CN101481460B - Preparation of cellulose liquid crystal solution - Google Patents
Preparation of cellulose liquid crystal solution Download PDFInfo
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- CN101481460B CN101481460B CN2009100456367A CN200910045636A CN101481460B CN 101481460 B CN101481460 B CN 101481460B CN 2009100456367 A CN2009100456367 A CN 2009100456367A CN 200910045636 A CN200910045636 A CN 200910045636A CN 101481460 B CN101481460 B CN 101481460B
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Abstract
The invention relates to a preparation method for fibrin liquid crystal solution, which comprises the following steps: double solvents of phosphoric acid/polyphosphoric acid are added into a kneader and precooled to be 3 to 8 DEG C; fibrin powder is added in the double solvents and kneaded in the temperature of 3 to 8 DEG C for 2-6min so that the fibrin fully swells, is heated up to be 30-35 DEG C and kneaded for 3-15min to cause the fibrin to dissolve, thus obtaining the fibrin liquid crystal solution. The fibrin liquid crystal solution presents anisotropism at a very wide temperature range. The preparation method is simple and rapid, has low cost and is environment friendly.
Description
Technical field
The invention belongs to the preparation field of liquid crystal solution, particularly relate to a kind of preparation method of cellulose liquid crystal solution.
Background technology
Mierocrystalline cellulose is the abundantest natural high moleculer eompound of standing stock in the world, extensively is present in the Nature.All contain a large amount of Mierocrystalline celluloses in the secretory product of plants such as trees, cotton, wheat straw, rice bar, corn, reed, bamboo, fiber crops, mulberry skin, paper mulberry skin, sugarcane even some bacteriums.Along with the worsening shortages of petroleum resources, cellulosic utilization is more and more come into one's own, in today of energy shortage, cellulosic fibre has irreplaceable status.Yet, owing to contain a large amount of hydroxyls in the cellulosic molecule, can form very strong intramolecularly and intermolecular hydrogen bond, degree of crystallinity is higher, and the molecule chain rigidity is stronger relatively, is difficult to dissolve with general solvent; On the other hand, because cellulosic decomposition temperature than its melt temperature height, is difficult to carry out melt-processed.Therefore, cellulosic application is subjected to limiting greatly.At present, had been found that many solvents can dissolving cellulos, but exist that dissolution process is numerous and diverse, problem such as contaminate environment and cost height.In the viscose process technology as present large-scale industrial production regenerated cellulose fibre, when the dissolving soda cellulose, need to use a large amount of CS
2, and emit H
2S, SO
2, serious environment pollution influences HUMAN HEALTH, and complex process.Other method such as cuprammonium process exist that dissolution process is numerous and diverse, environmental pollution and solvent recuperation problem; Carbamate method (USP 4404369) then owing to the amount of urea height, have by product etc. to be restricted.The method of other direct dissolving cellulos is as direct solvent DMSO/N
2O
4(USP 3236669), ZnCl
2There are environmental pollution in the aqueous solution (USP 5290349), LiCl/DMAc (USP 4302252) etc., and the solvent recuperation difficulty perhaps to problems such as equipment requirements height, is difficult to carry out suitability for industrialized production.At present, relatively successful novel solvent is N-methylmorpholine-N-oxide compound (NMMO) (ZL 02151225.6, and ZL 200510097102.0), but because solvent costs an arm and a leg, there is certain problem in recovery, and the spinning temperature height, blast has influenced its suitability for industrialized production easily.In addition, professor Zhang Lina of Wuhan University has invented NaOH/ thiourea solution, NaOH/ aqueous solution of urea and LiOH/ aqueous solution of urea system (ZL200310111447.8; ZL 00114486.3; ZL 200310111567.8; CN 101100518A) etc., but the molecular weight of the dissolving cellulos that has in these solvent systems is not high, and the solid content of the gained solution that has is lower, and the conditions such as temperature that the dissolving that has needs are relatively harsher.Recently, ionic liquid causes people's extensive attention and is used for cellulosic direct solvent that owing to advantages such as having good thermostability, environmentally safe (USP 20030157351; ZL 02823875.3; ZL02147004.9; ZL 200610023543.0 etc.), but because ionic liquid costs an arm and a leg, reclaim also problems such as not solution, industrial prospect is remote.
