CN105693872B - A kind of preparation method of salt-resistance carboxymethyl starch - Google Patents
A kind of preparation method of salt-resistance carboxymethyl starch Download PDFInfo
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- CN105693872B CN105693872B CN201610204177.2A CN201610204177A CN105693872B CN 105693872 B CN105693872 B CN 105693872B CN 201610204177 A CN201610204177 A CN 201610204177A CN 105693872 B CN105693872 B CN 105693872B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
- C08B31/006—Crosslinking of derivatives of starch
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Abstract
The present invention relates to a kind of preparation methods of salt-resistance carboxymethyl starch.It is to be denaturalized the multistep of tapioca using ethyl alcohol and isopropyl alcohol mixed solvent as reaction medium and carry out in the slurry using mixed solvent as medium.Starch swelling is first specially prepared into starch milk, is added after surfactant and the denaturation such as is alkalized, is etherified using " method before acid ", add crosslinking agent and carry out micro- cross-linking reaction.Surfactant is added into starch milk system as bleeding agent for the method for the present invention, promotes reagent molecule infiltration, diffuses to inside starch granules, improves alkalization, etherificate efficiency；Using the generation for first adding etherifying agent that basifier is added to can be reduced side reaction again, so that alkalizing, being etherified while carrying out, guarantee that etherification reaction is more thorough；Micro- be crosslinked with finally is carried out to starch to be conducive to improve its structural viscosity, enhances salt tolerance；Product of the present invention viscosity 4% reaches 40000 or more, and degree of substitution reaches 1.0 or more, and salt is viscous than can replace CMC applied to many technical fields 0.5 or more.
Description
Technical field
The invention belongs to natural macromolecular material field of chemical modification, and in particular to one kind is adopted using tapioca as raw material
The method for carrying out polynary denaturation preparation salt-resistance carboxymethyl starch with slurry process.
Background technique
Carboxymethyl starch is that shallow lake prepared by bimolecular nucleophilic subsititution occurs under alkaline condition for starch and monoxone
Powder derivative, is commonly called as CMS.It is a kind of white or micro-yellow powder, tasteless nontoxic, and the colloid for being dissolved in water energy formation stiff is molten
Liquid has good thickening property, caking property, dispersibility, emulsibility, water-retaining property, film forming etc..Its structure and performance and carboxymethyl
Cellulose is similar, can many occasions replace carboxymethyl cellulose and be applied to food, medicine, daily use chemicals, weaving, papermaking, petroleum,
The technical fields such as agricultural production.And with the continuous expansion of application field, it is desirable that degree of substitution is high, replace more evenly, salt-resistance
Good carboxymethyl starch has become the main trend of domestic and international market.Develop good salt tolerance, the more superior CMS of performance also increasingly
Concern by domestic and international researcher.
The synthetic method of CMS has dry method, water-borne method and solvent method.These methods respectively have advantage and disadvantage: dry method be starch and
Reagent is reacted in solid phase, and uneven heating is even, unstable, and the reagents such as sodium hydroxide, monoxone are difficult to penetrate into starch
Inside particle, therefore product degree of substitution is not high, and transparency and salt tolerance are bad, is easily layered, and goes bad；Water-borne method be easy to cause starch
Gelatinization, and the utilization rate of etherifying agent is low, cannot generally produce the product that degree of substitution is greater than 0.1；Traditional solvent is usually with methanol
Or ethanol as solvent carries out single carboxy methylation to starch and is denaturalized, which improves carboxylic using the aq slurry process of high bath raio
Methylation reaction efficiency, product degree of substitution is relatively high, but product degree of substitution unstable, the salt tolerance that reaches a certain level rear viscosity
And acid resistance is not good enough yet.And traditional solvent consumes a large amount of organic solvents, production cost is higher.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of traditional solvent, a kind of preparation side of salt-resistance carboxymethyl starch is provided
Method, the present invention is using ethyl alcohol and isopropanol as solvent, by multi-sections reactions of degeneration (RD) such as starch alkalization, etherificate, micro- crosslinkings in same slurry
Middle progress, easy to operate, preparation cost is lower.
To achieve the above object, the present invention provides a kind of preparation methods of salt-resistance carboxymethyl starch, including following step
It is rapid:
In the mixed solvent is dispersed according to starch and mixed solvent mass ratio 1:1 by tapioca, continuously stirs 30 points
Clock is to slowly warm up to 50 DEG C, is swollen it sufficiently, forms starch milk.
