CN100491401C - Process of preparing non-ionic starch by initiating irradiation - Google Patents
Process of preparing non-ionic starch by initiating irradiation Download PDFInfo
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- CN100491401C CN100491401C CNB2006100197496A CN200610019749A CN100491401C CN 100491401 C CN100491401 C CN 100491401C CN B2006100197496 A CNB2006100197496 A CN B2006100197496A CN 200610019749 A CN200610019749 A CN 200610019749A CN 100491401 C CN100491401 C CN 100491401C
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Abstract
The irradiation initiation process of preparing no-ionic starch includes the following steps: 1. adding propylene oxide into starch material via stirring to obtain mixture with the propylene oxide adding amount being 2-100 wt% of starch; 2. irradiating the mixture in Co-60 irradiation field of irradiation dose 3-15 KGy to initiate reaction in the presence of oxygen to prepare blend; and 3. post-treatment of the blend through stoving at 130-150 deg.c or 180-200 deg.c inside stove, stirring, crushing and 100 mesh sieving to obtain the no-ionic starch product. The process is environment friendly, simple and low in cost.
Description
Technical field
The invention belongs to the technology of preparing of papermaking, textile sizing use modified starch size, be specifically related to a kind of method of preparing non-ionic starch by initiating irradiation.
Background technology
Because the modified starch product is various, purposes is wide, and the added value height carries out deep processing to starch and produces various modified starches, is called " sunrise industry " or " gold industry " by some countries, and strides into high-tech area.Hydroxyalkyl starch, particularly hydroxypropylated starch since the forties in last century, have been obtained a large amount of achievements in research as the important kind of a class in numerous modified starches.
Hydroxypropylated starch belongs to the non-ionic type modified starch, and it is high that it replaces ehter bond stability, in hydrolysis, and oxidation, the crosslinked not easy fracture of ehter bond that waits in the chemical reaction process.Hydroxypropylated starch is mainly used in paper industry and fiber industry.Owing to the introducing of hydroxyl, increased the wetting ability of starch molecule, the gelatinization point of starch is reduced, expanded by heating is very fast, and the transparency and the tackiness of paste are higher, a little less than the retrogradation, can form transparent, softish film after the drying, be used for the printing paper surface treatment, can suppress soaking into of printing ink, make the printing ink distinctness, evenly, and can reduce the consumption of printing ink, increase economic efficiency, because its good flowability, smoothness, water-retentivity can improve transaction capabilities and quality product.It can be used as the internal additives and the surface sizing agent of cardboard binding agent, paper industry.The hydroxyalkyl starch of high substitution value also has higher use value in textile industry.Substitution value is higher, and the characteristic value of film is higher, and it can increase and cellulosic avidity, and is good with the intermiscibility of PVA, and destarch is easy.
Through the research and development of decades, the hydroxyalkyl starch production technique has had significant progress.Summarize and get up to have the starch milk wet method, non-aqueous solvent method is breathed out the dry method three major types, wherein most representative a kind of in the wet current hydroxyalkyl starch of production both at home and abroad of starch milk wet method, this method is that starch is made into 30%～40% emulsion, for preventing starch granules swelling in water, need to add the sodium sulfate of dry starch weight 5%～10%, the sodium hydroxide that adds dry starch weight 1%～3% again, the propylene oxide that under brute force stirs, adds reacting weight, sealed reactor reacted 8～24 minutes under 35 ℃～40 ℃ temperature.Reaction is finished after neutralize, filtration washing, and drying promptly becomes product after the pulverizing, this production technique is simple, and is not high to equipment requirements, constant product quality, color and luster is good, but its shortcoming is the product that can not prepare high substitution value, thereby is restricted in the application of many industrial circles.Non-aqueous solvent method promptly is that starch is dispersed in the non-aqueous solvent, and non-aqueous solvent commonly used has methyl alcohol, ethanol, Virahol, acetone benzene class etc., wherein best with the Virahol effect, under agitation add basic catalyst then, as sodium hydroxide, hydrogen-oxygen is drawn potassium etc., then add propylene oxide, after reaction finishes, through neutralization, remove solvent, washing is filtered, drying is pulverized, and sub-sieve promptly gets product.It is a little that can to prepare substitution value bigger that product and yield are higher that this method gets maximum, but non-aqueous solvent costs an arm and a leg, inflammable, and some has must toxicity, the production cost height.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing non-ionic starch by initiating irradiation, this method non-environmental-pollution, production technique is simple, cost is low.
To achieve these goals, technical scheme of the present invention is: a kind of method of preparing non-ionic starch by initiating irradiation is characterized in that it comprises the steps:
1), will add propylene oxide in the ative starch, the add-on of propylene oxide is 2%～100% of an ative starch quality, stir, mixture;
2), mixture is placed
60Carry out irradiation in the Co irradiation field, under aerobic conditions, initiation reaction, by the control irradiation time irradiation dose is controlled, (different irradiation sources is different according to the different irradiation times of irradiatometer dose rate to make irradiation dose be controlled at 3KGy～15KGy, satisfying total irradiation dose gets final product), make blend;
3), the blend that obtains behind the irradiation is carried out aftertreatment processing: blend is placed the baking oven drying of 130～150 ℃ or 180～200 ℃, stir, so that peroxide breakdown, free radical fully reacts, and pulverizes at last, crosses 100 mesh sieves, promptly get non-ionic starch, substitution value is 0.01～0.7.
