CN1194272A - Process of producing cold soluble particular cationic starch by predextrination - Google Patents

Process of producing cold soluble particular cationic starch by predextrination Download PDF

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Publication number
CN1194272A
CN1194272A CN 98113172 CN98113172A CN1194272A CN 1194272 A CN1194272 A CN 1194272A CN 98113172 CN98113172 CN 98113172 CN 98113172 A CN98113172 A CN 98113172A CN 1194272 A CN1194272 A CN 1194272A
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Prior art keywords
starch
etherifying agent
cationic
parts
reaction
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CN 98113172
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CN1079098C (en
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宋荣钊
曾梅珍
潘松汉
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Guangzhou Chemical Co Ltd of CAS
Guangzhou Institute of Chemistry of CAS
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Guangzhou Institute of Chemistry of CAS
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Abstract

The present invention provides one-step predextrination process of preparing cold soluble particular cationic starch. While predextrination of starch material, cationic etherifying agent and dexstrinated starch produce homogeneous reaction with the reaction rate of reagent being raised to over 95%. The said simple method can produce granular powder product capable of being gelatinated in cold water at low cost.

Description

The method of producing cold soluble particular cationic starch by predextrination
The invention belongs to the chemical modification of starch method.
Cationic starch can be used as purposes such as flocculation agent, paper making intensifier and retention aid, sewage-treating agent, tackiness agent.In the prior art about the manufacture method of particular cationic starch, be earlier with starch by the cationization reaction after, more after filtration, washing, drying and other steps make the particular cationic dry starch.In use again with the dry powder redispersion in water, can use after become sticking with paste through boiling.This just makes that step is various and complicated in production and application process, and cost also increases, (U.S3778431, WP92-109316, WP87-006870) report.File is also arranged, and (U.S3770472 U.S5604085) be reported in the use scene and prepare gluey water-dispersion build cationic starch paste on the spot, but this can only now do existing usefulness, and all there are very big difficulty in packing, transportation, storage, therefore are difficult to commercialization.
The present invention is to provide a kind of method that adopts pre-gelatinization prepared particular cationic starch, can overcome the deficiency that exists in the above-mentioned prior art, a step is finished the cationization reaction.This method reacts raw starch and positively charged ion donor with alkali as a catalyst.The both available synthetics cationic etherifying agent of positively charged ion donor, also available cationoid reagent and the monomeric blend of bridge agent.The cationic etherifying agent that is suitable for has four classes: alkyl aminoethyl muriate; 2,3-epoxypropyl trialkyl ammonium salts; 4-chloro-crotyl alkylammonium salt; Alkyl ammonia nitrile compound.The cationic reagent that is suitable for is: Trimethylamine 99, triethylamine, dimethylamine, diethylamine, amino piperazine, pyridine alkane etc.; The multi-functional bridging agent that is suitable for is: both had a functional group and combined with cationoid reagent, have again a functional group under base catalysis can with the hydroxyl reaction of starch, bridging agent can be wire, ring-type, heterocycle shape, aromatic series etc.
The characteristics of this method are to make pasted starch and cationic etherifying agent be equal phase reaction by pre-gelatinization technology, 80~170 ℃ of temperature of reaction, and in 1~10 minute reaction times, resultant need not filter and be dry, and its basic recipe comprises:
100 parts of starch
Tap water 100-2000 part
Solid alkali 1-10 part
Etherifying agent 3-16 part
Reaction method is that starch is starched with tap water furnishing powder earlier, and dripping alkali liquid and etherifying agent remain between the PH9-11 farinaceous size again, then the powder slurry is flowed in the rotary dryer, makes the reaction of pasted starch and etherifying agent.Also can directly in starch slurry, add cationoid reagent and bridging agent, add alkali lye again and transfer PH=9-11, flow in the rotary dryer again after stirring and react.For avoiding the bridging agent cross-linking starch, in the prescription if with ative starch then powder slurry concentration should be lower than 5%; Powder slurry concentration as if then being made into degraded starch about 30% is no more than 5 minutes with the reaction time, can prevent or reduce cross-linking of starch like this.
Method provided by the present invention can make the reactivity of etherifying agent bring up to more than 95%, and technology is easy, and a step is finished cationization reaction, and product is that particulate state dry powder again can easily gelation in cold water, and is easy to use.
