CN101089257B - Stabilizing agent for cellulose fibre prepared by solvent method - Google Patents
Stabilizing agent for cellulose fibre prepared by solvent method Download PDFInfo
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- CN101089257B CN101089257B CN2006100277221A CN200610027722A CN101089257B CN 101089257 B CN101089257 B CN 101089257B CN 2006100277221 A CN2006100277221 A CN 2006100277221A CN 200610027722 A CN200610027722 A CN 200610027722A CN 101089257 B CN101089257 B CN 101089257B
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- solvent
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- nmmo
- propyl propionate
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Abstract
The present invention relates to a kind of stabilizer for preparing cellulose fiber by using solvent method. Said stabilizer contains (by wt%) 0.3-15 of propyl gallate and 99-99.75 of NMMO solvent, in which the concentration of NMMO solvent is 40-50%.
Description
Technical field
The present invention relates to a kind of stabilizing agent for cellulose fibre prepared by solvent method, in particular, the present invention relates to a kind of employed bud propyl propionate (Propyl-3,4,5-trihydroxybenzoate for synthesis) solution in the cellulose fibre production that is applied to.
Background technology
Cellulose fibre is called as the green fiber of 21 century.Main material pulp, solvent NMMO (N-methylmorpholine N oxide) are added in the equipment by a certain percentage, become spinning slurry until dissolving and homogeneity,, obtain finished fiber by spinning and a series of post processing through mixing homogenizing, dehydration.But when cellulose pulp was dissolved in the NMMO solution at a certain temperature, the cellulosic degree of polymerization can descend, and can cause the fracture of cellulose macromolecule chain when particularly having metal ion to exist, and cellulose is degraded.On the other hand, the heat endurance of NMMO is limited, and its heat endurance becomes with structure, when cellulose and solvent and when heating, degraded can take place and emit aminated compounds in solvent NMMO, as N methyl morpholine and morpholine, along with the carrying out of degraded, solution viscosity descends, and darkens.For preventing the oxidative degradation in course of dissolution of cellulose and solvent, in course of dissolution, add an amount of stabilizing agent usually, use in the world at present and maximum be, as stabilizing agent, the cellulose solution that obtains through dissolving has stability and higher viscosity and thermoplasticity preferably like this with antioxidant bud propyl propionate.
Because the bud propyl propionate is a solid granular, addition is small, and need to add synchronously in proportion with cellulose and solvent, the control suitable difficulty of getting up, so generally be with solvent with its dissolving, be deployed into bud propyl propionate solution and be added in the dissolution system according to a certain percentage with cellulose and solvent again.For example: the technology of German eastern Thueringisches Institut Fuer Textil-Und Kunststoff-Forschung E.V. (TITK), adopt the bud propyl propionate as stabilizing agent.With concentration is that NMMO more than 60% is that dissolution with solvents bud propyl propionate is made solution.But redeployed like this solution needs the supporting temperature that the hot water thermal insulating system accurately controls solution that goes up, otherwise will crystallization when room temperature is lower than 19 ℃, so just higher temperature control capability need be arranged technically, particularly must use supporting heat-insulation system could guarantee the needs of producing, increase production cost at winter-spring season.
In the bud propyl propionate solution of preparation as stabilizing agent, the NMMO that working concentration is low more allocates bud propyl propionate solution as solvent and just is not easy to produce crystallization more, if it is but on the low side as the concentration of solvent NMMO, bring more water into will for the cellulose dissolution system, can increase the weight of the load of follow-up workshop section dissolving like this, and then influence whole spinning process and normally move.
Summary of the invention
For solving the problem in the above-mentioned production, order of the present invention provides and employedly in a kind of cellulose fibre prepared by solvent method course of dissolution is difficult for crystallization, is convenient to control again, effectively and economic stabilizing agent---bud propyl propionate solution.
The bud propyl propionate solution of using in the cellulose fibre course of dissolution of the present invention is:
The percentage by weight of bud propyl propionate is 0.3～1%
The percentage by weight of NMMO solvent is 99～99.7%
The concentration of above-mentioned NMMO solvent is 40-50%.
