CN101787383B - Synthesis method of starch-based N-butyl glucose lauramide used as surfactant - Google Patents

Abstract

The invention discloses a synthesis method of starch-based N-butyl glucose lauramide used as a surfactant, which comprises the following steps of: adding water to starch to prepare starch milk, regulating the pH value, adding calcium chloride and amylase, heating in a water bath to enable the starch to be subjected to liquefaction reaction, inactivating enzymes at high temperature after complete liquefaction, regulating the pH value, adding saccharifying enzymes, heating in the water bath, carrying out saccharification, inactivating enzymes at high temperature, cooling and filtering to obtain a hydrolyzed glucose solution; adding the hydrolyzed glucose solution and n-butylamine by the amino-sugar ratio, adding water, a color resisting agent and a polymer rhodium catalyst simultaneously, heating while stirring, controlling the pH value of the system, and carrying out amination to prepare N-butyl glucosamine; and adding aminate and lauric acid, adding aminoacylase simultaneously, heating while stirring, controlling the pH value of the system, and carrying out acidylation to prepare the N-butyl glucose lauramide. The invention has the advantages of simple process, low cost and high utilization ratio of raw materials and the product has low surface tension, excellent foaming performance, no toxicity and no stimulation and can be biologically degraded easily.

Description

The compound method of starch-based N-butyl glucose lauramide used as surfactant

Technical field

The present invention relates to a kind of compound method of starch-based N-butyl glucose lauramide used as surfactant, belong to polymer chemistry, Surface Science and technological field of biochemistry.

Background technology

Along with people's is to the pay attention to day by day of global ecological environment; The production of tensio-active agent and exploitation also more and more turn to attention environmentally friendly and are taken from the recyclability raw material, and the tensio-active agent of 21 century just develops towards the direction of safety, gentleness and readily biodegradable." green surfactant " or " eco-friendly tensio-active agent " becomes the tensio-active agent hot research fields gradually.Belong to one type of principal item of a new generation's " green surfactant " with the novel surfactant of renewable resourcess such as starch, glucose exploitations, its progressively commodity turn to national economy and social development and provide the new millennium to meet the novel product of human temperature and safety and environmental protection requirement.

Owing to have a plurality of hydroxyls in starch or the glucose molecule structure, thus glucone can be used as in the surfactant molecule a good hydrophilic group because of.But glucose itself is the relatively more responsive material of a kind of chemically reactive; Be prone to take place redox reaction; Easy to change, the decomposition etc. of being heated; So behind condensation reactions such as the semi-acetal hydroxyl in the glucose molecule structure and aliphatic amide, lipid acid generation alkyl polyhydroxy glucose amide, its chemicalstability strengthens greatly.With starch etc. is that starting raw material synthetic alkylamide tensio-active agent is then at once given birth to.

In the research and development and the application facet of starch-based tensio-active agent, though there are some kinds (like APG, Soxylat A 25-7 glucoside, STAG, APA, glucose amine salt) to put on market successively abroad, and obtained to use widely.But because of majority adopts glucose is starting raw material, has shortcomings such as production cost height, has influenced applying of this series products.The starch resource of China is very abundant; Tensio-active agent there is lack of raw materials with situation about constantly appreciating under; It is the effective way that starch utilizes that renewable resource starch that develops cheapness and enrich and Dian Fentang are produced tensio-active agent, must have bigger competitive power and great market potentiality economically.And the main raw material of N-butyl glucose laurylamide adopts is starch, therefore has comparatively wide application prospect and good society and economic benefit.

Aspect the research and development of mild starch-based tensio-active agent; The present main production company such as the P&G company of the U.S.; System is main production raw material with glucose; And adopt comparatively harsh processing condition such as HTHP shortening, limited applying of such tensio-active agent, the then rarely seen report of research of alkyl polyhydroxy glucose amide class tensio-active agent aspects such as synthetic and application at normal temperatures and pressures.

Summary of the invention

Problems such as the object of the invention provides a kind of starch-based N-butyl glucose lauramide used as surfactant synthetic process at normal temperatures and pressures, and is big with the pungency that solves some conventional surfactants, that biological degradability is undesirable.