ToMiddle addition surfactant, 40-50 DEG C reaction 0.5-1 hours.
ToIn add etherifying agent solid powdery sodium chloroacetate, be then continuously added to basifier NaOH, 60 DEG C of reactions
3 hours.
50 DEG C are cooled to, crosslinking agent is added, is reacted 1-2 hours.
Cooling is adjusted to neutrality with the hydrochloric acid that concentration of volume percent is 30%, is centrifugated, then dense with mass percent
Degree is washed for 88% ethanol solution by ethanol solution and starch quality=10:1, and centrifuge separation, drying smash up to salt-resistance carboxylic
Methyl starch.
A kind of preparation method of salt-resistance carboxymethyl starch: the stepMiddle mixed solvent is that ethyl alcohol and isopropanol press 7-
The solvent that the mass percent concentration that 12:1 is made into is 92% or more.
: the stepIn surfactant be nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether, poly alkyl alcohol
One of ethylene oxide ether, aliphatic amine polyoxyethylene ether are several.
The stepIn surfactant additional amount be starch quality 1-5%.
The stepMiddle sodium chloroacetate need to be uniformly added into 0.5 hour, and temperature is no more than 40 when chlorination sodium acetate
℃。
The stepIn added crosslinking agent be epoxychloropropane, dichloropropane, sodium trimetaphosphate, one in phosphorus oxychloride
Kind, additional amount is the 0.01%-0.2% of starch quality
Compared with prior art, the invention has the following advantages:
1-5% surfactant is added in preparation process of the present invention as bleeding agent, promotes reagent molecule infiltration, diffuse to
Inside starch granules, alkalization, etherificate efficiency are improved；Using first plus etherifying agent adds basifier to can be reduced the generation of side reaction again,
So that alkalizing, being etherified while carrying out, it is ensured that etherification reaction is more thorough, ensure that homogeneity and stabilization that carboxymethyl starch replaces
Property；The crosslinking agent that 0.01%-0.2% is added carries out micro- crosslinking to starch milk, can effectively improve the structural viscosity of product, to a certain degree
The upper transparency and potential resistance to electrolyte contamination ability for improving CMS paste liquid.
Preparation process of the present invention, easy to operate, production cost is low.Product viscosity 4% reaches 40000 or more, and degree of substitution reaches
1.0 or more, salt is viscous than 0.5 or more, product is uniformly dissolved quickly, and paste liquid is transparent, good salt tolerance, and quality is stablized, and class is high, can
To replace CMC to be applied to the technical fields such as weaving, printing and dyeing, papermaking, petroleum drilling and mining, agricultural production.
Specific embodiment
Below by specific example, the invention will be further described
Embodiment one
By 460kg mass percent concentration be 93% ethyl alcohol and 40kg isopropanol be pumped into 3m3 jacketed stainless steel
In reaction kettle, tapioca 500kg is then added in the state of continuously stirring, is to slowly warm up to 50 DEG C, keeps the temperature 0.5 hour,
Making it, sufficiently swelling prepares starch milk.
ToIn add the nonylphenol polyoxyethylene ether of 1kg, open recirculated cooling water and be cooled to 45 DEG C, reaction 0.5 is small
When.
Sodium chloroacetate is uniformly added into 0.5 hourIn reaction kettle in, add during keep starch system
Temperature hereinafter, then uniformly add 160kg piece alkali, adds piece alkali at 40 DEG C, and 60 DEG C are reacted 3 hours.
50 DEG C are cooled to, epoxychloropropane 600ml is added, covers reaction kettle lid immediately, is reacted 2 hours.
It will40 DEG C are cooled to hereinafter, being adjusted to neutrality, centrifugal dehydration with the hydrochloric acid that concentration of volume percent is 30%；Again
It is washed with the ethanol solution 5000kg that mass percent concentration is 88%, is centrifugated, dries, smashing up to product.
The above product is through detecting, primary quality measure: DS=1.06；4%(over dry product) solution viscosity 46000cps(NDJ-
1 viscosimeter, 25 DEG C, No. 4 rotors, 6rpm)；Salt sticks ratio 0.54.
Embodiment two
By 440kg mass percent concentration be 92% ethyl alcohol and 60kg isopropanol be pumped into 3m3 jacketed stainless steel
In reaction kettle, tapioca 500kg is then added in the state of continuously stirring, is to slowly warm up to 50 DEG C, keeps the temperature 0.5 hour,
Making it, sufficiently swelling prepares starch milk.
