing concern, and its Application Areas is also constantly expanded.Except at fire retardant, outside textile field was used, it was at makeup, lubricating oil, and waterproofing also has application in the glass coating; In addition, it also is used for thermosetting resin, can improve the Restoration of thermosetting resin, and can be easier to break away from depanning.The boracic tensio-active agent has a lot of special purposes as a kind of special surface active agent, but present kind also seldom, mainly is the fatty acid anionic and the non-ionic type of diacylglycerol.
Boracic tensio-active agent boiling point height, non-volatile, high temperature resistant, anti-fire-retardant; Low toxicity, readily biodegradable also has germicidal action; And good compound property is all arranged with negatively charged ion, nonionogenic tenside.Because glycosyl amide surfactants and boracic tensio-active agent respectively have many outstanding advantages, therefore provide a kind of novel tensio-active agent that the constructional feature of saccharides glucose acidamide surfactant and boron surface promoting agent is combined, have great importance.
Summary of the invention
The novel boracic glycosyl amide compound that the purpose of this invention is to provide a kind of novel structure, excellent property.
Concrete, novel boracic glycosyl amide compound of the present invention is a class Gemini boric acid ester glucose acylamine compound, its structure such as general formula (I) expression:
Wherein, R is the C that is selected from straight or branched
6-C
18Alkyl, C
6～C
18Cycloalkyl, C
6～C
18Aryl, C
7～C
18Alkaryl and C
7～C
18Aralkyl; Preferred described R is selected from the C of straight chain
6-C
18Alkyl.In compound of the present invention, the position of boron is not limited in the represented connection of structural formula (I), and boron also may connect into key with the hydroxyl on two any adjacent carbon atoms of two sugar units; Vertical two hydroxyls of preferred boron and two sugar units connect into key.
Preferred Gemini boric acid ester glucose acylamine compound of the present invention by being raw material with glucose acylamine compound, boric acid with structural formula (II), carries out esterification and prepares
The glucose acylamine compound that more preferably described raw material has structural formula (II) prepares by the following method: with aliphatic amide and maltonic acid-delta-lactone is raw material, solvent or solvent-free in the presence of, react, reaction finishes, and leaving standstill lowers the temperature separates out white solid, obtain white crystal with recrystallizing methanol behind the suction filtration, be the glucose acylamine compound of structural formula (II).
Another object of the present invention provides the preparation method of Gemini boric acid ester glucose acylamine compound of the present invention.
Preparation method of the present invention may further comprise the steps:
(1) being raw material with glucose amide, the boric acid with structural formula (II), serves as the band aqua forming the azeotropic solvent with water, and preferably being with aqua is benzene, toluene or hexanaphthene; In the reactor that temperature control system, branch aqueous systems are housed, at N
2Protection, temperature is 50～150 ℃, preferably use oil bath temperature control, temperature is 80-90 ℃, stirs down, is preferably magnetic agitation, react preferably 9-10 hour 9-15 hour;
(2) reaction product that step (1) is obtained is evaporated, and suction filtration obtains the brilliant white solid, with gained solid recrystallization, obtains the white powder solid and is compound of the present invention.
In step of the present invention (1), the white opacity phenomenon that occurs in branch aqueous systems such as the water trap in the reaction process is the mixture of the reaction water that generates and the band aqua that refluxes, growth along with the time, the layering gradually of solution in the water trap, upper strata are clarifying band aqua, and lower floor is a water layer; When a minute aquifer yield reaches theoretical value, with stopped reaction after the tlc analysis detection reaction terminal point.
In described step (2), preferably use N, dinethylformamide or other solvents such as methylene dichloride, acetone and N, the mixture of dinethylformamide etc. carries out recrystallization.
In a preferred embodiment of the invention, in described step 1), the glucose acylamine compound that raw material has structural formula (II) prepares by the method that may further comprise the steps:
(1) be raw material with aliphatic amide and maltonic acid-delta-lactone, mol ratio is 1: 1～1.6: 1, preferred 1: 1～1.3: 1, dissolve with solvent, and solvent is selected from water, methyl alcohol, ethanol, Virahol, ethylene glycol and propylene glycol, particular methanol;
(2) material that step (1) is obtained preferably uses under 40～80 ℃ of conditions of oil bath temperature control and stirs 20～120 ℃ of temperature controls, to the dissolving of maltonic acid-delta-lactone, white solid appears and after, keep 40～80 ℃, 0.5～2 hour;
(3) material of step (2) is continued to heat up 10～20 ℃, make the solid dissolving, keep this temperature to obtaining clear solution, stop heating, leave standstill, separate out white crystal gradually, suction filtration obtains white crystal, is the have structural formula glucose acylamine compound of (II).
