CN1052986C - Process for preparing high substitution value hydroxypropyl starch - Google Patents
Process for preparing high substitution value hydroxypropyl starch Download PDFInfo
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- CN1052986C CN1052986C CN 97118325 CN97118325A CN1052986C CN 1052986 C CN1052986 C CN 1052986C CN 97118325 CN97118325 CN 97118325 CN 97118325 A CN97118325 A CN 97118325A CN 1052986 C CN1052986 C CN 1052986C
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Abstract
The present invention relates to a method for preparing hydroxypropyl starch with high substitution value, and the hydroxypropyl starch is prepared from 1 portion of starch, 5 to 10 portions of cyclohexane, 0.04 to 0.1 portion of sodium (potassium) hydroxide and 2 to 6 portions of propylene oxide by weight. The method comprises the steps: 1 portion of starch and 5 to 10 portions of cyclohexane are put in a reaction tank by weight, and are rapidly mixed, and 0.04 to 0.1 portion of sodium hydroxide is dissolved in water by weight and flows into the reaction tank. Nitrogen is led in the tank from the bottom and is stirred, and 2 to 6 portions of propylene oxide are slowly added to the reaction tank and are hermetically stirred. The reaction tank is heated for about 1 hour and keeps the temperature of 80 to 130 DEG C for etherification reaction for 0.5 to 3 hours, the solution is cooled, neutralized for demineralization and filtered to obtain the hydroxypropyl starch after flocculation. The present invention has the advantages of optimized raw material proportion and advanced and reasonable process, and can prepare the hydroxypropyl starch with high substitution value to satisfy various industrial requirements.
Description
The present invention is high substitution value hydroxypropyl starch (glue) preparation method, belongs to the technology of preparing of various industrial flocculation agents, tensio-active agent and tackiness agent.
Hydroxypropylated starch is a purposes modified starch very widely, is widely used in the industry such as food, medicine, papermaking, weaving, daily-use chemical industry, fine chemistry industry, oil drilling, and its character and purposes depend mainly on the denaturation degrees of starch, i.e. molecule substitution value MS.The existing production technology of hydroxypropylated starch has dry method, water dispersion and non-aqueous solvent method, and dry production is that starch and propylene oxide directly carry out gas-solid reaction under certain condition.Concrete preparation method mainly contains alr mode, boiling mode and fashion of extrusion etc.The dry production reaction efficiency is low, and the molecule substitution value of products therefrom is low, heterogeneity, and product separation purification difficult.Water dispersion is the most widely used technology of hydroxypropylated starch of producing at present, and its advantage is that technology is simple, easy handling, and product is purified easily, and high purity product is easy to get.Shortcoming is because hydroxypropylated starch swelling, gelatinization easily in water can not make the substitution value product.The molecule substitution value MS of water dispersion production technique gained hydroxypropylated starch is not more than 0.3; Non-aqueous solvent method is that starch is scattered in alcohol or the ketone organic solvent, and then with propylene oxide reaction, this method can make than high substitution value hydroxypropyl starch, but the sub-substitution value of the best result of products obtained therefrom is below 2.0.Generally speaking, the existing the whole bag of tricks of producing hydroxypropylated starch exists the production reaction efficiency low, low, the heterogeneity of molecule substitution value MS of gained hydroxypropylated starch, perhaps product separation purification difficult.
Purpose of the present invention exists the production reactivity low with regard to being in order to overcome and to solve the existing method and technology of producing hydroxypropylated starch, low, the heterogeneity of molecule substitution value MS of gained hydroxypropylated starch, the perhaps shortcoming and the problem of product separation purification difficult etc., it is higher to study a kind of production reaction efficiency, can make have good flocculence, the hydroxypropylated starch of tackiness and surface-active high substitution value MS, and product separation is purified and is easy to a kind of preparation method of high substitution value hydroxypropyl starch.
