CN107056953A - A kind of preparation method of the high sodium carboxymethylcellulose of whiteness - Google Patents
A kind of preparation method of the high sodium carboxymethylcellulose of whiteness Download PDFInfo
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- CN107056953A CN107056953A CN201710351794.XA CN201710351794A CN107056953A CN 107056953 A CN107056953 A CN 107056953A CN 201710351794 A CN201710351794 A CN 201710351794A CN 107056953 A CN107056953 A CN 107056953A
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- sodium carboxymethylcellulose
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- whiteness
- high sodium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/08—Alkali cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
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Abstract
The invention discloses a kind of preparation method of the high sodium carboxymethylcellulose of whiteness, comprise the following steps：(1) cellulose quaternization；(2) etherification reaction；(3) process is handled afterwards, and sodium carboxymethylcellulose CMC~Na is made.The remaining quantity of the bleaching agent of the present invention is few, and viscosity declines seldom, can effectively improve in whiteness, CMC~Na powder, not detect hydrogen peroxide, CMC~Na viscosity is higher.
Description
Technical field
The invention belongs to technical field of material, more particularly, to a kind of system of the high sodium carboxymethylcellulose of whiteness
Preparation Method.
Background technology
Country manufacture sodium carboxymethylcellulose CMC~Na, is mostly, using kneading machine equipment, to be produced with semidry method.
It is ethanol as solvent.In hydrous ethanol, allow cellulose to be reacted with sodium hydroxide, destroying raw cellulose
After crystal structure, etherifying agent is made with monoxone etc., is reacted with alkali cellulose, CMC~Na is manufactured.
General high with the high chemical cellulose of the degree of polymerization, the high cotton fiber of whiteness usually manufactures CMC~Na, its CMC~Na product
Whiteness be high, the high CMC~Na of its whiteness, the aqueous solution being configured to, its transparency is also high.Such a CMC~
Na is high due to whiteness, exactly people institute Cup of tea feelings.
But the reason for being due to economic, manufacture sodium carboxymethylcellulose CMC~Na, also commonly use wood pulps and make raw material, but wood
In pulp, also containing compositions such as lignin, many poly-pentoses, mannosans.Because the powder containing these compositions, CMC~Na is in
Isabelline, the CMC~Na aqueous solution prepared with it also presents very thin isabelline.So usually evaluating common fibre with alpha fibers
The purity of element is tieed up, chemical cellulose is high, then cellulose whiteness is just high.Composition on wood pulps is as shown in table 1.Japan【Paper パ Le プ
The full Books of System Zao Ji Intraoperative To The Ru analysis examples of volume 2】Page 370~375 (1996) have been described.In order to improve CMC~Na's
Whiteness, substantially must be removed completely using the lignin in wood pulps as the coloring material of representative.
In the past, it is the bleaching agent using volume except the coloring material of delignification etc..But single bleaching agent is only leaned on,
Then completely except the coloring material of delignification etc. is difficult.If volume is not only impossible using the whiteness rising of bleaching agent,
And cellulosic molecule is degraded, the reduction of CMC~Na viscosity, this is inevitable.More seriously bleaching agent remains in CMC~Na
In, leave hidden danger to product.
As bleaching agent, with hydrogen peroxide, this is well-known.But whiteness improves few, if volume is used, then viscosity
It can substantially reduce.Such as Japanese Patent, JP 2000~119303 is indicated, when hydrogen peroxide (35%)/wood pulps=1%, hydrogen peroxide
When being added with monoxone simultaneously, 2% solution viscosity is in 10mPas；It is double when hydrogen peroxide (35%)/wood pulps=0.5%
Oxygen water and monoxone are added simultaneously when, 2% solution viscosity is in 20mPas.Viscosity is too low, and practical value is small.
The content of the invention
Regarding the issue above, the present invention provides a kind of viscosity of raising CMC~Na powder declines seldom white
The preparation method of the high sodium carboxymethylcellulose of degree.
To reach above-mentioned purpose, present invention employs following technical proposal：The carboxymethyl that a kind of whiteness of the present invention is high is fine
The preparation method of the plain sodium of dimension, comprises the following steps：
(1) cellulose quaternization
The aqueous solution and 2200 parts of ethanol waters that 810 parts of sodium hydroxides are dissolved into buck concentration about 50% are separately added into
Into the biaxial kneader of 50 liters, while stirring, is 5 minutes while adding 1400 parts of fragment shape raw celluloses；20~
25 DEG C alkalize 50 minutes, and alkali cellulose is made；
(2) etherification reaction
After alkalization, temperature control, 1360 parts of etherificate agent solutions, was dripped in 90 minutes at 30 DEG C, first individually drips 870
Part etherifying agent, as the 60% of etherifying agent total amount individually drips, after termination, rapidly remaining 580 portions of etherifying agents and bleaching agent
Solution, 288 parts drip parallel, and etherifying agent and bleaching agent drip after end of a period, are stirred 30 minutes at 40 DEG C, afterwards, in 40 minutes
Be warming up to 80 DEG C, 80 DEG C again constant temperature 50 minutes terminate etherification reaction；
(3) process is handled afterwards
After etherification reaction terminates, 50 DEG C are cooled to, into washing pot, is washed, is used before washing with 10 times of 75% ethanol
31% technical hydrochloric acid, the hydrochloric acid for being diluted with ethanol to less than 10% neutralizes superfluous sodium hydroxide first, pH is reached that 7.0 is left
The right side, is washed 2 times, centrifugal filtration；Drying, crushes to obtain powdery, and sodium carboxymethylcellulose CMC~Na is made.
