CN106749712A - A kind of method that semidry method prepares CMS - Google Patents
A kind of method that semidry method prepares CMS Download PDFInfo
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- CN106749712A CN106749712A CN201710029541.0A CN201710029541A CN106749712A CN 106749712 A CN106749712 A CN 106749712A CN 201710029541 A CN201710029541 A CN 201710029541A CN 106749712 A CN106749712 A CN 106749712A
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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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Abstract
A kind of method that semidry method prepares CMS.With starch as raw material, ethanol solution is moistening medium, adding NaOH and absolute ethyl alcohol makes starch alkalize, and then mixes with a certain amount of sodium chloroacetate, and etherification reaction occurs at a certain temperature, cooling, cleaned with methyl alcohol, suction filtration, washed, dry to constant weight and residual methanol is volatilized completely, sieve.The present invention takes alkalization and etherification reaction under organic solvent wetting conditions, and replace monoxone to cook etherifying agent with sodium chloroacetate, both having avoided solvent method needs the shortcomings of consuming a large amount of organic solvents and consersion unit utilization rate not high, turn avoid the shortcomings of mixing of dry method material is uneven, reaction is uneven, it is thus also avoided that chloroacetic toxicity and corrosivity.0.58 is can reach with CMS substitution value (DS) obtained in semidry method.
Description
Technical field
The present invention relates to field of deep processing of farm products, more particularly, to a kind of preparation method of CMS.
Background technology
The research of CMS starts from nineteen twenty-four, during the development of China's CMS starts from the eighties in last century
Phase.CMS (abbreviation CMS) is the important etherification starch derivative of a class, be starch in the basic conditions with sodium chloroacetate
Carry out a kind of polyelectrolyte for being dissolved in cold water of etherification reaction generation, be widely used at present food, weaving, medicine,
Papermaking, agricultural and petrochemical industry etc..In recent years, the country was on the action oriented research of carboxymethyl, occurring in that new focus.Such as food
The antistaling agent and stabilizer of texture characteristic；The excipient and disintegrant of medicine；The agent of washing anti-dirt reprecipitation, the ring of sewage disposal
Protect flocculant；The coating agent of seed, the sustained release agent of chemical fertilizer and with the green high score such as PVA, sodium alginate or water-soluble cellulose
Sub- blending prepares complete biodegradable water-saving liquid mulch film etc..
Current country CMS productions use water soluble method and organic solvent method mostly.Product substitution value prepared by solvent method is high, instead
Industrialized production should be gently easy to, but due to using substantial amounts of organic solvent, existing, energy consumption is big, production cost is high and environment is dirty
The problems such as contaminating serious, and raw material chloroacetic acid has strong corrosivity and toxicity, influences the service life of reaction unit.One
A little researchers can add alkaline agent cetyl trimethylammonium bromide (CTAB) to improve substitution value, and this is a Toxic
Matter, obtained CMS should not be used in food pharmaceuticals industry, and the CMS substitution values that food and medicine field uses are also and need not
It is very high.Also researcher prepares CMS (CMS) using dry process.Dry preparation process solvent is added less, pollution is small,
Flow is short, energy consumption is low, simple equipments.But the problems such as dry process raw material mixes uneven, starch alkalinization easily lumps is tight
Ghost image rings the substitution value of CMS.
The content of the invention
The solvent method pollution that exists for prior art is big, solvent consumption is big, equipment is easily corroded, and dry method raw material
The problems such as mixing uneven, starch alkalinization easily lumps, reacts uneven, the applicant prepares there is provided a kind of semidry method
The method of CMS.The present invention takes alkalization and etherification reaction under organic solvent wetting conditions, and uses sodium chloroacetate generation
Etherifying agent is done for monoxone, has both avoided that solvent method needs to consume a large amount of organic solvents and consersion unit utilization rate is not high lacks
Point, turn avoid the shortcomings of mixing of dry method material is uneven, reaction is uneven, it is thus also avoided that chloroacetic toxicity and corrosivity.
0.58 is can reach with CMS substitution value (DS) obtained in semidry method.It is any due to not applied in whole course of reaction
CMS prepared by eventually harmful reactant, therefore the method is highly suitable for medicine, food, biology
Etc. industry.