The present invention and original processing method be at material consumption, the contrast of aspects such as reaction conditions and product performance such as following table:
The contrast project Original processing method The inventive method
Dry method Wet method Preparation method on the spot
The anti-paste of starch cation donor (etherifying agent) catalyst (caustic soda) (salt) reaction temperature reaction time substitution value (D.S) 6% solution viscosity (mpa.s) etherifying agent reactivity (%) face shaping becomes formulating method 2% aqueous stability 40-110 ℃ of 1-6 hour 0.01-0.04 600-6000 40-60 white powder heating of 100 parts of 3-16 part 1-10 parts gelatinization is more than 24 hours 40-55 ℃ of 3-12 hour 0.01-0.04 600-6000 70-80 white powder heating of 100 parts of 3-16 part 1-10 part 2-20 parts gelatinization 24 hours But the gelatinization of 80-160 ℃ of 5 minutes-2 hours 0.01-0.05 600-6000 80-90 paste shape cold water of 100 parts of 3-16 part 1-10 parts is more than 48 hours But 80-170 ℃ of 1-10 minute 0.01-0.05 600-6000 of 100 parts of 3-16 part 1-10 parts 95 above white powder cold water gelatinizations are more than 48 hours
Embodiment 1:
This example is to be raw material with fresh cassava starch, and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (forming 2 under the alkali effect, 3-epoxypropyl trimethylammonium chloride ammonium salt) is an etherifying agent, and sodium hydroxide is catalyzer, and material proportion is:
High-quality tapioca (flour): 100 parts
Tap water: 150 parts
Industrial solid caustic soda: 1.58 parts
Etherifying agent (concentration 65%): 8 parts
Water is the starch pulping, under agitation stream adds alkali lye (about concentration 3%) and stirs well even back and add etherifying agent liquid, and transfer PH=9~11 with alkali, slurries are flowed in the rotary drum rolling dryer, 80~160 ℃ of following gelatinization reactions 3~10 minutes, the powder slurry is dried to sheet by roll extrusion, and scraper scrapes, and pulverizes, sieves, packs.The product white granular, 6% solution viscosity η>10000mpa.s, substitution value D.S>0.05, the liquid homogeneous transparent is stuck with paste in easily gelation in cold water, and 2% to stick with paste liquid 4 days not stratified.Embodiment 2:
This example replaces 8 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chlorides (concentration 65%) in the example 1 with 10 parts of 4-chloro-crotyl trimethyl ammonium chlorides (concentration 65%), and solid alkali is with 1.78 parts, and other are with example 1.Product performance are close with example 1.Embodiment 3:
This example replaces 8 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chlorides (concentration 65%) in the example 1 with 9 parts of diethylamino diethylaluminum monochlorides (concentration 65%), and solid alkali is with 1.6 parts, and other are with example 1.The product white granular, 6% solution viscosity η>10000mpa.s, substitution value D.S>0.05, the liquid homogeneous transparent is stuck with paste in the easy gelation of cold water, and 2% sticks with paste liquid stability height, and 48 hours are not stratified.Embodiment 4:
This example replaces 8 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chlorides (concentration 65%) in the example 1 with 10 parts of diethylamino nitrile compounds (concentration is transferred to 65%), and solid alkali is with 1.8 parts, and other are with example 1.Product performance are close with example 1.Embodiment 5:
This example is to be raw material and epoxy chloropropane, Trimethylamine 99 reaction with acid degradation starch, and single stage method prepares cationic starch.With 200 parts of tap water+2.1 part NaOH+100 part acidified starch+7.7 parts of epoxy chloropropane (90% concentration)+13.4 parts of trimethylamine aqueous solutions (30% concentration), transfer PH=10~11 behind the mixing, solid content is 30% powder slurry.These slurries are flowed in the rotary drum rolling dryer, and 120~160 ℃ of following gelatinization reactions 1~5 minute, the powder slurry was dried to laminar by roll extrusion, and scraper scrapes, crushing screening, packing.The product white granular, 6% solution viscosity η=1000~6000mpa.s, substitution value D.S>0.015, the easy adhesive pasteization of cold water is stuck with paste the liquid homogeneous transparent, and 2% to stick with paste liquid 2 days not stratified.Embodiment 6:
This example is raw material and 1 with the cassava ative starch, and 4-dichlorobutylene, diethylamine reaction single stage method prepare cationic starch.With 2000 parts of tap water+3.7 part NaOH+100 part cassava ative starch+11 part 1,4-dichlorobutylene+6.33 part diethylamine, PH=10~11 are transferred in the even back that is mixed, and solid content is 4.7%, and other technologies are with example 5.Product performance are close with example 5.Embodiment 7:
This example is that raw material and 1,2 ethylene dichloride, triethylamine reaction single stage method prepare cationic starch with viscous maize starch.With 2000 parts of tap water+8 part NaOH+100 part starch+8.33 part of 1,2 ethylene dichloride+8.7 part triethylamine, PH=10~11 are transferred in the even back that is mixed, and solid content is 4.7%, and other technologies are with example 5.Product performance and example 5 are close.