Detailed process is following:

Steps A: starch is hydrolyzation of glucose liquid through enzymatic hydrolysis

(1) to use massfraction be that 10% sodium hydroxide solution quality of regulation mark is pH to 6.0～6.5 of 20%～40% milk of starch to starch-liquefying, adds calcium chloride then, makes the calcium ion massfraction reach 1%; Add AMS by 5～10 units/g starch again, fully stir, in water-bath, slowly be heated to 85～90 ℃, under this temperature, continue to stir 20～40min, then with iodine liquid check liquefaction terminal point; Be warming up to 100 ℃ of high temperature enzyme 10min that goes out after the liquefaction fully;

(2) after the starch saccharification liquefaction liquid cooling but; With mass fraction is that 10% watery hydrochloric acid is regulated pH about 4.5; In flask, add carbohydrase by 80～130 units/g starch then; After being warming up to 45～65 ℃ under stirring; Constant temperature continues to stir 15min down; Saccharification rest 16～20h then, the high temperature enzyme that goes out is treated saccharification liquid cooled and filtered;

Step B: hydrolyzation of glucose liquid and n-Butyl Amine 99 generate N-butyl glycosamine through reductive amination process

In the reaction kettle that whisking appliance and reflux condensation mode pipe unit are housed; Press osamine mol ratio 0.8～1.6 and add saccharification liquid and n-Butyl Amine 99; Add entry simultaneously, making the massfraction of glucose in solvent is 25%～35%, adds the resistance toner that accounts for glucose quality percentage ratio 0.5%～2.0%; Stirring intensification down fast and keeping reacting liquid temperature is 50～75 ℃; Add the polymer rhodium catalyst that accounts for glucose quality percentage ratio 0.5%～1.5%, pH is 7～11 in control, and reaction 12～72h obtains N-butyl glycosamine;

Step C: aminate and LAURIC ACID 99 MIN acylation reaction generate product N-butyl glucose laurylamide

Press saccharic acid mol ratio 1～3.5 and add LAURIC ACID 99 MIN, add the L-Aminoacylase that accounts for glucose quality percentage ratio 1.0%～2.5% simultaneously, the pH of conditioned reaction liquid is 7～10, and keeping reacting liquid temperature is 40～60 ℃, finishes reaction behind reaction 4～8h.

Said resistance toner is 2,6 di tert butyl 4 methyl phenol, NaHSO ₃A kind of with in the vitamin c.

Said polymer rhodium catalyst is RhCl ₃/ PPh ₃, RhCl ₃/ PHPh ₂And RhCl (PPh ₃) ₃In a kind of.

The present invention does not need harsh reaction conditions such as HTHP, shortening, and technology is simple, and equipment does not have particular requirement; Less investment; Cost is low, and raw material availability is high, and product surface tension force is low, lathering property is good, compound synergic, nontoxic, non-stimulated, readily biodegradable.

Description of drawings

Fig. 1 is the glucose IR figure of embodiment of the invention preparation.

Fig. 2 is the N-butyl glycosamine IR figure of embodiment of the invention preparation.

Fig. 3 is the N-butyl glucose laurylamide IR figure of embodiment of the invention preparation.

Embodiment

Embodiment:

Using massfraction is that 10% sodium hydroxide solution quality of regulation mark is the pH value to 6.0 of 30% milk of starch, adds calcium chloride then, makes the calcium ion massfraction reach 1%.Add AMS by 6 units/g starch again, fully stir, be heated to 85 ℃, continue to stir 30min, then with iodine liquid check liquefaction terminal point.Be warming up to 100 ℃ of high temperature enzyme 10min that goes out after the liquefaction fully.After the cooling, using massfraction is that 10% Hydrogen chloride is regulated about pH to 4.5, in flask, adds saccharifying enzyme by 100 units/g starch then; After being warming up to 60 ℃ under stirring, continue to stir 15min, saccharification rest 18h then; The high temperature enzyme that goes out is treated but after-filtration of saccharification liquid cooling.By the osamine mol ratio is 1.2 adding saccharification liquid and n-Butyl Amine 99s, adds entry simultaneously, and making the massfraction of glucose in solvent is 30%, adds the NaHSO that accounts for glucose quality percentage ratio 0.5% ₃, stirring intensification down fast and keeping reacting liquid temperature is 50 ℃, adds the polymer rhodium catalyst RhCl of the mass percent 1% that accounts for glucose ₃/ PPh ₃, regulate pH to 10, reaction 60h.Be 2.75 adding LAURIC ACID 99 MIN by the saccharic acid mol ratio again, add the L-Aminoacylase of the mass percent 1.5% that accounts for glucose simultaneously, the pH to 9 of conditioned reaction liquid, keeping reacting liquid temperature is 40 ℃, finishes to react behind the reaction 8h.

