CN110357973A - A kind of sodium carboxymethylcellulose and its preparation method and application - Google Patents
A kind of sodium carboxymethylcellulose and its preparation method and application Download PDFInfo
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- CN110357973A CN110357973A CN201810317511.4A CN201810317511A CN110357973A CN 110357973 A CN110357973 A CN 110357973A CN 201810317511 A CN201810317511 A CN 201810317511A CN 110357973 A CN110357973 A CN 110357973A
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- cellulose
- sodium carboxymethylcellulose
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- chain alcohol
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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]
Abstract
The invention discloses a kind of sodium carboxymethylcelluloses and its preparation method and application.This method includes the following steps: that cellulose, short chain alcohol, water and sodium hydroxide hybrid reaction are obtained mixture A by (1), the volume ratio of the quality of the cellulose and the short chain alcohol is 1:15~1:25g/mL, the quality of the cellulose and the volume ratio of the water are 1:1~1:10g/mL, the mass ratio of the quality of the cellulose and the sodium hydroxide is 1:0.1~1:0.8, and the short chain alcohol is the alcohol of carbon atom number 1~3 in carbochain；(2) by mixture A described in step (1) be etherified to get.The degree of substitution of sodium carboxymethylcellulose produced by the present invention is low, and crystallinity and the position of substitution meet the requirements, and replaces uniformly, and moisture pick-up properties is good, has good application value in moisturizing Material Field.
Description
Technical field
The present invention relates to a kind of sodium carboxymethylcelluloses and its preparation method and application.
Background technique
Sodium carboxymethylcellulose (abbreviation CMCNa) is one kind for obtaining after chemical modification using natural fiber as raw material
Polyanionic high-molecular compound is washed in weaving, printing and dyeing, petroleum, papermaking, leather, ink, ceramics, artificial fur, synthesis
It washs, the industries such as powder of lacquer putty for use on, imitation porcelain coating, adhesive for building, cigarette, putty paste, ceramics, food, medicine and battery all have extensively
Application, have the title of " industrial monosodium glutamate ".CMCNa has various properties, can be used as pharmaceutical carrier, adhesive, emulsifier, increasing
Thick dose and dispersing agent etc..
Measure sodium carboxymethylcellulose quality index have it is multiple, it is most common include purity, degree of substitution (degree of
Substitution, DS) and viscosity etc., in general, the property of CMCNa is different with DS difference, for example, when DS increases
When, the transparency and stability of solution also improve therewith.It is reported that transparent when CMCNa degree of substitution is in 0.7~1.2 range
Preferably, solution viscosity is maximum when pH is 6~9 for degree.It has been generally acknowledged that only when CMCNa degree of substitution is greater than 0.35, ability
It is dissolved in the water, when degree of substitution further decreases, CMCNa cannot be completely dissolved.
But find in actual application, for CMCNa of the degree of substitution between 0.7~1.2, even if identical
In the case where degree of substitution and viscosity, there is also differences, such as albumen dispersion stabilization etc. for the property of CMCNa.
Also some researches show that the CMCNa of low degree of substitution can be shown than degree of substitution 0.7~1.2 in some aspects at present
The more excellent performance of CMCNa prevent other for example, low degree of substitution CMCNa can show fabulous dispersion stabilization in water
Suspended particles agglomerate and disperse again；Also there is good emulsion stability simultaneously.These performances food, cosmetics, daily use chemicals,
The fields such as filtering, construction material, paint and battery all have a wide range of applications.
The low preparation for replacing CMCNa is for extending and extending CMCNa in the purposes of medicine and field of food with very heavy
The meaning wanted.And the research of most of CMCNa is limited to production technology at present and detection means is single, to reach using upper mesh
, it is more the CMCNa of high substituted degree in research preparation.Also, after reducing degree of substitution, the control of the position of substitution is more difficult,
Sodium carboxymethylcellulose molecular structural formula as follows:
Wherein 2,3 and 6 hydroxyls can be by carboxymethyl etherification, it is difficult to be prepared that the position of substitution is satisfactory low to be taken
For degree CMCNa.
Therefore, how to prepare crystallinity and the satisfactory low degree of substitution sodium carboxymethylcellulose of the position of substitution is this field
Urgent problem to be solved.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome crystallinity in the prior art and the position of substitution satisfactory
Low degree of substitution sodium carboxymethylcellulose is difficult to the defect prepared, and provide a kind of sodium carboxymethylcellulose and preparation method thereof and
Using.The degree of substitution of sodium carboxymethylcellulose produced by the present invention is 0.06~0.45；Crystallinity is 30~80%, and percentage is
Refer to that crystal region quality accounts for the ratio of sodium carboxymethylcellulose gross mass；The sum of 2- substitute proportions and 6- substitute proportions are not more than
88%, percentage refers to that the sum of 2- substitutions and 6- substitutions account for the ratio of the sum of 2,3 and 6 substitutions in sodium carboxymethylcellulose
Example.
