CN101067002A - Kneading process of preparing polyanionic cellulose - Google Patents
Kneading process of preparing polyanionic cellulose Download PDFInfo
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- CN101067002A CN101067002A CN 200710118976 CN200710118976A CN101067002A CN 101067002 A CN101067002 A CN 101067002A CN 200710118976 CN200710118976 CN 200710118976 CN 200710118976 A CN200710118976 A CN 200710118976A CN 101067002 A CN101067002 A CN 101067002A
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Abstract
The low bath ratio kneading process of preparing polyanionic cellulose has the cellulose alkalizing reaction and etherifying reaction in different conditions completed separately in a kneading machine and a plough type reactor. The preparation process includes alkalizing cellulose with organic solvent and alkali metal hydroxide in a kneading machine, adding etherifying agent and mixing homogeneous through stirring, etherifying reaction in a plough type reactor, flushing the resultant without being cooled to the neutralizing kettle, neutralizing excessive alkali with acetic acid or hydrochloric acid, centrifuging, washing and drying. The present invention has shortened preparation period, low production cost and reduced power consumption.
Description
Technical field
The present invention relates to a kind of preparation method of Polyanionic Cellulose, particularly mediate the method that legal system is equipped with Polyanionic Cellulose, it belongs to technical field of polymer chemistry.
Background technology
Polyanionic Cellulose is under certain liquid-solid ratio condition or the uniform carboxymethyl cellulose of replacement for preparing under the special process condition; be to adopt alkalization, etherification reaction on cellulose molecular chain, to introduce the sodium carboxymethyl group; belong to the ionic ether of cellulose; have thickening, dispersion, film forming, cohere and characteristics such as protective colloid, be widely used in petroleum drilling, weaving, printing and dyeing, pottery, coating, building materials, papermaking, food, sewage disposal, daily use chemicals and medicine and other fields.
The preparation method of Polyanionic Cellulose and carboxymethyl cellulose is basic identical, and Mierocrystalline cellulose obtains crude product through alkalization, etherification reaction, again through neutralization, washing purification.Alkalization and etherification reaction are the cores of whole process of preparation, also are the keys of decision product performance.
The early stage method of making carboxymethyl cellulose is that Mierocrystalline cellulose is impregnated in the aqueous sodium hydroxide solution, and excess base is removed in squeezing, obtains soda cellulose, adds etherifying agent and carry out etherification reaction in kneader.But the pickling process troublesome poeration, efficient is low, and alkali number is not easy to be adjusted to preset value.
Patent CN88101790 and CN95111052.7 adopt different material, and alkalization and etherificate are carried out in same kneader.Need different temperature in alkalization and etherification reaction process, alkalizing needs temperature low, and etherificate needs the temperature height, has reduced the repeating utilization factor of kneader so inevitably.In addition, it is different with the state of material in the etherification procedure to alkalize, and the stirring intensity that needs is also had any different.
It is solvent that patent US4306061 discloses with acetone, adds borax and improves the method that the inhomogeneity slurry process of replacement prepares carboxymethyl cellulose.Patent 02133901.5 immersion process for preparing soda cellulose, adopting Virahol again is that the slurry process of solvent is with the soda cellulose etherificate.Patent CN99116674.4 slurry process is an organic medium with the Virahol, adds pyridine and borax prepares carboxymethyl cellulose.Adopt the slurry process of a large amount of organic mediums, the mass transfer in the reaction process, easier carry out and more even of conducting heat, the product substituting group distributes also even.But the reaction times of slurry process is far longer than the kneading method, and plant factor is low, and a large amount of uses of organic solvent, must increase the cost that solvent recuperation is purified.
Patent CN99116674.4 has reported that also Mierocrystalline cellulose carries out pre-treatment in mineral acid example hydrochloric acid, sulfuric acid etc., be dissolved in lithium chloride/dimethylacetamide solution again, add caustic soda and make soda cellulose, thereby be that etherifying agent carries out etherification reaction and makes the Xylo-Mucine product again with the Monochloro Acetic Acid under homogeneous phase condition.Cellosolve lithium chloride/N,N-DIMETHYLACETAMIDE price is high, does not also have good recovery method at present.
The present invention adopts the kneading legal system to be equipped with Polyanionic Cellulose, and quaternization is carried out in different equipment with etherification reaction, can improve production efficiency when guaranteeing quality product, reduces production costs.
Summary of the invention
As everyone knows, because the complicacy of this body structure of Mierocrystalline cellulose, make it in multiphase medium during etherificate, the velocity of diffusion of chemical reaction velocity and reagent is unequal, and chemical reaction velocity is greater than the speed of response of reagent, causes reacting the ununiformity with product.The objective of the invention is according to Mierocrystalline cellulose in alkalization and the difference during etherification reaction, propose a kind of in distinct device, alkalize and etherificate to prepare the method for Polyanionic Cellulose.