ToIn add the nonylphenol polyoxyethylene ether of 1.5kg, 50 DEG C are reacted 0.5 hour.
Sodium chloroacetate is uniformly added into 0.5 hourIn reaction kettle in, while opening cooling water, added
It keeps starch system temperature at 40 DEG C hereinafter, then uniformly add 160kg piece alkali in journey, adds piece alkali, 60 DEG C are reacted 3 hours.
50 DEG C are cooled to, dichloropropane 800ml is added, covers reaction kettle lid immediately, is reacted 2 hours.
It will40 DEG C are cooled to hereinafter, being adjusted to neutrality, centrifugal dehydration with the hydrochloric acid that concentration of volume percent is 30%；Again
It is washed with the ethanol solution 5000kg that mass percent concentration is 88%, is centrifugated, dries, smashing up to product.
The above product is through detecting, primary quality measure: DS=1.08；4%(over dry product) solution viscosity 44000cps(NDJ-
1 viscosimeter, 25 DEG C, No. 4 rotors, 6rpm)；Salt sticks ratio 0.51.
Embodiment three
By 450kg mass percent concentration be 92.5% ethyl alcohol and 50kg isopropanol be pumped into 3m3 jacketed it is stainless
In steel reaction kettle, tapioca 500kg is then added in the state of continuously stirring, and is to slowly warm up to 50 DEG C, heat preservation 0.5 is small
When, making it, sufficiently swelling prepares starch milk.
ToIn add the octyl phenol polyoxyethylene ether of 2.5kg, open recirculated cooling water and be cooled to 45 DEG C, reaction 1 is small
When.
Sodium chloroacetate is uniformly added into 0.5 hourIn reaction kettle in, add during keep starch system
Temperature hereinafter, then uniformly add 160kg piece alkali, adds piece alkali at 40 DEG C, and 60 DEG C are reacted 3 hours.
50 DEG C are cooled to, epoxychloropropane 250ml is added, covers reaction kettle lid immediately, is reacted 2 hours.
It will40 DEG C are cooled to hereinafter, being adjusted to neutrality, centrifugal dehydration with the hydrochloric acid that concentration of volume percent is 30%；Again
It is washed with the ethanol solution 5000kg that mass percent concentration is 88%, is centrifugated, dries, smashing up to product.
The above product is through detecting, primary quality measure: DS=1.03；4%(over dry product) solution viscosity 49000cps(NDJ-
1 viscosimeter, 25 DEG C, No. 4 rotors, 6rpm)；Salt sticks ratio 0.62
Example IV
By 450kg mass percent concentration be 93% ethyl alcohol and 50kg isopropanol be pumped into 3m3 jacketed stainless steel
In reaction kettle, tapioca 500kg is then added in the state of continuously stirring, is to slowly warm up to 50 DEG C, keeps the temperature 0.5 hour,
Making it, sufficiently swelling prepares starch milk.
ToIn add the fatty alcohol polyoxyethylene ether of 2.5kg, 50 DEG C, react 1 hour.
Sodium chloroacetate is uniformly added into 0.5 hourIn reaction kettle in, while opening cooling water, added
It keeps starch system temperature hereinafter, then uniformly add 160kg piece alkali, to add piece alkali at 40 DEG C in journey, is warming up to 60 DEG C of reactions 3
Hour.
50 DEG C are cooled to, phosphorus oxychloride 1kg is added, covers reaction kettle lid immediately, is reacted 2 hours.
It will40 DEG C are cooled to hereinafter, being adjusted to neutrality, centrifugal dehydration with the hydrochloric acid that concentration of volume percent is 30%；Again
It is washed with the ethanol solution 5000kg that mass percent concentration is 88%, is centrifugated, dries, smashing up to product.
The above product is through detecting, primary quality measure: DS=1.06；4%(over dry product) solution viscosity 47500cps(NDJ-
1 viscosimeter, 25 DEG C, No. 4 rotors, 6rpm)；Salt sticks ratio 0.54
Embodiment five
By 450kg mass percent concentration be 93% ethyl alcohol and 50kg isopropanol be pumped into 3m3 jacketed stainless steel
In reaction kettle, tapioca 500kg is then added in the state of continuously stirring, is to slowly warm up to 50 DEG C, keeps the temperature 0.5 hour,
Making it, sufficiently swelling prepares starch milk.
Cooling water is opened, is cooled to 40 DEG C, toIn add the aliphatic amine polyoxyethylene ether of 2.5kg, reaction 0.5 is small
When.