A further object of the present invention provides Gemini boric acid ester glucose acylamine compound of the present invention as the application in the green surfactant.Compound of the present invention had good performance as tensio-active agent, the inventor has measured the performance of compound of the present invention as tensio-active agent from several respects such as froth stability, surface tension, contact angles, from measurement result as can be seen, Gemini boric acid ester glucose acylamine compound of the present invention is a kind of green surfactant of excellent performance, can be applicable to fields such as weaving, household chemicals, food, medicine, paint, coating.
The inventor has carried out structural characterization with compound of the present invention, can confirm to have obtained compound of the present invention from the measurement result of infrared spectrogram and electrospray ionization mass spectrum.
Description of drawings
Fig. 1 is the infrared spectrogram of n-hexyl glucose amide of the present invention
Fig. 2 is the infrared spectrogram of Gemini boric acid ester n-hexyl glucose acylamine compound of the present invention
Fig. 3 is the electrospray ionization mass spectrum figure of Gemini boric acid ester n-hexyl glucose acylamine compound of the present invention.
Fig. 4 is the infrared spectrogram of Gemini boric acid ester n-octyl glucose acylamine compound of the present invention.
Fig. 5 is the electrospray ionization mass spectrum figure of Gemini boric acid ester n-octyl glucose acylamine compound of the present invention
Fig. 6 is the infrared spectrogram of Gemini boric acid ester dodecyl glucose acylamine compound of the present invention
Fig. 7 is the electrospray ionization mass spectrum figure of Gemini boric acid ester dodecyl glucose acylamine compound of the present invention.
Fig. 8 is the capillary mensuration curve of Gemini boric acid ester n-hexyl glucose acylamine compound of the present invention.
Fig. 9 is the capillary mensuration curve of Gemini boric acid ester n-octyl glucose acylamine compound of the present invention.
Embodiment
(1) the n-hexyl glucose amide is synthetic
In being housed, the 50ml there-necked flask of spherical condensating tube and thermometer adds normal hexyl Amine 2.65ml (0.02mol), maltonic acid-delta-lactone 2.85g (0.016mol), methyl alcohol 30ml, the oil bath temperature control is 40 ℃ then, magnetic agitation, delta-lactone dissolving after 10 minutes, white solid appearred again after 30 minutes, keep this temperature half hour, be warmed up to 50 ℃ then, solid dissolves again, will separate out solid at leisure when temperature is lower than 49 ℃, 50 ℃ of insulations 3 hours, obtain clear solution, stop heating, leave standstill, separate out white crystal gradually, suction filtration obtains white crystal.Productive rate 92.9%.
Reaction equation is as follows:
From infrared spectrogram shown in Figure 1, can see at 1649.87cm
-1The vC=0 absorption peak has appearred in the place, and this is the charateristic avsorption band of amido linkage, is acid amides I band; 1540.74cm
-1Be acid amides II band.And at 1300-1150cm
-1Neighbouring strong peak and 1140-1030cm
-1Near lactone peak disappears substantially, and through thin-layer chromatography detection reaction terminal point, ester linkage breaking has generated amido linkage in the deducibility reaction process, and reaction is comparatively complete.
(2) Gemini boric acid ester n-hexyl glucose acylamine compound is synthetic
In the there-necked flask that thermometer, water trap and spherical condensation tube are housed, add the n-hexyl glucose amide 6.14g (0.022mol) that step (1) makes, boric acid 0.62g (0.01mol), benzene 30ml.N
2The balloon protection, magnetic agitation, 80 ℃ of oil bath temperature controls, reaction times 9-10 hour.Occurring the white opacity phenomenon in the reaction process in the water trap, is the water of reaction generation and the mixture of backflow benzene, along with the growth of time, and the layering gradually of the solution in the water trap, the upper strata is clarifying benzene, lower floor is a water layer.Tell following water with graduated cylinder, when the amount of minute water outlet during in the theoretical value left and right sides, with stopped reaction behind the tlc analysis detection reaction terminal point.Leave standstill cooling,, there is waxy substance at the bottle end, the upper strata is a yellow solution, suction filtration obtains faint yellow solid, with the angled spoon compression, help obtaining uniform pressed powder like this in the process of suction filtration, suction filtration finishes and obtains faint yellow solid 3.6g, the gained solid is used an amount of N again, and dinethylformamide carries out recrystallization.