Technical scheme is as follows：
A kind of method that semidry method prepares CMS, comprises the following steps：
(1) according to the mass fraction, 4~6 parts of NaOH and 4~7 part of water are mixed, adds 40~50 parts of absolute ethyl alcohols fully to stir
Mix uniform and so that NaOH thoroughly dissolves, then mix this solution with 15~17 parts of starch, so that starch is sufficiently humidified so as to, obtain
Slurry-mud shape mixture；
(2) foregoing slurry-mud shape mixture is put into box reactor, carried out at 30~45 DEG C quaternization 50~
70min, after alkalization terminates, is cooled to room temperature, is sufficiently mixed in pulverizer with 5~6 parts of powdered sodium chloroacetates；
(3) during the mixture by pulverizer out places into box reactor, carried out at 66~75 DEG C etherification reaction 2~
3h, after reaction terminates, is cooled to room temperature；
(4) product after cooling down washs 1 with the methanol aqueous solution that 200~220 parts of mass fractions are 75~85%~
1.5h, and add in acetic acid and unreacted alkali is to neutrality, filtering is washed with the methanol aqueous solution that mass fraction is 75~85%
Filter cake, to non-sodium chloride, dry and residual methanol is volatilized completely, crush after obtain the CMS of white powder.
Mixing speed described in step (1) is 150~180r/min.
It is to be checked with silver nitrate aqueous solution that filter cake to the detection method of non-sodium chloride is washed described in step (4), without white
It is then non-sodium chloride that sediment is produced.
Dried described in step (4) is filter cake 50~60 DEG C of dryings in drier.
Starch described in step (1) is the separation rice starch or corn, potato, tapioca of market purchase, substantially
Without thick protein.
The present invention is beneficial to be had technical effect that：
(1) preparation method of the invention, replaces monoxone to make etherifying agent with sodium chloroacetate, and with a small amount of water and appropriate nothing
Used as wetting agent, without using poisonous consisting of phase-transferring agent, efficiently solve the reactant uneven, monoxone of mixing has water-ethanol
Poison and severe corrosion equipment and the problems such as react uneven, obtained CMS substitution value (DS) can reach 0.58, and
Its substitution value can be adjusted between 0.42~0.58 and be easier control according to demand.Due in whole preparation process
In the absence of to the poisonous and hazardous material of human body (such as quaternary ammonium salt, monoxone), therefore it is particularly suitable for food, medicine and biological
Product industry is used.
(2) preparation method of the invention, due to considerably reducing the consumption of organic solvent, therefore can substantially reduce solvent
The shortcomings of method equipment volume is huge, energy resource consumption is high.
(3) preparation method of the invention has simple and easy to apply, stable reaction, can be big the features such as product substitution value is moderate
The deep processing of rice and other starch provides a kind of new method.
(4) the technology of the present invention method gained CMS there is good hydrophily, possible complete swelling in hot water,
Have good freeze-thaw stability and anti-freezing property and it is good freeze after thawing resistance.
Specific embodiment
With reference to embodiment, the present invention is specifically described.
Embodiment 1
(1) with rice starch as raw material, ethanol solution is moistening medium, according to the mass fraction, by 4 parts of NaOH and 5
The mixing of part water, adds 40 parts of absolute ethyl alcohols to stir and so that NaOH thoroughly dissolves, and mixing speed is 160r/min, so
This solution is mixed with 15 parts of starch afterwards, so that starch is sufficiently humidified so as to, obtains slurry-mud shape mixture；
(2) foregoing slurry-mud shape mixture is put into box reactor, quaternization 55min is carried out at 35 DEG C, alkalized
After end, room temperature is cooled to, is sufficiently mixed in pulverizer with 6 parts of powdered sodium chloroacetates；
(3) during the mixture by pulverizer out places into box reactor, etherification reaction 2.5h is carried out at 67 DEG C, instead
After should terminating, room temperature is cooled to；
(4) product after cooling down washs 1h with the methanol aqueous solution that 200 parts of mass fractions are 80%, and adds acetic acid
Unreacted alkali to neutrality is neutralized, is filtered, filter cake is washed with the methanol aqueous solution that mass fraction is 80%, (used to non-sodium chloride
Silver nitrate aqueous solution is checked, and is produced without white depositions), filter cake 50 DEG C of dryings and makes residual methanol wave completely in drier
Hair, obtains the CMS of white powder after crushing.