The present invention realizes by following method and technology scheme: the inventive method comprises proportioning raw materials and production technique, it is characterized in that: its proportioning raw materials (weight part ratio) is:
Starch 1
Hexanaphthene 5～10
Sodium hydroxid or potassium hydroxide 0.04～0.1
Propylene oxide 2～6 its technological process of production figure as shown in Figure 1.Its production craft step is: 1. be the starch dispersant of preparation high substitution value hydroxypropyl starch with the non-polar organic solvent cyclohexane give, the 1 weight part starch (as W-Gum, tapioca (flour) or yam starch etc.) and the starch dispersant hexanaphthene of 5～10 weight parts are put into retort, stir rapidly and make the outstanding breast of starch, disperse.Used retort requires and can seal, and has chuck or heating coil, and can be with steam or heated oil heat temperature raising, also can fast cooling, and the pressure that ability 1.2MPa is above, and have whipping appts; 2. the catalyzer of the etherification reaction of 0.04～0.1 weight part---sodium hydroxide or potassium hydroxide are used earlier water dissolution, slowly stream is added in the interior starch dispersion liquid of retort then, stream adds on one side stirring rapidly on one side, after stream adds, stirred rapidly again 20～40 minutes, in the whipping process, constantly feed nitrogen, to get rid of the air in the material neutralization reaction jar from pot bottom; 3. the propylene oxide of 2～6 weight parts is slowly joined in the retort, add back confined reaction jar and continue to stir.Slowly heat up then, until 80～130 ℃ of needed temperature of reaction, about 1 hour of heating-up time.Along with temperature of charge raises, a jar internal pressure increases rapidly, can be up to 0.3～0.8MPa.Along with the carrying out of etherification reaction, the propylene oxide amount reduces gradually, the retort internal pressure is reached behind the maximum reduce gradually again, the etherification reaction time is 0.5～3 hour, after reaction finishes, be cooled to room temperature, reaction product is dense jelly, the dispersion agent hexanaphthene is recyclable to be applied mechanically; 4. use H
+In the type storng-acid cation exchange resin and desalination, reacted product added 6～15 times of this product weight and be lower than 25 ℃ cold water soak and stirred 8～12 hours, after jelly is water-soluble, add H
+Type storng-acid cation exchange resin (as 732 Zeo-karbs) neutralizes, restir reduces to 6.0～7.0 until its pH, the filtered and recycled Zeo-karb, renewable back is reused, and filtrate is the high substitution value hydroxypropyl starch solution behind the desalination; 5. will in and the hydroxypropylated starch solution behind the desalination place interlayer caldron heating, and slowly stir, along with temperature rising solution begins to become muddy, being warming up to 40～80 ℃ flocculates, and forms micelle at last, takes out promptly to get high substitution value hydroxypropyl starch glue product.The molecule substitution value MS of product is 2～5, water content 40～70%.According to different application requiring, this product can be added again the cold water of 6～15 times of weight, stirring and dissolving repeats to heat, flocculates, gets operations such as glue again, just can obtain the hydroxypropylated starch glue of more highly purified high substitution value.If necessary, further vacuum-drying, pulverize, make solid powdery product (732 above-mentioned Zeo-karbs are strongly acidic styrene type cation exchange resin, by manufacturer production such as Shanghai Resin Factory).
The present invention compared with prior art has following advantage and beneficial effect: 1. because selected starch dispersant hexanaphthene boiling point low (81 ℃), so from reaction product, remove easily, and since nontoxic, the high substitution value hydroxypropyl starch product that multiple use (comprising foodstuffs industry, medicine industry etc.) uses just be applicable to; 2. the invention provides the proportioning raw materials of optimization, practicable vanguard technology process and processing condition and rational purification, process for refining, molecule substitution value MS can be made and be 2～5 high substitution value hydroxypropyl starch, the demand of all types of industries can be adapted to; 3. the present invention overcomes and has solved in the prior art and produces reaction efficiency molecule substitution value MS low, the gained hydroxypropylated starch low (MS＜2), heterogeneity, and the shortcoming of purification difficult etc. and problem, provide a kind of and produced the reaction efficiency height, can make have good flocculence, the hydroxypropylated starch of tackiness and surface-active high substitution value (MS is 2～5) MS, and product separation is purified and is easy to a kind of preparation method of high substitution value hydroxypropyl starch.
Below Figure of description is further specified as follows: Fig. 1 is preparation technology's schema of high substitution value hydroxypropyl starch.