From infrared spectrogram shown in Figure 2, as can be seen at 1438.12cm
-1Absorption peak has appearred in the place; In addition at 862.36cm
-1Absorption peak has also appearred in the place.Can judge to have generated the O-B key in the reaction process, and be cyclic.And through thin-layer chromatography detection reaction terminal point, thereby the reaction of expection has taken place in deducibility.
From electrospray ionization mass spectrum figure shown in Figure 3 as can be seen 565.3 molecular ion peak be the M-1 peak, so the molecular weight M of product is 566; 278.6 locate the peak is the molecular ion peak of intermediate n-hexyl glucose amide.
From mass spectrum, obtained target product as can be seen.
Reaction equation is as follows:
(1) the n-octyl glucose amide is synthetic
In being housed, the 50ml there-necked flask of spherical condensating tube and thermometer adds n-octyl amine 3.31ml (0.02mol), maltonic acid-delta-lactone 2.85g (0.016mol), methyl alcohol 30ml, the oil bath temperature control is 40 ℃ then, magnetic agitation, maltonic acid after 10 minutes-delta-lactone dissolving, white solid appearred again after 30 minutes, keep this temperature half hour, be warmed up to 55 ℃ then, solid dissolves again, keeps this temperature 3 hours, obtain clear solution, stop heating, leave standstill, separate out white crystal gradually, suction filtration obtains white crystal, productive rate 92.3%.
(2) Gemini boric acid ester n-octyl glucose acylamine compound is synthetic
In the there-necked flask that thermometer, water trap and spherical condensation tube are housed, add positive hot glucose amide 6.75g (0.022mol), boric acid 0.62g (0.01mol), benzene 30ml.Other condition leaves standstill cooling with embodiment 1, and white solid appears in the bottle end, and the upper strata is a benzene, and suction filtration obtains brilliant white solid 4.8g.With an amount of N of gained solid, the dinethylformamide heating for dissolving, the cooling back adds proper amount of acetone or re-crystallizing in ethyl acetate obtains white powder solid 3.2g.
From infrared spectrogram shown in Figure 4, as can be seen at 1436.78cm
-1Absorption peak has appearred in the place; In addition at 862.26cm
-1Strong absorption peak has also appearred in the place.Can judge to have generated the 0-B key in the reaction process, and be cyclic.Thereby the reaction of expection has taken place in deducibility.
From electrospray ionization mass spectrum shown in Figure 5 as can be seen, peak, 621.1 place is molecular ion peak M-1 peak, and the molecular weight M of product is 622; 306.6 locate the molecular ion peak that the peak is an intermediate.From mass spectrum, obtained the set goal product as can be seen.
Synthesizing of embodiment 3 Gemini boric acid ester dodecyl glucose acylamine compounds
(1) the dodecyl glucose amide is synthetic
In the 100ml there-necked flask, add maltonic acid-delta-lactone 2.85g (0.016mol), amino dodecane 0.018mol, mol ratio is 1: 1.125, methyl alcohol 25ml, oil bath is warming up to 60 ℃ then, it is muddy state that reaction has just begun solution, dissolving after 10 minutes, increase 2.5 solution produces solid after hour, at this moment generated glucose amide, add 20ml methyl alcohol sustained reaction again in the system reacted fully and carries out in 2 hours, obtain the white opacity solution of brightness, the system suction filtration is obtained the solid of brilliant white, again solid is removed unnecessary amino dodecane (because product is water-fast at normal temperatures) for three times with distilled water wash, then the gained white solid is heated recrystallization with distilled water, white solid is dissolved into clear solution when water is at a simmer, leaves standstill cooling again and can separate out brilliant white solid, suction filtration, drying obtains white solid.Productive rate 93.3%
(2) Gemini boric acid ester dodecyl glucose acylamine compound is synthetic
In the there-necked flask that thermometer, water trap and spherical condensation tube are housed, add dodecyl glucose amide 7.99g (0.022mol), boric acid 0.62g (0.01mol), benzene 30ml.Other condition such as embodiment 1.Leave standstill cooling, obtain light gray solution, the solution rotating evaporation is made the solvent evaporate to dryness, obtain the light gray solid.
