CN104877033B - A kind of preparation method of carboxymethyl modified nano-cellulose - Google Patents
A kind of preparation method of carboxymethyl modified nano-cellulose Download PDFInfo
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- CN104877033B CN104877033B CN201510297501.5A CN201510297501A CN104877033B CN 104877033 B CN104877033 B CN 104877033B CN 201510297501 A CN201510297501 A CN 201510297501A CN 104877033 B CN104877033 B CN 104877033B
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Abstract
The invention belongs to cellulose modified technical fields, and in particular to a kind of preparation method of carboxymethyl modified nano-cellulose includes the following steps：Nano-cellulose and isopropanol are added in the three-necked flask equipped with condenser pipe and mechanical stirring device, whole system is placed in constant temperature water bath apparatus after stirring evenly, add in aqueous slkali, carry out nano-cellulose first time alkalinization, continue to be added dropwise the mixed solution of isopropanol-chloroacetic acid, carry out etherification reaction, aqueous slkali is added dropwise into above-mentioned reaction system again, second of alkalinization is carried out, products therefrom is filtered, washed, drying obtains carboxymethyl nano-cellulose under the conditions of vacuum and low temperature.A kind of preparation method of carboxymethyl modified nano-cellulose of the present invention, it is simple and efficient, the carboxymethyl nano-cellulose redispersibility of preparation is good, effectively improve the performance of nano-cellulose, it is added in the dispersion of polar functionalities, the High performance nanometer composite material of particular requirement is met available for preparing.
Description
Technical field
The invention belongs to cellulose modified technical fields, and in particular to a kind of preparation side of carboxymethyl modified nano-cellulose
Method.
Background technology
Nano-cellulose has that size is small, density is low, excellent in mechanical performance, translucency is good, self assembly is functional, source
Extensively, the advantages that biodegradable and renewable, has broad application prospects in enhancing field of compound material.However, its height
Specific surface area and numerous surface-active hydroxyls, make it in the drying process, are easily made between particle by Van der Waals force and hydrogen bond
With and reunite, and temperature is higher, irreversible reunion degree is bigger, the nano-cellulose after reunion be difficult with physical method reality
Existing redisperse, this greatly limits its application mode and ranges.How ensure its crystalline texture be not damaged or only by
Under the premise of lower degree is destroyed, the redispersibility to improve it is modified to nano-cellulose, becomes the field in recent years
One of research hotspot.
At present, it focuses mostly on hydrophobic modified to the study on the modification of nano-cellulose, hydrophilically modified aspect has no phase
Close report.It is hydrophobic modified to improve its redispersibility in nonpolar dispersion, but also there are many problems.It is first
First, during the reaction, it is difficult to which the larger lyophobic dust of different polarities is sufficiently mixed with hydrophilic nano-cellulose, mixes
Reaction product after conjunction there are it is inhomogenous the shortcomings that.Secondly, using the modified methods such as be graft-polymerized, not only severe reaction conditions,
And there are the problems such as grafting efficiency is low, graft homopolymer is more.
It can be seen that a kind of method of modifying for improving nano-cellulose redispersibility can be invented, and with preparation
It is simple for process, it easily realizes, the advantages of modified effect is good, becomes the technical issues of those skilled in the art are urgently to be resolved hurrily.
Invention content
An object of the present invention is the redispersibility to solve to improve nano-cellulose, provides a kind of carboxymethyl modified receive
The preparation method of rice cellulose, the present invention improve the redispersibility of nano-cellulose using a kind of method being simple and efficient.It is real
In testing, with the part of hydroxyl on carboxymethyl substitution nano-cellulose surface, by increasing intermolecular electrostatic repulsion, drying process is reduced
In cause cellulose that the effect of irreversible keratinization occurs due to hydrogen bond locking, can reach the purpose for improving crystal redisperse, will
It is added in the dispersion of polar functionalities, and the High performance nanometer composite material of particular requirement is met available for preparing.
In order to reach above-mentioned technique effect, technical scheme of the present invention includes：
A kind of preparation method of carboxymethyl modified nano-cellulose, includes the following steps：It is stirred equipped with condenser pipe and machinery
It mixes and the isopropyl that parts by weight are 1~3 part of nano-cellulose and parts by weight are 35~105 parts is added in the three-necked flask of device
Whole system is placed in constant temperature water bath apparatus by alcohol after stirring evenly, and under 20~30 DEG C of constant temperatures, is added in aqueous slkali, is stirred
It mixes 60min and carries out nano-cellulose first time alkalinization, after completing alkalization, continue to be added dropwise parts by weight as 15 parts of isopropyls
The mixed solution of alcohol-chloroacetic acid carries out etherification reaction, then aqueous slkali is added dropwise into above-mentioned reaction system, carries out second
Secondary alkalinization, the parts by weight summation for the aqueous slkali that the alkalinization twice uses is 1.4~4.32 parts, and alkalization terminates
Afterwards, products therefrom is filtered, washed, drying obtains carboxymethyl nano-cellulose under the conditions of vacuum and low temperature.