The DS values of gained rice CMS are 0.45.
Gained CMS has good hydrophily, and possible complete swelling has good freeze-thaw stability in hot water
Property and anti-freezing property and it is good freeze after thawing resistance
Embodiment 2
(1) with cornstarch as raw material, ethanol solution is moistening medium, according to the mass fraction, by 5 parts of NaOH and 6
The mixing of part water, adds 45 parts of absolute ethyl alcohols to stir and so that NaOH thoroughly dissolves, and mixing speed is 150r/min, so
This solution is mixed with 15 parts of starch afterwards, so that starch is sufficiently humidified so as to, obtains slurry-mud shape mixture；
(2) foregoing slurry-mud shape mixture is put into box reactor, quaternization 70min is carried out at 40 DEG C, alkalized
After end, room temperature is cooled to, is sufficiently mixed in pulverizer with 5 parts of powdered sodium chloroacetates；
(3) during the mixture by pulverizer out places into box reactor, etherification reaction 2h is carried out at 73 DEG C, is reacted
After end, room temperature is cooled to；
(4) product after cooling down washs 1.2h with the methanol aqueous solution that 210 parts of mass fractions are 85%, and adds second
Acid neutralizes unreacted alkali to neutrality, and filtering washs filter cake, to non-sodium chloride with the methanol aqueous solution that mass fraction is 85%
(being checked with silver nitrate aqueous solution, produced without white depositions), filter cake 60 DEG C of dryings and makes residual methanol complete in drier
Volatilization, obtains the CMS of white powder after crushing.
The DS values of gained carboxymethyl corn starch are 0.51.
Gained CMS has good hydrophily, and possible complete swelling has good freeze-thaw stability in hot water
Property and anti-freezing property and it is good freeze after thawing resistance
Embodiment 3
(1) with rice starch as raw material, ethanol solution is moistening medium, according to the mass fraction, by 6 parts of NaOH and 7
The mixing of part water, adds 50 parts of absolute ethyl alcohols to stir and so that NaOH thoroughly dissolves, and mixing speed is 180r/min, so
This solution is mixed with 16 parts of starch afterwards, so that starch is sufficiently humidified so as to, obtains slurry-mud shape mixture；
(2) foregoing slurry-mud shape mixture is put into box reactor, quaternization 50min is carried out at 30 DEG C, alkalized
After end, room temperature is cooled to, is sufficiently mixed in pulverizer with 5.5 parts of powdered sodium chloroacetates；
(3) during the mixture by pulverizer out places into box reactor, etherification reaction 3h is carried out at 68 DEG C, is reacted
After end, room temperature is cooled to；
(4) product after cooling down washs 1.5h with the methanol aqueous solution that 220 parts of mass fractions are 75%, and adds second
Acid neutralizes unreacted alkali to neutrality, and filtering washs filter cake, to non-sodium chloride with the methanol aqueous solution that mass fraction is 75%
(being checked with silver nitrate aqueous solution, produced without white depositions), filter cake 55 DEG C of dryings and makes residual methanol complete in drier
Volatilization, obtains the CMS of white powder after crushing.
The DS values of gained rice CMS are 0.58.