About liquid crystal solution, that is to say optically anisotropic solution, all be that fiber spinning from crystalline state prepares the necessary spinning solution of high-mechanical property fiber for a long time, as preparation aramid fiber (USP 3767756) and aromatic polyester fiber (USP4746694).Because it is semi-rigid that cellulosic molecule has, people begin to explore preparation based on cellulosic liquid crystal solution.As being dissolved in, cellulose ester and ether of cellulose form liquid crystal solution (DE 3035084) in the mineral acid; Cellulose acetate is dissolved in formic acid or methylene dichloride as forming liquid crystal solution in the trifluoracetic acid of cosolvent and having prepared high-intensity fiber (USP4464323; USP 4501886); The Mierocrystalline cellulose methyl esters is dissolved in the mixed solution of formic acid and phosphoric acid and forms liquid crystal solution, the cellulose formiate fiber of spinning has made high-strength high-modulus fibre (WO 8505115) through saponification.But the above-mentioned liquid crystal solution that is derivatived cellulose need relate to preparation of derivatived cellulose and cellulosic afterwards regeneration, and is comparatively loaded down with trivial details.Obtain liquid crystal solution for direct dissolving cellulos, people also once did a lot of the trial.As can obtaining anisotropic solution in the mixed solvent that among the USP 4278790 Mierocrystalline cellulose is dissolved in DMAc and LiCl, but the anisotropy of this system is slight, can not fully concentrate and obtain spinning solution.Among the USP 4416698 Mierocrystalline cellulose directly is dissolved among the NMMO and can makes anisotropic solution, but Mierocrystalline cellulose forms the concentration of liquid crystal solution and needs more than 20% in NMMO, and the temperature that obtains highly concentrated solution like this has approached the decomposition temperature of solvent, is absolutely unsafe.Cellulose dissolution has made cellulosic anisotropic solution among the JP 4258648 in the mixed solvent of sulfuric acid and phosphoric acid, but the existence of two kinds of acid will cause reclaimer operation complicated, and vitriolic uses and will cause cellulosic severely degrade, thereby very difficult spinning.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of cellulose liquid crystal solution, and cellulose liquid crystal solution of the present invention all presents anisotropy in very wide temperature range; This preparation method is simply quick, and is with low cost, environmentally friendly.
The preparation method of a kind of cellulose liquid crystal solution of the present invention comprises:
The double solvents of phosphoric acid/polyphosphoric acid is joined in the kneader, be chilled to 3～8 ℃ in advance, add cellulose powder, and under this temperature, mediate 2～6min, and make the abundant swelling of Mierocrystalline cellulose, be warming up to 30～35 ℃ then, and mediate 3～15min, and make cellulose dissolution, make cellulose liquid crystal solution.
The double solvents of described phosphoric acid/polyphosphoric acid is by mixed melting phosphoric acid, tetra-sodium, Vanadium Pentoxide in FLAKES (P
2O
5) and water in two or more obtain P in the double solvents
2O
5The quality percentage composition be 73～76%;
The granularity of described cellulose powder is 50～400 orders, and the polymerization degree is 800～2800, and it is moisture to be 4～6%;
The quality percentage composition of described Mierocrystalline cellulose in double solvents is 10～38%;
Described preparation method is with P
2O
5The quality percentage composition be that the double solvents of phosphoric acid/polyphosphoric acid of 73% joins in the kneader, be chilled to 5 ℃ in advance, sneak into granularity then and be 50 orders, the polymerization degree and be 800, moisture be about 5% cellulose powder, making the quality percentage composition of Mierocrystalline cellulose in double solvents is 25%, mediate and mixed 3 minutes, be warming up to 30 ℃ then, and mediated 5 minutes.
Beneficial effect
(1) cellulose liquid crystal solution of the present invention all presents anisotropy in very wide temperature range;
(2) this preparation method is simply quick, and is with low cost, environmentally friendly.
Description of drawings
Photo when Fig. 1 is sheared for the cellulose liquid crystal solution of embodiment 1 preparation under polarizing microscope;
Photo when Fig. 2 is sheared for the cellulose liquid crystal solution of embodiment 2 preparations under polarizing microscope;
Photo when Fig. 3 is sheared for the cellulose liquid crystal solution of embodiment 3 preparations under polarizing microscope.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With P
2O
5The quality percentage composition be that the double solvents of phosphoric acid/polyphosphoric acid of 73% joins in the kneader, be chilled to 5 ℃ in advance, sneak into granularity then and be 50 orders, the polymerization degree and be 800, moisture be about 5% cellulose powder, making the quality percentage composition of Mierocrystalline cellulose in mixing solutions is 25%, keeping low temperature to mediate mixed 3 minutes, be warming up to 30 ℃ then and continue to mediate 5 minutes, discharging makes cellulose liquid crystal solution 1, and the photo when this liquid crystal solution is sheared under polarizing microscope is seen Fig. 1.
