CN101074498B - Wood liquefied spinning liquid and its one-step synthesis - Google Patents
Wood liquefied spinning liquid and its one-step synthesis Download PDFInfo
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- CN101074498B CN101074498B CN2007101003651A CN200710100365A CN101074498B CN 101074498 B CN101074498 B CN 101074498B CN 2007101003651 A CN2007101003651 A CN 2007101003651A CN 200710100365 A CN200710100365 A CN 200710100365A CN 101074498 B CN101074498 B CN 101074498B
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Abstract
This invention supplies one spinning solution for the liquefaction of timber and its method. The spinning solution is produced by the one-step synthesis method using liquefaction of timber as raw materials. This invention solves the key technologies for producing timber fibrosis, lowers defects of the process for the traditional wood materials fibrosis, reduce the waste of raw materials. The carbon fiber precursor can be made by the spinning solution so that it eases the impact of shortage of Fossils resources on carbon fiber materials, raises the comprehensive utilization value of the timber.
Description
Technical field
The present invention relates to a kind of novel spinning liquid and synthetic technology thereof, specifically, the present invention relates to utilize the one-step synthesis process technology of the spinning solution and this spinning solution of timber liquefied matter synthesizing new.
Background technology
Along with the shortage day by day of fossil resource, biomass resource becomes its important substitute gradually.Timber is only reproducible natural material in the four great tradition raw material, and aboundresources is an indispensable important materials during national product is built, and is widely used in every field, also becomes the first-selection that substitutes fossil resource.Because timber is the natural polymers of infusibility indissoluble, is processed into fibrous material and has bigger difficulty.Traditional fibrous material that Wood Processing is become mainly contains two kinds of methods: the one, and mechanical defibrator process; The 2nd, Chemical Decomposition goes out cellulose, is reprocessed into viscose.Though these two kinds of methods can become fibrous material with Wood Processing, and weak point is all arranged.The fiber of first method processing is very short, and diameter is bigger and wayward, and is difficult to realize continuous long filament; Though second method can form long filament, need Chemical Decomposition to go out cellulose and be prepared into pulp again, the process complexity, operation easier is big.And two kinds of methods all can produce a large amount of pollutants, are unfavorable for environmental protection, owing to can only utilize the part composition of timber in preparation process, the timber resources waste is serious simultaneously.Utilize Wood liquefied technology timber can be converted into the liquid with reactivity in the presence of some organic matter or catalyst, thereby can be used as fuel or industrial chemicals use.So just can directly the timber product after the liquefaction be modulated into spinning solution by chemical method, but utilize its spinning solution Direct Spinning to make the fibration material.Timber liquefied matter has unique character, and the modulation of itself and traditional living beings spinning solution pulp has very big difference, and has not found relevant report and patent both at home and abroad.
Summary of the invention
The objective of the invention is with the timber liquefied matter is raw material, and a kind of new spinning solution and one-step method synthetic technology thereof are provided, and with the key technology of the preparation that solves the lumber fibre formed material, reduces the manufacturing deficiency of traditional timber fibration material, reduces raw-material waste; Can be spun into carbon fibre precursor owing to this spinning solution simultaneously, thereby alleviate the influence of fossil resource shortage, improve the whole synthesis value of timber carbon fiber material.
The inventive method comprises step down:
1) with getting wood powder after the timber pulverizing, wood powder is mixed according to weight ratio 1: 3～7 with phenol, press phenol weight 5～10% and add acidic catalysts, 150～180 ℃ were reacted 1～3.0 hour, and obtained timber liquefied matter; Preferably wood powder is mixed according to weight ratio with phenol at 1: 6, press phenol weight 8% and add acidic catalyst, 160 ℃ were reacted 2.5 hours, and obtained timber liquefied matter;
2) spinning solution is synthetic: synthetics 3～6% is joined in the timber liquefied matter by weight, evenly be heated to 110～130 ℃ from room temperature through 20～60min, reaction 2～10min.Preferably, synthetics 5% is joined in the timber liquefied matter by weight, evenly be heated to 120 ℃ through 40min, reaction 5min from room temperature.