The etherification reaction condition for regulating thermostatic bath temperature to 40~60 DEG C, react 50min.
Second of alkalinization condition is that constant temperature water bath apparatus is warming up to 50~70 DEG C, reacts 90min.
The aqueous slkali parts by weight that the aqueous slkali that the first time alkalinization adds in is added in second of alkalinization
Number is than being 3:1.
In the mixed solution of the isopropanol-chloroacetic acid, the ratio of weight and number of the isopropanol and the chloroacetic acid
It is 5~15：1.
The aqueous slkali is the sodium hydroxide solution of concentration 50%.
The mode of washing is：The product of filtering is suspended in 80% methanol, pH7.5 is neutralized to 90% acetic acid
~9, it is washed 3 times with 70% ethyl alcohol, methanol is washed 1 time, completes washing step.
The carboxymethyl nano-cellulose prepared, the degree of substitution of carboxymethyl is 1.100~1.500.
The carboxymethyl nano-cellulose grain size prepared is 30~50nm, viscosity<28mpas, purity>95.5%.
Beneficial effects of the present invention include：A kind of preparation method of carboxymethyl modified nano-cellulose of the present invention is simple high
Effect, the carboxymethyl nano-cellulose redispersibility of preparation is good, effectively improves the performance of nano-cellulose, is added to containing pole
Property group dispersion in, meet the High performance nanometer composite material of particular requirement available for preparing.
Description of the drawings
Fig. 1 show the unmodified nano-cellulose transmission electron microscope picture (scale of the present invention:100nm).
Fig. 2 show the unmodified nano-cellulose transmission electron microscope picture (scale of the present invention:50nm).
Fig. 3 show the carboxymethyl nano-cellulose transmission electron microscope picture (scale prepared by the present invention:100nm).
Fig. 4 show the carboxymethyl nano-cellulose transmission electron microscope picture (scale prepared by the present invention:50nm).
Specific embodiment
The specific embodiment of the invention is described in detail below in conjunction with specific attached drawing.It should be noted that in following embodiments
The combination of the technical characteristic or technical characteristic of description is not construed as isolated, they can be combined with each other to reach
To superior technique effect.
Embodiment 1
A kind of preparation method of carboxymethyl modified nano-cellulose, includes the following steps：It is stirred equipped with condenser pipe and machinery
The nano-cellulose and 35 parts of isopropanol for adding in that parts by weight are 1 part in the three-necked flask of device are mixed, it will be whole after stirring evenly
A system is placed in constant temperature water bath apparatus, and under 20~30 DEG C of constant temperatures, it is 1.05 parts a concentration of 50% to add in parts by weight
Sodium hydroxide solution, stirring 60min carry out nano-cellulose first time alkalinization, complete alkalization after, continue to be added dropwise
Mixed solution of the parts by weight for 15 parts of isopropanol-chloroacetic acids, regulating thermostatic bath temperature be etherified anti-to 40~60 DEG C
It answers, reaction 50min, the ratio of weight and number of isopropanol and the chloroacetic acid in the mixed solution of the isopropanol-chloroacetic acid
It is 5：1, then the sodium hydroxide solution that parts by weight are 0.35 part a concentration of 50% is added dropwise into above-mentioned reaction system and carries out
Constant temperature water bath apparatus is warming up to 50~70 DEG C, reaction 90min, after alkalization, the product that will be obtained by second of alkalinization
Filtering, the product of filtering is suspended in 80% methanol, pH7.5~9 are neutralized to 90% acetic acid, washes 3 times with 70% ethyl alcohol, first
Alcohol is washed 1 time, is dried under the conditions of vacuum and low temperature and is obtained carboxymethyl nano-cellulose.
The carboxymethyl nano-cellulose prepared, the degree of substitution of carboxymethyl is 1.100~1.500, with theoretical prediction
Value 1.364 is consistent.
The carboxymethyl nano-cellulose grain size prepared is 30~50nm, viscosity<28mpas, purity>95.5%.
