Technical background:
Starch is widely used high polymers, not only because of the natural product that it is cheap, and is easy to by chemical modification and physical treatment the physicochemical property changing starch.Starch and its derivative are widely used in the industries such as food, medicine, textile printing and dyeing, papermaking, daily-use chemical industry water treatment and mining usually.By chemistry or physical modification, functional group is introduced starch, improve the characteristic of starch, further expand the application of starch.Rice is the main farm produce of China, starch is the main component in rice, due to Starch rice there is the general function that other starch possess while also have a series of special performance as high crystalline, particle fine uniform, the excellent speciality such as easily digested, the water suction of hypoallergenic, starch paste is fast, therefore, with the modified starch of its processing, there is the irreplaceable characteristic of other kind modified starch.Carboxymethyl starch is one of important modified starch, tie up to after starch glucose hydroxyl introduces carboxymethyl and form carboxymethyl starch ether structure, it has, and hydrophilicity is good, the easy gelation of normal temperature, the stable viscosity of paste, the advantage such as transparency is high, retrogradation performance is good, freeze-thaw stability is good.Carboxymethyl starch is a kind of novel inexpensive, excellent property, safety, environmentally friendly industrial chemicals, has been widely used in the fields such as medicine, printing and dyeing, weaving, papermaking, daily-use chemical industry; Also have broad prospect of application in foodstuffs industry harmless, can be absorbed by the body, also can increase and increase immunizing power by Tumor suppression, non-environmental-pollution is environmentally friendly machine simultaneously.
The research of carboxymethyl starch starts from nineteen twenty-four, and the development of China's carboxymethyl starch starts from the mid-80 in last century.Through the development of nearly 20 years, although China's carboxymethyl starch industry obtains tremendous development, and have been reported with wheat starch, W-Gum, tapioca (flour) research, but the research of carboxymethyl starch is also in the primary stage, and especially the carboxymethyl modified research of Starch rice is not yet reported.Just because of the high crystalline of Starch rice and particle tiny, its reaction system viscosity after adding Mono Chloro Acetic Acid is caused to increase too fast, starch in reactor is easy to form floc sedimentation, cause reaction system unstable, finally make substitution value low, reaction terminates after product and is difficult to cleaning, drying, sometimes can not get qualified carboxymethyl starch product even at all.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of carboxymethyl Starch rice, for the common solvent method of utilization, new Raw Materials Rice starch is carried out existing in carboxymethyl-modification process reaction system instability, reaction system viscosity increases too fast, conglomeration problem and cause the problems such as products collection efficiency is low, reaction can not normally be carried out, substitution value is not high, and improve, be intended to for the deep processing of Starch rice provides new approach.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
Fed-batch legal system, for a method for rice carboxymethyl starch, comprises the following steps:
(1) in 100 parts of Starch rices, 50 ~ 60 parts of NaOH and 5 ~ 7 part catalyzer are added by mass;
(2) dissolve with aqueous isopropanol, in the water-bath of 50 DEG C, abundant stirring heating 30 ~ 35min, makes starch alkalize;
(3) after being warming up to 60 DEG C, add 40 ~ 85 parts of Mono Chloro Acetic Acids altogether for 2 ~ 6 times by 100 parts of Starch rice intervals in batches, and regulate stirring velocity to 400 ~ 600r/min immediately after adding Mono Chloro Acetic Acid at every turn, after 5 ~ 20min, speed is turned down to 300 ~ 400r/min, whole reaction process fully stirs 180 ~ 220min, makes it etherificate;
(4) question response terminates rear adjust pH is 6.5 ~ 7.0, filters, filter residue washing with alcohol, dries, grinding, screening.
In described step (1), catalyzer is phase-transfer catalyst, is preferably cetyl trimethylammonium bromide catalyzer, accelerates the speed of response of heterogeneous organic reaction.
In described step (2), the add-on of Virahol is that every 100 parts of Starch rices add 1200 ~ 1350 parts of Virahols and 45 ~ 60 parts of distilled water, and stirring velocity is 200 ~ 300r/min;
Described alkalinization completes and is warming up to the etherification reaction temperature time and is not counted in the etherification reaction time, and this temperature-rise period approximately needs ten minutes.
For keeping the alkaline environment of system in reaction process in described step (3), often criticize add Mono Chloro Acetic Acid after add a certain amount of sodium hydroxide after 10 ~ 20min.
