CN1730495A - Hydroxy ethyl cellulose preparation method - Google Patents
Hydroxy ethyl cellulose preparation method Download PDFInfo
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- CN1730495A CN1730495A CN 200510019340 CN200510019340A CN1730495A CN 1730495 A CN1730495 A CN 1730495A CN 200510019340 CN200510019340 CN 200510019340 CN 200510019340 A CN200510019340 A CN 200510019340A CN 1730495 A CN1730495 A CN 1730495A
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Abstract
The invention discloses a novel process for synthesizing hydroxyethyl cellulose through homogeneous phase aqueous solution system, which comprises completely dissolving cellulose into 7-8% by weight percentage concentration of NaOH / 10-13% aqueous solution of urea, so as to obtain cellulose solution, then charging chlorethanol into the cellulose solution for homogeneous phase hydroxyethylation reaction, thus obtaining the needed hydroxyethyl cellulose with high rate of product purity and high viscosity of water-soluble product.
Description
Technical field
The present invention relates to a kind of method for preparing Natvosol, specifically in cellulosic sodium hydroxide/urea homogeneous phase aqueous solution system, carry out the method that ethoxyl etherification prepares Natvosol.
Background technology
Natvosol (HEC) is a kind of water miscible non-ionic celluloses ether.Because the consistency of water-soluble polymers, tensio-active agent and the salt of it and broad range, with do not have gelation point not have the characteristic of set point yet, and have thickening, suspension, dispersion, emulsification, bonding, film forming, protection moisture and improve excellent properties such as protective colloid, numerous areas (R.Donges such as oil production, coating, building, medicine food, weaving, papermaking and high molecular polymerization have been widely used in, British Polym.J., 1990,23,315-326; Noble and unsullied, Tang Liegui, Mierocrystalline cellulose science, Science Press, 1999).Owing to have very strong intramolecularly and intermolecular hydrogen bonding effect, Mierocrystalline cellulose is difficult to be dissolved in usual vehicle, also is difficult to melt-processed.At present, the production technique of HEC has vapor phase process and liquid phase method.These two kinds of production technique all need prepare soda cellulose in advance.Exquisite wood pulp or linters are mixed the generation soda cellulose mutually with the NaOH solution of high density, again the Mierocrystalline cellulose that obtains be impregnated in concentration and be degreasing among about 18% the NaOH in about 20 ℃, add oxyethane then and carry out etherificate, the removal of impurity, drying, grind and make the finished product.In the production process of above two kinds of HEC, all need to add a large amount of organic solvents such as Virahol, propyl carbinol, acetone etc. as thinner (Th.G.Majewicz, Walter G.Ropp, Method of preparing hydroxyethyl ethers ofcellulose, US Patent 4298728, Nov.3,1981.), increased production cost undoubtedly and brought serious environmental to pollute.Simultaneously, owing to be reflected under the out-of-phase condition and carry out, reaction process is difficult to control, the homogeneity and the quality of product all are difficult to be guaranteed.Thus, develop inexpensive, free of contamination cellulose homogeneous-phase derivatize system and become a focus of present Mierocrystalline cellulose research (T.Heinze, T.Liebert, Prog.Polym.Sci., 2001,26,1689-1762.).
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing Natvosol.This method is cheap, and is easy and simple to handle, pollution-free, the good uniformity of products obtained therefrom, purity height.
For achieving the above object, technical scheme provided by the invention is: a kind of method for preparing Natvosol, it is to obtain cellulose solution in 7～8%NaOH/10～13% aqueous solution of urea that Mierocrystalline cellulose is dissolved in concentration expressed in percentage by weight fully, and adds chloroethanol carry out the homogeneous phase ethoxyl etherification and obtain required Natvosol in this cellulose solution.
The preparation of above-mentioned cellulose solution: with concentration expressed in percentage by weight is that 7～8%NaOH/10～13% aqueous solution of urea is cooled to-8～-15 ℃ in advance, adds Mierocrystalline cellulose then and also at room temperature stirs 3～5 minutes, and instant separating obtains transparent cellulose solution.