The present invention provides a kind of preparation methods of sodium carboxymethylcellulose comprising following step:
(1) cellulose, short chain alcohol, water and sodium hydroxide hybrid reaction are obtained into mixture A, the quality of the cellulose and institute
The volume ratio for stating short chain alcohol is 1:15~1:25g/mL, and the quality of the cellulose and the volume ratio of the water are 1:1~1:
The mass ratio of 10g/mL, the quality of the cellulose and the sodium hydroxide is 1:0.1~1:0.8, and the short chain alcohol is carbochain
The alcohol of middle carbon atom number 1~3；
(2) by mixture A described in step (1) be etherified to get.
In the present invention, those skilled in the art know that low degree of substitution sodium carboxymethylcellulose refers to that degree of substitution is lower than 0.5
Sodium carboxymethylcellulose.
In the present invention, the molecular structure of the sodium carboxymethylcellulose is shown in formula I, and those skilled in the art are according to the knot
Structure formula is it is found that the position of substitution is 2,3 and 6.
In step (1), the cellulose can be the cellulose of this field routine, preferably wood pulp and/or purified cotton.
In step (1), the degree of polymerization of the cellulose can be the degree of polymerization of this field routine, such as 800~900,900~
1000 or 1000~1100, preferably 1000~1100.
In step (1), the short chain alcohol can be one of methanol, ethyl alcohol, propyl alcohol and isopropanol or a variety of, preferably second
One of alcohol, propyl alcohol and isopropanol are a variety of, more preferably propyl alcohol and/or isopropanol.
In step (1), the concentration of the short chain alcohol is 70~90%, and percentage refers to the short chain alcohol and the mixture
The percent by volume of A.
In step (1), the volume ratio of the quality of the cellulose and the short chain alcohol is preferably 1:20~1:25g/mL, more
Preferably 1:20~1:24g/mL, such as 1:20,1:24 or 1:25g/mL.
In step (1), the volume ratio of the quality of the cellulose and the water is preferably 1:2~1:10g/mL, more preferably
For 1:4~1:9g/mL, such as 1:2,1:4,1:9 or 1:10g/mL.
In step (1), the mass ratio of the quality of the cellulose and the sodium hydroxide is preferably 1:0.1~1:0.48,
More preferably 1:0.15~1:0.3, such as 1:0.1,1:0.15,1:0.25,1:0.3 or 1:0.48.
When the short chain alcohol is isopropanol, the volume ratio of the quality of the cellulose and the isopropanol is preferably 1:20
~1:24g/mL, such as 10:200 or 10:240g/mL.
When the short chain alcohol is propyl alcohol, the volume ratio of the quality of the cellulose and the propyl alcohol is preferably 1:20g/
ML, such as 10:200g/mL.
When the short chain alcohol is ethyl alcohol, the volume ratio of the quality of the cellulose and the ethyl alcohol is preferably 1:24~1:
25g/mL, such as 10:240 or 10:250g/mL.
In step (1), it is preferable that the short chain alcohol, the water and the sodium hydroxide are mixed to obtain mixture for the first time
The cellulose is mixed to obtain mixture C with the mixture B by B for the second time.
Wherein, word " first time ", " for the second time " only indicate mixed sequencing without particular meaning.
Wherein, the temperature of described " mixing for the first time " can be the temperature of this field routine, generally at 30 DEG C hereinafter, preferably
25~30 DEG C.
Wherein, the temperature of described " second of mixing " can be the temperature of this field routine, generally at 30 DEG C hereinafter, preferably
25~30 DEG C.
Wherein, the charging duration of the cellulose can be this field routine duration, preferably 10~30min, more preferably
For 15~20min, such as 15min or 20min.
In step (1), the mixing temperature that the mixed temperature can advise often for the alkalization of this field cellulose, preferably 25
~35 DEG C.
In step (1), the alkalization time that the mixed time can advise often for the alkalization of this field cellulose, preferably 50
~90min, such as 60min, 65min, 70min or 80min.
In step (2), the method for the etherificate can be the etherification method of this field routine, generally will be described in step (1)
Mixture A is mixed with etherifying agent.