The weight percent content of bud propyl propionate in solution is preferably 0.5～0.7% among the present invention, and the preferred concentration of NMMO solvent is: 45～47%.
The compound method of bud propyl propionate solution of the present invention is:
At first compound concentration is 40～50% NMMO solvent, then the bud propyl propionate is dissolved in 40～50% the NMMO solvent.
The bud propyl propionate solution that adopts the present invention's preparation is as stabilizing agent, in the production of cellulose fiber by solvent method, can effectively avoid this solution to produce crystallization at low temperatures, particularly, can not use any heat-preserving equipment to be applied in the production of cellulose fiber by solvent method in winter-spring air temperature lower season.Use bud propyl propionate solution of the present invention as stabilizing agent simultaneously, also can avoid being lower than 40% when following, bring problem than juicy, the stability of control system effectively into can for the cellulose dissolution system as the concentration of solvent NMMO.
The cellulose fiber spinning slurries that use the present invention to produce as stabilizing agent adopt the test stone of German TITK to detect, and every index all meets international relevant criterion.
Adopting the NMMO solution of variable concentrations is solvent, and the crystallization temperature of the bud propyl propionate solution of preparation can see Table 1.
Table 1
From table 1, can clearly find out, when working concentration is higher than 50% NMMO and prepares bud propyl propionate solution as solvent, its crystallization temperature is made solvent apparently higher than the NMMO that adopts 50% following concentration, that is to say and use bud propyl propionate solution used as stabilizers of the present invention can solve bud propyl propionate solution is easy to generate crystallization when low temperature problem well, and in production application, can not bring more moisture into again to system.
The specific embodiment
The method for preparing bud propyl propionate solution of the present invention is successively by following steps:
1) is 50% left and right sides NMMO solution with commercially available concentration, is diluted to about 10%～40%, purify the impurity elimination of discoloring then by yin and yang resin with deionized water;
2) inspissation to the concentration under the condition of 10～15kpa and 50～70 ℃ of the solution after will purifying is 40～50%;
3) take out this concentration NMMO solution, add the bud propyl propionate of required amount, it is mixed by the agitator stirring.
Used bud propyl propionate is that MERCK produces among the embodiment; Used water cellulose element is that SAPPI company pulp passes through water submersion dehydration to 20～55%, pulverizes gained, perhaps passes through activation with SAPPI company pulp, dewaters to 20～55% the pulverizing gained again.
Embodiment 1
The adding percentage by weight is that 99.1% concentration is 43% NMMO solvent in the groove jar of band low-speed agitator, adds the bud propyl propionate of percentage by weight 0.9% again, and stirring with agitator makes it to become the solution of homogeneous.
Add in the dissolving machine in proportion above-mentioned solution that makes and 200kg water cellulose 88%NMMO solvent plain and 682kg synchronously, under 1～10kpa and 75～115 ℃ of conditions, dissolve and obtain spinning slurry, adopt the slurries test stone of German eastern Thueringisches Institut Fuer Textil-Und Kunststoff-Forschung E.V. (TITK) to detect, it the results are shown in Table 1.
Embodiment 2
The adding percentage by weight is that 99.3% concentration is 45% NMMO solvent in the groove jar of band low-speed agitator, and adding percentage by weight again is 0.7% bud propyl propionate, and stirring with agitator makes it to become the solution of homogeneous.
Add in the dissolving machine in proportion above-mentioned solution that makes and 200kg water cellulose 84%NMMO solvent plain and 711kg synchronously, under 1～10kpa and 75～115 ℃ of conditions, dissolve and obtain spinning slurry, adopt the slurries test stone of German eastern Thueringisches Institut Fuer Textil-Und Kunststoff-Forschung E.V. (TITK) to detect, it the results are shown in Table 1.
Embodiment 3
The adding percentage by weight is that 99.5% concentration is 47% NMMO solvent in the groove jar of band low-speed agitator, and adding percentage by weight again is 0.5% bud propyl propionate, and stirring with agitator makes it to become the solution of homogeneous.
