CN1205229C - Method for preparing hydroxypropyl cellulose - Google Patents
Method for preparing hydroxypropyl cellulose Download PDFInfo
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- CN1205229C CN1205229C CN 03128387 CN03128387A CN1205229C CN 1205229 C CN1205229 C CN 1205229C CN 03128387 CN03128387 CN 03128387 CN 03128387 A CN03128387 A CN 03128387A CN 1205229 C CN1205229 C CN 1205229C
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Abstract
The present invention discloses a preparation method for synthesizing hydroxypropyl cellulose. In the preparation method, propylene oxide is added to cellulose NaOH/ urea homogeneous phase water solution and is stirred at a temperature of 6 to 60 DEG C to react for 10 minutes to 80 hours, and then acetic acid is added to neutralize the reaction solution to be neutral, and the reaction stops; and after repeated acetone sedimentation, water dissolving, and vacuum drying after acetone precipitation or dialysis for one week, the reaction solution is performed for freeze drying to obtain hydroxypropyl cellulose or hydroxypropyl cellulose gel with high purity and high homogenization. The used cellulose solvent has asepsis, no pollution and low price; the entire synthetic method has the advantages of simple and convenient operation, mild reaction condition, high speed and high yield, and organic solvent does not need adding as a diluting agent; and obtained products have high purity, substituent is uniformly distributed on cellulose dextrose units and cellulose is basically undegraded. Thereby, the preparation method provides a new way for preparing the hydroxypropyl cellulose by a water solution system with low cost and no pollution.
Description
Technical field
The present invention relates to the preparation method of hydroxypropylcellulose, specifically carry out the method for hydroxypropylation prepared in reaction hydroxypropylcellulose in cellulosic sodium hydroxide/aqueous solution of urea system.
Background technology
Mierocrystalline cellulose is a renewable resources the abundantest on the earth, and because its unique response function and molecular characterization such as nontoxic, safety, biological degradability, wetting ability, chirality and semi-rigid, to become one of following main industrial chemicals (J.Schurz, Prog.Polym.Sci., 1999,24,481).At present, the plain derivative of commercial fibres is mainly synthetic under out-of-phase condition by slurry process, makes the purity of product and homogeneity be subjected to certain restriction.Nearly two during the last ten years, and many Mierocrystalline cellulose novel solvent systems are by R and D in succession.In these solvent systems, have only a few organic solvent system to be suitable for the homogeneous phase derivative reaction, wherein lithium chloride (LiCl)/N,N-dimethylacetamide (DMAc) the most representative [C.L.McCormick, US Patent 4278790 (1981); A.F.Turbak, A.E1-Katrawy, F.Synder, A.Auerbach, US Patent 4302252 (1981)].The cellulose ester, Mierocrystalline cellulose carbonic ether, the cellulose sulfonate derivative (C.L.McCormick, P.A.Callais, Polymer, 1998,12,749) that in the LiCl/DMAc system, successfully synthesize high purity, high uniformity.Yet, destroyed easily when DMAc heats in strong base solution (S.Langlois, A.Broche, Bull.Soc.Chim.France, 1964,812), and heating is to carry out the etherification reaction essential condition with halogenated alkane as etherifying agent.Simultaneously, the preparation ether of cellulose needs the very long reaction times in the LiCl/DMAc system, and severe reaction conditions and substitution value are difficult to reach desired value.So far, Mierocrystalline cellulose is reported seldom at the derivative reaction of water solution system.Once [Ni (tren) (OH) with the triaminotriethylamine complex compound of nickel hydroxide for T.Heinze etc.
2] aqueous solution and lithium perchlorate crystalline hydrate (LiClO
43H
2O) melts all is combined to and prepares carboxymethyl cellulose (T.Heinze, T.Liebert, P.Kl ü fers, F.Meister, Cellulose, 1999,6,153) as cellulosic solvent.Recently, this seminar develops a kind of inexpensive, free of contamination Mierocrystalline cellulose novel solvent-sodium hydroxide (NaOH)/aqueous solution of urea [Zhang Lina, Zhou Jinping, " solvent compositions and uses thereof ", patent publication No.: CN 1318575A (2000); J.Zhou, L.Zhang, Polym.J., 2000,32,866; L.Zhang, D.Ruan, J.Zhou, Ind.Eng.Chem.Res.2001,40,5923.].Since cellulosic etherification reaction usually with highly basic as catalyzer, so this novel alkali aqueous solution system is expected to become Mierocrystalline cellulose etherificate reaction medium.
Hydroxypropylcellulose is a kind of ether of cellulose of non-ionic type, can be widely used in fields such as injection molding device, medicine, coating, makeup, food and papermaking, and has obtained FDA Food and Drug Administration (FDA) permission.At present the industrial production hydroxypropylcellulose mainly utilize the soda cellulose slurry adopt two step method carry out the out-phase reaction [E.D.Klug, US Patent 3131176, (1964), USPatent 3278521, (1966); R.G.Bishop, US Patent 3351583, (1967); S.Orii, Y.Sasagawa, A.Ito; M.Hiromi, Y.Sakai, US Patent 4292426; (1981)], need to add a large amount of organic solvents such as hexane, heptane, benzene, toluene, propyl alcohol, propyl carbinol etc. in the reaction process, be unfavorable for environment protection as thinner.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of hydroxypropylcellulose.This method is cheap, and is easy and simple to handle, good uniformity, the purity height of pollution-free and products obtained therefrom.