With gained solid methylene dichloride heating for dissolving, the cooling back adds re-crystallizing in ethyl acetate, leaves standstill for some time, and the light gray solid is separated out at the bottle end, and suction filtration obtains the light gray crystal.
1428.61cm as can be seen from infrared spectrogram shown in Figure 6
-1Absorption peak has appearred; In addition at 861.89cm
-1One relative more weak absorption peak has appearred in the place.Can judge to have generated the 0-B key in the reaction process, and be cyclic.Thereby the reaction of expection has taken place in deducibility.
733.1 molecular ion peak is the M-1 peak as can be seen from electrospray ionization mass spectrum figure shown in Figure 7, and the molecular weight M of product is 734; 362.6 locate the molecular ion peak that the peak is an intermediate; 398.5 locate the peak is intermediate+Cl peak.From mass spectrum, obtained the set goal product as can be seen.
Synthesizing of embodiment 4 octadecyl glucose amides
In the there-necked flask that thermometer, water trap and spherical condensation tube are housed, add 18 glucose amides 4.92 (0.011mol), boric acid 0.31g (0.005mol), benzene 30ml.N
2The balloon protection, magnetic agitation, 80 ℃ of oil bath temperature controls, reaction times 9-10 hour.Occurring the white opacity phenomenon in the reaction process in the water trap, is the water of reaction generation and the mixture of backflow benzene, along with the growth of time, and the layering gradually of the solution in the water trap, the upper strata is clarifying benzene, lower floor is a water layer.When minute water yield during in the theoretical value left and right sides, stopped reaction behind the tlc analysis detection reaction terminal point.Leave standstill cooling, obtain canescence solution, the solution rotating evaporation is made the solvent evaporate to dryness, obtain white solid 4.6g, thick product yield 91.1%.
With gained solid N, the dinethylformamide heating for dissolving, recrystallization is left standstill in cooling, leaves standstill for some time, and white solid is separated out at the bottle end, and suction filtration obtains white crystal.Fusing point: 145.3-146.0 ℃.
The measurement of 1 froth stability (Luo Shi Latherometer mensuration)
The Gemini boric acid ester n-hexyl glucose amide tensio-active agent of embodiment 1 and embodiment 2 preparations and the test data of Gemini boric acid ester n-octyl glucose amide tensio-active agent are as shown in Table 1 and Table 2.
The foam stability of table 1 Gemini boric acid ester n-hexyl glucose amide can be tested
| t(s) | 2 | 4 | 6.93 | 8 | 12 | 13 | 18.8 | 22 | 25.4 | 31 | 36.2 |
| V t | 0.5 | 1 | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 | 4.5 | 5 | 5.5 |
| V 0-V t | 5.5 | 5 | 4.5 | 4 | 3.5 | 3 | 2.5 | 2 | 1.5 | 1 | 0.5 |
The foam stability of table 2 Gemini boric acid ester n-octyl glucose amide can be tested
| t(s) | 16 | 36 | 64 | 96 | 135 | 193 | 275 | 414 | 857 |
| V t | 0.5 | 1 | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 | 4.5 |
| V 0-V t | 4.5 | 4 | 3.5 | 3 | 2.5 | 2 | 1.5 | 1 | 0.5 |
Relatively Gemini boric acid ester n-octyl glucose amide and the Gemini boric acid ester n-hexyl glucose amide foam stability energy data in distilled water as can be seen, the foaming of eight carbon and foam stability can be all good than six carbon, the foam of eight carbon is fine and smooth abundant, and half foam life period is longer relatively.
2 capillary mensuration (decylization method)
Surface tension test data such as Fig. 8 and shown in Figure 9 of the Gemini boric acid ester glucose acidamide surfactant of embodiment 1 and embodiment 2 preparations.
As can be seen from Figure 8, the lowest surface tension of Gemini boric acid ester n-hexyl methyl glucamine is 37.9mN/m.With Gemini boric acid ester n-octyl glucose amide ratio, it is obviously more weak that Gemini boric acid ester n-hexyl glucose amide reduces capillary ability.May be shorter because contain the hydrophobic chain of six carbon, surfactivity be just relatively low.