Wherein, the etherifying agent can be the etherifying agent of this field routine, preferably chloroacetic short chain alcohol solution, the chlorine
Short chain alcohol in the short chain alcohol solution of acetic acid is the alcohol of carbon atom number 1~3 in carbochain.The chloroacetic dosage can be ability
The dosage of domain routine, it is preferable that the cellulose is 1:0.1~1:0.8 with the chloroacetic mass ratio；It is highly preferred that institute
It states cellulose and the chloroacetic mass ratio is 1:0.1~1:0.45；Such as 1:0.1,1:0.2,1:0.3,1:0.4 or 1:
0.45。
Wherein it is preferred to which the etherifying agent is added dropwise in step (1) the mixture A.The time of the dropwise addition can root
It is carried out according to common sense in the field, preferably 10~30min, such as 15min, 20min, 25min or 30min.The temperature of the mixture A
Spending can be the temperature of this field routine, preferably 30~35 DEG C.
Wherein, in the method for the etherificate, the mixed temperature can be etherified the temperature advised often for cellulose in this field
Degree, preferably 60~80 DEG C, such as 70 DEG C.Those skilled in the art know, should slowly heat up in etherification procedure.
Wherein, in the method for the etherificate, the mixed time can be advised often for cellulose etherificate in this field when
Between, preferably 50~90min, such as 60min, 65min, 70min or 80min.
In step (2), it is preferable that the mixture A after etherificate is adjusted pH to 7~8.
Wherein, the reagent for adjusting pH can be the reagent of this field routine, such as one in hydrochloric acid, acetic acid and citric acid
Kind is a variety of.
In step (2), it is preferable that the mixture A after etherificate is washed and/or is centrifuged.It is highly preferred that mixed after etherificate
After conjunction object A is washed and/or is centrifuged, then dries and/or crush.
Wherein, the solvent of the washing can be the cleaning solvent of this field routine, and preferably 60~80% ethyl alcohol is water-soluble
Liquid, such as 75% ethanol water, percentage refer to percent by volume.
Wherein, the method for the centrifugation can be the centrifugal method of this field routine, such as the centrifugation of Horizontal sedimentation method.
In an of the invention preferred embodiment, the volume ratio of the quality of the cellulose and the short chain alcohol be 1:20~
The volume ratio of 1:25g/mL, the quality of the cellulose and the water is 1:2~1:10g/mL, the quality of the cellulose and institute
The mass ratio for stating sodium hydroxide is 1:0.1~1:0.48, and the short chain alcohol is the alcohol of carbon atom number 1~3 in carbochain.
In an of the invention preferred embodiment, the volume ratio of the quality of the cellulose and the short chain alcohol be 1:20~
The volume ratio of 1:24g/mL, the quality of the cellulose and the water is 1:4~1:9g/mL, the quality of the cellulose and institute
The mass ratio for stating sodium hydroxide is 1:0.15~1:0.3, and the short chain alcohol is the alcohol of carbon atom number 1~3 in carbochain.
In a preferred embodiment of the invention, the volume ratio of the quality of the cellulose and the short chain alcohol is 1:24g/
The volume ratio of mL, the quality of the cellulose and the water is 1:9g/mL, the quality of the cellulose and the sodium hydroxide
Mass ratio is 1:0.1, and the short chain alcohol is the alcohol of carbon atom number 1~3 in carbochain.
In a preferred embodiment of the invention, the volume ratio of the quality of the cellulose and the short chain alcohol is 1:25g/
The volume ratio of mL, the quality of the cellulose and the water is 1:10g/mL, the quality of the cellulose and the sodium hydroxide
Mass ratio be 1:0.15, the short chain alcohol be carbochain in carbon atom number 1~3 alcohol.
In a preferred embodiment of the invention, the volume ratio of the quality of the cellulose and the short chain alcohol is 1:20g/
The volume ratio of mL, the quality of the cellulose and the water is 1:2g/mL, the quality of the cellulose and the sodium hydroxide
Mass ratio is 1:0.25, and the short chain alcohol is the alcohol of carbon atom number 1~3 in carbochain.
In a preferred embodiment of the invention, the volume ratio of the quality of the cellulose and the short chain alcohol is 1:24g/
The volume ratio of mL, the quality of the cellulose and the water is 1:4g/mL, the quality of the cellulose and the sodium hydroxide
Mass ratio is 1:0.3, and the short chain alcohol is the alcohol of carbon atom number 1~3 in carbochain.
In a preferred embodiment of the invention, the volume ratio of the quality of the cellulose and the short chain alcohol is 1:20g/
The volume ratio of mL, the quality of the cellulose and the water is 1:4g/mL, the quality of the cellulose and the sodium hydroxide
Mass ratio is 1:0.48, and the short chain alcohol is the alcohol of carbon atom number 1~3 in carbochain.
