CN102093483A - Preparation of cellulose carbamate from bamboo fibers - Google Patents
Preparation of cellulose carbamate from bamboo fibers Download PDFInfo
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- CN102093483A CN102093483A CN2009102586295A CN200910258629A CN102093483A CN 102093483 A CN102093483 A CN 102093483A CN 2009102586295 A CN2009102586295 A CN 2009102586295A CN 200910258629 A CN200910258629 A CN 200910258629A CN 102093483 A CN102093483 A CN 102093483A
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Abstract
The invention relates to preparation of cellulose carbamate from bamboo fibers. The cellulose carbamate is prepared by the following steps of: fully activating the bamboo fibers in an alkali liquor; fully degrading (aging); fully mixing the degraded product with an amino compound; reacting in a solvent to generate cellulose carbamate; and washing with warm water and purifying after the reaction. In the process, natural raw material bamboo fibers are taken as a main raw material, cellulose is activated to a required extent with the alkali liquor, urea is added as required, and the loss of the raw material in the reaction process is avoided. The obtained cellulose carbamate has stable property, is very easy to treat, transport and store, can be stably stored for over six months, can be well dissolved in a NaOH (Sodium Hydroxide) solution, and can form a good and stable solution.
Description
Technical field:
The present invention relates to bamboo fibers and prepare cellulose carbamate, belong to that family is spun, clothes and health care product field.
Background of invention:
Cellulose carbamate (being called for short CC) is the cellulose ester that is generated by Mierocrystalline cellulose and urea reaction, and raw material sources are extensive, and production process is not polluted environment.Its exploitation essence provides a kind of brand-new excellent material for the adhering process produce cellulose fibers, can utilize greatly original viscose glue production unit
Cellulose carbamate is the resultant by Mierocrystalline cellulose and urea reaction, and this reaction is in fact comparatively complicated, and has side reaction to take place.Cyanic acid (HNCO) is intermediate in the reaction that generates CC, and cyanic acid can generate cyanogen ammonia (NH with the ammonia generation side reaction that generates in the main reaction
4NCO), another side reaction is that urea and cyanic acid form biuret.Because it is the amount of the by product that side reaction generates is little, and can remove by washing, therefore little to the influence of resultant.
Bamboo fibers can be divided into bamboo fiber and bamboo pulp fiber according to the selection of fiber and the difference of complete processing.Bamboo fiber claims natural bamboo fibres or primary bamboo fibers again, generally is to adopt machinery, and impurity such as the xylogen in the method removal bamboo of physics, pentosan, bamboo powder, pectin directly extract Mierocrystalline cellulose from bamboo wood.Bamboo pulp fiber claims regenerated bamboo fiber or bamboo viscose fiber again, be to be raw material with the bamboo, through artificial catalysis content of cellulose is purified to more than 93% at the bamboo fibers about 35%, makes and satisfy the bamboo pulp that fiber production requires, the fiber of making through spinning processing again.There are a lot of space, groove and crackles not of uniform size on the bamboo fiber surface, just as kapillary, and can be at transient absorption and transpiring moisture, so bamboo fibers is otherwise known as " fiber that can breathe ".But characteristics such as bamboo fibers has nontoxic, pollution-free complete regression nature are the environmental protection fibers.Simultaneously, bamboo fibers has natural antibacterial effect, and chlorophyll in its composition and chlorophyll copper sodium have good deodorizing effect, and chlorophyll copper sodium still is safe, good UV light absorber.
The linters or the cotton pulp dregs of rice are adopted in the production of cellulose carbamate at present mostly, technology still exists complex process, cost is higher and problem of environmental pollution, make acid anhydrides and the organic salt and the inorganic salt of gas phase as the LODZ operational path, Zimmer uses organic carrier toluene or o-Xylol, Yin Cuiyu uses supercritical co, and I expires the river. and Ai Li uses inert solvent dimethylbenzene.
This invention technology has the following advantages:
With the bamboo fibers of natural environmental-protective and aminocompound as main raw material(s), be not confined to use urea.