Further, in step (1), the equipment is biaxial kneader, and the ethanol is 70 with water quality ratio:30~
90:10；The ratio between solvent consumption/cellulose be 1.5~3.0 between.
Further, in step (1), the alkalization temperature is 10~40 DEG C, and alkalization time is 20~90 minutes.
Further, in step (2), the cellulose is one in wood pulps, bamboo pulp, Cotton Pulp, purified cotton
Plant or several combinations；Described bleaching agent is any one in hydrogen peroxide, sodium perborate or SODIUM PERCARBONATE.
Further, in step (2), the bleaching agent is the 0.0175%~0.525% of cellulose quality, by pure
H2O2Meter；The etherifying agent is monoxone.
Further, in step (2), described bleaching agent is hydrogen peroxide, the hydrogen peroxide H2O2Concentration is
1.75%, the etherifying agent and H2O2After adding, incorporation time is 40~50 minutes, after 30~55 DEG C of temperature, with 20~60
Minute, 80 DEG C are warming up to, constant temperature 30~120 minutes terminates etherification reaction.
Further, in step (2), the mass percent of described etherifying agent account for etherifying agent total amount 40%~
165%；The addition of the hydrogen peroxide, if 35% concentration of hydrogen peroxide, H2O2/ cellulose is 0.05%~1.5%.
Further, in step (2), the mass percent of described etherifying agent account for etherifying agent total amount 50%~
80%.
Further, in step (2), the mass percent of described etherifying agent accounts for the 55~65% of etherifying agent total amount.
Further, in step (2), the degree of etherification falling DS of product is 0.6~1.0, and as DS ＜ 0.50, solution is easily muddy
It is turbid；As DS ＞ 2.0, manufacturing cost is high.
Beneficial effect：The remaining quantity of the bleaching agent of the present invention is few, and viscosity declines few, can effectively improve whiteness, and CMC~
In Na powder, hydrogen peroxide is not detected, CMC~Na viscosity is higher.
Embodiment
Following examples only exist in illustrative purpose, without being intended to limit the scope of the present invention.
Embodiment 1~8 and comparative example 1~4
Table 1, table 2 have recorded raw material and reagent used.CMC-Na is manufactured according to above-mentioned technique.According to above-mentioned analysis
And assay method, analyzed.The analysis result of each example is also recorded in Tables 1 and 2 in the lump.The He of comparative example 1 in Tables 1 and 2
Comparative example 3 is after being dripped first the 60% of etherifying agent total amount, to continue the remaining etherifying agent that individually drips.Comparative example 2 and compare
Example 4 is after etherifying agent full dose is dripped, to continue individually to drip bleaching agent in 10 minutes.
Effect of the present invention：From Tables 1 and 2, it is evident that the present invention manufacture method, compared with comparative example, obtained CMC-
Na whiteness is high, moreover, in CMC-Na powder, not detecting hydrogen peroxide.Furthermore, CMC-Na viscosity is higher, with reality
With value.
According to CMC-Na produced by the present invention, whiteness is high, and without remaining hydrogen peroxide, has higher viscosity, can be used for
The extensive field such as food, pharmaceuticals, feed, coating, binding agent.And belong to first-class goods.
Table 1
Table 2
Experiment 1
The analysis of the product of embodiment produced by the present invention and assay method
(1) measure of powder whiteness
Using SBD type measuring brightness instrument.Sample powder is pressed into round pie under a certain pressure, is 457nm's with wavelength
Light beam, sample is irradiated in 45° angle, the whiteness of its reflectivity and the ratio, as sample of standard chlorination magnesium plate reflectivity.Specifically
GB/T9107~1999 are shown in operation.
(2) detection of hydrogen peroxide remaining quantity
Pure dry CMC~Na 10.0g are weighed, are put into 200ml beakers, 100ml methanol is added with graduated cylinder, are stirred within 5 minutes.
After stirring, quantitatively it is put into centrifugal sedimentation pipe, is centrifuged within 10 minutes in 2000r.p.m.Clarified solution above is taken to be put into band plug
300ml flasks in, add hydrogen peroxide enzyme aqueous solution (0.1%) 2ml, 10 minutes vibrate.Add sulfuric acid solution (10%)
10ml.After KI solution (10%) 10ml and ammonium molybdate solution (3%) 2~3 drip, titrated with 0.02N hypo solutions.Drop
Regularly, brown buret is used, and using without CMC~Na samples, same processing experiment does blank test, then hydrogen peroxide
Remaining quantity %, with following formula meter mark：
Note：The titer of titer=sample of hypo solution~blank titration amount
The effect of the thio sodium sulfide solutions of f=
(3) viscosimetric analysis.Test specimen, is made 1% aqueous solution, and its viscosity is determined with Brookfield viscosimeters.Remaining
Physical and chemical index is analyzed all in accordance with the testing standard of GB1904~2005.