Gained CMS has good hydrophily, and possible complete swelling has good freeze-thaw stability in hot water
Property and anti-freezing property and it is good freeze after thawing resistance
Embodiment 4
(1) with potato starch as raw material, ethanol solution is moistening medium, according to the mass fraction, by 4 parts of NaOH and 4
The mixing of part water, adds 32 parts of absolute ethyl alcohols to stir and so that NaOH thoroughly dissolves, and mixing speed is 170r/min, so
This solution is mixed with 17 parts of starch afterwards, so that starch is sufficiently humidified so as to, obtains slurry-mud shape mixture；
(2) foregoing slurry-mud shape mixture is put into box reactor, quaternization 55min is carried out at 45 DEG C, alkalized
After end, room temperature is cooled to, is sufficiently mixed in pulverizer with 5 parts of powdered sodium chloroacetates；
(3) during the mixture by pulverizer out places into box reactor, etherification reaction 2h is carried out at 75 DEG C, is reacted
After end, room temperature is cooled to；
(4) product after cooling down washs 1.3h with the methanol aqueous solution that 200 parts of mass fractions are 78%, and adds second
Acid neutralizes unreacted alkali to neutrality, and filtering washs filter cake, to non-sodium chloride with the methanol aqueous solution that mass fraction is 78%
(being checked with silver nitrate aqueous solution, produced without white depositions), filter cake 58 DEG C of dryings and makes residual methanol complete in drier
Volatilization, obtains the CMS of white powder after crushing.
The DS values of gained potato CMS are 0.42.
Gained CMS has good hydrophily, and possible complete swelling has good freeze-thaw stability in hot water
Property and anti-freezing property and it is good freeze after thawing resistance
Embodiment 5
(1) with tapioca as raw material, ethanol solution is moistening medium, according to the mass fraction, by 5.5 parts of NaOH and
The mixing of 5.5 parts of water, adds 40 parts of absolute ethyl alcohols to stir and so that NaOH thoroughly dissolves, and mixing speed is 160r/
Min, then mixes this solution with 16 parts of starch, so that starch is sufficiently humidified so as to, obtains slurry-mud shape mixture；
(2) foregoing slurry-mud shape mixture is put into box reactor, quaternization 60min is carried out at 42 DEG C, alkalized
After end, room temperature is cooled to, is sufficiently mixed in pulverizer with 5.6 parts of powdered sodium chloroacetates；
(3) during the mixture by pulverizer out places into box reactor, etherification reaction 2.6h is carried out at 72 DEG C, instead
After should terminating, room temperature is cooled to；
(4) product after cooling down washs 1.4h with the methanol aqueous solution that 210 parts of mass fractions are 82%, and adds second
Acid neutralizes unreacted alkali to neutrality, and filtering washs filter cake, to non-sodium chloride with the methanol aqueous solution that mass fraction is 82%
(being checked with silver nitrate aqueous solution, produced without white depositions), filter cake 58 DEG C of dryings and makes residual methanol complete in drier
Volatilization, obtains the CMS of white powder after crushing.
The DS values of gained cassava CMS are 0.55.
Gained CMS has good hydrophily, and possible complete swelling has good freeze-thaw stability in hot water
Property and anti-freezing property and it is good freeze after thawing resistance
Embodiment 6
(1) with cornstarch as raw material, ethanol solution is moistening medium, according to the mass fraction, by 4.5 parts of NaOH and
The mixing of 6 parts of water, adds 38 parts of absolute ethyl alcohols to stir and so that NaOH thoroughly dissolves, and mixing speed is 150r/min,
Then this solution is mixed with 16 parts of starch, so that starch is sufficiently humidified so as to, obtains slurry-mud shape mixture；
(2) foregoing slurry-mud shape mixture is put into box reactor, quaternization 65min is carried out at 32 DEG C, alkalized
After end, room temperature is cooled to, is sufficiently mixed in pulverizer with 6 parts of powdered sodium chloroacetates；
(3) during the mixture by pulverizer out places into box reactor, etherification reaction 2.8h is carried out at 66 DEG C, instead
After should terminating, room temperature is cooled to；
(4) product after cooling down washs 1h with the methanol aqueous solution that 220 parts of mass fractions are 80%, and adds acetic acid
Unreacted alkali to neutrality is neutralized, is filtered, filter cake is washed with the methanol aqueous solution that mass fraction is 80%, (used to non-sodium chloride
Silver nitrate aqueous solution is checked, and is produced without white depositions), filter cake 55 DEG C of dryings and makes residual methanol wave completely in drier
Hair, obtains the CMS of white powder after crushing.
The DS values of gained carboxymethyl corn starch are 0.48.