2. Mierocrystalline cellulose and aminocompound reaction generates cellulose carbamate, and side reaction is very weak, and is unimportant for main reaction;
3. cellulose carbamate character is very stable, very easily handles, transports and store, can stably stored at least six months, and almost non-toxic property;
4. cellulose carbamate can well be dissolved in the NaOH solution and forms good stable solution.This soltion viscosity is stable, and strainability is good.Mierocrystalline cellulose carboxylamine vinegar solution can be dissolved in the sulfuric acid precipitation bath cellulosic fibre of regenerating;
5. the properties of bamboo excellence is liked by masses that as the new function fiber therefore, the research and development of bamboo fibers are extremely important to the ecology of weaving;
6. this invented technology process is simple, and production process is not polluted environment.
Summary of the invention:
Bamboo fibers involved in the present invention prepares cellulose carbamate, is with bamboo fibers fully activation in alkali lye, fully degraded (experienced), and with the aminocompound thorough mixing, reaction generates cellulose carbamate, and concrete steps are as follows:
A. an amount of bamboo fibers is 20 ℃-60 ℃ of temperature, and concentration is abundant activation 1h-3h in the alkali lye of 10%-20%, and alkali lye is fully flooded to Mierocrystalline cellulose inside, takes out squeezing and removes unnecessary alkali lye;
B. the soda cellulose that has certain press ratio takes out at 30 ℃ of-50 ℃ of experienced 2h-6h, and 10 ℃ of-20 ℃ of warm water washings are to neutral;
C. (mass ratio of Mierocrystalline cellulose and aminocompound is 1: 1.5-4), stir, 30 ℃-50 ℃ are fully soaked 1h-3h down to be washed till the adding aminocompound aqueous solution in the neutral soda cellulose;
D. add an amount of solvent, temperature of reaction is 120 ℃-150 ℃, reaction times 1h-3h, and with 10 ℃ of-20 ℃ of warm water washings, suction filtration was dried 24h, is promptly obtained cellulose carbamate (CC) for 45 ℃ after reaction was finished.
Embodiment 1: take by weighing an amount of bamboo fibers, with the massfraction for preparing is that 10% alkali lye mixes, place thermostat container, place 1h down at 20 ℃, alkali lye is fully flooded to Mierocrystalline cellulose inside, take out, unnecessary alkali lye is removed in squeezing, to have the soda cellulose of certain press ratio to place thermostat container again, remain on 30 ℃ of experienced 2h after, take out and repeatedly to be washed to neutrality.In being washed till the neutral soda cellulose, add the aminocompound aqueous solution (mass ratio of Mierocrystalline cellulose and aminocompound is 1: 1.5), after stirring, soak 1h at 30 ℃.Be placed on then in the three-necked bottle, add an amount of solvent again, 120 ℃ of reaction 1h, with 10 ℃ of-20 ℃ of warm water washings, suction filtration was dried 24h for 45 ℃, can obtain the cellulose carbamate (CC) of favorable solubility after reaction was finished.
Embodiment 2: take by weighing an amount of bamboo fibers, with the massfraction for preparing is that 12% alkali lye mixes, place thermostat container, place 1.5h down at 30 ℃, alkali lye is fully flooded to Mierocrystalline cellulose inside, take out, unnecessary alkali lye is removed in squeezing, to have the soda cellulose of certain press ratio to place thermostat container again, remain on 35 ℃ of experienced 3h after, take out and repeatedly to be washed to neutrality.In being washed till the neutral soda cellulose, add the aminocompound aqueous solution (mass ratio of Mierocrystalline cellulose and aminocompound is 1: 2), after stirring, soak 1.5h at 35 ℃.Be placed on then in the three-necked bottle, add an amount of solvent again, 130 ℃ of reaction 1.5h, with 10 ℃ of-20 ℃ of warm water washings, suction filtration was dried 24h for 45 ℃, can obtain the cellulose carbamate (CC) of favorable solubility after reaction was finished.
Embodiment 3: take by weighing an amount of bamboo fibers, with the massfraction for preparing is that 14% alkali lye mixes, place thermostat container, place 2h down at 40 ℃, alkali lye is fully flooded to Mierocrystalline cellulose inside, take out, unnecessary alkali lye is removed in squeezing, to have the soda cellulose of certain press ratio to place thermostat container again, remain on 40 ℃ of experienced 4h after, take out and repeatedly to be washed to neutrality.In being washed till the neutral soda cellulose, add the aminocompound aqueous solution (mass ratio of Mierocrystalline cellulose and aminocompound is 1: 2.5), after stirring, soak 2h at 40 ℃.Be placed on then in the three-necked bottle, add an amount of solvent again, 140 ℃ of reaction 2h, with 10 ℃ of-20 ℃ of warm water washings, suction filtration was dried 24h for 45 ℃, can obtain the cellulose carbamate (CC) of favorable solubility after reaction was finished.
