CN1546530A - Etherified-cross linked-pregelated ternary composite modified starch, its preparing process and application - Google Patents
Etherified-cross linked-pregelated ternary composite modified starch, its preparing process and application Download PDFInfo
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- CN1546530A CN1546530A CNA2003101126846A CN200310112684A CN1546530A CN 1546530 A CN1546530 A CN 1546530A CN A2003101126846 A CNA2003101126846 A CN A2003101126846A CN 200310112684 A CN200310112684 A CN 200310112684A CN 1546530 A CN1546530 A CN 1546530A
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Abstract
The invention discloses an etherified - cross bond - pregelatinized ternary composite modified starch, its preparing process and application, wherein the product is prepared through the simultaneous process of etherification, cross bonding and pre-gelatinization denaturization to the starch, the product can be used for thickening and stabilizing the high acid, high salt and frozen food in food-processing industry, and also as the sizing agent in paper making and textile industry.
Description
Technical field
A kind of etherificate-crosslinked-pre-gelatinization ternary compound modified starch and its production and application belongs to the starch denaturalization technical field.
Background technology
At home, systematically to the history of the existing recent two decades of modified starch development research, the denaturation method that starch adopts also mostly is single sex change or two sex change greatly.By literature search, have the bibliographical information of binary sex change is carried out in the pre-gelatinization of starch, etherificate, crosslinked combination in twos, but do not see the domestic and foreign literature report that starch etherificate, three kinds of denaturation methods of crosslinked, pre-gelatinization are organically combined.
Summary of the invention
The object of the present invention is to provide a kind of etherificate-crosslinked-pre-gelatinization ternary compound modified starch and its production and application.By adding a certain proportion of chemical reagent, crosslinked with starch molecule formation ester bond, thereby obtain cross-linking starch, this cross-linking starch has improved the performance of starch greatly, carries out etherificate simultaneously and introduces the hydroxypropyl group, so that reach requirements such as thickening stabilities in the foodstuffs industry, acidproof, salt tolerant, freeze-thaw-, carry out pre-gelatinization on this basis, it is big to make that modified starch has viscosity again, visco-elasticity height, rapid characteristics such as dissolving in cold water.Etherificate, three kinds of denaturation methods of crosslinked, pre-gelatinization are combined, thus characteristics such as antiacid, the anti-salt of raising starch, freeze-thaw-, cold water Yi Rong, and this product can be used as the thickening stabilizer of peracid, high salt, frozen product.
Technical scheme of the present invention: a kind of etherificate-crosslinked-pre-gelatinization ternary compound modified starch, it is to have used starch is carried out the preparation method of etherificate, crosslinked, pre-gelatinization sex change simultaneously and makes, and makes it have the characteristic of etherification starch, cross-linking starch, pre-gelatinized starch simultaneously.
The preparation method of described etherificate-crosslinked-pre-gelatinization ternary compound modified starch, be to be that raw material, Jia Shui are deployed into the starch milk that massfraction is about 40% (W/W) with starch, add catalyzer, expansion inhibitor, drip etherifying agent and carry out etherification reaction, neutralization, drip linking agent, or after neutralizing, washing, drip linking agent again and carry out crosslinking reaction, after neutralization, the washing, adopt cylinder technology to carry out pre-gelatinization, make etherificate-crosslinked-pre-gelatinization ternary compound modified starch.
Starch material can be waxy corn starch, conventional corn starch, wheat starch, potato starch etc.
The used catalyzer of etherificate sex change is sodium hydroxide or yellow soda ash; The expansion inhibitor is sodium sulfate or sodium-chlor; Etherifying agent is a propylene oxide.
The used linking agent of crosslinked sex change can be hexanodioic acid and acetic anhydride (ratio is 1: 45~1: 15), three inclined to one side (or trimerization) sodium phosphates, phosphorus oxychloride etc.
Pre-gelatinization sex change can be adopted technologies such as spray method, extruding puffing method and roller drying.
Preparation technology's basic recipe (W/W) is:
Starch 100
Water 100-150
Catalyzer 0.5-3.0
Expansion inhibitor 5-25
Etherifying agent 3-25
Linking agent 0.01-5
The principal reaction processing condition are: etherifying agent, linking agent adopt the method that drips, and the reaction conditions pH value of etherification reaction is 8-12, and temperature of reaction is 30-50 ℃, reaction times is 8-24h, the reaction conditions pH value of crosslinking reaction is 7.5-12, and temperature of reaction 25-50 ℃, the reaction times is 0.5-5h.Dropping and reaction are all under agitation carried out, and reactant must be through the pre-again gelatinization of water washing, and pre-gelatinization condition is 110 ℃~150 ℃, and the time is 2~8min, gets product.
The application of described ternary compound modified starch is mainly used in the thickening stabilizer in the foodstuffs industry, also can be used for the sizing agent of industry such as papermaking, weaving.
