CN100369935C - A kind of preparation method of carboxymethyl cellulose cross-linked amide derivative - Google Patents
A kind of preparation method of carboxymethyl cellulose cross-linked amide derivative Download PDFInfo
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- CN100369935C CN100369935C CNB2006100399712A CN200610039971A CN100369935C CN 100369935 C CN100369935 C CN 100369935C CN B2006100399712 A CNB2006100399712 A CN B2006100399712A CN 200610039971 A CN200610039971 A CN 200610039971A CN 100369935 C CN100369935 C CN 100369935C
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Abstract
一种羧甲基纤维素交联酰胺衍生物的制备方法，属于生物化学技术领域。本发明是在羧基活化剂和活性助剂存在下，由分子结构中具有两个或两个以上氨基的高聚物或低聚物与羧甲基纤维素进行酰胺化交联反应而制得非水溶性的、羧甲基纤维素交联酰胺衍生物产品。本发明为羧甲基纤维素的交联改性提供了新的途径，用本发明方法制备的衍生物产品具有较高的热稳定性、生物相容性等优点，在医药、外科手术、化妆品、重金属回收方面有着广泛的用途。
The invention discloses a preparation method of carboxymethyl cellulose cross-linked amide derivatives, belonging to the technical field of biochemistry. In the present invention, in the presence of a carboxyl activator and an active auxiliary agent, the high polymer or oligomer with two or more amino groups in the molecular structure and carboxymethyl cellulose are subjected to amidation crosslinking reaction to prepare non-toxic Water-soluble, carboxymethylcellulose cross-linked amide derivative product. The present invention provides a new approach for the cross-linking modification of carboxymethyl cellulose, and the derivative products prepared by the method of the present invention have the advantages of high thermal stability, biocompatibility, etc., and are used in medicine, surgery, cosmetics, etc. , Heavy metal recovery has a wide range of uses.
Description
Technical field
A kind of preparation method of carboxymethyl cellulose crosslinked amide derivative, particularly relate to a kind of non-water-soluble carboxymethyl cellulose crosslinked amide derivative, described derivative is to have two or more amino superpolymer or oligopolymer and carboxymethyl cellulose in the molecular structure by amidate action the product that obtains after crosslinked to take place, and belongs to technological field of biochemistry.
Technical background
Mierocrystalline cellulose is through β-1 by D-Glucopyranose ring, the straight-chain polysaccharide that 4 glycosidic links are formed, there is a large amount of hyperergic hydroxyls on the carboxymethyl cellulose molecule, very help forming intramolecularly and intermolecular hydrogen bond, make cellulose molecular chain be easy to flock together, be tending towards being arranged in parallel and form crystalline fibrillar structure.Mierocrystalline cellulose is present in a large amount of abundant green plantss as a kind of macromolecular material of natural reproducible, is the inexhaustible resource of nature.Therefore, say today that benefit reduces at the reserves of coal, oil, Sweet natural gas, Mierocrystalline cellulose can be used as a kind of resource of Sustainable development and studies, and natural plant fibre aboundresources, cheap, outstanding advantage is to have biodegradability and recyclability, and is significant aspect human resource, the energy and the environmental problem that is faced of solution.
Mierocrystalline cellulose is as a kind of natural high moleculer eompound, has some shortcoming on performance, and, viscosity limited as not resistance to chemical attack, intensity is lower or the like, thereby has limited its range of application.In order fully to develop Mierocrystalline cellulose potential functional property, cellulosic modification and product processing technique become people's one big research direction, mainly contain derivatize modification, graft modification, composite crosslinking modification and blending and modifying at present.
Cellulosic being of wide application after the modification is the raw material of producing viscose rayon and glassine paper as the carboxymethyl cellulose xanthate; Cellulose acetate also is used to make simultaneously the raw material of non-flame properties cinefilm, varnish, plastics, artificial silk and isolation of purified film mainly as the fibrous bundle and the decoration fiber board of cigarette filter; Soluble cotton is powerful explosive, also can be used for making the raw material of varnish, varnish etc.; Cellulose sulfuric acid ester is used for anticoagulation, antiviral medical material etc.; Water-soluble cellulose derivative such as carboxymethyl cellulose, methylcellulose gum, Natvosol, diethylaminoethyl cellulose, and the plain derivative of water insoluble fiber also has ethyl cellulose, cellulose propionate etc. also to have been widely used except that cellulose acetate, nitrocellulose etc.
As mentioned above, the method for carboxymethyl cellulose modification is a lot, carries out modification by amidate action and does not also see any report at present but make linking agent with diamines or polyamine compounds.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of non-water-soluble, carboxymethyl cellulose crosslinked amide derivative, is to prepare by the amidation crosslinking reaction by having two or more amino superpolymer or oligopolymer and carboxymethyl cellulose in the molecular structure.
Another object of the present invention provides non-water-soluble, the carboxymethyl cellulose crosslinked amide derivative product for preparing with aforesaid method.