Embodiment 2
A kind of preparation method of carboxymethyl modified nano-cellulose, includes the following steps：It is stirred equipped with condenser pipe and machinery
The nano-cellulose and 70 parts of isopropanol for adding in that parts by weight are 2 parts in the three-necked flask of device are mixed, it will be whole after stirring evenly
A system is placed in constant temperature water bath apparatus, and under 20~30 DEG C of constant temperatures, it is 2.16 parts a concentration of 50% to add in parts by weight
Sodium hydroxide solution, stirring 60min carry out nano-cellulose first time alkalinization, complete alkalization after, continue to be added dropwise
Mixed solution of the parts by weight for 15 parts of isopropanol-chloroacetic acids, regulating thermostatic bath temperature be etherified anti-to 40~60 DEG C
It answers, reaction 50min, the ratio of weight and number of isopropanol and the chloroacetic acid in the mixed solution of the isopropanol-chloroacetic acid
It is 10：1, then the sodium hydroxide solution that parts by weight are 0.72 part a concentration of 50% is added dropwise into above-mentioned reaction system and carries out
Constant temperature water bath apparatus is warming up to 50~70 DEG C, reaction 90min, after alkalization, the product that will be obtained by second of alkalinization
Filtering, the product of filtering is suspended in 80% methanol, pH7.5~9 are neutralized to 90% acetic acid, washes 3 times with 70% ethyl alcohol, first
Alcohol is washed 1 time, is dried under the conditions of vacuum and low temperature and is obtained carboxymethyl nano-cellulose.
The carboxymethyl nano-cellulose prepared, the degree of substitution of carboxymethyl is 1.100~1.500, with theoretical prediction
Value 1.364 is consistent.
The carboxymethyl nano-cellulose grain size prepared is 30~50nm, viscosity<28mpas, purity>95.5%.
Embodiment 3
A kind of preparation method of carboxymethyl modified nano-cellulose, includes the following steps：It is stirred equipped with condenser pipe and machinery
The nano-cellulose and 105 parts of isopropanol for adding in that parts by weight are 3 parts in the three-necked flask of device are mixed, it will be whole after stirring evenly
A system is placed in constant temperature water bath apparatus, and under 20~30 DEG C of constant temperatures, it is 3.24 parts a concentration of 50% to add in parts by weight
Sodium hydroxide solution, stirring 60min carry out nano-cellulose first time alkalinization, complete alkalization after, continue to be added dropwise
Mixed solution of the parts by weight for 15 parts of isopropanol-chloroacetic acids, regulating thermostatic bath temperature be etherified anti-to 40~60 DEG C
It answers, reaction 50min, the ratio of weight and number of isopropanol and the chloroacetic acid in the mixed solution of the isopropanol-chloroacetic acid
It is 15：1, then the sodium hydroxide solution that parts by weight are 1.08 parts a concentration of 50% is added dropwise into above-mentioned reaction system and carries out
Constant temperature water bath apparatus is warming up to 50~70 DEG C, reaction 90min, after alkalization, the product that will be obtained by second of alkalinization
Filtering, the product of filtering is suspended in 80% methanol, pH7.5~9 are neutralized to 90% acetic acid, washes 3 times with 70% ethyl alcohol, first
Alcohol is washed 1 time, is dried under the conditions of vacuum and low temperature and is obtained carboxymethyl nano-cellulose.
The carboxymethyl nano-cellulose prepared, the degree of substitution of carboxymethyl is 1.100~1.500, with theoretical prediction
Value 1.364 is consistent.
The carboxymethyl nano-cellulose grain size prepared is 30~50nm, viscosity<28mpas, purity>95.5%.
As shown in figures 1-4, by embodiment 1 prepare carboxymethyl nano-cellulose for and nano-cellulose, do transmission electricity
Mirror figure compares Fig. 1~2 it is found that modified carboxymethyl nano-cellulose still remains original basic knot with Fig. 3~4
Structure, only grain size slightly increases, and surface texture is more loose.Carboxymethyl modified nano-cellulose prepared by the present invention is used
The part of hydroxyl on carboxymethyl substitution nano-cellulose surface, by increasing intermolecular electrostatic repulsion, reduce in drying process due to
Hydrogen bond locking causes cellulose that irreversible keratinization effect occurs, and can reach the purpose for improving crystal redisperse, is added
Into the dispersion of polar functionalities, the High performance nanometer composite material of particular requirement is met available for preparing.
Above-mentioned detailed description is illustrating for the possible embodiments invented, which is not to limit this hair
Bright the scope of the claims, all equivalence enforcements or change without departing from the present invention should all be contained in the scope of the claims of the present invention.
In addition, those skilled in the art can also the claims in the present invention scope of disclosure and spirit in do other forms and
Various modifications, addition and replacement in details.Certainly, these spirit is done according to the present invention various modifications, addition and replacements
Deng variation, should all include within scope of the present invention.