As can be seen from Figure 9, the surface tension of Gemini boric acid ester n-octyl glucose amide increases on a declining curve with concentration, and the decline degree is apparent in view.It is relatively good to illustrate that Gemini boric acid ester n-octyl glucose amide reduces capillary ability.Its aqueous solution is that 0.16% o'clock lowest surface tension is 20.2mN/m in mass concentration, clear and definite micelle-forming concentration (cmc) is arranged, and micelle is formed in the smaller concentration range.
3 measurement of contact angle (contact angle instrument mensuration)
The contact angle test data of the Gemini boric acid ester n-octyl glucose acylamine compound that embodiment 2 makes as
Shown in the table 3.Contact angle instrument AC220 volt.
The contact angle determination of table 3 Gemini boric acid ester n-octyl methyl glucamine
| Water | Slide | The paraffin plate | 0.02％ | Slide | The paraffin plate | 0.04％ | Slide | The paraffin plate |
| A left | 17 | 87 | A left side | 21 | 82 | A | 15 | 89 |
| Right | 18 | 87 | Right | 18 | 86 | Right | 14 | 89 |
| On average | 17.5 | 87 | On average | 19.5 | 84 | On average | 14.5 | 89 |
| 0.06％ | Slide | The paraffin plate | 0.08％ | Slide | The paraffin plate | 0.10％ | Slide | The paraffin plate |
| A left side | 23 | 82 | A |
19 | 88 | A left side | 13 | 82 |
| Right | 23 | 81 | |
20 | 86 | Right | 16 | 80 |
| On average | 23 | 81.5 | On average | 19.5 | 87 | On average | 14.5 | 81 |
| 0.12％ | Slide | The paraffin plate | 0.14％ | Slide | The paraffin plate | 0.16％ | Slide | The paraffin plate |
| A left |
19 | 71 | A |
12 | 65 | A left side | 7 | 51 |
| |
17 | 69 | Right | 11 | 64 | |
8 | 52 |
| On average | 18 | 70 | On average | 11.5 | 64.5 | On average | 7.5 | 51.5 |
| 0.18％ | Slide | The paraffin plate | 0.20％ | Slide | The paraffin plate | |||
| A left |
6 | 45 | A |
6 | 31 | |||
| |
8 | 52 | Right | 7 | 36 | |||
| On average | 7 | 48.5 | On average | 6.5 | 33.5 |
From the experimental result shown in the table 3 as can be seen, along with Gemini boric acid ester n-octyl methyl glucamine concentration increases, its contact angle on slide and paraffin plate all diminishes gradually, and spreading property strengthens, and wettability strengthens.And because the slide smoother, its in the wettability on the slide significantly better than on the paraffin plate.
Claims (10)
1, a kind of Gemini boric acid ester glucose acylamine compound, its structure is shown in general formula (I):
Wherein, R is selected from the C of straight or branched
6-C
18Alkyl, C
6～C
18Cycloalkyl, C
6～C
18Aryl, C
7～C
18Alkaryl and C
7～C
18Aralkyl; In general formula (I), boron respectively with two sugar units on any adjacent carbon atom on two hydroxyls connect into key.
2, Gemini boric acid ester glucose acylamine compound according to claim 1 is characterized in that: described R is selected from the C of straight chain
6-C
18Alkyl.
3, Gemini boric acid ester glucose acylamine compound according to claim 1 is characterized in that: it carries out esterification and prepares by being raw material with glucose acylamine compound, boric acid with structural formula (II)
4, Gemini boric acid ester glucose acylamine compound according to claim 3, it is characterized in that: the glucose acylamine compound that described raw material has structural formula (II) prepares by the following method: with aliphatic amide and maltonic acid-delta-lactone is raw material, reacts; Reaction finishes and leaves standstill, lowers the temperature, separates out white solid, behind the suction filtration, uses recrystallizing methanol, promptly obtains the white crystal of the glucose acylamine compound of structural formula (II).
5, the preparation method of the described Gemini boric acid ester glucose acylamine compound of one of claim 1-4 may further comprise the steps:
(1) being raw material with glucose acylamine compound, the boric acid with structural formula (II), serves as the band aqua forming the azeotropic solvent with water; In the reactor that temperature control system, branch aqueous systems are housed, be 50～150 ℃ in N2 protection, temperature, stir under, reacted 9-15 hour;
(2) reaction product that step (1) is obtained is evaporated, and obtains the brilliant white solid, with gained solid recrystallization, obtains the white powder solid and is compound of the present invention.