Sodium chloroacetate is uniformly added into 0.5 hourIn reaction kettle in, while opening cooling water, added
It keeps starch system temperature hereinafter, then uniformly add 160kg piece alkali, to add piece alkali at 40 DEG C in journey, is warming up to 60 DEG C of reactions 3
Hour.
50 DEG C are cooled to, sodium tripolyphosphate 1kg is added, covers reaction kettle lid immediately, is reacted 1.5 hours.
It will40 DEG C are cooled to hereinafter, being adjusted to neutrality, centrifugal dehydration with the hydrochloric acid that concentration of volume percent is 30%；Again
It is washed with the ethanol solution 5000kg that mass percent concentration is 88%, is centrifugated, dries, smashing up to product.
The above product is through detecting, primary quality measure: DS=1.05；4%(over dry product) solution viscosity 42000cps(NDJ-
1 viscosimeter, 25 DEG C, No. 4 rotors, 6rpm)；Salt sticks ratio 0.55
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (3)
1. a kind of preparation method of salt-resistance carboxymethyl starch, comprising the following steps:
1. dispersing in the mixed solvent according to starch and mixed solvent mass ratio 1:1 for tapioca, continuously stir 30 minutes, delays
Slowly 50 DEG C are warming up to, are swollen it sufficiently, form starch milk；
Mixed solvent is the solvent that ethyl alcohol and isopropanol are 92% or more by the mass percent concentration that 7-12:1 is made into；
2. promoting reagent molecule infiltration as bleeding agent to the 1. middle surfactant that is added, diffusing to inside starch granules, improve
Alkalization, etherificate efficiency, 40-50 DEG C reaction 0.5-1 hours；
Surfactant is nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty amine polyoxy
One of vinethene is several；
The additional amount of surfactant is the 1-5% of starch quality；
3. being then continuously added to basifier NaOH to etherifying agent solid powdery sodium chloroacetate is added in 2., 60 DEG C of reactions 3 are small
When；Using the generation for first adding etherifying agent that basifier is added to can be reduced side reaction again, so that alkalizing, being etherified while carrying out, it is ensured that etherificate
It reacts more thorough, ensure that homogeneity and stability that carboxymethyl starch replaces；
4. being cooled to 50 DEG C, crosslinking agent is added, reacts 1-2 hours；
5. cooling down, it is adjusted to neutrality with the hydrochloric acid that concentration of volume percent is 30%, is centrifugated, then be with mass percent concentration
88% ethanol solution is washed by ethanol solution and starch quality=10:1, and centrifuge separation, drying smash up to salt-resistance carboxylic first
Base starch, under the conditions of 25 DEG C, using NDJ-1 viscosimeter, No. 4 rotors, revolving speed 6rpm, 4% solution viscosity of over dry product
40000cps or more, degree of substitution reach 1.0 or more, and salt glues ratio 0.5 or more.
2. a kind of preparation method of salt-resistance carboxymethyl starch as described in the appended claim 1, it is characterised in that: the step 3. in
Sodium chloroacetate need to be uniformly added into 0.5 hour, and temperature is no more than 40 DEG C when chlorination sodium acetate.
3. a kind of preparation method of salt-resistance carboxymethyl starch as described in the appended claim 1, it is characterised in that: the step 4. in
Added crosslinking agent is one of epoxychloropropane, dichloropropane, sodium trimetaphosphate, phosphorus oxychloride, and additional amount is starch quality
0.01%-0.2%.
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| CN109420469B (en) * | 2017-08-22 | 2021-01-05 | 中国石油化工股份有限公司 | Cationic doped starch microsphere material and preparation method and application thereof |
| CN108084282A (en) * | 2018-01-19 | 2018-05-29 | 广东汇美淀粉科技有限公司 | A kind of phosphate and the compound esterification and crosslinking pyrolysis dextrin preparation method of organic acid anhydride |
| CN108774506B (en) * | 2018-04-17 | 2021-09-21 | 中原工学院 | High-temperature-resistant etherified modified starch filtrate reducer and preparation method thereof |
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| CN101230105A (en) * | 2008-01-14 | 2008-07-30 | 王进平 | Carboxymethyl starch ether and production method thereof |
| CN101348528A (en) * | 2008-08-29 | 2009-01-21 | 华南理工大学 | Preparation of amorphous particulate carboxymethyl starch |
| CN103102837A (en) * | 2012-11-13 | 2013-05-15 | 苏州谷力生物科技有限公司 | Preparation method for production of tobacco sheet adhesive |
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