Claims (9)
1. a kind of preparation method of carboxymethyl modified nano-cellulose, which is characterized in that include the following steps：Equipped with condenser pipe
It is 1~3 part of nano-cellulose and parts by weight are 35~105 with parts by weight are added in the three-necked flask of mechanical stirring device
Whole system, is placed in constant temperature water bath apparatus by the isopropanol of part after stirring evenly, and under 20~30 DEG C of constant temperatures, adds in alkali
Solution, stirring 60min carry out nano-cellulose first time alkalinization, complete alkalization after, continue that parts by weight are added dropwise be
The mixed solution of 15 parts of isopropanol-chloroacetic acids carries out etherification reaction, then aqueous slkali is added dropwise into above-mentioned reaction system,
Second of alkalinization is carried out, the parts by weight summation for the aqueous slkali that the alkalinization twice uses is 1.4~4.32
Part, after alkalization, products therefrom is filtered, washed, drying obtains carboxymethyl nano-cellulose under the conditions of vacuum and low temperature.
A kind of 2. preparation method of carboxymethyl modified nano-cellulose according to claim 1, which is characterized in that the ether
Change reaction condition for regulating thermostatic bath temperature to 40~60 DEG C, react 50min.
3. the preparation method of a kind of carboxymethyl modified nano-cellulose according to claim 1, which is characterized in that described
Double alkalisation process condition is that constant temperature water bath apparatus is warming up to 50~70 DEG C, reacts 90min.
4. the preparation method of a kind of carboxymethyl modified nano-cellulose according to claim 1, which is characterized in that described
The aqueous slkali that alkalinization adds in is 3 with the aqueous slkali ratio of weight and number that second of alkalinization adds in:1.
5. the preparation method of a kind of carboxymethyl modified nano-cellulose according to claim 1, which is characterized in that described different
In the mixed solution of propyl alcohol-chloroacetic acid, the ratio of weight and number of the isopropanol and the chloroacetic acid is 5~15：1.
6. the preparation method of a kind of carboxymethyl modified nano-cellulose according to claim 1, which is characterized in that described
Aqueous slkali is the sodium hydroxide solution of concentration 50%.
7. the preparation method of a kind of carboxymethyl modified nano-cellulose according to claim 1, which is characterized in that described
Mode of washing is：The product of filtering is suspended in 80% methanol, pH7.5~9 are neutralized to 90% acetic acid, with 70% ethyl alcohol
It washes 3 times, methanol is washed 1 time, completes washing step.
8. according to a kind of preparation method of carboxymethyl modified nano-cellulose of claim 1~7 any one of them, feature exists
In the carboxymethyl nano-cellulose of preparation, the degree of substitution of carboxymethyl is 1.100~1.500.
9. according to a kind of preparation method of carboxymethyl modified nano-cellulose of claim 1~7 any one of them, feature exists
In the carboxymethyl nano-cellulose grain size of, preparation be 30~50nm, viscosity<28mpas, purity>95.5%.
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| CN105601756A (en) * | 2015-12-17 | 2016-05-25 | 华南理工大学 | Acetylation modification method for preparing nano cellulose |
| WO2017138574A1 (en) * | 2016-02-08 | 2017-08-17 | 日本製紙株式会社 | Modified carboxymethylated cellulose nanofiber dispersion and method for manufacturing same |
| CN108530545A (en) * | 2017-03-03 | 2018-09-14 | 重庆市曾东燃纳米科技合伙企业（有限合伙） | A kind of nano-cellulose and preparation method thereof |
| CN107602709B (en) * | 2017-10-25 | 2020-07-10 | 北京理工大学 | Clean preparation method of carboxymethyl nano-cellulose material |
| CN111448218B (en) * | 2017-12-07 | 2023-05-05 | 日本制纸株式会社 | Carboxymethylated cellulose nanofibers |
| CN108330558A (en) * | 2018-03-08 | 2018-07-27 | 唐卫兵 | A kind of preparation method of the hydrophobic fibre element chitosan nano fiber spinning solution of antibacterial functions |
| CN113956365B (en) * | 2020-07-21 | 2023-05-30 | 中国石油化工股份有限公司 | Composition for preparing filtrate reducer and filtrate reducer |
| CN114409811A (en) * | 2021-12-21 | 2022-04-29 | 浙江金昌特种纸股份有限公司 | Nano cellulose capable of being stably dispersed in high-salt environment and preparation method thereof |
| CN115353762A (en) * | 2022-08-09 | 2022-11-18 | 江苏海晟涂料有限公司 | High-weather-resistance water-based paint for metal surface |
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| CN103242453A (en) * | 2012-08-14 | 2013-08-14 | 常熟威怡科技有限公司 | Method for preparing low-viscosity sodium carboxymethylcellulose |
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| CN1386763A (en) * | 2002-05-27 | 2002-12-25 | 中国科学院广州化学研究所 | Surface modified nano cellulose crystal and its preparing process |
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| CN104558206A (en) * | 2014-12-24 | 2015-04-29 | 青岛文创科技有限公司 | Method for preparing sodium carboxymethylcellulose |
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