Technical scheme of the present invention is:
1) cellulosic alkalization: cool off kneader in advance.40%～50% sodium hydroxide solution and mass concentration are not less than 90% organic solvent and mix with certain proportion, on the Mierocrystalline cellulose that in 10～35 minutes, in kneader, constantly stirs by the jet pipe spray, the control alkalization temperature is at 5～35 ℃, alkalization time 0.5～3.0 hour, make the abundant swollen of Mierocrystalline cellulose, activation, in the hope of obtaining the uniform soda cellulose that alkalizes.
The mass ratio of Mierocrystalline cellulose and organic solvent is 1: 1～5, and organic solvent can be Virahol, ethanol, methyl alcohol, Virahol/ethanol, isopropylcarbinol etc.The mass ratio of Mierocrystalline cellulose and alkali metal hydroxide is 1: 0.4～1.2.
2) cellulosic transfer: after quaternization finishes, evenly spray Mono Chloro Acetic Acid/organic solvent solution by the acid spraying tube in the kneader under 5～35 ℃, the concentration of Mono Chloro Acetic Acid/organic solvent solution is 50%～70%.After stirring, discharging is in plough formula reactor.Mierocrystalline cellulose and chloroacetic mass ratio are 1: 0.5～1.2, and the time that adds chloroacetic acid solution is 20～40 minutes.
3) cellulosic etherificate: material at the uniform velocity heats by adding cover in plough formula reactor, the beginning etherification reaction.Etherification reaction temperature is 45～80 ℃, 40～180 minutes reaction times.
4) neutralization and aftertreatment: after reaction finishes, need not cooling, directly with washing medium flushing material in and still, with excessive alkali in acetic acid or the hydrochloric acid and in the system, centrifugal, washing, drying.Washing medium can be methyl alcohol, ethanol or Virahol; Flushing can contain certain density inorganic salt or not contain inorganic salt with washing medium.
The substitution value of product is 0.5～1.15.
Inventive point of the present invention is:
1) is equipped with Polyanionic Cellulose by mediating legal system;
2) different according to quaternization and etherification reaction, alkalization is carried out in different equipment with etherification reaction;
3) mixed solution of alkali lye and organic solvent and chloroacetic acid solution slowly evenly add in the spray mode;
4) after etherification reaction finishes, need not cooling, directly with washing medium flushing material in and still.
Beneficial effect of the present invention is:
With the kneading method in distinct device respectively the alkalization and etherificate prepare Polyanionic Cellulose, can shorten preparation cycle, save production cost, cut down the consumption of energy easy handling.
Specific embodiment
Followingly explain the present invention, but the present invention is not limited to embodiment according to embodiment.
Embodiment 1:
Cool off kneader in advance, under agitation condition, the 240kg Mierocrystalline cellulose is joined in the kneader, 700L sodium hydroxide and alcoholic acid mixing solutions join in the kneader by the alkali wine shower of pinching in the machine, fully contact with Mierocrystalline cellulose under the stirring of kneader.Drive anti-car twice during this time, each 1-5 minute.Sodium hydroxide concentration is 50%, and add-on is 280L.Reacted 60 minutes down in 18 ℃.Mono Chloro Acetic Acid/the ethanolic soln that adds 330L 60% (wt), discharging is to plough formula reactor.
Material is warming up to 75 ℃ of reactions 60 minutes in plough formula reactor.After reaction finishes, open flush valve, put into flushing wine flushing material to and still, with the hydrochloric acid neutralization, wash then, centrifugal, drying.
According to the GB2005 testing standard, measuring the product substitution value is 0.96.
Embodiment 2:
Cool off kneader in advance, under agitation condition, the 240kg Mierocrystalline cellulose is joined in the kneader, the mixing solutions of 800L sodium hydroxide and Virahol joins in the kneader by the alkali wine shower of pinching in the machine, fully contacts with Mierocrystalline cellulose under the stirring of kneader.Drive anti-car twice during this time, each 1-5 minute.Sodium hydroxide concentration is 50%, and add-on is 300L.Reacted 45 minutes down in 20 ℃.Mono Chloro Acetic Acid/the aqueous isopropanol that adds 305L 65% (wt), discharging is to plough formula reactor.
Material is warming up to 78 ℃ of reactions 50 minutes in plough formula reactor.After reaction finishes, open flush valve, put into flushing wine flushing material to and still, with the hydrochloric acid neutralization, wash then, centrifugal, drying.
According to the GB2005 testing standard, measuring the product substitution value is 1.12.
Embodiment 3:
Cool off kneader in advance, under agitation condition, the 240kg Mierocrystalline cellulose is joined in the kneader, 600L sodium hydroxide and alcoholic acid mixing solutions join in the kneader by the alkali wine shower of pinching in the machine, fully contact with Mierocrystalline cellulose under the stirring of kneader.Drive anti-car twice during this time, each 1-5 minute.Sodium hydroxide concentration is 45%, and add-on is 180L.Reacted 45 minutes down in 20 ℃.Mono Chloro Acetic Acid/the ethanolic soln that adds 270L 50% (wt), discharging is to plough formula reactor.
Material is warming up to 78 ℃ of reactions 60 minutes in plough formula reactor.After reaction finishes, open flush valve, put into flushing wine flushing material to and still, with the hydrochloric acid neutralization, wash then, centrifugal, drying.