Above-mentionedly obtain wood powder, preferably wood powder to be broken into the wood powder of 20～80 mesh sieves, more preferably to cross 60 mesh sieves in the timber step 1) timber being pulverized; The wood powder that obtains is dried to over dry in 105 ℃ will help liquefaction to handle.
Above-mentioned acidic catalyst can be a hydrochloric acid, also can be sulfuric acid or phosphoric acid.
Above-mentioned synthetics is preferably a kind of in paraformaldehyde, furfural, hexamethylenetetramine, the metaformaldehyde.
The present invention also comprises the spinning solution that obtains by said method.
Wood liquefied spinning liquid one-step method synthetic method of the present invention, by the liquid solution that the Wood liquefied one-tenth of infusibility indissoluble is had certain reactivity, but add the spinning solution that synthetics reacts the generation wire drawing under certain condition, have easy to operate, of reduced contamination, timber utilization rate is than advantages such as height, and thoroughly solved and can't directly utilize timber to carry out the difficult problem of spinning, can require to spin out the fibrous material of different-diameter according to reality, good processability by spinning machine.
The spinning solution of timber liquefied matter one-step method preparation of the present invention, utilizing its timber phenol that can prepare liquefaction fibres average diameter is 27 μ m, TENSILE STRENGTH is at 230～356MPa, the stretching amount of touching is at 15～31GPa, elongation at break is 2.17%～3.72%, and its mechanical property is better than common phenolic fibre.
The specific embodiment
Following embodiment is used for that the invention will be further described, but is not used for limiting the scope of the invention.
Embodiment 1
Wood powder is broken into the powder of 60 orders (mesh screen aperture 0.18mm), then 6 times phenol of this wood powder and timber weight and catalyst phosphoric acid (phosphoric acid addition be phenol addition 8%) are joined in three mouthfuls of vials, place and be preheated to 160 ℃ oil bath in advance, install condenser, start agitating device (rotating speed 1058rpm) and carry out the liquefaction of timber, liquefying time is 2.5 hours, obtains timber liquefied matter.
The paraformaldehyde 40min of adding 5% is heated to the Wood liquefied spinning liquid that 120 ℃ of reaction 5min can obtain having wire-drawing performance from room temperature in the liquefaction thing, the tensile strength of fiber of measuring its spinning is at 39～49MPa, stretch modulus is at 5.6～8.8GPa, and elongation at break is 1.21～1.52%.
Embodiment 2
Wood powder is broken into the powder of 80 orders (mesh screen aperture 0.18mm), then 7 times phenol of this wood powder and timber weight and catalyst hydrochloric acid (hydrochloric acid addition be phenol addition 5%) are joined in three mouthfuls of vials, place and be preheated to 150 ℃ oil bath in advance, install condenser, start agitating device (rotating speed 1058rpm) and carry out the liquefaction of timber, liquefying time is 3 hours, obtains timber liquefied matter.
The furfural 20min of adding 3% is heated to the Wood liquefied spinning liquid that 110 ℃ of reaction 10min can obtain having wire-drawing performance from room temperature in the liquefaction thing, the tensile strength of fiber of measuring its spinning is at 59～73MPa, stretch modulus is at 6.5～9.2GPa, and elongation at break is 0.9～1.11%.
Embodiment 3
Wood powder is broken into the powder of 20 orders (mesh screen aperture 0.18mm), then 5 times phenol of this wood powder and timber weight and catalyst sulfuric acid (sulfuric acid addition be phenol addition 8%) are joined in three mouthfuls of vials, place and be preheated to 170 ℃ oil bath in advance, install condenser, start agitating device (rotating speed 1058rpm) and carry out the liquefaction of timber, liquefying time is 1 hour, obtains timber liquefied matter.
Six first class tetramine 60min of adding 6% are heated to the Wood liquefied spinning liquid that 120 ℃ of reaction 2min can obtain having wire-drawing performance from room temperature in the liquefaction thing, the tensile strength of fiber of measuring its spinning is at 90～129MPa, stretch modulus is at 8～24GPa, and elongation at break is 0.47～1.56%.