Technical scheme of the present invention: in the presence of carboxyl activator and coagent, carboxymethyl cellulose and linking agent are carried out crosslinking reaction, its technology is: carboxymethyl cellulose is dissolved in the distilled water, be made into the cmc soln of 4～50mg/ml, add linking agent, make the carboxyl of carboxymethyl cellulose: the mole proportioning of linking agent is 1: 0.1～1: 10, transfer pH to 4～6 with dilute hydrochloric acid, add carboxyl activator and coagent then, the addition of carboxyl activator is 1～5mg/ml, the addition of coagent is 1～5mg/ml, and crosslinking reaction 2～20h under 10～40 ℃ of temperature regulates in the reaction process and maintenance pH4～6, reaction finishes, with the reaction solution 24h that dialyses, dialysis finishes, and adds the dehydrated alcohol precipitation, lyophilize gets the carboxymethyl cellulose crosslinked amide derivative product.
Described linking agent is to have two or more amino superpolymer or oligopolymer in the molecular structure.
Described carboxyl activator is the water-soluble carbodiimide compounds.
Described coagent is succimide class, phentriazine class or benzotriazole compound.
According to the present invention, the example that has two or more amino superpolymer or oligopolymer in the molecular structure can be selected from: 1, and 6-hexanediamine, adipic dihydrazide, have two or more and can react and can accept the amino acid of amino of proton or polypeptide etc.
Add the example that is used for the carboxyl promoting agent of activated carboxyl in the amidate action water-soluble carbodiimide compounds is arranged.Preferred carbodiimide is selected from compound soluble in water, as EDC[1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide hydrochloride], have 1-alkyl-3-(3-dimethyl aminopropyl) Carbodiimides or the CMC (1-cyclohexyl-3-(2-morpholino ethyl) carbodiimide) of analog structure with EDC.
More preferably, above-mentioned amidate action optionally adds coagent.Water soluble, the material that can form active ester all can be used as the coagent of above-mentioned amidate action.The example of coagent can be selected from: NHS (N-maloyl imines), HOBt (I-hydroxybenzotriazole), HOOBt (3,4-dihydro-3-hydroxyl-4-oxo-1,2,3-phentriazine), HOAt (1-hydroxyl-7-azepine benzotriazole) or Sulfo-NHS (N-hydroxyl sulfo group succimide).
Compare with not making used additives, make used additives such as NHS, can reduce the generation of by product such as O-uride and N-uride, in both cases the material behavior of resulting carboxymethyl cellulose crosslinked amide derivative and there was no significant difference.
Beneficial effect of the present invention: the purposes of the carboxymethyl cellulose crosslinked amide derivative that makes aspect medicine, surgical operation, makeup, heavy metal recovery is very extensive, can be used as the weighting agent of cartilaginous tissue, the packing material of shaping and beauty, can also and be used for adsorbing heavy metal as slow releasing carrier of medication.
Non-water-soluble, the carboxymethyl cellulose crosslinked amide derivative that make according to the present invention have following feature: this derivative not only has higher thermostability, temperature reaches 200 ℃ and just decomposes, has the characteristic of acceptable material biologically, promptly have biocompatibility, a class has overcome the novel biomaterial that existing derivatived cellulose is easy to degrade and is easy to shortcomings such as dissolving under severe condition such as acidity especially.
Preparation method of the present invention has the feature that reaction is easy, the separation and purification operation simply and not needs to use deleterious organic solvent.
Description of drawings
The electron-microscope scanning figure of Fig. 1 carboxymethyl cellulose crosslinked amide derivative.
Specific embodiments
Embodiment 1: with the preparation of the crosslinked carboxymethyl cellulose amide derivatives of adipic dihydrazide
Claim 5g (0.021mol carboxyl) carboxymethyl cellulose to separate in the distilled water of 100ml, after dissolving finishes, add 0.365g (0.0021molADH) adipic dihydrazide (ADH), fully after the dissolving, hydrochloric acid with 0.1mol/L is regulated pH to 4.0～4.5, add 0.1g carbodiimide (EDC) and 0.3gNHS then, 40 ℃ were reacted 2 hours down, regulated the pH value in reaction process between 4.0～4.5.After reaction finishes, reaction solution was dialysed 24 hours, dialysis finishes, and adds the dehydrated alcohol precipitation, and lyophilize obtains membranaceous carboxymethyl cellulose crosslinked amide derivative.
Embodiment 2: with 1, and the preparation of the carboxymethyl cellulose amide derivatives that the 6-hexanediamine is crosslinked
Claim 3g (0.0124mol carboxyl) carboxymethyl cellulose to be dissolved in the distilled water of 100ml, after dissolving finishes, add 1.4384g (0.0124mol) 1, the 6-hexanediamine, fully after the dissolving, regulate pH to 4.5～5.5, add 0.3g1-propyl group-3-(3-dimethyl aminopropyl) carbodiimide and 0.1gHOBt then with the hydrochloric acid of 0.1mol/L, 25 ℃ were reacted 7 hours down, regulated the pH value in reaction process between 4.5～5.5.After reaction finishes, reaction solution was dialysed 24 hours, dialysis finishes, and adds the dehydrated alcohol precipitation, and lyophilize obtains membranaceous carboxymethyl cellulose crosslinked amide derivative.