For achieving the above object, technical scheme provided by the invention is: the preparation method of hydroxypropylcellulose, with cellulose dissolution in 5～12wt%NaOH/1～20wt% aqueous solution of urea, and in this cellulose aqueous solution, add propylene oxide, obtain required hydroxypropylcellulose in-6 ℃～60 ℃ stirring reactions.
The concentration of above-mentioned cellulose aqueous solution is 0.5～10wt%.
Above-mentioned propylene oxide is not added quantitative limitation, but its add-on is preferably 0.5～30 times of the Mierocrystalline cellulose molar weight.
In aforesaid method, propylene oxide is disposable or add in batches or be added drop-wise in the cellulose solution, reacted 10 minutes～80 hours, add acetic acid neutralization reaction liquid then to neutral stopped reaction; Reaction product solution through acetone precipitation repeatedly, water-soluble and acetone precipitation final vacuum drying or dialysis after lyophilize obtains the hydroxypropylcellulose of high purity, high uniformity.
Compared with the prior art, the present invention has remarkable technical progress.At first present method is a synthetic hydroxypropylcellulose in the cellulose homogeneous-phase aqueous solution, and used cellulose solution is nontoxic, pollution-free, cheap, and simple synthetic method, temperature of reaction is low, speed is fast, productive rate is high.And do not need to add organic solvent and make thinner, products obtained therefrom purity height, substituting group is evenly distributed on the Mierocrystalline cellulose glucose unit, and the reaction process Mierocrystalline cellulose is not gone up degraded substantially.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention and application are described further:
Embodiment 1～5
With 2 grams～4 gram cellulose powder (CF-11, the polymerization degree is about 220, Whatman, Britain) be dispersed in the 98 gram 6wt%NaOH/4wt% aqueous solution of urea, stir and be placed on refrigerator freezing (5～-10 ℃) in 1～5 minute, then freeze solid being thawed and stirred in room temperature obtains transparent cellulose solution.Get above-mentioned cellulose solution 50 grams, disposable or add the propylene oxide of metering in batches, and, add acetic acid neutralization reaction liquid then to neutral stopped reaction as required in-6 ℃～60 ℃ stirred in water bath reactions 10 minutes～80 hours.Reaction gained solution is dialysed a week after lyophilize or vacuum-drying obtain the pure product of white powder hydroxypropylcellulose.The reaction conditions of embodiment 1～5 and productive rate are listed in subordinate list 1, and the products obtained therefrom branch is labeled as HPC-1, HPC-2, HPC-3, HPC-4 and HPC-5.The molar substitution of hydroxypropylcellulose (MS), substitution value (DS) and the position distribution of substituting group on the Mierocrystalline cellulose glucose unit are listed in subordinate list 2.Weight-average molecular weight (the M of hydroxypropylcellulose
w), number-average molecular weight (M
N), dispersity index (d) and their solvabilities in different solvents come together in subordinate list 3.
Experimental result shows, adopts method provided by the invention successfully to synthesize the hydroxypropylcellulose with different solubility characteristics, and synthetic method is simple, and is friendly process, and the replacement of gained hydroxypropylcellulose position is evenly distributed, and productive rate is higher.
Reaction conditions and the productive rate of subordinate list 1 embodiment 1～5
Embodiment Mierocrystalline cellulose mol ratio (fiber-reactive condition productive rate production code member
The dense plain glucose list of solution (%)
Hydroxyl in degree (%) unit:
Propylene oxide)
Embodiment 121: 3 disposable adding propylene oxide 4mL, stir 102.2 HPC-1 in 25 ℃
Mix reaction 4 hours
Embodiment 221: 3 disposable adding propylene oxide 4mL, stir 108.2 HPC-2 in 25 ℃
Mix reaction 9 hours
Embodiment 321: 5 disposable adding propylene oxide 6.5mL, and in 25 ℃ of 111.9 HPC-3
Stirring reaction 22.5 hours
Embodiment 441: 3 added propylene oxide 0.5mL every 30 minutes (amounts to 114.8 HPC-4
Add 8mL) in 25 ℃ of stirring reactions 21.5 hours
Embodiment 521: the disposable adding propylene oxide 4mL of 6 elder generations, stir 115.3 HPC-5 in 25 ℃
Mix reaction 23 hours, be warming up to 50 ℃ of stirrings then
Reacted 22.5 hours, and added propylene oxide at last again
4mL was in 25 ℃ of stirring reactions 27 hours
The molar substitution (MS) of subordinate list 2 hydroxypropylcelluloses, substitution value (DS) and the position distribution of substituting group on the Mierocrystalline cellulose glucose unit
The position distribution of numbering MS DS substituting group on the Mierocrystalline cellulose glucose unit
C2 C3 C6
HPC-2 0.85 0.83 0.28 0.26 0.29
HPC-3 1.03 0.85 0.25 0.30 0.30
HPC-4 1.18 0.93 0.33 0.30 0.30
HPC-5 1.73 1.18 0.38 0.41 0.39
Annotate: above data are by liquid
13The C nuclear magnetic resonance spectrum records, and solvent is deuterated dimethyl sulfoxide (DMSO-d
6).