According to the GB2005 testing standard, measuring the product substitution value is 0.67.
Claims (9)
1. mediate the method that legal system is equipped with Polyanionic Cellulose for one kind, it is characterized in that: in kneader, make the Mierocrystalline cellulose alkalization with organic solvent-alkali metal hydroxide; Add etherifying agent/organic solvent solution then, stir, discharging is to plough formula reactor; In plough formula reactor, carry out etherification reaction; After reaction finishes, need not cooling, directly with washing medium flushing material in and still, with in acetic acid or the hydrochloric acid and the alkali in the system, product is centrifugal, washing, drying.
2. according to claims 1 described a kind of method for preparing Polyanionic Cellulose, it is characterized in that cellulosic quaternization carries out in kneader.
3. according to claims 1 described a kind of method for preparing Polyanionic Cellulose, it is characterized in that alkali metal hydroxide aqueous solution sprays adding, 10～35 minutes joining days after organic solvent mixes; Mierocrystalline cellulose can be gossypin or wood cellulose.
4. according to claims 3, wherein Mierocrystalline cellulose and organic solvent mass ratio are 1: 1～5, and organic solvent can be Virahol, ethanol, Virahol/ethanol, isopropylcarbinol etc., and the mass concentration of organic solvent is not less than 90%.
5. according to claims 3, the mass ratio of Mierocrystalline cellulose and alkali metal hydroxide is 1: 0.4～1.2, and the concentration of alkali hydroxide soln is 40%～50%, alkalization time 0.5～3.0 hour, 5～35 ℃ of temperature; Alkali metal hydroxide can be sodium hydroxide, potassium hydroxide.
6. according to claims 1 described a kind of method for preparing Polyanionic Cellulose, it is characterized in that in kneader, adding etherifying agent; Etherifying agent is dissolved in and forms 50%～70% solution in the organic solvent, adds reactor with the form of spraying, and 20～40 minutes joining days, the back discharging that stirs is to plough formula reactor.
7. according to claims 1 described a kind of method for preparing Polyanionic Cellulose, it is characterized in that etherification reaction carries out in plough formula reactor.
8. according to claims 1 described a kind of method for preparing Polyanionic Cellulose, it is characterized in that etherification reaction temperature is 45～80 ℃, in 40～180 minutes reaction times, Mierocrystalline cellulose and chloroacetic mass ratio are 1: 0.5～1.2.
9. according to claims 1 described a kind of method for preparing Polyanionic Cellulose, it is characterized in that etherification reaction finishes after, need not cooling, directly with washing medium flushing material in and still; Washing medium can be methyl alcohol, ethanol or Virahol; Flushing contains 0～5% inorganic salt with washing medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2007101189769A CN100494219C (en) | 2007-06-15 | 2007-06-15 | Kneading process of preparing polyanionic cellulose |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007101189769A CN100494219C (en) | 2007-06-15 | 2007-06-15 | Kneading process of preparing polyanionic cellulose |
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| CN101067002A true CN101067002A (en) | 2007-11-07 |
| CN100494219C CN100494219C (en) | 2009-06-03 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417541A (en) * | 2011-10-18 | 2012-04-18 | 杭州弘博化工有限公司 | Preparation method of sodium carboxymethylcellulose for adding into wet part of papermaking machine and product thereof |
| CN103087202A (en) * | 2012-12-20 | 2013-05-08 | 杭州弘博化工有限公司 | Preparation method of polyanionic cellulose with ultrahigh viscosity for water-based drilling fluid |
| CN108579687A (en) * | 2018-04-17 | 2018-09-28 | 陕西科技大学 | A kind of method and its application preparing carboxymethyl cellulose using solvent method |
| CN109021118A (en) * | 2018-07-24 | 2018-12-18 | 河南正弘药用辅料有限公司 | A kind of production method of hydroxypropyl cellulose |
| CN112457418A (en) * | 2020-11-30 | 2021-03-09 | 泸州北方纤维素有限公司 | Preparation method of hydroxyethyl cellulose |
-
2007
- 2007-06-15 CN CNB2007101189769A patent/CN100494219C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417541A (en) * | 2011-10-18 | 2012-04-18 | 杭州弘博化工有限公司 | Preparation method of sodium carboxymethylcellulose for adding into wet part of papermaking machine and product thereof |
| CN103087202A (en) * | 2012-12-20 | 2013-05-08 | 杭州弘博化工有限公司 | Preparation method of polyanionic cellulose with ultrahigh viscosity for water-based drilling fluid |
| CN108579687A (en) * | 2018-04-17 | 2018-09-28 | 陕西科技大学 | A kind of method and its application preparing carboxymethyl cellulose using solvent method |
| CN109021118A (en) * | 2018-07-24 | 2018-12-18 | 河南正弘药用辅料有限公司 | A kind of production method of hydroxypropyl cellulose |
| CN112457418A (en) * | 2020-11-30 | 2021-03-09 | 泸州北方纤维素有限公司 | Preparation method of hydroxyethyl cellulose |
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| Publication number | Publication date |
|---|---|
| CN100494219C (en) | 2009-06-03 |
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