Described for keeping the alkaline environment of system in reaction process, add 1/3 ~ 2/3 solid sodium hydroxide of Mono Chloro Acetic Acid amount, the pH of solution is remained between 7.0 ~ 8.0.
In described step (3), lower interval adds the chloroacetic timed interval is in batches 20min ~ 60min.
In described step (4), it is 6.5 ~ 7.0 that reaction terminates rear Glacial acetic acid adjust pH.
In described step (4), the filter residue ethanolic soln washes clean of 90% ~ 95% volume fraction, is dried to constant weight in 45 DEG C ~ 50 DEG C baking ovens, grinding, and sieves with 80 object sieves.
Raw Materials Rice starch of the present invention is the separation Starch rice that market is bought, through measuring, substantially not containing crude protein.
Beneficial effect of the present invention:
Method of the present invention, in the process of Starch rice etherificate, take interval to add Mono Chloro Acetic Acid in batches, and in reaction process, regulate stirring velocity and keep the alkaline environment of reaction system, replace once adding the chloroacetic existing general operation method of reactant with this, improve the stability of reaction system significantly, reaction is normally carried out, efficiently solve in reaction process and cause conglomeration problem because viscosity increases too fast, obtained carboxymethyl starch substitution value (DS) can reach more than 0.70, and its substitution value can adjust between 0.4 ~ 0.75 according to demand and compare be easier to control.
The preparation method of the rice carboxymethyl modified starch designed in the present invention has simple, reacts more stable, product substitution value high, and the deep processing that can be Starch rice provides a kind of new method.
Embodiment:
A kind of fed-batch legal system is for the method for carboxymethyl Starch rice, 50 ~ 60 parts of NaOH and 5 ~ 7 part catalyzer are added by mass in 100 parts of Starch rices, after adding NaOH in Starch rice, dissolve with aqueous isopropanol, the add-on of Virahol is that every 100 parts of Starch rices add 1200 ~ 1350 parts of Virahols and 45 ~ 60 parts of distilled water, stirring velocity is 200 ~ 300r/min, abundant stirring heating 30 ~ 35min in the water-bath of 50 DEG C, starch is alkalized, add 40 ~ 85 parts of Mono Chloro Acetic Acids altogether for 2 ~ 6 times by 100 parts of Starch rice intervals after being warming up to 60 DEG C in batches, and regulate stirring velocity to 400 ~ 600r/min immediately after adding Mono Chloro Acetic Acid at every turn, after 5 ~ 20min, speed is turned down to 300 ~ 400r/min, often criticize add Mono Chloro Acetic Acid after add about 1/3 ~ 2/3 of Mono Chloro Acetic Acid amount after 10 ~ 20min solid sodium hydroxide regulate, the pH of solution is made to remain on 7 ~ 8.It is 20min ~ 60min that next batch and last consignment of add the chloroacetic timed interval.Whole etherification reaction process fully stirs 180 ~ 220min, makes it etherificate.The alkaline environment of system is kept in reaction process.It is 6.5 ~ 7.0 that question response terminates rear adjust pH, and filter, the filter residue ethanolic soln washes clean of 90% ~ 95% volume fraction, is dried to constant weight in 45 DEG C ~ 50 DEG C baking ovens, grinding, and sieves with 80 object sieves.
The measuring method of carboxymethyl starch substitution value (DS) is:
Main measuring method mainly contains ashing method, mantoquita complexometry, acid wash and spectrophotometry.Comparatively speaking, mantoquita complexometry is a kind of fast and simple, preci-sion and accuracy measuring method all preferably, meets production actual requirement.So adopt the substitution value of the mantoquita complexometric titration carboxymethyl starch improved.
Main step: accurately take sample about 0.625g, is placed in 200ml beaker, adds 1ml dehydrated alcohol, 50ml deionized water, adds the NH of 20ml after dissolving
4cl buffered soln, uses 0.1mlL
-1hCl or 0.1mlL
-1naOH, the pH of solution is transferred to 6.0-7.0, accurately adds 50.00ml0.05molL
-1cuSO
4standardized solution, shakes up, and is transferred in 250mL volumetric flask, places 15min, is diluted to scale, shakes up, filtered on buchner funnel.Get filtrate 100mL, regulate its pH to 7.5-8.0, make indicator with PAN, be titrated to solution in green with EDTA standardized solution, be terminal.CuSO is under the same terms
4blank test.The substitution value of sample is gone out according to formulae discovery below.