The present invention also provides one kind sodium carboxymethylcellulose as made from above-mentioned preparation method, the carboxymethyl celluloses
The degree of substitution of sodium is 0.06~0.45；Crystallinity is 30~80%, and percentage refers to that crystal region quality accounts for carboxymethyl cellulose
The ratio between sodium gross mass；The sum of 2- substitute proportions and 6- substitute proportions be not more than 88%, percentage refer to account for 2- replace with
The sum of 6- substitutions account for the ratio of the sum of 2,3 and 6 substitutions in sodium carboxymethylcellulose.
The present invention also provides a kind of sodium carboxymethylcelluloses, wherein the degree of substitution of the sodium carboxymethylcellulose is
0.06~0.45；Crystallinity is 30~80%, and percentage refers to that crystal region quality accounts for the ratio between sodium carboxymethylcellulose gross mass；
The sum of 2- substitute proportions and 6- substitute proportions are not more than 88%, and percentage refers to that accounting for the sum of 2- substitutions and 6- substitutions accounts for
The ratio of the sum of 2,3 and 6 substitutions in sodium carboxymethylcellulose.
In the present invention, the sum of the 2- position substitute proportion of the sodium carboxymethylcellulose and 6- substitute proportions preferably 81~
88%, such as 81%, 84%, 85%, 87% or 88%, percentage refers to that accounting for the sum of 2- substitutions and 6- substitutions accounts for carboxymethyl
The ratio of the sum of 2,3 and 6 substitutions in sodium cellulosate；More preferably 47% position 2- replace and 34% the substitution of the position 6-, 38%
The position 2- replace and 46% position 6- replaces, 53% position 2- replaces and 32% position 6- substitution, 62% position 2- substitution and
25% position 6- substitution or 47% position 2- replace and 41% position 6- replaces, and percentage refers to that the substitution of each position accounts for respectively
The ratio of the sum of 2,3 and 6 substitutions in sodium carboxymethylcellulose.
The present invention also provides a kind of application of above-mentioned sodium carboxymethylcellulose in moisturizing material.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
(1) preparation method of the invention is simple, process stabilizing, and the degree of substitution of sodium carboxymethylcellulose obtained is 0.06~
0.42, crystallinity is 30~80%, and percentage refers to that crystal region quality accounts for the ratio between sodium carboxymethylcellulose gross mass.
(2) sodium carboxymethylcellulose produced by the present invention replaces uniformly, the sum of 2- substitute proportions and 6- substitute proportions
No more than 88%, percentage refers to that accounting for 2- replaces and the sum of 6- replace accounts in sodium carboxymethylcellulose 2,3 and 6 and replace it
The ratio of sum.
(3) sodium carboxymethylcellulose moisture pick-up properties produced by the present invention is good, and every gram of sodium carboxymethylcellulose water suction is reachable
12.6~18.5 grams, there is good application value in moisturizing Material Field.
Detailed description of the invention
Fig. 1 is the X diffraction spectrogram of 1 sodium carboxymethylcellulose of embodiment (CMCNa).
Fig. 2 is the X diffraction spectrogram of 2 sodium carboxymethylcellulose of embodiment (CMCNa).
Fig. 3 is the X diffraction spectrogram of 3 sodium carboxymethylcellulose of embodiment (CMCNa).
Fig. 4 is the X diffraction spectrogram of 4 sodium carboxymethylcellulose of embodiment (CMCNa).
Fig. 5 is the X diffraction spectrogram of 5 sodium carboxymethylcellulose of embodiment (CMCNa).
Fig. 6 is the X diffraction spectrogram of commercially available sodium carboxymethylcellulose -1.
Fig. 7 is the X diffraction spectrogram of commercially available sodium carboxymethylcellulose -2.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
The crystallinity of cellulose I type is generally measured by X diffractometer (such as Shimadzu XRD-6000).Crystallinity uses Segal
Method is calculated.
In the present invention, the measuring method of sodium carboxymethylcellulose crystallinity are as follows:
Sample is put in glass guide channel, the diffracted intensity by X diffraction pattern in 2 θ=10-60 ° or 10-90 ° is scanned work
Figure.Crystallinity is calculated through following equation, and when with the diffracted intensity in 002 face when 2 θ=22.6 ° and 2 θ=18.5 ° noncrystalline portion
The diffracted intensity divided calculates.
Xc=(I002C-Ia)/I002C × 100%；
Xc represents the crystallinity of cellulose I type；
The diffracted intensity in 002 face when θ=22.6 ° I002C:2；
The diffracted intensity of non-crystallized part when θ=18.5 ° Ia:2.