Embodiment 4: take by weighing an amount of bamboo fibers, with the massfraction for preparing is that 16% alkali lye mixes, place thermostat container, place 2.5h down at 45 ℃, alkali lye is fully flooded to Mierocrystalline cellulose inside, take out, unnecessary alkali lye is removed in squeezing, to have the soda cellulose of certain press ratio to place thermostat container again, remain on 45 ℃ of experienced 4h after, take out and repeatedly to be washed to neutrality.In being washed till the neutral soda cellulose, add the aminocompound aqueous solution (mass ratio of Mierocrystalline cellulose and aminocompound is 1: 3), after stirring, soak 2h at 40 ℃.Be placed on then in the three-necked bottle, add an amount of solvent again, 145 ℃ of reaction 2h, with 10 ℃ of-20 ℃ of warm water washings, suction filtration was dried 24h for 45 ℃, can obtain the cellulose carbamate (CC) of favorable solubility after reaction was finished.
Embodiment 5: take by weighing an amount of bamboo fibers, with the massfraction for preparing is that 18% alkali lye mixes, place thermostat container, place 3h down at 50 ℃, alkali lye is fully flooded to Mierocrystalline cellulose inside, take out, unnecessary alkali lye is removed in squeezing, to have the soda cellulose of certain press ratio to place thermostat container again, remain on 45 ℃ of experienced 5h after, take out and repeatedly to be washed to neutrality.In being washed till the neutral soda cellulose, add the aminocompound aqueous solution (mass ratio of Mierocrystalline cellulose and aminocompound is 1: 3.5), after stirring, soak 2.5h at 45 ℃.Be placed on then in the three-necked bottle, add an amount of solvent again, 145 ℃ of reaction 2.5h, with 10 ℃ of-20 ℃ of warm water washings, suction filtration was dried 24h for 45 ℃, can obtain the cellulose carbamate (CC) of favorable solubility after reaction was finished.
Embodiment 6: take by weighing an amount of bamboo fibers, with the massfraction for preparing is that 20% alkali lye mixes, place thermostat container, place 2h down at 60 ℃, alkali lye is fully flooded to Mierocrystalline cellulose inside, take out, unnecessary alkali lye is removed in squeezing, to have the soda cellulose of certain press ratio to place thermostat container again, remain on 50 ℃ of experienced 6h after, take out and repeatedly to be washed to neutrality.In being washed till the neutral soda cellulose, add the aminocompound aqueous solution (mass ratio of Mierocrystalline cellulose and aminocompound is 1: 4), after stirring, soak 3h at 50 ℃.Be placed on then in the three-necked bottle, add an amount of solvent again, 150 ℃ of reaction 3h, with 10 ℃ of-20 ℃ of warm water washings, suction filtration was dried 24h for 45 ℃, can obtain the cellulose carbamate (CC) of favorable solubility after reaction was finished.
Claims (6)
1. the preparation of cellulose carbamate is characterized in that the bamboo fibers that uses environmental protection with health role to human body.With bamboo fibers fully activation in alkali lye, fully degraded (experienced), with aminocompound aqueous solution thorough mixing, reaction generates cellulose carbamate, and concrete steps are as follows:
A. an amount of bamboo fibers is 20 ℃-60 ℃ of temperature, and concentration is abundant activation 1h-3h in the alkali lye of 10%-20%, and alkali lye is fully flooded to Mierocrystalline cellulose inside, takes out squeezing and removes unnecessary alkali lye;
B. the soda cellulose that has certain press ratio takes out at 30 ℃ of-50 ℃ of experienced 2h-6h, and 10 ℃ of-20 ℃ of warm water washings are to neutral;
C. (mass ratio of Mierocrystalline cellulose and aminocompound is 1: 1.5-4), stir, 30 ℃-50 ℃ are fully soaked 1h-3h down to be washed till the adding aminocompound aqueous solution in the neutral soda cellulose;
D. add an amount of solvent, temperature of reaction is 120 ℃-150 ℃, reaction times 1h-3h, and with 10 ℃ of-20 ℃ of warm water washings, suction filtration was dried 24h, is promptly obtained cellulose carbamate (CC) for 45 ℃ after reaction was finished.