Wherein: B-sodium acetate base content;
W-sample weighting amount, g;
V
1-consume the volume of EDTA, mL when making sample;
V
2the volume of the EDTA consumed when-work is blank, mL;
C
1the concentration of-EDTA, molL-1;
Embodiment 1
55 parts of NaOH and 6 part cetyl trimethylammonium bromides are added in 100 parts of Starch rices, dissolve with 1200 parts of Virahols and 50 parts of distilled water, stirring velocity is 200r/min, in the water-bath of 50 DEG C, abundant stirring heating 30min makes starch alkalize, after being warming up to 60 DEG C, add total 80 parts of reactant Mono Chloro Acetic Acids in six batches, first adds 20 parts of chloroacetate reactions, second batch 20 parts of chloroacetate reactions are added after 30min, the 3rd batch of 10 parts of chloroacetate reactions are added after 30min, the 4th batch of 10 parts of chloroacetate reactions are added after 30min, the 5th batch of 10 parts of chloroacetate reactions are added after 30min, the 6th batch of 10 parts of chloroacetate reactions are added after 30min.After adding Mono Chloro Acetic Acid, regulate stirring velocity to 400r/min immediately at every turn, after 20min, speed is turned down to 300r/min, in order to keep the alkaline environment of system in reaction process, often criticize add Mono Chloro Acetic Acid after add about 7 parts after 15min solid sodium hydroxide regulate, make the pH of solution remain on about 7.5.Whole etherification reaction process fully stirs 200min.It is 7.0 that question response terminates rear Glacial acetic acid adjust pH.Suction filtration, the filter residue ethanolic soln washes clean of 95% volume fraction, is dried to constant weight in 45 DEG C of baking ovens, grinding, and sieves with 80 object sieves.Obtained carboxymethyl starch substitution value (DS) is 0.74.
Embodiment 2
60 parts of NaOH and 7 part cetyl trimethylammonium bromides are added in 100 parts of Starch rices, dissolve with 1210 parts of Virahols and 52 parts of distilled water, stirring velocity is 250r/min, in the water-bath of 50 DEG C, abundant stirring heating 32min makes starch alkalize, after being warming up to 60 DEG C, add 82 parts of Mono Chloro Acetic Acids in five batches, first adds 20 parts of chloroacetate reactions, second batch 20 parts of chloroacetate reactions are added after 30min, the 3rd batch of 20 parts of chloroacetate reactions are added after 60min, add the 4th batch of 12 parts of chloroacetate reactions after 30min, after 30min, add the 5th batch of 10 parts of chloroacetate reactions.After adding Mono Chloro Acetic Acid, regulate stirring velocity to 450r/min immediately at every turn, after 15min, speed is turned down to 300r/min, in order to keep the alkaline environment of system in reaction process, often criticize add Mono Chloro Acetic Acid after add about 6 parts after 15min solid sodium hydroxide regulate, make the pH of solution remain on about 7..Whole etherification reaction process fully stirs 190min.It is 7 that question response terminates rear Glacial acetic acid adjust pH.Suction filtration, the filter residue ethanolic soln washes clean of 94% volume fraction, is dried to constant weight in 50 DEG C of baking ovens, grinding, and sieves with 80 object sieves.Obtained carboxymethyl starch substitution value (DS) is 0.735.
Embodiment 3
52 parts of NaOH and 6.5 part cetyl trimethylammonium bromides are added in 100 parts of Starch rices, dissolve with 1250 parts of Virahols and 55 parts of distilled water, stirring velocity is 200r/min, in the water-bath of 50 DEG C, abundant stirring heating 35min makes starch alkalize, and after being warming up to 60 DEG C, adds 80 parts of Mono Chloro Acetic Acids in four batches, first adds 20 parts of chloroacetate reactions, add second batch 20 parts of chloroacetate reactions after 30min, after 60min, add the 3rd batch of 20 parts of chloroacetate reactions, after 60min, add the 4th batch of 20 parts of chloroacetate reactions.After adding Mono Chloro Acetic Acid, regulate stirring velocity to 400r/min immediately at every turn, after 15min, speed is turned down to 300r/min, in order to keep the alkaline environment of system in reaction process, often criticize add Mono Chloro Acetic Acid after add about 5 parts after 15min solid sodium hydroxide regulate, make the pH of solution remain on about 7.It is 7.0 that question response terminates rear Glacial acetic acid adjust pH.Suction filtration, the filter residue ethanolic soln washes clean of 95% volume fraction, is dried to constant weight in 45 DEG C of baking ovens, grinding, and sieves with 80 object sieves.Obtained carboxymethyl starch substitution value (DS) is 0.66.