In following embodiments, measures sodium carboxymethylcellulose the position of substitution ratio and degree of substitution uses NMR spectrum
Method, specific as follows:
Instrument: Bruker 500MHz Nuclear Magnetic Resonance；
Method: dispersing the sodium carboxymethylcellulose (150mg) after drying in heavy water (1.0mL) and stir, then slow
Slow heavy water/sulfuric acid mixture liquid (V/V=1/1) that 2.0mL is added, then system is heated to 90 DEG C and constant temperature two under agitation
Hour, lurid homogeneous phase solution is finally obtained, takes a part of solution to be added in nuclear-magnetism test tube and measures, the position of substitution ratio
It can be obtained from nuclear magnetic spectrogram with degree of substitution.
CMCNa- reference substance is purchased in this Reagent Company of Adama, and the viscosity of CMCNa- control 1 is 300~800MPas
Viscosity with CMCNa- control 2 is 800~1200MPas.
Embodiment 1
(1) mixed liquor is prepared in advance, and 240mL isopropanol (90% or more purity), 90mL water and 1.0g are added into system
Sodium hydroxide (95% or more purity) is uniformly mixed under stirring state, then stablizes system temperature between 25~30 DEG C.
(2) alkalinization step: system temperature is stablized between 25~30 DEG C, and (the polymerization of 10g wood pulp is added into reaction system
Degree: 900~1000), charging process control is stablized at 30 DEG C hereinafter, charging process control is in 20min or so；Then system is 25
It alkalizes between~35 DEG C, reaction time 60min；
(3) aqueous isopropanol containing 1.0g monoxone (95% or more purity) etherification step: is slowly added into step 2
Etherification reaction is carried out in material after reaction, feeds process control temp between 30~35 DEG C, and feed time control exists
20min or so.System is warming up to 70 DEG C the reaction was continued 70min after charging；
(4) it neutralizes and washing step: the material of step 3 after reaction being separated, then with acetic acid by system tune
It is 7~8 to pH, is then washed three times with 75% ethanol solution, finally dried and crushed and be equivalent to anhydrous Portugal to obtain the final product
The low degree of substitution sodium carboxymethylcellulose that grape sugar unit degree of substitution by carboxymethyl is 0.06, crystallinity is 34% (as shown in Figure 1), hundred
Ratio is divided to refer to that crystal region quality accounts for the ratio of sodium carboxymethylcellulose gross mass.It finds after tested, the position of substitution proportion is such as
Under: it be 15%, 6- substitution accountings is 32% that 2- substitution accountings, which are 53%, 3- substitution accountings, and percentage refers to each position
Substitution account in sodium carboxymethylcellulose the ratio of the sum of 2,3 and 6 substitutions respectively.
Embodiment 2
(1) mixed liquor is prepared in advance, and 250mL ethyl alcohol (90% or more purity), 100mL water and 1.5g hydrogen are added into system
Sodium oxide molybdena (95% or more purity) is uniformly mixed under stirring state, then stablizes system temperature between 25~30 DEG C.
(2) alkalinization step: system temperature is stablized between 25~30 DEG C, and (the polymerization of 10g wood pulp is added into reaction system
Degree: 900~1000), the process control temp that feeds is at 30 DEG C hereinafter, charging process control is in 20min or so；Then system is 25
It alkalizes between~35 DEG C, reaction time 65min；
(3) it is anti-that the ethanol solution containing 2.0g monoxone (95% or more purity) etherification step: is slowly added into step 2
Etherification reaction is carried out in material after answering, feeds process control temp between 30~35 DEG C, and feed time control exists
30min or so.System is warming up to 70 DEG C the reaction was continued 60min after charging；
(4) it neutralizes and washing step: the material of step 3 after reaction being separated, then with hydrochloric acid by system tune
It is 7~8 to pH, is then washed three times with 75% ethanol solution, finally dried and crushed and be equivalent to anhydrous Portugal to obtain the final product
The low degree of substitution sodium carboxymethylcellulose that grape sugar unit degree of substitution by carboxymethyl is 0.17, crystallinity is 31% (as shown in Figure 2), hundred
Ratio is divided to refer to that crystal region quality accounts for the ratio of sodium carboxymethylcellulose gross mass.It finds after tested, the position of substitution proportion is such as
Under: it be 13%, 6- substitution accountings is 25% that 2- substitution accountings, which are 62%, 3- substitution accountings, and percentage refers to each position
Substitution account in sodium carboxymethylcellulose the ratio of the sum of 2,3 and 6 substitutions respectively.
Embodiment 3
(1) mixed liquor is prepared in advance, and 200mL isopropanol (90% or more purity), 20mL water and 2.5g are added into system
Sodium hydroxide (95% or more purity) is uniformly mixed under stirring state, then stablizes system temperature between 25~30 DEG C.