The composition of wood pulps is as shown in table 3,
Table 3
Note：The degree of polymerization, chemical cellulose are detected by Hangzhou Hongbo New Materials Co., Ltd..
Specific embodiment described herein is only to spirit explanation for example of the invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement to described specific embodiment or be replaced using similar mode
Generation, but without departing from the spiritual of the present invention or surmount scope defined in appended claims.
Claims (10)
1. the preparation method of the high sodium carboxymethylcellulose of a kind of whiteness, it is characterised in that comprise the following steps：
(1) cellulose quaternization
The aqueous solution and 2200 parts of ethanol waters that 810 parts of sodium hydroxides are dissolved into buck concentration about 50% are added separately to 50
In the biaxial kneader of liter, while stirring, is 5 minutes while adding 1400 parts of fragment shape raw celluloses；At 20~25 DEG C
Alkalization 50 minutes, is made alkali cellulose；
(2) etherification reaction
After alkalization, temperature control 1360 parts of etherificate agent solutions, was dripped, first individually drip 870 parts of ethers at 30 DEG C in 90 minutes
Agent, as the 60% of etherifying agent total amount are individually dripped, after termination, rapidly remaining 580 portions of etherifying agents and bleaching agent solution,
288 parts drip parallel, and etherifying agent and bleaching agent drip after end of a period, stir 30 minutes, afterwards, are warming up in 40 minutes at 40 DEG C
80 DEG C, 80 DEG C again constant temperature 50 minutes terminate etherification reaction；
(3) process is handled afterwards
After etherification reaction terminates, 50 DEG C are cooled to, into washing pot, is washed with 10 times of 75% ethanol, with 31% before washing
Technical hydrochloric acid, the hydrochloric acid for being diluted with ethanol to less than 10% neutralizes superfluous sodium hydroxide first, pH is reached 7.0 or so, washes
Wash 2 times, centrifugal filtration；Drying, crushes to obtain powdery, and sodium carboxymethylcellulose CMC~Na is made.
2. the preparation method of the high sodium carboxymethylcellulose of whiteness according to claim 1, it is characterised in that：In step
(1) in, the equipment is biaxial kneader, and the ethanol is 70 with water quality ratio:30~90:10；Solvent consumption/cellulose it
Than between 1.5~3.0.
3. the preparation method of the high sodium carboxymethylcellulose of whiteness according to claim 1, it is characterised in that：In step
(1) in, the alkalization temperature is 10~40 DEG C, and alkalization time is 20~90 minutes.
4. the preparation method of the high sodium carboxymethylcellulose of whiteness according to claim 1, it is characterised in that：In step
(2) in, the cellulose is one or more of combinations in wood pulps, bamboo pulp, Cotton Pulp, purified cotton；Described bleaching
Agent is any one in hydrogen peroxide, sodium perborate or SODIUM PERCARBONATE.
5. the preparation method of the high sodium carboxymethylcellulose of whiteness according to claim 4, it is characterised in that：In step
(2) in, the bleaching agent is the 0.0175%~0.525% of cellulose quality, by pure H2O2Meter；The etherifying agent is monoxone.
6. the preparation method of the high sodium carboxymethylcellulose of whiteness according to claim 5, it is characterised in that：In step
(2) in, described bleaching agent is hydrogen peroxide, the hydrogen peroxide H2O2Concentration is 1.75%, the etherifying agent and H2O2Add
Afterwards, after incorporation time is 40~50 minutes, 30~55 DEG C of temperature, with 20~60 minutes, 80 DEG C, constant temperature 30~120 are warming up to
Minute, terminate etherification reaction.
7. the preparation method of the high sodium carboxymethylcellulose of whiteness according to claim 6, it is characterised in that：In step
(2) in, the mass percent of described etherifying agent accounts for the 40%~165% of etherifying agent total amount；The H2O2/ cellulose is
0.05%~1.5%.
8. the preparation method of the high sodium carboxymethylcellulose of whiteness according to claim 1, it is characterised in that：In step
(2) in, the mass percent of described etherifying agent accounts for the 50%~80% of etherifying agent total amount.
9. the preparation method of the high sodium carboxymethylcellulose of whiteness according to claim 1, it is characterised in that：In step
(2) in, the mass percent of described etherifying agent accounts for the 55~65% of etherifying agent total amount.
10. the preparation method of the high sodium carboxymethylcellulose of whiteness according to any one of claim 1 to 9, its feature exists
In：In step (3), the degree of etherification falling DS of product is 0.6~1.0, and as DS ＜ 0.50, solution is easily muddy；As DS ＞ 2.0.
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Application publication date: 20170818 |