Beneficial effect of the present invention: the present invention is directed to the requirement of peracid, high salt and frozen product to modified starch performance singularity, the modified starch novel process and the product of targeted exploitation, etherificate, three kinds of denaturation methods of crosslinked, pre-gelatinization are combined the practicality of technological design science.Product performance are better than widely used modified starch kind in peracid in the present foodstuffs industry, high salt and the frozen product, can partly substitute the higher pectin of present domestic price, xanthan gum etc., and are easy to utilize.
Table 1: the comparison of the compound wax modified corn starch of ternary freeze-thaw stability
Sample | Bleed rate % | |||
Freeze-thaw number of times/number of times | ||||
????1 | ????2 | ????3 | ????4 | |
The crosslinked waxy corn starch of the crosslinked waxy corn starch hydroxypropyl of waxy corn ative starch waxy corn starch hydroxypropyl | ????9.9 ????6.7 ? ????0.0 ????0.0 | ????30.7 ????8.3 ? ????0.0 ????0.0 | ????53.8 ????20.5 ? ????5.2 ????0.0 | ????56.2 ????30.6 ? ????23.9 ????0.0 |
Table 2:1% salt brine solution is to the influence of starch paste character
Sample | One-tenth paste temperature/℃ | Maximum viscosity temperature/℃ | High viscosity/BU | Viscosity/BU in the time of 95 ℃ | 95 ℃ keep the viscosity/BU behind the 30min | Viscosity BU in the time of 50 ℃ | 50 ℃ keep the viscosity/BU behind 30 min | Drop value/BU | Denseness/BU | |
?WS | ?0%NaCl | ?71.4 | ?78.3 | ?244 | ?110 | ?70 | ?116 | ?108 | ?174 | ?43 |
?1%NaCl | ?76.0 | ?82.5 | ?231 | ?114 | ?67 | ?108 | ?104 | ?164 | ?41 | |
?DWS | ?0%NaCl | ?69.7 | ?75.8 | ?256 | ?226 | ?227 | ?317 | ?281 | ?29 | ?90 |
?1%NaCl | ?74.9 | ?80.5 | ?246 | ?229 | ?224 | ?336 | ?295 | ?22 | ?112 | |
?HPWS | ?0%NaCl | ?60.0 | ?64.9 | ?298 | ?126 | ?88 | ?151 | ?127 | ?210 | ?63 |
?1%NaCl | ?64.9 | ?70.6 | ?275 | ?125 | ?87 | ?153 | ?126 | ?188 | ?66 | |
?HPDWS | ?0%NaCl | ?51.4 | ?58.9 | ?382 | ?232 | ?244 | ?364 | ?343 | ?138 | ?120 |
?1%NaCl | ?57.9 | ?65.1 | ?330 | ?225 | ?222 | ?351 | ?340 | ?110 | ?129 |
Annotate: the crosslinked waxy corn starch of WS-waxy corn ative starch DWS-
The crosslinked waxy corn starch of HPWS-hydroxypropyl waxy corn starch HPDWS-hydroxypropyl
The starch milk massfraction is 6%
Description of drawings
Accompanying drawing is etherificate-crosslinked-pre-gelatinization ternary compound modified starch preparation technology synoptic diagram
Embodiment
Embodiment 1:
800g starch is added water size mixing into the starch milk that massfraction is 40% (butt), the by specification said ratio, add catalyzer and expansion inhibitor, the propylene oxide that adds 64g then, temperature is controlled at 45-50 ℃ in airtight container, pH10.5-12.0, reaction 8-24h, neutralization, washing sizes mixing 40%, and temperature is controlled at 25-30 ℃, regulate pH7.5-9.0 with 3% hydrochloric acid soln, drip hexanodioic acid and acetic anhydride mixed solution 36g while stirring, the dropping time is 0.5-4h, neutralization, washing, the pre-gelatinization of cylinder on 40% of sizing mixing, 110 ℃~150 ℃ of temperature, the time is 2~8min, gets product.
Claims (9)
1, a kind of etherificate-crosslinked-pre-gelatinization ternary compound modified starch is characterized in that having used the preparation method who starch is carried out simultaneously etherificate, crosslinked, pre-gelatinization sex change, makes it have the characteristic of etherification starch, cross-linking starch and pre-gelatinized starch simultaneously.
2, a kind of preparation method of ternary compound modified starch as claimed in claim 1, it is characterized in that with starch being raw material, add water and be deployed into 40%, W/W, starch emulsion, add catalyzer, expansion inhibitor, drip etherifying agent and carry out etherification reaction, neutralization drips linking agent, or after the neutralization washing, drip linking agent again, neutralization, washing, the pre-gelatinization of last cylinder is prepared from.
3, preparation method according to claim 2 is characterized in that with waxy corn starch, conventional corn starch, wheat starch, potato starch be starch material.
4, preparation method according to claim 2 is characterized in that the etherifying agent that the etherificate sex change is used is propylene oxide, and the catalyzer that uses is sodium hydroxide or yellow soda ash, and the expansion inhibitor that uses is sodium-chlor or sodium sulfate.