The concentration expressed in percentage by weight of above-mentioned cellulose solution is 0.5～10%.Used cellulosic highest weight is 16.0 * 10
4, the optimum weight scope is 3.0 * 10
4～12.0 * 10
4
The add-on of above-mentioned chloroethanol is unrestricted, but its add-on is preferably 2～6 times of Mierocrystalline cellulose institute hydroxyl molar weight.
In aforesaid method, chloroethanol is joined in the cellulose solution, in 0 ℃～90 ℃ stirring reactions 1～48 hour, add acetic acid neutralization reaction liquid then to neutral stopped reaction; With the Natvosol that reaction solution separates, drying obtains high purity, high uniformity.
Compared with the prior art, the present invention has remarkable technical progress.At first present method is a synthetic Natvosol in the cellulose homogeneous-phase aqueous solution, and used cellulose solution is nontoxic, pollution-free, and is cheap, simple synthetic method, productive rate height, and reaction process is easy to control.And do not need to add organic solvent and make thinner and extra catalyst, products obtained therefrom purity height, substituting group is evenly distributed on the Mierocrystalline cellulose glucose unit, the low and viscosity height of the preparation desired substitution value of water-soluble products, and also the reaction process Mierocrystalline cellulose is gone up not degraded substantially.The present invention can make the Natvosol of higher molecular weight, has higher industrial application value.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention and application are described further:
Embodiment 1～7
With 196 gram weight percentage concentrations is that the 7.5%NaOH/11% aqueous solution of urea is cooled to-12 ℃ in advance, and (cotton linter pulp, molecular weight are 11.4 * 10 to add 4 gram Mierocrystalline celluloses then
4) at room temperature stirred 3～5 minutes, promptly obtain concentration expressed in percentage by weight and be 2% cellulose solution.Get above-mentioned cellulose solution 200 grams, add the chloroethanol of metering, and, add acetic acid neutralization reaction liquid then to neutral stopped reaction in 25 ℃～80 ℃ stirred in water bath reactions 3～6 hours.Reaction gained solution is dialysed a week after lyophilize or vacuum-drying obtain the pure product of white powder Natvosol.The substitution value of the reaction conditions of embodiment 1～7, productive rate and products obtained therefrom (DS), molar substitution (MS), the limiting viscosity in the aqueous solution ([η]) and viscosity-average molecular weight (M
η) compile subordinate list 1.Embodiment 1～7 prepared Natvosol all has good solvability in water and methyl-sulphoxide.
The substitution value (DS) of reaction conditions, productive rate and the products obtained therefrom of subordinate list 1 embodiment 1～7, molar substitution (MS), the limiting viscosity in the aqueous solution ([η]) and weight-average molecular weight (M
w)
| Embodiment | Mol ratio | Reaction conditions | Productive rate (gram) | MS | DS | The position distribution of substituting group on the Mierocrystalline cellulose glucose unit | [η] (mL/g) | M w (×10 4g/mol) |
| C2 C3 C6 | ||||||||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 | 1∶3 1∶3 1∶3 1∶3 1∶3 1∶2.5 1∶4 | Room temperature reaction is warming up to 1.5 hours room temperature reactions of 50 ℃ of reactions and is warming up to 3 hours room temperature reactions of 50 ℃ of reactions after 2 hours and is warming up to 3.5 hours room temperature reactions of 50 ℃ of reactions after 2.5 hours and is warming up to 25 hours room temperature reactions of 65 ℃ of reactions after 25 hours and is warming up to 3.5 hours room temperature reactions of 80 ℃ of reactions after 1.5 hours and is warming up to 3.5 hours room temperature reactions of 50 ℃ of reactions after 15 hours and is warming up to 50 ℃ of reactions 3.5 hours after 1.5 hours after 1.5 hours | 4.49 4.50 4.62 4.57 4.55 4.43 4.67 | 0.90 1.04 1.06 1.00 1.10 0.86 1.44 | 0.77 0.84 0.86 0.83 0.84 0.72 1.14 | 0.29 0.19 0.25 0.29 0.26 0.29 0.29 0.26 0.31 0.32 0.22 0.29 0.30 0.26 0.28 0.28 0.21 0.23 0.44 0.30 0.40 | 389.8 391.2 397.0 387.4 391.4 392.9 398.6 | 15.5 15.9 15.9 16.1 15.3 14.8 16.2 |
Annotate 1: mol ratio is the hydroxyl on the Mierocrystalline cellulose glucose unit and the mol ratio of chloroethanol.