Add in the dissolving machine in proportion above-mentioned solution that makes and 200kg water cellulose 81%NMMO solvent plain and 732kg synchronously, under 1～10kpa and 75～115 ℃ of conditions, dissolve and obtain spinning slurry, adopt the slurries test stone of German eastern Thueringisches Institut Fuer Textil-Und Kunststoff-Forschung E.V. (TITK) to detect, it the results are shown in Table 1.
Embodiment 4
The adding percentage by weight is that 99.6% concentration is the 49%NMM0 solvent in the groove jar of band low-speed agitator, and adding percentage by weight again is 0.4% bud propyl propionate, and stirring with agitator makes it to become the solution of homogeneous.
Add in the dissolving machine in proportion above-mentioned solution that makes and 200kg water cellulose 78%NMMO solvent plain and 755kg synchronously, under 1～10kpa and 75～115 ℃ of conditions, dissolve and obtain spinning slurry, adopt the slurries test stone of German eastern Thueringisches Institut Fuer Textil-Und Kunststoff-Forschung E.V. (TITK) to detect, it the results are shown in Table 2.
Table 2
The test data of each embodiment explanation in the table 2, its quality of the slurries of gained meet the international technological requirement of cellulose fiber spinning at present, and bud propyl propionate solution just of the present invention has well been brought into play function of stabilizer.
Claims (2)
1. stabilizing agent for cellulose fibre prepared by solvent method is characterized in that:
The percentage by weight of bud propyl propionate is 0.3～1%
The percentage by weight of NMMO solvent is 99～99.7%
The concentration of above-mentioned NMMO solvent is 45～47%.
2. stabilizing agent for cellulose fibre prepared by solvent method according to claim 1, feature are that the weight percent content of described bud propyl propionate is: 0.5～0.7%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100277221A CN101089257B (en) | 2006-06-13 | 2006-06-13 | Stabilizing agent for cellulose fibre prepared by solvent method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100277221A CN101089257B (en) | 2006-06-13 | 2006-06-13 | Stabilizing agent for cellulose fibre prepared by solvent method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101089257A CN101089257A (en) | 2007-12-19 |
| CN101089257B true CN101089257B (en) | 2011-01-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100277221A Expired - Fee Related CN101089257B (en) | 2006-06-13 | 2006-06-13 | Stabilizing agent for cellulose fibre prepared by solvent method |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5556452A (en) * | 1993-09-14 | 1996-09-17 | Lenzing Aktiengesellschaft | Moulding materials and spinning materials containing cellulose |
| US5702515A (en) * | 1994-10-20 | 1997-12-30 | Courtaulds Fibres (Holdings) Limited | Stabilised solutions of polysaccharide |
-
2006
- 2006-06-13 CN CN2006100277221A patent/CN101089257B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5556452A (en) * | 1993-09-14 | 1996-09-17 | Lenzing Aktiengesellschaft | Moulding materials and spinning materials containing cellulose |
| US5702515A (en) * | 1994-10-20 | 1997-12-30 | Courtaulds Fibres (Holdings) Limited | Stabilised solutions of polysaccharide |
Non-Patent Citations (2)
| Title |
|---|
| Enrico Marsano,et al..Wet spinning of Bombyx mori silk fibroin dissolved in N-methyl morpholine N-oxide and properties of regenerated fibres.International Journal of Biological Macromolecules.2005,(37),179-188. * |
| 吴翠玲等.纤维素溶剂研究现状及应用前景.中国造纸学报.2004,19(2),171-175. * |
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| CN101089257A (en) | 2007-12-19 |
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Inventor after: Wang Xin Inventor after: Xuan Jianxin Inventor after: Jiang Kun Inventor after: Wang Xiaoliang Inventor after: Xiao Nianyu Inventor after: Zhang Yihua Inventor after: Yang Danrong Inventor before: Xiao Nianyu Inventor before: Wang Xin Inventor before: Xuan Jianxin Inventor before: Zhang Yihua Inventor before: Yang Danrong |
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Free format text: CORRECT: INVENTOR; FROM: XIAO NIANYU WANG XIN XUAN JIANXIN ZHANG YIHUA YANG DANRONG TO: WANG XIN XUAN JIANXIN JIANG KUN WANG XIAOLIANG XIAO NIANYU ZHANG YIHUA YANG DANRONG |
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