5, preparation method according to claim 2 is characterized in that the employed linking agent of crosslinked sex change is the mixed solvent of hexanodioic acid and acetic anhydride, and ratio is 1: 45~1: 15, or phosphorus oxychloride or Trisodium trimetaphosphate.
6, preparation method according to claim 2 is characterized in that basic recipe, W/W, for:
Starch 100
Water 100-150
Catalyzer 0.5-3.0
Expansion inhibitor 5-25
Etherifying agent 3-25
Linking agent 0.01~5
7, preparation method according to claim 2 is characterized in that the reaction conditions pH value of etherification reaction is 8-12, and temperature of reaction is 30-50 ℃, and the reaction times is 8-24h; The reaction conditions pH value of crosslinking reaction is 7.5-12.0, and temperature of reaction 25-50 ℃, the reaction times is 0.5-5h; Reinforced and reaction is all under agitation carried out.
8, preparation method according to claim 2 is characterized in that the operable technology of pre-gelatinization sex change is roller drying, and temperature is 110 ℃~150 ℃, and the time is 2~8min.
9, a kind of application of ternary compound modified starch as claimed in claim 1 is characterized in that as thickening stabilizer, and the peracid in the thick stabilization foodstuffs industry, high salt and frozen product also can be used for the sizing agent of papermaking, textile industry.
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CN1293159C (en) * | 2005-05-18 | 2007-01-03 | 江南大学 | Method for preparing starch glue for lumber |
CN102030832A (en) * | 2010-12-10 | 2011-04-27 | 浙江大学 | Method for preparing compound modified starch for replacing gelatin |
CN103030698A (en) * | 2013-01-14 | 2013-04-10 | 郝庆阳 | Compound modified starch prepared by four modification methods |
CN105694898A (en) * | 2016-03-21 | 2016-06-22 | 河南恒瑞淀粉科技股份有限公司 | Modified starch composition for soil water retention and preparation method thereof |
CN105968218A (en) * | 2016-06-30 | 2016-09-28 | 陈灼 | Preparation method of modified starch |
CN106008728A (en) * | 2016-06-30 | 2016-10-12 | 陈灼 | Preparing method for modified starch |
CN106608919A (en) * | 2015-10-23 | 2017-05-03 | 金东纸业(江苏)股份有限公司 | Preparation method of cationic starch |
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CN111196860A (en) * | 2020-04-02 | 2020-05-26 | 河南恒瑞淀粉科技股份有限公司 | Double-etherification cross-linking modified starch for water shutoff profile control agent, preparation method thereof and water shutoff profile control agent |
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CN1293159C (en) * | 2005-05-18 | 2007-01-03 | 江南大学 | Method for preparing starch glue for lumber |
CN102030832A (en) * | 2010-12-10 | 2011-04-27 | 浙江大学 | Method for preparing compound modified starch for replacing gelatin |
CN102030832B (en) * | 2010-12-10 | 2012-06-27 | 浙江大学 | Method for preparing compound modified starch for replacing gelatin |
CN103030698A (en) * | 2013-01-14 | 2013-04-10 | 郝庆阳 | Compound modified starch prepared by four modification methods |
CN103030698B (en) * | 2013-01-14 | 2015-10-07 | 郝庆阳 | By composite modified starch prepared by four kinds of denaturation methods |
CN106608919A (en) * | 2015-10-23 | 2017-05-03 | 金东纸业(江苏)股份有限公司 | Preparation method of cationic starch |
CN106983866A (en) * | 2016-01-20 | 2017-07-28 | 甘肃圣大方舟马铃薯变性淀粉有限公司 | A kind of converted starch plant capsule and preparation method thereof |
CN106983866B (en) * | 2016-01-20 | 2020-10-27 | 甘肃中发方舟变性淀粉有限公司 | Modified starch plant capsule and preparation method thereof |
CN105694898A (en) * | 2016-03-21 | 2016-06-22 | 河南恒瑞淀粉科技股份有限公司 | Modified starch composition for soil water retention and preparation method thereof |
CN106008728A (en) * | 2016-06-30 | 2016-10-12 | 陈灼 | Preparing method for modified starch |
CN105968218A (en) * | 2016-06-30 | 2016-09-28 | 陈灼 | Preparation method of modified starch |
CN107163153A (en) * | 2017-06-06 | 2017-09-15 | 佛山市南海华昊华丰淀粉有限公司 | A kind of roller drying preparation method of carboxymethyl starch with high substitution degree |
CN110386990A (en) * | 2019-07-30 | 2019-10-29 | 诸城兴贸玉米开发有限公司 | A kind of production method and its sauce of seasoning sauce material converted starch |
CN111196860A (en) * | 2020-04-02 | 2020-05-26 | 河南恒瑞淀粉科技股份有限公司 | Double-etherification cross-linking modified starch for water shutoff profile control agent, preparation method thereof and water shutoff profile control agent |
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