The present inventor through for many years creative research and test, has many successful embodiment to preparation method of the present invention, enumerates three specific embodiments below:
Embodiment 1:500 restrains tapioca (flour), is scattered in the 2400 gram hexanaphthenes, injects interlayer stainless steel reaction jar, stirs.30 gram sodium hydroxide are soluble in water, and slowly stream is added in the starch dispersion liquid then, stirs rapidly simultaneously.After stream adds, continue to stir 30 minutes, and at the bottom of jar, feed nitrogen so that the oxygen in the eliminating material neutralization tank.Again 1700 gram propylene oxide are added in the retort, stir while adding.After adding, all valves of off-response jar begin slowly heat temperature raising, are warming up to 110 ℃ in 60 minutes, keep 90 minutes.Cool to 30 ℃.In retort, emit hexanaphthene, again reaction product is moved in retort the caldron, add 5 liters of cold water, slowly stir soaked overnight.After the reaction product dissolving, solution is alkalescence, adds H
+Type 732 Zeo-karbs neutralize, and stir while add, and reduce to till 6.5 until pH value of solution.Filter, filter in the immigration caldron, filter residue is a Zeo-karb, and after cleaning with clear water, regeneration is used for next batch, and with the solution in the hot caldron, stirring at a slow speed is warming up to about 45 ℃ and begins flocculation, and 55～60 ℃ flocculate into micelle.Take out micelle, promptly get high substitution value hydroxypropyl starch glue 1520 grams, dry substance 48.3%, molecule substitution value MS is 3.14.
Embodiment 2:500 restrains W-Gum, is scattered in the 2800 gram hexanaphthenes.Dispersion liquid is joined in the stainless steel reaction jar, stir.Get 30 gram dissolution of sodium hydroxide in water, slowly be added to after the cooling in the starch dispersion liquid, stir rapidly simultaneously, stream adds the follow-up continuous stirring 30 minutes that finishes, and feeds nitrogen at the bottom of jar, in order to get rid of the air in the material neutralization tank.Again 1200 gram propylene oxide are slowly added in the retort, constantly stir simultaneously.Add the back valve-off, begin to heat up, approximately after 1 hour, rise to 100 ℃, kept this temperature 60 minutes.Cool then to 30 ℃.Following operation such as embodiment 1.Flocculate into 60～70 ℃ of glue temperature.Make high substitution value hydroxypropyl starch glue 1280 grams.Dry solids content 46.1%, molecule substitution value MS is 2.51.
Embodiment 3:500 gram tapioca (flour) is scattered in the 2400 gram hexanaphthenes.Starch dispersion liquid is joined in the high-pressure reaction pot, stir it.Get 50 gram sodium hydroxide with after the water dissolution cooling slowly stream be added in the retort, and stir rapidly.After stream adds, continue to stir half an hour fast, and feed nitrogen, get rid of the air in the starch dispersion liquid neutralization reaction jar.Again 2800 gram propylene oxide are slowly added in the jar, stir rapidly simultaneously, valve-off subsequently, beginning slowly heats up and constantly stirs, and is warming up to 110 ℃ in 1 hour, keeps 120 minutes, and reaction finishes, and interlayer feeds cooling water temperature to 30 ℃ then.Operation is according to embodiment 1 below.Flocculate into 50～60 ℃ of glue temperature, make high substitution value hydroxypropyl starch glue 1820 grams, contain dry substance 50.9%, molecule substitution value MS is 4.45.