2. according to claims 1, bamboo fibers is bamboo bamboo fiber or the bamboo pulp (polymerization degree is 400-600) that gets of 2-4 setation.
3. according to claims 1, alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide aluminium hydroxide.The dipping volume ratio of alkali lye and bamboo fibers is 3: 1.
4. according to claims 1, aminocompound is urea, thiocarbamide.The concentration of the aminocompound aqueous solution is 0.375mol/L-2.5mol/L
5. according to claims 1, solvent is N, dinethylformamide, N,N-dimethylacetamide.
6. according to claims 1, the gained cellulose carbamate has good solvability, has good film-forming properties simultaneously.
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| CN2009102586295A CN102093483A (en) | 2009-12-11 | 2009-12-11 | Preparation of cellulose carbamate from bamboo fibers |
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| CN2009102586295A CN102093483A (en) | 2009-12-11 | 2009-12-11 | Preparation of cellulose carbamate from bamboo fibers |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653562A (en) * | 2012-05-04 | 2012-09-05 | 湖北天思科技股份有限公司 | Method for preparing high-stability cellulose carbamate suspension |
| CN102702364A (en) * | 2012-06-19 | 2012-10-03 | 天津工业大学 | Method for preparing cellulose carbamate |
| CN102766216A (en) * | 2012-08-16 | 2012-11-07 | 天津工业大学 | Preparation method for cellulose carbamic acid ester |
| CN103980368A (en) * | 2014-05-28 | 2014-08-13 | 天津工业大学 | Method for preparing cellulose carbamate through liquid-solid-phase reaction |
| CN106544745A (en) * | 2015-09-17 | 2017-03-29 | 宜宾丝丽雅集团有限公司 | Production method of cellulose carbamate fiber filament |
| CN106588459A (en) * | 2016-12-04 | 2017-04-26 | 西北农林科技大学 | Preparation method of chicken feather crosslinked cellulose multifunctional zinc fertilizer |
| CN106661131A (en) * | 2014-06-27 | 2017-05-10 | 斯道拉恩索公司 | Method for making cellulose carbamate |
| CN107501415A (en) * | 2017-08-25 | 2017-12-22 | 孙飞勇 | The preparation method of cellulose carbamate |
| CN108864692A (en) * | 2018-05-18 | 2018-11-23 | 许水仙 | A kind of preparation method of high tenacity flame retardant polyurethane grouting material |
-
2009
- 2009-12-11 CN CN2009102586295A patent/CN102093483A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653562A (en) * | 2012-05-04 | 2012-09-05 | 湖北天思科技股份有限公司 | Method for preparing high-stability cellulose carbamate suspension |
| CN102653562B (en) * | 2012-05-04 | 2013-11-27 | 湖北天思科技股份有限公司 | Method for preparing high-stability cellulose carbamate suspension |
| CN102702364A (en) * | 2012-06-19 | 2012-10-03 | 天津工业大学 | Method for preparing cellulose carbamate |
| CN102766216A (en) * | 2012-08-16 | 2012-11-07 | 天津工业大学 | Preparation method for cellulose carbamic acid ester |
| CN103980368A (en) * | 2014-05-28 | 2014-08-13 | 天津工业大学 | Method for preparing cellulose carbamate through liquid-solid-phase reaction |
| CN106661131A (en) * | 2014-06-27 | 2017-05-10 | 斯道拉恩索公司 | Method for making cellulose carbamate |
| CN106661131B (en) * | 2014-06-27 | 2020-03-03 | 斯道拉恩索公司 | Process for producing cellulose carbamate |
| CN106544745A (en) * | 2015-09-17 | 2017-03-29 | 宜宾丝丽雅集团有限公司 | Production method of cellulose carbamate fiber filament |
| CN106588459A (en) * | 2016-12-04 | 2017-04-26 | 西北农林科技大学 | Preparation method of chicken feather crosslinked cellulose multifunctional zinc fertilizer |
| CN107501415A (en) * | 2017-08-25 | 2017-12-22 | 孙飞勇 | The preparation method of cellulose carbamate |
| CN108864692A (en) * | 2018-05-18 | 2018-11-23 | 许水仙 | A kind of preparation method of high tenacity flame retardant polyurethane grouting material |
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Application publication date: 20110615 |