Embodiment 2
With P
2O
5The quality percentage composition be that the double solvents of phosphoric acid/polyphosphoric acid of 74% joins in the kneader, be chilled to 3 ℃ in advance, sneak into granularity then and be 100 orders, the polymerization degree and be 2000, moisture be about 5% cellulose powder, making the quality percentage composition of Mierocrystalline cellulose in mixing solutions is 18%, keeping low temperature to mediate mixed 5 minutes, be warming up to 30 ℃ then and continue to mediate 10 minutes, discharging makes cellulose liquid crystal solution 2, and the photo when this liquid crystal solution is sheared under polarizing microscope is seen Fig. 2.
Embodiment 3
With P
2O
5The quality percentage composition be that the double solvents of phosphoric acid/polyphosphoric acid of 74.5% joins in the kneader, be chilled to 5 ℃ in advance, sneak into granularity then and be 200 orders, the polymerization degree and be 2800, moisture be about 5% cellulose powder, making the quality percentage composition of Mierocrystalline cellulose in mixing solutions is 12%, keeping low temperature to mediate mixed 5 minutes, be warming up to 35 ℃ then and continue to mediate 12 minutes, discharging makes cellulose liquid crystal solution 3, and the photo when this liquid crystal solution is sheared under polarizing microscope is seen Fig. 3.
Claims (2)
1. the preparation method of a cellulose liquid crystal solution comprises:
The double solvents of phosphoric acid/polyphosphoric acid is joined in the kneader, be chilled to 3～8 ℃ in advance, add cellulose powder, and under this temperature, mediate 2～6min, and make the abundant swelling of Mierocrystalline cellulose, be warming up to 30～35 ℃ then, and mediate 3～15min, and make cellulose dissolution, make cellulose liquid crystal solution; Wherein, the double solvents of phosphoric acid/polyphosphoric acid is by mixed melting phosphoric acid, tetra-sodium, Vanadium Pentoxide in FLAKES (P
2O
5) and water in two or more obtain P in the double solvents
2O
5The quality percentage composition be 73～76%; The granularity of cellulose powder is 50～400 orders, and the polymerization degree is 800～2800, and it is moisture to be 4～6%, and the quality percentage composition of Mierocrystalline cellulose in double solvents is 10～38%.
2. the preparation method of a kind of cellulose liquid crystal solution according to claim 1 is characterized in that: with P
2O
5The quality percentage composition be that the double solvents of phosphoric acid/polyphosphoric acid of 73% joins in the kneader, be chilled to 5 ℃ in advance, sneak into granularity then and be 50 orders, the polymerization degree and be 800, moisture be 5% cellulose powder, making the quality percentage composition of Mierocrystalline cellulose in double solvents is 25%, mediate and mixed 3 minutes, be warming up to 30 ℃ then, and mediated 5 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100456367A CN101481460B (en) | 2009-01-21 | 2009-01-21 | Preparation of cellulose liquid crystal solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100456367A CN101481460B (en) | 2009-01-21 | 2009-01-21 | Preparation of cellulose liquid crystal solution |
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|---|---|
| CN101481460A CN101481460A (en) | 2009-07-15 |
| CN101481460B true CN101481460B (en) | 2011-07-20 |
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|---|---|---|---|
| CN2009100456367A Expired - Fee Related CN101481460B (en) | 2009-01-21 | 2009-01-21 | Preparation of cellulose liquid crystal solution |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731800B (en) * | 2012-08-01 | 2014-01-15 | 石家庄学院 | Anhydrous phosphoric acid/phosphate solvent and application thereof in dissolving cellulose |
| CN106192041B (en) * | 2016-07-15 | 2019-06-25 | 吉林富博纤维研究院有限公司 | A kind of preparation method of cellulose fibre |
| CN106350080B (en) * | 2016-07-29 | 2018-04-17 | 天津工业大学 | Cellulose solution crystal composite and preparation method thereof |
| CN113150310B (en) * | 2021-04-02 | 2022-08-23 | 东华大学 | Method for dissolving cellulose at low temperature by phosphoric acid with controllable polymerization degree |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164866A (en) * | 1994-09-19 | 1997-11-12 | 米什兰研究和技术股份公司 | Liquid crystal solutions based on cellulose and at least one phosphoric acid |
-
2009
- 2009-01-21 CN CN2009100456367A patent/CN101481460B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164866A (en) * | 1994-09-19 | 1997-11-12 | 米什兰研究和技术股份公司 | Liquid crystal solutions based on cellulose and at least one phosphoric acid |
Non-Patent Citations (3)
| Title |
|---|
| H.Boerstoel, H.Maatman, et. al.Liquid crystalline solutions of cellulose in phosphoric acid.《POLYMER》.2001,第42卷(第17期),7371-7379. * |
| JP特开平4-258648A 1992.09.14 |
| 张滇溪，许海霞，李振国等.纤维素在多聚磷酸中的液晶性.《合成纤维》.2006,(第11期),9-11. * |
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| CN101481460A (en) | 2009-07-15 |
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