The add-on of described propylene oxide is 3%～40% of an ative starch quality.
Described ative starch is corn ative starch, wheat ative starch, potato ative starch, cassava ative starch or Ipomoea batatas ative starch etc.
Described ative starch water ratio is 12%～16%.
The invention has the beneficial effects as follows: under the high-energy radiation condition, the epoxy bond in the propylene oxide will be opened, and disconnect to such an extent that form free radical on the epoxy bond; Ative starch with degraded and the oxidation that takes place to a certain degree, and produces free radical on starch molecule under radiation condition.By the control radiation dose, make the starch viscosity after the degraded be stabilized in the required level of product.Adopt aerobic mutual radiation technology, in the irradiation process, a part of etherifying agent combines with starch by free radical reaction, generates starch ethers, and other unreacted etherifying agents (propylene oxide) are reacted in follow-up high-temperature stirring process.Cause the preparation hydroxypropylated starch with respect to the traditional chemical method, because the free radical uniform distribution that irradiation forms, and quantity height very, so can realize the non-ionic starch ether of different degree of substitution as required.Owing to do not relate to chemical reagent such as acid, alkali, and do not need water washing, can accomplish environmentally safe; Has the resource utilization height, advantages such as production technique is simple, low cost product.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
In one 1000 milliliters beaker, add 285 gram corn ative starchs (water ratio is 14%), take by weighing 15 gram propylene oxide liquid and pour in the ative starch, with the abundant blended under agitation thing of glass stick 30 minutes, make the mixture thorough mixing; Then mixture is packed into polyethylene from sealing in the polythene bag, seal; The polythene bag that mixture is housed is placed
60The Co irradiation field (
60CO-gamma-ray irradiation field) carry out irradiation under aerobic conditions, irradiation dose is 5KGy; The taking-up of product behind the irradiation is poured in the sealed vessel, place 140 ℃ constant temperature oven, drying 120 minutes stirs, cooling at normal temperatures then, and crushing screening is crossed 100 mesh sieves, and packing both can make product.Substitution value MS=0.07.
Embodiment 2:
Get method irradiation according to example 1 and prepare blend, change the drying temperature in the aftertreatment complete processing into 200 ℃, the crushing screening packing can make the nonionic starch product of cold water solubles, substitution value MS=0.07.
Embodiment 3:
Get water ratio and be 14% wheat ative starch 291 grams, add 9 gram propylene oxide, stir, mixture; Mixture is placed
60Carry out irradiation in the Co irradiation field, under aerobic conditions, initiation reaction is controlled irradiation dose by the control irradiation time, makes irradiation dose at 4KGy, gets blend; Blend is placed 130 ℃ baking oven drying, stir, so that peroxide breakdown, free radical fully reacts, and pulverizes at last, crosses 100 mesh sieves, promptly gets non-ionic starch, and substitution value is 0.027.
Embodiment 4:
Get water ratio and be 13% potato ative starch 291 grams, add 9 gram propylene oxide, stir, mixture; Mixture is placed
60Carry out irradiation in the Co irradiation field, under aerobic conditions, initiation reaction is controlled irradiation dose by the control irradiation time, makes irradiation dose at 4KGy, gets blend; Blend is placed 130 ℃ baking oven drying, stir, so that peroxide breakdown, free radical fully reacts, and pulverizes at last, crosses 100 mesh sieves, promptly gets non-ionic starch, and substitution value is 0.027.
Embodiment 5:
Get water ratio and be 15% cassava ative starch 180 grams, add 120 gram propylene oxide, stir, mixture; Mixture is placed
60Carry out irradiation in the Co irradiation field, under aerobic conditions, initiation reaction is controlled irradiation dose by the control irradiation time, makes irradiation dose at 10KGy, gets blend; Blend is placed 130 ℃ baking oven drying, stir, so that peroxide breakdown, free radical fully reacts, and pulverizes at last, crosses 100 mesh sieves, promptly gets non-ionic starch, and substitution value is 0.7.
Embodiment 6:
Get water ratio and be 14% Ipomoea batatas ative starch 180 grams, add 120 gram propylene oxide, stir, mixture; Mixture is placed
60Carry out irradiation in the Co irradiation field, under aerobic conditions, initiation reaction is controlled irradiation dose by the control irradiation time, makes irradiation dose at 15KGy, gets blend; Blend is placed 130 ℃ baking oven drying, stir, so that peroxide breakdown, free radical fully reacts, and pulverizes at last, crosses 100 mesh sieves, promptly gets non-ionic starch, and substitution value is 0.68.
The bound value and the interval value of the add-on of propylene oxide of the present invention, and the bound value of irradiation dose and interval value can both realize the present invention, just do not enumerate embodiment one by one at this.