Product is analyzed (tetracol phenixin liquid-film method) through IR, and we can find out the spectrogram (like Fig. 2) of amination reaction intermediate product N-butyl glucose amine: 3300cm ^-1The place is into key-OH absorption peak, 1642.6cm ^-1The place is the C-O-C skeletal vibration absorption peak of glucone, 1092.7cm ^-1The place is than the C-N absorption peak in the n-Butyl Amine 99 tangible red shift is arranged by the absorption peak of C-N, and the group that preliminary judgement links to each other with the N atom is a glucose, proves that new product glycamine generates.The spectrogram (like Fig. 3) of final product N-butyl glucose laurylamide: 3303.9cm ^-1The place is into key-OH absorption peak, 2926.7cm ^-1And 2852.7cm ^-1The place is for the CH stretching vibration absorption peak of aliphatic fat stable hydrocarbon, at 1641.7cm ^-1There is amido linkage C=O stretching vibration absorption peak at the place, influenced by amido, absorbs to move to the lower wave number direction.Equally, at 1048.4cm ^-1The place is influenced by carboxyl for the C-N stretching vibration absorption peak of amido linkage, absorb to move 1466.4cm to the lower wave number direction ^-1And 1376.2cm ^-1The place is followed successively by crooked CH ₂And CH ₃Absorption peak.At 1730cm ^-1Near tangible ester group C=O stretching vibration does not appear, show that content of by-products such as free carboxylic acid in the product, amine soap and amino ester are lower, product purity is higher.

The product analysis result is: outward appearance is light yellow transparent liquid, and recording the active matter quality percentage composition is 40.1%; Mass percent is that the foam height of 0.1% product solution is 40.25mm in the time of 25 ℃, and viscosity is 360mPas.Explaining that N-butyl glucose laurylamide has characteristics such as surface tension is low, lathering property is good, is a kind of novel gentle tensio-active agent of excellent property.

Claims (1)

1. the compound method of a starch-based N-butyl glucose lauramide used as surfactant is characterized in that concrete steps are:

(1) using massfraction is that 10% sodium hydroxide solution quality of regulation mark is pH to 6.0～6.5 of 20%～40% milk of starch, adds calcium chloride then, makes the calcium ion massfraction reach 1%; Add AMS by 5～10 units/g starch again, fully stir, in water-bath, slowly be heated to 85～90 ℃, under this temperature, continue to stir 20～40min,, be warming up to 100 ℃ of high temperature enzyme 10min that goes out after liquefaction is complete then with iodine liquid check liquefaction terminal point;

(2) after the liquefier cooling; With mass fraction is that 10% watery hydrochloric acid is regulated pH 4.5; In flask, add carbohydrase by 80～130 units/g starch then; After being warming up to 45～65 ℃ under stirring; Constant temperature continues to stir 15min down; Saccharification rest 16～20h then, the high temperature enzyme that goes out is treated saccharification liquid cooled and filtered;

(3) in the reaction kettle that whisking appliance and reflux condensation mode pipe unit are housed; Press osamine mol ratio 0.8～1.6 and add saccharification liquid and n-Butyl Amine 99; Add entry simultaneously, making the massfraction of glucose in solvent is 25%～35%, adds the resistance toner that accounts for glucose quality percentage ratio 0.5%～2.0%; Stirring intensification down fast and keeping reacting liquid temperature is 50～75 ℃; Add the polymer rhodium catalyst that accounts for glucose quality percentage ratio 0.5%～1.5%, pH is 7～11 in control, and reaction 12～72h obtains N-butyl glycosamine;

(4) press saccharic acid mol ratio 1～3.5 and add LAURIC ACID 99 MIN, add the L-Aminoacylase that accounts for glucose quality percentage ratio 1.0%～2.5% simultaneously, the pH of conditioned reaction liquid is 7～10, and keeping reacting liquid temperature is 40～60 ℃, finishes reaction behind reaction 4～8h;

Said resistance toner is 2,6 di tert butyl 4 methyl phenol, NaHSO ₃A kind of with in the vitamin c;

Said polymer rhodium catalyst is RhCl ₃/ PPh ₃, RhCl ₃/ PHPh ₂And RhCl (PPh ₃) ₃In a kind of.

Images