Gained CMS has good hydrophily, and possible complete swelling has good freeze-thaw stability in hot water
Property and anti-freezing property and it is good freeze after thawing resistance
It is only above better embodiment of the invention, above-mentioned design of the invention, those skilled in the art
Can also to this various modification can be adapted and conversion.For example, the addition time of the species of starch, sodium chloroacetate, mode and speed, alkalization
And the proportioning between etherification reaction temperature and time, each component, and drying temperature and mode etc.；However, similar this change
Change and modification belongs to essence of the invention.
Claims (5)
1. a kind of method that semidry method prepares CMS, it is characterised in that comprise the following steps：
(1) according to the mass fraction, 4~6 parts of NaOH and 4~7 part of water are mixed, adds 40~50 parts of absolute ethyl alcohols to be sufficiently stirred for
It is even and cause NaOH thoroughly dissolve, then this solution is mixed with 15~17 parts of starch so that starch is sufficiently humidified so as to, obtain slurry-mud
Shape mixture；
(2) foregoing slurry-mud shape mixture is put into box reactor, 50~70min of quaternization is carried out at 30~45 DEG C,
After alkalization terminates, room temperature is cooled to, is sufficiently mixed in pulverizer with 5~6 parts of powdered sodium chloroacetates；
(3) during the mixture by pulverizer out places into box reactor, 2~3h of etherification reaction is carried out at 66~75 DEG C,
After reaction terminates, room temperature is cooled to；
(4) product after cooling down washs 1~1.5h with the methanol aqueous solution that 200~220 parts of mass fractions are 75~85%,
And add in acetic acid and unreacted alkali is to neutrality, filtering washs filter cake with the methanol aqueous solution that mass fraction is 75~85%,
To non-sodium chloride, dry and residual methanol is volatilized completely, crush after obtain the CMS of white powder.
2. method according to claim 1, it is characterised in that mixing speed described in step (1) is 150~180r/min.
3. method according to claim 1, it is characterised in that starch described in step (1) is to separate rice starch or jade
Rice, potato, tapioca.
4. method according to claim 1, it is characterised in that the detection of filter cake to non-sodium chloride is washed described in step (4)
Method is to be checked with silver nitrate aqueous solution, and it be then non-sodium chloride to be produced without white depositions.
5. method according to claim 1, it is characterised in that dried described in step (4) for filter cake 50 in drier~
60 DEG C of dryings.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628357A (en) * | 2019-06-06 | 2019-12-31 | 杭州纸友科技有限公司 | Semi-dry preparation method of modified starch rich in nano particles for wallpaper adhesive |
| CN116041558A (en) * | 2022-12-09 | 2023-05-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of carboxymethyl starch for vanadium-titanium magnetite concentrate pellets |
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| CN101348528A (en) * | 2008-08-29 | 2009-01-21 | 华南理工大学 | Preparation of amorphous particulate carboxymethyl starch |
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| CN102731664A (en) * | 2012-07-17 | 2012-10-17 | 郑桂富 | Preparation method of pharmaceutical adjuvant sodium carboxymethyl starch |
| CN103790038A (en) * | 2014-01-17 | 2014-05-14 | 郝军元 | Method for preparing reactive printing paste taking starch as raw material |
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| JPS6143601A (en) * | 1984-08-07 | 1986-03-03 | Dai Ichi Kogyo Seiyaku Co Ltd | Preparation of carboxymethyl starch having high etherification degree |
| CN1191222A (en) * | 1998-03-04 | 1998-08-26 | 中国科学院广州化学研究所 | Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether |
| CN101348528A (en) * | 2008-08-29 | 2009-01-21 | 华南理工大学 | Preparation of amorphous particulate carboxymethyl starch |
| CN101704897A (en) * | 2009-11-12 | 2010-05-12 | 于雷 | High-substitution carboxymethyl glutinous rice starch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110628357A (en) * | 2019-06-06 | 2019-12-31 | 杭州纸友科技有限公司 | Semi-dry preparation method of modified starch rich in nano particles for wallpaper adhesive |
| CN116041558A (en) * | 2022-12-09 | 2023-05-02 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of carboxymethyl starch for vanadium-titanium magnetite concentrate pellets |
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