(2) alkalinization step: system temperature is stablized between 25~30 DEG C, and (the polymerization of 10g wood pulp is added into reaction system
Degree: 1000~1100), the process control temp that feeds is at 30 DEG C hereinafter, charging process control is in 20min or so；Then system exists
It alkalizes between 25~35 DEG C, reaction time 70min；
(3) aqueous isopropanol containing 3.0g monoxone (95% or more purity) etherification step: is slowly added into step 2
Etherification reaction is carried out in material after reaction, feeds process control temp between 30~35 DEG C, and feed time control exists
25min.System is warming up to 70 DEG C the reaction was continued 60min after charging；
(4) it neutralizes and washing step: the material of step 3 after reaction being separated, then with citric acid by system
Be adjusted to pH be 7~8, then washed three times with 75% ethanol solution, finally dried and crushed be equivalent to obtain the final product it is anhydrous
The sodium carboxymethylcellulose that glucose unit degree of substitution by carboxymethyl is 0.34, crystallinity is 58% (as shown in Figure 3), percentage are
Refer to that crystal region quality accounts for the ratio of sodium carboxymethylcellulose gross mass.It finds after tested, the position of substitution proportion is as follows: 2-
Replacing accounting be 38%, 3- substitution accountings be 16%, 6- substitution accountings is 46%, and percentage refers to that the substitution of each position divides
The ratio of the sum of 2,3 and 6 substitutions in sodium carboxymethylcellulose is not accounted for.
Embodiment 4
(1) mixed liquor is prepared in advance, and 240mL ethyl alcohol (90% or more purity), 40mL water and 3.0g hydrogen are added into system
Sodium oxide molybdena (95% or more purity) is uniformly mixed under stirring state, then stablizes system temperature between 25~30 DEG C.
(2) alkalinization step: system temperature is stablized between 25~30 DEG C, and (the polymerization of 10g wood pulp is added into reaction system
Degree: 800~900), the process control temp that feeds is at 30 DEG C hereinafter, charging process control is in 20min or so；Then system is 25
It alkalizes between~35 DEG C, reaction time 80min；
(3) it is anti-that the ethanol solution containing 4.0g monoxone (95% or more purity) etherification step: is slowly added into step 2
Etherification reaction is carried out in material after answering, feeds process control temp between 30~35 DEG C, and feed time control exists
20min or so.System is warming up to 70 DEG C the reaction was continued 65min after charging；
(4) it neutralizes and washing step: the material of step 3 after reaction being separated, then with hydrochloric acid by system tune
It is 7~8 to pH, is then washed three times with 75% ethanol solution, finally dried and crushed and be equivalent to anhydrous Portugal to obtain the final product
The low degree of substitution sodium carboxymethylcellulose that grape sugar unit degree of substitution by carboxymethyl is 0.22, crystallinity is 39% (as shown in Figure 4), hundred
Ratio is divided to refer to that crystal region quality accounts for the ratio of sodium carboxymethylcellulose gross mass.It finds after tested, the position of substitution proportion is such as
Under: it be 12%, 6- substitution accountings is 41% that 2- substitution accountings, which are 47%, 3- substitution accountings, and percentage refers to each position
Substitution account in sodium carboxymethylcellulose the ratio of the sum of 2,3 and 6 substitutions respectively.
Embodiment 5
(1) mixed liquor is prepared in advance, and 200mL propyl alcohol (90% or more purity), 40mL water and 4.8g hydrogen are added into system
Sodium oxide molybdena (95% or more purity) is uniformly mixed under stirring state, then stablizes system temperature between 25~30 DEG C.
(2) alkalinization step: system temperature is stablized between 25~30 DEG C, and (the polymerization of 10g wood pulp is added into reaction system
Degree: 1000~1100), the process control temp that feeds is at 30 DEG C hereinafter, charging process control is in 15min or so；Then system exists
It alkalizes between 25~35 DEG C, reaction time 70min；
(3) it is anti-that the propanol solution containing 4.5g monoxone (95% or more purity) etherification step: is slowly added into step 2
Etherification reaction is carried out in material after answering, feeds process control temp between 30~35 DEG C, and feed time control exists
15min or so.System is warming up to 70 DEG C the reaction was continued 80min after charging；
(4) it neutralizes and washing step: the material of step 3 after reaction being separated, then with acetic acid by system tune
It is 7~8 to pH, is then washed three times with 75% ethanol solution, finally dried and crushed and be equivalent to anhydrous Portugal to obtain the final product
The low degree of substitution sodium carboxymethylcellulose that grape sugar unit degree of substitution by carboxymethyl is 0.42, crystallinity is 46% (as shown in Figure 5), hundred
Ratio is divided to refer to that crystal region quality accounts for the ratio of sodium carboxymethylcellulose gross mass.It finds after tested, the position of substitution proportion is such as
Under: it be 19%, 6- substitution accountings is 34% that 2- substitution accountings, which are 47%, 3- substitution accountings, and percentage refers to each position
Substitution account in sodium carboxymethylcellulose the ratio of the sum of 2,3 and 6 substitutions respectively.