Embodiment 3: with the preparation of the crosslinked carboxymethyl cellulose amide derivatives of arginine
Claim 0.4g (0.00166mol carboxyl) carboxymethyl cellulose to be dissolved in the distilled water of 100ml, after dissolving finishes, add 0.0289g arginine (0.0166mol), fully after the dissolving, hydrochloric acid with 0.1mol/L is regulated pH to 5.5～6.0, add 0.5gl-cyclohexyl-3-(2-morpholino ethyl) carbodiimide and 0.5gHOOBt then, 10 ℃ were reacted 20 hours, regulated the pH value in reaction process between 5.5～6.0.After reaction finishes, reaction solution was dialysed 24 hours, dialysis finishes, and adds the dehydrated alcohol precipitation, and lyophilize obtains membranaceous carboxymethyl cellulose crosslinked amide derivative.
Claims (3)
1. the preparation method of a carboxymethyl cellulose crosslinked amide derivative, it is characterized in that in the presence of carboxyl activator and coagent, carboxymethyl cellulose and linking agent being carried out crosslinking reaction, its technology is: carboxymethyl cellulose is dissolved in the distilled water, be made into the cmc soln of 4～50mg/ml, add linking agent, make the carboxyl of carboxymethyl cellulose: the mole proportioning of linking agent is 1: 0.1～1: 10, transfer pH to 4～6 with dilute hydrochloric acid, add carboxyl activator and coagent then, the addition of carboxyl activator is 1～5mg/ml, the addition of coagent is 1～5mg/ml, crosslinking reaction 2～20h under 10～40 ℃ of temperature, regulate in the reaction process and keep pH4～6, reaction finishes, with the reaction solution 24h that dialyses, dialysis finishes, add the dehydrated alcohol precipitation, lyophilize gets the carboxymethyl cellulose crosslinked amide derivative product;
Described linking agent is selected from 1,6-hexanediamine, adipic dihydrazide or arginine;
Described carboxyl activator is the water-soluble carbodiimide compounds;
Described coagent is succimide class, phentriazine class or benzotriazole compound.
2. preparation method according to claim 1 is characterized in that carboxyl activator is selected from: 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide hydrochloride, 1-alkyl-3-(3-dimethyl aminopropyl) Carbodiimides or 1-cyclohexyl-3-(2-morpholino ethyl) carbodiimide.
3. preparation method according to claim 1, it is characterized in that coagent is selected from: N-maloyl imines, I-hydroxybenzotriazole, 3,4-dihydro-3-hydroxyl-4-oxo-1,2,3-phentriazine, 1-hydroxyl-7-azepine benzotriazole or N-hydroxyl sulfo group succimide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011099029A (en) * | 2009-11-05 | 2011-05-19 | Teijin Ltd | Polysaccharide derivative |
| CN101967232B (en) * | 2010-09-28 | 2012-06-06 | 徐国财 | Preparation method of croscarmellose sodium |
| CN107185028A (en) * | 2017-05-05 | 2017-09-22 | 惠州华阳医疗器械有限公司 | A kind of hemostatic anti-adhesion material and its preparation method and application |
| CN112107499B (en) * | 2020-09-22 | 2023-08-25 | 安徽三点清药业有限公司 | Preparation method of hand-washing-free disinfection preparation |
| JP2023100160A (en) * | 2022-01-05 | 2023-07-18 | 花王株式会社 | Method for producing modified cellulose fiber |
| CN115873137B (en) * | 2022-11-04 | 2023-06-30 | 胡晓黎 | Cellulose aminocarboxylic acid derivative and preparation method thereof |
| WO2025077637A1 (en) * | 2023-10-08 | 2025-04-17 | 重庆金赛星医疗科技有限公司 | Amino acid cross-linked polysaccharide polymer and preparation method therefor, and hydrogel |
| CN118580844B (en) * | 2024-08-07 | 2024-11-01 | 东营鸿创石油技术有限公司 | A heat-resistant and salt-resistant gel dispersion type flooding agent and preparation method thereof |
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| CN1343736A (en) * | 2000-09-20 | 2002-04-10 | 国家淀粉及化学投资控股公司 | Mono (hydroxyalkyl) urea and holoside cross-linked system |
| CN1733815A (en) * | 2005-04-28 | 2006-02-15 | 华南师范大学 | Preparation method of high-strength water-absorbing material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1343736A (en) * | 2000-09-20 | 2002-04-10 | 国家淀粉及化学投资控股公司 | Mono (hydroxyalkyl) urea and holoside cross-linked system |
| CN1733815A (en) * | 2005-04-28 | 2006-02-15 | 华南师范大学 | Preparation method of high-strength water-absorbing material |
Non-Patent Citations (2)
| Title |
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| 两种微交联羧甲基纤维素的结构和性能研究. 苏茂尧，王双一，董思民.油田化学，第16卷第1期. 1999 * |
| 多胺交联纤维素树脂的合成及吸附性能(XI). 曲荣君，王春华，阮文举，鞠录国.林产化学与工业，第17卷第3期. 1997 * |
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