6, preparation method according to claim 5 is characterized in that in described step 1), and the glucose acylamine compound that raw material has structural formula (II) prepares by the method that may further comprise the steps:
(1) be raw material with aliphatic amide and maltonic acid-delta-lactone, mol ratio is 1: 1～1.6: 1, dissolves with solvent, and solvent is selected from water, methyl alcohol, ethanol, Virahol, ethylene glycol and propylene glycol;
(2) material that step (1) is obtained stirs under 20～120 ℃ of conditions of temperature control, to the dissolving of maltonic acid-delta-lactone, white solid appears and after, keep 40～80 ℃, 0.5～2 hour;
(3) material with step (2) continues to heat up 10～20 ℃, makes the solid dissolving, keeps this temperature to obtaining clear solution, stops heating, leaves standstill, and separates out crystal gradually, and suction filtration promptly gets the glucose acylamine compound with structural formula (II).
7, preparation method according to claim 6 is characterized in that
The mol ratio of described aliphatic amide and maltonic acid-delta-lactone is 1: 1～1.3: 1;
Described solvent is a methyl alcohol; 40～80 ℃ of temperature controls.
8, preparation method according to claim 5 is characterized in that
Described band aqua is benzene, toluene or hexanaphthene; Described stirring is a magnetic agitation, and uses the oil bath temperature control, and temperature is 80-90 ℃, and the reaction times is 9-10 hour.
9, a kind of green surfactant is characterized in that containing the Gemini boric acid ester glucose acylamine compound just like shown in the general formula (I),
Wherein, R is selected from the C of straight or branched
6-C
18Alkyl, C
6～C
18Cycloalkyl, C
6～C
18Aryl, C
7～C
18Alkaryl and C
7～C
18Aralkyl; In general formula (I), boron respectively with two sugar units on any adjacent carbon atom on two hydroxyls connect into key;
Described Gemini boric acid ester glucose acylamine compound is by being raw material with glucose acylamine compound, boric acid with structural formula (II), carries out that esterification prepares
10, the described Gemini boric acid ester glucose acylamine compound of one of claim 1-4 is as the application in the green surfactant.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972615A (en) * | 2010-10-19 | 2011-02-16 | 中国林业科学研究院林产化学工业研究所 | Glycosyl-contained surface active agent as well as preparation method and measuring method thereof |
| CN102020785A (en) * | 2010-12-02 | 2011-04-20 | 河北科技大学 | Compatilizer, application thereof in polyphenyleneoxide/nylon alloy and preparation method of polyphenyleneoxide/nylon alloy |
| CN102962004A (en) * | 2012-11-26 | 2013-03-13 | 齐齐哈尔大学 | Glucosamide surfactant and method for preparing same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4303445A (en) * | 1980-07-18 | 1981-12-01 | Exxon Research & Engineering Co. | Ink jet printing formulations |
| JPH06501688A (en) * | 1990-10-12 | 1994-02-24 | ザ、プロクター、エンド、ギャンブル、カンパニー | Process for producing N-alkyl polyhydroxyamines and fatty acid amides therefrom in hydroxy solvents |
-
2005
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972615A (en) * | 2010-10-19 | 2011-02-16 | 中国林业科学研究院林产化学工业研究所 | Glycosyl-contained surface active agent as well as preparation method and measuring method thereof |
| CN101972615B (en) * | 2010-10-19 | 2013-01-02 | 中国林业科学研究院林产化学工业研究所 | Glycosyl-contained surface active agent as well as preparation method and measuring method thereof |
| CN102020785A (en) * | 2010-12-02 | 2011-04-20 | 河北科技大学 | Compatilizer, application thereof in polyphenyleneoxide/nylon alloy and preparation method of polyphenyleneoxide/nylon alloy |
| CN102020785B (en) * | 2010-12-02 | 2013-02-13 | 河北科技大学 | Compatilizer, application thereof in polyphenyleneoxide/nylon alloy and preparation method of polyphenyleneoxide/nylon alloy |
| CN102962004A (en) * | 2012-11-26 | 2013-03-13 | 齐齐哈尔大学 | Glucosamide surfactant and method for preparing same |
| CN102962004B (en) * | 2012-11-26 | 2015-04-15 | 齐齐哈尔大学 | Glucosamide surfactant and method for preparing same |
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