The CMCNa- control 1 of Examples 1 to 5, the sodium carboxymethylcellulose that comparative example 1 is prepared and commercial source,
The degree of substitution and crystallinity values of CMCNa- control 2 are as shown in table 1, wherein crystallinity testing result such as Fig. 6 of CMCNa- control 1
Shown, the crystallinity testing result of CMCNa- control 2 is as shown in Figure 7.
Table 1
Effect example 1
Moisture absorption type test: when temperature is 20 DEG C, copper/saturated copper sulphate solution is added in drier bottom, controls in drier
Relative humidity is 98%.1.000g Examples 1 to 5 is accurately weighed respectively, the sodium carboxymethylcellulose that comparative example 1 is prepared,
And CMCNa- control 1, the CMCNa- control 2 of commercial source, it is put into the crystallising dish that diameter is 25mm, is respectively put into phase
To sucting wet experiment in constant humidity drier, is carried out, crystallising dish is taken out after 120h and is weighed, the carboxymethyl of separate sources is calculated
The moisture absorption weight of sodium cellulosate, the results are shown in Table 2, therefrom it can be concluded that sodium carboxymethylcellulose prepared by the present invention is in hygroscopicity side
Face is substantially better than commercially available similar product.
The hygroscopicity of the sodium carboxymethylcellulose of 2. separate sources of table
| Sample | Moisture absorption weight (gram) |
| Embodiment 1 | 12.6 |
| Embodiment 2 | 14.3 |
| Embodiment 3 | 18.5 |
| Embodiment 4 | 17.2 |
| Embodiment 5 | 15.0 |
| Comparative example 1 | 8.5 |
| CMCNa- control 1 | 6.7 |
| CMCNa- control 2 | 3.6 |
Comparative example 1
(1) mixed liquor is prepared in advance, and 240mL ethyl alcohol (90% or more purity), 20mL water and 9.0g hydrogen are added into system
Sodium oxide molybdena (95% or more purity) is uniformly mixed under stirring state, then stablizes system temperature between 25~30 DEG C.
(2) alkalinization step: system temperature is stablized between 25~30 DEG C, and (the polymerization of 10g wood pulp is added into reaction system
Degree: 800~900), the process control temp that feeds is at 30 DEG C hereinafter, charging process control is in 20min or so；Then system is 25
It alkalizes between~35 DEG C, reaction time 80min；
(3) it is anti-that the ethanol solution containing 3.0g monoxone (95% or more purity) etherification step: is slowly added into step 2
Etherification reaction is carried out in material after answering, feeds process control temp between 30~35 DEG C, and feed time control exists
20min or so.System is warming up to 70 DEG C the reaction was continued 65min after charging；
(4) it neutralizes and washing step: the material of step 3 after reaction being separated, then with hydrochloric acid by system tune
It is 7~8 to pH, is then washed three times with 75% ethanol solution, finally dried and crushed and be equivalent to anhydrous Portugal to obtain the final product
The low degree of substitution sodium carboxymethylcellulose that grape sugar unit degree of substitution by carboxymethyl is 0.52, crystallinity is 38%, percentage refer to knot
Brilliant regional quality accounts for the ratio of sodium carboxymethylcellulose gross mass.It finds after tested, the position of substitution proportion is as follows: 2- substitutions
It is 16%, 6- substitution accountings is 61% that accounting, which is 23%, 3- substitution accountings, and percentage refers to that the substitution of each position accounts for respectively
The ratio of the sum of 2,3 and 6 substitutions in sodium carboxymethylcellulose.
The experiment condition and properties of product of Examples 1 to 5 and comparative example 1 summarize such as table 3.
Table 3
Claims (10)
1. a kind of preparation method of sodium carboxymethylcellulose, which is characterized in that it includes the following steps:
(1) cellulose, short chain alcohol, water and sodium hydroxide hybrid reaction are obtained into mixture A, the quality of the cellulose with it is described short
The volume ratio of chain alcohol is 1:15~1:25g/mL, and the volume ratio of the quality of the cellulose and the water is 1:1~1:10g/mL,
The mass ratio of the quality of the cellulose and the sodium hydroxide is 1:0.1~1:0.8, and the short chain alcohol is carbon atom in carbochain
The alcohol of number 1~3；
(2) by mixture A described in step (1) be etherified to get.