Embodiment 4
55 parts of NaOH and 5 part cetyl trimethylammonium bromides are added in 100 parts of Starch rices, dissolve with 1280 parts of Virahols and 55 parts of distilled water, stirring velocity is 200r/min, in the water-bath of 50 DEG C, abundant stirring heating 30min makes starch alkalize, after being warming up to 60 DEG C, add 60 parts of Mono Chloro Acetic Acids in three batches, first adds 20 parts of chloroacetate reactions, add second batch 20 parts of chloroacetate reactions after 30min, after 60min, add the 3rd batch of 20 parts of chloroacetate reactions.After adding Mono Chloro Acetic Acid, regulate stirring velocity to 400r/min immediately at every turn, after 15min, speed is turned down to 300r/min, in order to keep the alkaline environment of system in reaction process, often criticize add Mono Chloro Acetic Acid after add about 8 parts after 15min solid sodium hydroxide regulate, make the pH of solution remain on about 7.It is 7.2 that question response terminates rear Glacial acetic acid adjust pH.Suction filtration, the filter residue ethanolic soln washes clean of 95% volume fraction, is dried to constant weight in 50 DEG C of baking ovens, grinding, and sieves with 80 object sieves.Obtained carboxymethyl starch substitution value (DS) is 0.51.
Embodiment 5
50 parts of NaOH and 5 part cetyl trimethylammonium bromides are added in 100 parts of Starch rices, dissolve with 1300 parts of Virahols and 55 parts of distilled water, stirring velocity is 200r/min, in the water-bath of 50 DEG C, abundant stirring heating 30min makes starch alkalize, after being warming up to 60 DEG C, divide two batches and add 40 parts of Mono Chloro Acetic Acids, first adds 20 parts of chloroacetate reactions, adds second batch 20 parts of chloroacetate reactions after 30min.After adding Mono Chloro Acetic Acid, regulate stirring velocity to 400r/min immediately at every turn, after 15min, speed is turned down to 300r/min, in order to keep the alkaline environment of system in reaction process, often criticize add Mono Chloro Acetic Acid after add about 8 parts after 15min solid sodium hydroxide regulate, make the pH of solution remain on about 7.It is 7.0 that question response terminates rear Glacial acetic acid adjust pH.Suction filtration, the filter residue ethanolic soln washes clean of 94% volume fraction, is dried to constant weight in 45 DEG C of baking ovens, grinding, and sieves with 80 object sieves.Obtained carboxymethyl starch substitution value (DS) is 0.34.
Embodiment 6
55 parts of NaOH and 5 part cetyl trimethylammonium bromides are added in 100 parts of Starch rices, dissolve with 1300 parts of Virahols and 55 parts of distilled water, stirring velocity is 250r/min, in the water-bath of 50 DEG C, abundant stirring heating 30min makes starch alkalize, and after being warming up to 60 DEG C, adds 70 parts of Mono Chloro Acetic Acids in four batches, first adds 20 parts of chloroacetate reactions, add second batch 20 parts of chloroacetate reactions after 30min, after 30min, add the 3rd batch of 10 parts of chloroacetate reactions, after 60min, add the 4th batch of 10 parts of chloroacetate reactions.After adding Mono Chloro Acetic Acid, regulate stirring velocity to 450r/min immediately at every turn, after 15min, speed is turned down to 350r/min, in order to keep the alkaline environment of system in reaction process, often criticize add Mono Chloro Acetic Acid after add about 6 parts after 20min solid sodium hydroxide regulate, make the pH of solution remain on about 7.It is 7.0 that question response terminates rear Glacial acetic acid adjust pH.Suction filtration, the filter residue ethanolic soln washes clean of 95% volume fraction, is dried to constant weight in 45 DEG C of baking ovens, grinding, and sieves with 80 object sieves.Obtained carboxymethyl starch substitution value (DS) is 0.58.
Below be only better embodiment of the present invention, according to above-mentioned design of the present invention, those skilled in the art also can make various amendment and conversion to this.Such as, chloroacetic interpolation time, mode and number of times, the consumption of catalyzer, the proportioning between alkalization and etherification reaction temperature and time, each component, adjustment
pthe means of H and consumption, the size of stirring velocity and drying temperature and mode etc. in reaction process; But similar this conversion and amendment all belong to essence of the present invention.