CN1313495C - Hydroxy ethyl cellulose preparation method - Google Patents
Hydroxy ethyl cellulose preparation method Download PDFInfo
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- CN1313495C CN1313495C CNB200510019340XA CN200510019340A CN1313495C CN 1313495 C CN1313495 C CN 1313495C CN B200510019340X A CNB200510019340X A CN B200510019340XA CN 200510019340 A CN200510019340 A CN 200510019340A CN 1313495 C CN1313495 C CN 1313495C
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- 229920000663 Hydroxyethyl cellulose Polymers 0.000 title abstract 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 title abstract 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 title abstract 3
- 238000002360 preparation method Methods 0.000 title description 3
- 229940071826 hydroxyethyl cellulose Drugs 0.000 title 1
- 229920002678 cellulose Polymers 0.000 claims abstract description 50
- 239000001913 cellulose Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- -1 ethoxyl Chemical group 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 41
- 238000006467 substitution reaction Methods 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
本发明公开了一种均相水溶液体系合成羟乙基纤维素的新方法。其方法是将纤维素完全溶解在重量百分浓度为7～8%NaOH/10～13%尿素水溶液中得到纤维素溶液，并在该纤维素溶液中加入氯乙醇进行均相羟乙基化反应得到所需羟乙基纤维素。本发明所用溶剂无毒、无污染，价格低廉，而且纤维素基本上未降解；整个合成方法操作简便，反应条件温和，速度快，产率高，而且不需要加入有机溶剂作稀释剂和任何催化剂；所得产品纯度高，水溶性产品粘度高。The invention discloses a new method for synthesizing hydroxyethyl cellulose in a homogeneous aqueous solution system. The method is to completely dissolve cellulose in 7-8% NaOH/10-13% urea aqueous solution to obtain a cellulose solution, and add chloroethanol to the cellulose solution for homogeneous hydroxyethylation reaction The desired hydroxyethyl cellulose was obtained. The solvent used in the present invention is non-toxic, non-polluting, low in price, and the cellulose is basically not degraded; the whole synthesis method is easy to operate, with mild reaction conditions, fast speed and high yield, and does not need to add organic solvents as diluents and any catalysts ; The resulting product has high purity and high viscosity of the 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),
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 2.5 hours room temperature reactions of 65 ℃ of reactions after 2.5 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 1.5 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 0.29 0.29 0.32 0.30 0.28 0.44 | 0.19 0.26 0.26 0.22 0.26 0.21 0.30 | 0.25 0.29 0.31 0.29 0.28 0.23 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-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 (3)
1. method for preparing Natvosol, it 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, adding Mierocrystalline cellulose then also at room temperature stirred 3～5 minutes, obtain cellulose solution, and in this cellulose solution, add chloroethanol and carry out the homogeneous phase ethoxyl etherification and obtain required Natvosol.
2. method according to claim 1 is characterized in that: the concentration of above-mentioned cellulose solution is 0.5～10wt%.
3. 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 true CN1313495C (en) | 2007-05-02 |
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Families Citing this family (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 |
| CN104119453B (en) * | 2014-07-06 | 2016-04-06 | 福建农林大学 | A kind of method utilizing bamboo pulp to prepare Natvosol |
| CN111333735B (en) * | 2020-04-16 | 2021-03-02 | 江南大学 | Method for preparing hydroxyethyl cellulose solution with low substitution degree for spinning |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318575A (en) * | 2000-04-17 | 2001-10-24 | 武汉大学 | Solvent composition and its use |
| CN1318582A (en) * | 2000-04-17 | 2001-10-24 | 武汉大学 | Cellulose film preparing method |
| CN1377895A (en) * | 2002-04-09 | 2002-11-06 | 武汉大学 | Process for preparing hydroxy ethyl cellulose |
| CN1482143A (en) * | 2003-07-25 | 2004-03-17 | 武汉大学 | The preparation method of hydroxypropyl cellulose |
| CN1482159A (en) * | 2003-07-25 | 2004-03-17 | 武汉大学 | A kind of solvent composition and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318575A (en) * | 2000-04-17 | 2001-10-24 | 武汉大学 | Solvent composition and its use |
| CN1318582A (en) * | 2000-04-17 | 2001-10-24 | 武汉大学 | Cellulose film preparing method |
| CN1377895A (en) * | 2002-04-09 | 2002-11-06 | 武汉大学 | Process for preparing hydroxy ethyl cellulose |
| CN1482143A (en) * | 2003-07-25 | 2004-03-17 | 武汉大学 | The preparation method of hydroxypropyl cellulose |
| CN1482159A (en) * | 2003-07-25 | 2004-03-17 | 武汉大学 | A kind of solvent composition and its preparation method and application |
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