2. the preparation method of sodium carboxymethylcellulose as described in claim 1, which is characterized in that
In step (1), the cellulose is wood pulp and/or purified cotton；
And/or in step (1), the degree of polymerization of the cellulose is 800~900,900~1000 or 1000~1100；
And/or in step (1), the short chain alcohol is one of ethyl alcohol, propyl alcohol and isopropanol or a variety of, preferably propyl alcohol and/
Or isopropanol；
And/or in step (1), the concentration of the short chain alcohol is 70~90%, and percentage refers to that the short chain alcohol is mixed with described
The percent by volume of object A；
And/or in step (1), the volume ratio of the quality of the cellulose and the short chain alcohol is 1:20~1:25g/mL, preferably
For 1:20~1:24g/mL；
And/or in step (1), the volume ratio of the quality of the cellulose and the water is 1:2~1:10g/mL, preferably 1:4
~1:9g/mL；
And/or in step (1), the mass ratio of the quality of the cellulose and the sodium hydroxide is 1:0.1~1:0.48, excellent
It is selected as 1:0.15~1:0.3；
And/or in step (1), the mixed temperature is 25~35 DEG C；
And/or in step (1), the mixed time is 50~90min.
3. the preparation method of sodium carboxymethylcellulose as described in claim 1, which is characterized in that
When the short chain alcohol is isopropanol, the volume ratio of the quality of the cellulose and the isopropanol is 1:20~1:24g/
mL；
Or, the volume ratio of the quality of the cellulose and the propyl alcohol is 1:20g/mL when the short chain alcohol is propyl alcohol；
Or, the volume ratio of the quality of the cellulose and the ethyl alcohol is 1:24~1:25g/ when the short chain alcohol is ethyl alcohol
mL。
4. the preparation method of sodium carboxymethylcellulose as described in claim 1, which is characterized in that, will be described short in step (1)
Chain alcohol, the water and the sodium hydroxide mix to obtain mixture B for the first time, by the cellulose and second of the mixture B
Mix to obtain mixture C.
5. the preparation method of sodium carboxymethylcellulose as claimed in claim 4, which is characterized in that described " mixing for the first time "
Temperature is 25~30 DEG C；
And/or the temperature of " second of mixing " is 25~30 DEG C；
And/or the cellulose charging when a length of 10~30min, preferably 15~20min.
6. the preparation method of sodium carboxymethylcellulose as described in claim 1, which is characterized in that in step (2), the etherificate
Method be mixture A described in step (1) is mixed with etherifying agent；
The etherifying agent is preferably chloroacetic short chain alcohol solution, and the short chain alcohol in the chloroacetic short chain alcohol solution is carbochain
The alcohol of middle carbon atom number 1~3；Cellulose described in step (1) and the chloroacetic mass ratio are preferably 1:0.1~1:
0.8；More preferably 1:0.1~1:0.45；
Preferably, the etherifying agent being added dropwise in step (1) the mixture A, the time of the dropwise addition is preferably 10~
30min；Wherein, the temperature of the mixture A is preferably 30~35 DEG C；
In the method for the etherificate, the mixed temperature is preferably 60~80 DEG C；
In the method for the etherificate, the mixed time is preferably 50~90min.
7. the preparation method of sodium carboxymethylcellulose as described in claim 1, which is characterized in that in step (2), after etherificate
Mixture A adjust pH to 7~8；The reagent for adjusting pH is preferably one of hydrochloric acid, acetic acid and citric acid or a variety of；
And/or in step (2), the mixture A after etherificate is washed and/or is centrifuged；The solvent of the washing is preferably 60~
80% ethanol water；The method of the centrifugation is preferably the centrifugation of Horizontal sedimentation method.
8. carboxymethyl cellulose made from a kind of preparation method of sodium carboxymethylcellulose as described in any one of claims 1 to 7
Plain sodium, which is characterized in that the degree of substitution of the sodium carboxymethylcellulose is 0.06~0.45；Crystallinity is 30~80%, percentage
Than referring to that crystal region quality accounts for the ratio between sodium carboxymethylcellulose gross mass；The sum of 2- substitute proportions and 6- substitute proportions are no
Greater than 88%, percentage refers to that the sum of 2- substitutions and 6- substitutions account for the sum of 2,3 and 6 substitutions in sodium carboxymethylcellulose
Ratio.
9. a kind of sodium carboxymethylcellulose, which is characterized in that the degree of substitution of the sodium carboxymethylcellulose is 0.06~0.45；Knot
Brilliant degree is 30~80%, and percentage refers to that crystal region quality accounts for the ratio between sodium carboxymethylcellulose gross mass；2- substitute proportions
It is not more than 88% with the sum of 6- substitute proportions, percentage refers to that 2- replace and the sum of 6- replace accounts for sodium carboxymethylcellulose
In 2,3 and 6 substitution the sum of ratio.
10. a kind of application of sodium carboxymethylcellulose as claimed in claim 8 or 9 in moisturizing material.
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