Claims (3)

1. method of giving gelatinization manufactured cold cut cationic starch, this method is with alkali as a catalyst, raw starch and the reaction of positively charged ion donor, it is characterized in that making pasted starch and cationic etherifying agent be homogeneous reaction by giving gelatinization technology, 80~170 ℃ of temperature, in 7~10 minutes reaction times, resultant need not filter and be dry, and basic recipe comprises:
100 parts of starch
Tap water 100-2000 part
Solid alkali 1-10 part
Etherifying agent 3-16 part.
2. according to the method described in the claim 1, it is characterized in that the type of cationic etherifying agent is: alkyl aminoethyl muriate; 2,3-epoxypropyl trialkyl ammonium salts; 4-chloro-crotyl alkylammonium salt; Alkyl ammonia nitrile compound.
3. according to the method described in the claim 1, it is characterized in that the positively charged ion donor can be that cationic etherifying agent also can be the monomeric blend of cationics and bridging agent.
CN98113172A 1998-04-13 1998-04-13 Process of producing cold soluble particular cationic starch by predextrination Expired - Fee Related CN1079098C (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628944B (en) * 2009-07-15 2011-05-18 聚祥(厦门)淀粉有限公司 Complex modified starch
CN101190950B (en) * 2006-11-19 2011-06-22 江门市科恒实业股份有限公司 Modified starch containing ester group chain substituent group and preparation method thereof
CN102532328A (en) * 2011-12-14 2012-07-04 金东纸业(江苏)股份有限公司 Starch pigment and preparation method thereof as well as coating and coated paper using the starch pigment
CN103717538A (en) * 2011-07-22 2014-04-09 罗盖特公司 Potabilisation method
CN104774274A (en) * 2015-04-13 2015-07-15 江南大学 Method for preparing cationic starch slurry
CN106220745A (en) * 2016-08-29 2016-12-14 上海东升新材料有限公司 The preparation method of a kind of cationic starch solution and related application
CN106220746A (en) * 2016-08-29 2016-12-14 上海东升新材料有限公司 A kind of preparation method and applications of solution-type cationic starch
CN106243233A (en) * 2016-08-29 2016-12-21 上海东升新材料有限公司 The preparation method of a kind of cold water solubles cationic starch and related application
CN107585841A (en) * 2017-09-27 2018-01-16 山东神州翔宇科技集团有限公司 A kind of preparation method of modified starch flocculant
CN115806424A (en) * 2022-03-16 2023-03-17 安徽海雪新材料科技有限公司 Low-starch paper-surface gypsum board

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US2876217A (en) * 1956-12-31 1959-03-03 Corn Products Co Starch ethers containing nitrogen and process for making the same
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JPS6011921B2 (en) * 1978-02-06 1985-03-29 ライオン株式会社 Method for producing cationically modified starch derivatives
DE2949886A1 (en) * 1979-12-12 1981-06-19 Degussa Ag, 6000 Frankfurt METHOD FOR THE PRODUCTION OF CATIONIC STARCH KEEPERS
US4281109A (en) * 1980-03-03 1981-07-28 National Starch And Chemical Corporation Pollution-free cationization of starch
JPS60502211A (en) * 1984-08-02 1985-12-19 ザ ダウ ケミカル カンパニ− Method for producing cationic starch
DE3604796A1 (en) * 1986-02-15 1987-08-20 Degussa METHOD FOR DRYING THE STARCH
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CN1043135A (en) * 1989-10-13 1990-06-20 茹国军 The production method of highgrade cationic starch

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101190950B (en) * 2006-11-19 2011-06-22 江门市科恒实业股份有限公司 Modified starch containing ester group chain substituent group and preparation method thereof
CN101628944B (en) * 2009-07-15 2011-05-18 聚祥(厦门)淀粉有限公司 Complex modified starch
CN103717538B (en) * 2011-07-22 2016-04-20 罗盖特公司 Potabilisation method
CN103717538A (en) * 2011-07-22 2014-04-09 罗盖特公司 Potabilisation method
CN102532328B (en) * 2011-12-14 2015-11-25 金东纸业(江苏)股份有限公司 Starch Based Pigments and preparation method thereof, applies coating and the White Board of this Starch Based Pigments
CN102532328A (en) * 2011-12-14 2012-07-04 金东纸业(江苏)股份有限公司 Starch pigment and preparation method thereof as well as coating and coated paper using the starch pigment
CN104774274A (en) * 2015-04-13 2015-07-15 江南大学 Method for preparing cationic starch slurry
CN106220745A (en) * 2016-08-29 2016-12-14 上海东升新材料有限公司 The preparation method of a kind of cationic starch solution and related application
CN106220746A (en) * 2016-08-29 2016-12-14 上海东升新材料有限公司 A kind of preparation method and applications of solution-type cationic starch
CN106243233A (en) * 2016-08-29 2016-12-21 上海东升新材料有限公司 The preparation method of a kind of cold water solubles cationic starch and related application
CN107585841A (en) * 2017-09-27 2018-01-16 山东神州翔宇科技集团有限公司 A kind of preparation method of modified starch flocculant
CN107585841B (en) * 2017-09-27 2020-06-26 山东神州翔宇科技集团股份有限公司 Preparation method of modified starch flocculant
CN115806424A (en) * 2022-03-16 2023-03-17 安徽海雪新材料科技有限公司 Low-starch paper-surface gypsum board
CN115806424B (en) * 2022-03-16 2023-12-12 安徽海雪新材料科技有限公司 Low-starch paper gypsum board

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