Claims (2)
1, a kind of preparation method of high substitution value hydroxypropyl starch is characterized in that: its proportioning raw materials (weight part) is:
Starch 1
Hexanaphthene 5～10
Sodium hydroxid or potassium hydroxide 0.04～0.1
Propylene oxide 2～6 its production craft step are: 1. be the starch dispersant of preparation high substitution value hydroxypropyl starch with the non-polar organic solvent cyclohexane give, the starch dispersant hexanaphthene of 1 weight part starch and 5～10 weight parts is put into retort, stir rapidly and make the outstanding breast of starch, disperse; 2. the catalyzer of the etherification reaction of 0.04～0.1 weight part---sodium hydroxide or potassium hydroxide are used earlier water dissolution, slowly stream is added in the interior starch dispersion liquid of retort then, stream adds on one side stirring rapidly on one side, after adding, stirred rapidly again 20～40 minutes stream, in the whipping process, constantly feed nitrogen, to get rid of the air in the material neutralization reaction jar from pot bottom; 3. the propylene oxide of 2～6 weight parts is slowly joined in the retort, add back confined reaction jar and continue to stir, slowly heat up then, until 80～130 ℃ of needed temperature of reaction, 1 hour heating-up time is along with temperature of charge raises, the jar internal pressure increases rapidly, up to 0.3～0.8MPa; Along with the carrying out of etherification reaction, the propylene oxide amount reduces gradually, the retort internal pressure is reached behind the maximum reduce gradually again, the etherification reaction time is 0.5～3 hour, and reaction is cooled to room temperature after finishing, reaction product is dense jelly, and dispersion agent hexanaphthene recovery set is used; 4. use H
+In the type storng-acid cation exchange resin and desalination, reacted product added 6～15 times of this product weight and be lower than 25 ℃ cold water soak and stirred 8～12 hours, after jelly is water-soluble, add H
+The type storng-acid cation exchange resin neutralizes, and restir reduces to 6.0～7.0 until its pH, the filtered and recycled Zeo-karb, and the regeneration back is reused, and filtrate is the high substitution value hydroxypropyl starch solution behind the desalination; 5. will in and the hydroxypropylated starch solution behind the desalination place interlayer caldron heating, and slowly stir, along with temperature rising solution begins to become muddy, being warming up to 40～80 ℃ flocculates, form micelle at last, take out and promptly get high substitution value hydroxypropyl starch glue product, the molecule substitution value MS of product is 2～5, and water content 40～70% (weight) is according to different application requiring, the cold water that this product can be added again 6～15 times of weight, stirring and dissolving repeats heating again, flocculation, get the glue operation, just can obtain the hydroxypropylated starch glue of more highly purified high substitution value, if necessary, further vacuum-drying, pulverize, make the solid powdery product.
2, press the preparation method of the described high substitution value hydroxypropyl starch of claim 1, it is characterized in that the retort in the described processing step should be able to seal, have chuck or heating coil, and can be with steam or heated oil heat temperature raising, also can fast cooling, the pressure that ability 1.2MPa is above, and have whipping appts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97118325 CN1052986C (en) | 1997-09-18 | 1997-09-18 | Process for preparing high substitution value hydroxypropyl starch |
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|---|---|---|---|
| CN 97118325 CN1052986C (en) | 1997-09-18 | 1997-09-18 | Process for preparing high substitution value hydroxypropyl starch |
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| CN1175587A CN1175587A (en) | 1998-03-11 |
| CN1052986C true CN1052986C (en) | 2000-05-31 |
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| CN 97118325 Expired - Fee Related CN1052986C (en) | 1997-09-18 | 1997-09-18 | Process for preparing high substitution value hydroxypropyl starch |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024706B (en) * | 2006-02-22 | 2010-10-13 | 西北师范大学 | Preparing method of composite catalytic solid-phase prepared hydroxypropyl starch |
| CN100491401C (en) * | 2006-07-28 | 2009-05-27 | 湖北省农业科学院辐照加工研究所 | Process of preparing non-ionic starch by initiating irradiation |
| CN101768224B (en) * | 2010-01-22 | 2012-01-11 | 鲁郑全 | Preparation method of hydroxypropyl starch |
| CN102344498B (en) * | 2011-10-26 | 2013-07-17 | 邹平福海科技发展有限公司 | Special starch ether for mortar and production method thereof |
| CN104072625A (en) * | 2013-03-26 | 2014-10-01 | 渔淮 | Novel preparation process for hydroxypropyl modified starch used for food |
| CN103421123A (en) * | 2013-08-22 | 2013-12-04 | 华南理工大学 | Method for modifying dextrin by means of hydroxypropylation |
| CN105481990B (en) * | 2016-01-06 | 2018-05-15 | 中州大学 | A kind of method that green high-pressure process prepares hydroxypropul starch |
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