Weight-average molecular weight (the M of subordinate list 3 hydroxypropylcelluloses and gel thereof
w), number-average molecular weight (M
n), dispersity index (d) and their solvabilities in different solvents
Numbering M
wM
nThe d dissolution characteristics
(* 10
-4) (* 10
-4) water methyl-sulphoxide tetrahydrofuran (THF) Virahol pyridine
HPC-1 - - - - + ○ - +
HPC-2 - - - - + ○ - +
HPC-3 5.41 3.61 1.5 + + + ρ +
HPC-4 5.54 4.01 1.4 + + + ρ +
HPC-5 6.28 4.36 1.4 + + + ρ +
Annotate 1: weight-average molecular weight (M
w), number-average molecular weight (M
n) and dispersity index (d) data record by size exclusion chromatogram (SEC) and multi-angle laser light scattering (MALLS) combined apparatus, solvent for use is a 0.1mol L-1 sodium chloride aqueous solution.
Annotate 2: solvability is at room temperature measuring, and it is 1Wt% that strength of solution is joined by institute, and each symbol is represented respectively :+, dissolving fully;-, do not dissolve fully; Zero, be partly dissolved; ρ, swelling.
Claims (5)
1. the preparation method of hydroxypropylcellulose, it is characterized in that: Mierocrystalline cellulose is dissolved in 5～12wt% NaOH/1～20wt% aqueous solution of urea fully, and in this cellulose aqueous solution, add propylene oxide, the add-on of propylene oxide is 0.5～30 times of Mierocrystalline cellulose molar weight, obtains required hydroxypropylcellulose in 10 minutes～80 hours in-6 ℃～60 ℃ stirring reactions.
2. preparation method according to claim 1 is characterized in that: the concentration of above-mentioned cellulose aqueous solution is 0.5～10wt%.
3. preparation method according to claim 1 and 2 is characterized in that: propylene oxide is joined in the cellulose solution, reacted 10 minutes～80 hours, add acetic acid neutralization reaction liquid then to neutral stopped reaction; Reaction product solution through acetone precipitation repeatedly, water-soluble and acetone precipitation final vacuum drying or dialysis after lyophilize obtains hydroxypropylcellulose.
4. preparation method according to claim 1 and 2 is characterized in that: disposable the joining in the cellulose solution of propylene oxide reacted.
5. preparation method according to claim 1 and 2 is characterized in that: with propylene oxide in batches or be added drop-wise in the cellulose solution and react.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03128387 CN1205229C (en) | 2003-07-25 | 2003-07-25 | Method for preparing hydroxypropyl cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03128387 CN1205229C (en) | 2003-07-25 | 2003-07-25 | Method for preparing hydroxypropyl cellulose |
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| CN1482143A CN1482143A (en) | 2004-03-17 |
| CN1205229C true CN1205229C (en) | 2005-06-08 |
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| CN 03128387 Expired - Fee Related CN1205229C (en) | 2003-07-25 | 2003-07-25 | Method for preparing hydroxypropyl cellulose |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313495C (en) * | 2005-08-24 | 2007-05-02 | 武汉大学 | Hydroxy ethyl cellulose preparation method |
| CN101891827B (en) * | 2010-07-29 | 2012-05-09 | 安徽山河药用辅料股份有限公司 | Method for preparing hydroxypropyl cellulose |
| CN102924609A (en) * | 2012-12-04 | 2013-02-13 | 新疆光大山河化工科技有限公司 | Method for producing low-substituted hydroxypropyl cellulose via fractional step method |
| CN103951764B (en) * | 2014-04-25 | 2016-01-20 | 武汉大学 | A kind of homogeneous phase prepares the method for the hydroxypropyl modified chitin of low deacetylation |
| CN104387609B (en) * | 2014-11-18 | 2018-06-01 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of cellulose porous adsorbing material |
| CN105601755A (en) * | 2015-11-05 | 2016-05-25 | 深圳多元拓展环保科技有限公司 | Preparation method and application method of cellulose xanthogenate heavy metal capturing agent |
| DE102020103195A1 (en) * | 2019-12-23 | 2021-06-24 | Universität Rostock | Manufacture of regenerated polysaccharides |
| CN111333735B (en) * | 2020-04-16 | 2021-03-02 | 江南大学 | Method for preparing hydroxyethyl cellulose solution with low substitution degree for spinning |
| CN114716573A (en) * | 2022-05-13 | 2022-07-08 | 南京林业大学 | Homogeneous phase synthesis method of hydroxypropyl cellulose |
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