Annotate 2: limiting viscosity ([η]) records with Ubbelohde viscometer under 25 ℃, and solvent is a water.
Annotate 3: substitution value (DS) and molar substitution (MS) record (Y.Tezuka, K.Imai, M.Oshima, T.Chiba, Polymer, 1989,30,2288 by nucleus magnetic resonance; J.Schaller, T.Heinze, Macromol.Biosci.2005,5,58).
Annotate 4: weight-average molecular weight (M
w) record by the chromatograph joint used device of laser light scattering one size exclusion, solvent is 0.1mol/L.
Embodiment 8
With 196 gram weight percentage concentrations is that the 7.5%NaOH/12% aqueous solution of urea is cooled to-12 ℃ in advance, and (cotton linter pulp, molecular weight are 11.4 * 10 to add 4 gram Mierocrystalline celluloses then
4) at room temperature stirred 3～5 minutes, promptly obtain concentration expressed in percentage by weight and be 2% cellulose solution.Get above-mentioned cellulose solution 200 grams, add chloroethanol 12 grams, reaction is 1 hour under room temperature, is warming up to 50 ℃ of reactions 4 hours then, adds acetic acid neutralization reaction liquid to neutral stopped reaction.Partly separate with water-insoluble water-soluble by centrifugation method, and precipitation, vacuum-drying obtains water-soluble and two white powder Natvosols of water-insoluble product.Wherein water-soluble portion weight is 1.70 grams, and substitution value (DS) is 0.48; Water-insoluble part weight is 2.77 grams, and substitution value (DS) is 0.45.
Embodiment 9
With 480 gram weight percentage concentrations is that the 7%NaOH/12% aqueous solution of urea is cooled to-12 ℃ in advance, and (cotton linter pulp, molecular weight are 11.4 * 10 to add 20 gram Mierocrystalline celluloses then
4) at room temperature stirred 3～5 minutes, promptly obtain concentration expressed in percentage by weight and be 4% cellulose solution.Get above-mentioned cellulose solution 500 grams, respectively add chloroethanol 46 grams at twice, reaction is 2 hours under room temperature, is warming up to 50 ℃ of reactions 6 hours then, adds acetic acid neutralization reaction liquid to neutral stopped reaction.Reaction product solution obtains water soluble ethoxyl cellulose prods 25 grams through acetone precipitation repeatedly, water-soluble and acetone precipitation final vacuum drying, and its substitution value (DS) and molar substitution (MS) are respectively 0.77 and 0.94.
Embodiment 10
With 186 gram weight percentage concentrations is that the 7%NaOH/13% aqueous solution of urea is cooled to-12 ℃ in advance, and (CF-11, molecular weight are 4.2 * 10 to add 14 gram Mierocrystalline celluloses then
4) at room temperature stirred 3～5 minutes, promptly obtain concentration expressed in percentage by weight and be 7% cellulose solution.Get above-mentioned cellulose solution 200 grams, add chloroethanol 64 grams, reaction is 2 hours under room temperature, is warming up to 50 ℃ of reactions 3 hours then, adds acetic acid neutralization reaction liquid to neutral stopped reaction.Reaction gained solution is dialysed a week after lyophilize or vacuum-drying obtain pure product 18 grams of white powder Natvosol, and its substitution value (DS) and molar substitution (MS) are respectively 0.81 and 1.2.