Claims (4)
1. the method for a preparing non-ionic starch by initiating irradiation is characterized in that it comprises the steps:
1), will add propylene oxide in the ative starch, the add-on of propylene oxide is 2%～100% of an ative starch quality, stir, mixture;
2), mixture is placed
60Carry out irradiation in the Co irradiation field, under aerobic conditions, initiation reaction makes irradiation dose be controlled at 3KGy～15KGy, makes blend;
3), the blend that obtains behind the irradiation is carried out aftertreatment processing: blend is placed the baking oven drying of 130～150 ℃ or 180～200 ℃, stir, pulverize at last, cross 100 mesh sieves, promptly get non-ionic starch.
2. the method for a kind of preparing non-ionic starch by initiating irradiation according to claim 1, it is characterized in that: the add-on of described propylene oxide is 3%～40% of an ative starch quality.
3. the method for a kind of preparing non-ionic starch by initiating irradiation according to claim 1, it is characterized in that: described ative starch is corn ative starch, wheat ative starch, potato ative starch, cassava ative starch or Ipomoea batatas ative starch.
4. the method for a kind of preparing non-ionic starch by initiating irradiation according to claim 1, it is characterized in that: described ative starch water ratio is 12%～16%.
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| CNB2006100197496A CN100491401C (en) | 2006-07-28 | 2006-07-28 | Process of preparing non-ionic starch by initiating irradiation |
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| CNB2006100197496A CN100491401C (en) | 2006-07-28 | 2006-07-28 | Process of preparing non-ionic starch by initiating irradiation |
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| CN100491401C true CN100491401C (en) | 2009-05-27 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101177457B (en) * | 2007-10-30 | 2010-10-06 | 广州辐照技术研究开发中心 | Method for preparing dicyandiamide-formaldehyde resin branched starch ether by employing radiation initiation |
| CN110105457A (en) * | 2019-05-29 | 2019-08-09 | 河南省科学院同位素研究所有限责任公司 | A kind of mutual radiation method prepares the method and product of hydroxypropul starch |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1425624A (en) * | 1973-08-10 | 1976-02-18 | Scholten Honig Research Bfv | Chemical modification of starches |
| DE19627259A1 (en) * | 1996-07-08 | 1998-01-15 | Suedstaerke Gmbh | Modification of starch by corpuscular irradiation |
| CN1175587A (en) * | 1997-09-18 | 1998-03-11 | 华南理工大学 | Process for preparing high substitution value hydroxypropyl starch |
| CN1389474A (en) * | 2002-06-25 | 2003-01-08 | 湖北高能材料科技有限公司 | Starch-modifying method |
| WO2003078471A1 (en) * | 2002-03-20 | 2003-09-25 | Tecnotessile Societa Nazionale Di Ricerca Tecnologica R.L. | Free-radical functionalized polysaccharides |
| CN1683417A (en) * | 2005-03-07 | 2005-10-19 | 中国科学院广州化学研究所 | Process for preparing high substituted degree hydroxyalkyl starch |
-
2006
- 2006-07-28 CN CNB2006100197496A patent/CN100491401C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1425624A (en) * | 1973-08-10 | 1976-02-18 | Scholten Honig Research Bfv | Chemical modification of starches |
| DE19627259A1 (en) * | 1996-07-08 | 1998-01-15 | Suedstaerke Gmbh | Modification of starch by corpuscular irradiation |
| CN1175587A (en) * | 1997-09-18 | 1998-03-11 | 华南理工大学 | Process for preparing high substitution value hydroxypropyl starch |
| WO2003078471A1 (en) * | 2002-03-20 | 2003-09-25 | Tecnotessile Societa Nazionale Di Ricerca Tecnologica R.L. | Free-radical functionalized polysaccharides |
| CN1389474A (en) * | 2002-06-25 | 2003-01-08 | 湖北高能材料科技有限公司 | Starch-modifying method |
| CN1683417A (en) * | 2005-03-07 | 2005-10-19 | 中国科学院广州化学研究所 | Process for preparing high substituted degree hydroxyalkyl starch |
Non-Patent Citations (4)
| Title |
|---|
| "利用60Coγ辐射聚合技术研制淀粉型农用高吸水材料". 王庆军.《核技术》，第26卷第4期. 2003 |
| "辐射对淀粉作用的研究概况". 汪树生.《粮油加工与食品机械》，第5期. 2004 |
| "利用60Coγ辐射聚合技术研制淀粉型农用高吸水材料". 王庆军.《核技术》，第26卷第4期. 2003 * |
| "辐射对淀粉作用的研究概况". 汪树生.《粮油加工与食品机械》，第5期. 2004 * |
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Effective date of registration: 20070427 Address after: 430064 No. 8 Yao yuan court, Hongshan District, Hubei, Wuhan Applicant after: Radiation Processing research Inst., Hubei prov. Agricultural Science Academy Co-applicant after: Wuhan University of Science and Technology Co-applicant after: Guangzhou Irradiation Technology Research Development Center, Wuhan Science and Address before: 430064 No. 8 Yao yuan court, Hongshan District, Hubei, Wuhan Applicant before: Radiation Processing research Inst., Hubei prov. Agricultural Science Academy Co-applicant before: Wuhan University of Science and Technology |
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