Embodiment 11
With 196 gram weight percentage concentrations is that the 7.5%NaOH/12% aqueous solution of urea is cooled to-12 ℃ in advance, and (regenerated cellulose, molecular weight are 15.6 * 10 to add 4 gram Mierocrystalline celluloses then
4) at room temperature stirred 3～5 minutes, promptly obtain concentration expressed in percentage by weight and be 2% cellulose solution.Get above-mentioned cellulose solution 200 grams, add chloroethanol 20 grams, reaction is 48 hours under room temperature, adds acetic acid neutralization reaction liquid to neutral stopped reaction.Reaction product solution obtains water soluble ethoxyl cellulose prods 3.7 grams through acetone precipitation repeatedly, water-soluble and acetone precipitation final vacuum drying, and its substitution value (DS) and molar substitution (MS) are respectively 0.79 and 1.05.
Experimental result shows, adopts method provided by the invention successfully to synthesize the Natvosol with different solubility characteristics, and synthetic method is simple, productive rate is higher, uniform substituent distribution, and be friendly process; Gained water soluble ethoxyl Mierocrystalline cellulose viscosity height.
Claims (4)
1. method for preparing Natvosol, it is characterized in that: it is to obtain cellulose solution in 7～8%NaOH/10～13% aqueous solution of urea that Mierocrystalline cellulose is dissolved in concentration expressed in percentage by weight fully, and adds chloroethanol carry out the homogeneous phase ethoxyl etherification and obtain required Natvosol in this cellulose solution.
2. method according to claim 1 is characterized in that: with concentration expressed in percentage by weight is that 7～8%NaOH/10～13% aqueous solution of urea is cooled to-8～-15 ℃ in advance, adds Mierocrystalline cellulose then and also at room temperature stirs 3～5 minutes, promptly obtains cellulose solution.
3. method according to claim 1 and 2 is characterized in that: the concentration of above-mentioned cellulose solution is 0.5～10wt%.
4. method according to claim 1 and 2 is characterized in that: chloroethanol is joined in the cellulose solution, in 0 ℃～90 ℃ stirring reactions 1～48 hour, add acetic acid neutralization reaction liquid then to neutral stopped reaction; Reaction solution separation, drying are obtained Natvosol.
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|---|---|---|---|
| CNB200510019340XA CN1313495C (en) | 2005-08-24 | 2005-08-24 | Hydroxy ethyl cellulose preparation method |
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|---|---|---|---|
| CNB200510019340XA CN1313495C (en) | 2005-08-24 | 2005-08-24 | Hydroxy ethyl cellulose preparation method |
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| CN1313495C CN1313495C (en) | 2007-05-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920181A (en) * | 2014-04-03 | 2014-07-16 | 石家庄亿生堂医用品有限公司 | Water soluble hemostatic material and preparation method thereof |
| CN104119453A (en) * | 2014-07-06 | 2014-10-29 | 福建农林大学 | Method for preparing hydroxyethyl cellulose by utilizing bamboo pulp |
| CN111333735A (en) * | 2020-04-16 | 2020-06-26 | 江南大学 | Method for preparing hydroxyethyl cellulose solution with low substitution degree for spinning |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112396C (en) * | 2000-04-17 | 2003-06-25 | 武汉大学 | Cellulose film preparing method |
| CN1125845C (en) * | 2000-04-17 | 2003-10-29 | 武汉大学 | Solvent composition and its use |
| CN1149225C (en) * | 2002-04-09 | 2004-05-12 | 武汉大学 | Process for preparing hydroxy ethyl cellulose |
| CN1193061C (en) * | 2003-07-25 | 2005-03-16 | 武汉大学 | Solvent composite and preparation method and use thereof |
| CN1205229C (en) * | 2003-07-25 | 2005-06-08 | 武汉大学 | Method for preparing hydroxypropyl cellulose |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920181A (en) * | 2014-04-03 | 2014-07-16 | 石家庄亿生堂医用品有限公司 | Water soluble hemostatic material and preparation method thereof |
| CN104119453A (en) * | 2014-07-06 | 2014-10-29 | 福建农林大学 | Method for preparing hydroxyethyl cellulose by utilizing bamboo pulp |
| CN111333735A (en) * | 2020-04-16 | 2020-06-26 | 江南大学 | Method for preparing hydroxyethyl cellulose solution with low substitution degree for spinning |
| CN111333735B (en) * | 2020-04-16 | 2021-03-02 | 江南大学 | Method for preparing hydroxyethyl cellulose solution with low substitution degree for spinning |
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