Embodiment 4
Wood powder is broken into the powder of 60 orders (mesh screen aperture 0.18mm), then 6 times phenol of this wood powder and timber weight and catalyst phosphoric acid (phosphoric acid addition be phenol addition 10%) are joined in three mouthfuls of vials, place and be preheated to 180 ℃ oil bath in advance, install condenser, start agitating device (rotating speed 1058rpm) and carry out the liquefaction of timber, liquefying time is 2 hours, obtains timber liquefied matter.
The metaformaldehyde 30min of adding 5% is heated to the Wood liquefied spinning liquid that 130 ℃ of reaction 8min can obtain having wire-drawing performance from room temperature in the liquefaction thing, the tensile strength of fiber of measuring its spinning is at 39～49MPa, stretch modulus is at 5.6～8.8GPa, and elongation at break is 1.21～1.52%.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, not departing from the these modifications or improvements basically of spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. Wood liquefied spinning liquid, it makes as follows:
1) with getting wood powder after the timber pulverizing, wood powder is mixed according to weight ratio 1: 3～7 with phenol, press phenol weight 5～10% and add acidic catalysts, 150～180 ℃ were reacted 1～3.0 hour, and obtained timber liquefied matter;
2) spinning solution is synthetic: synthetics 3～6% is joined in the timber liquefied matter by weight, evenly be heated to 110～130 ℃ from room temperature through 20～60min, reaction 2～10min.
2. spinning solution as claimed in claim 1, it makes as follows:
1) with getting wood powder after the timber pulverizing, wood powder is mixed according to weight ratio with phenol at 1: 6, press phenol weight 8% and add acidic catalyst, 160 ℃ were reacted 2.5 hours, and obtained timber liquefied matter;
2) synthetics 5% is joined in the timber liquefied matter by weight, evenly be heated to 120 ℃ through 40min, reaction 5min from room temperature.
3. spinning solution as claimed in claim 1 or 2 is characterized in that, described preparation process 1) before liquefaction reaction, also comprise wood powder is made dried.
4. spinning solution as claimed in claim 1 or 2 is characterized in that, described acidic catalyst is phosphoric acid, hydrochloric acid or sulfuric acid.
5. spinning solution as claimed in claim 1 or 2 is characterized in that, described synthetics is selected from a kind of in paraformaldehyde, furfural, hexamethylenetetramine, the metaformaldehyde.
6. method for preparing timber liquefied matter, it comprises the steps:
1) with getting wood powder after the timber pulverizing, wood powder is mixed according to weight ratio 1: 3～7 with phenol, press phenol weight 5～10% and add acidic catalysts, 150～180 ℃ were reacted 1～3.0 hour, and obtained timber liquefied matter;
2) spinning solution is synthetic: synthetics 3～6% is joined in the timber liquefied matter by weight, evenly be heated to 110～130 ℃ from room temperature through 20～60min, reaction 2～10min.
7. method as claimed in claim 6, it comprises the steps:
1) with getting wood powder after the timber pulverizing, wood powder is mixed according to weight ratio with phenol at 1: 6, press phenol weight 8% and add acidic catalyst, 160 ℃ were reacted 2.5 hours, and obtained timber liquefied matter;
2) synthetics 5% is joined in the timber liquefied matter by weight, evenly be heated to 120 ℃ through 40min, reaction 5min from room temperature.
8. method as claimed in claim 1 or 2 is characterized in that, described preparation process 1) before liquefaction reaction, also comprise wood powder is made dried.
9. method as claimed in claim 1 or 2 is characterized in that, described acidic catalyst is phosphoric acid, hydrochloric acid or sulfuric acid.
10. method as claimed in claim 1 or 2 is characterized in that, described synthetics is selected from a kind of in paraformaldehyde, furfural, hexamethylenetetramine, the metaformaldehyde.
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| CN2007101003651A CN101074498B (en) | 2007-06-08 | 2007-06-08 | Wood liquefied spinning liquid and its one-step synthesis |
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| CN2007101003651A CN101074498B (en) | 2007-06-08 | 2007-06-08 | Wood liquefied spinning liquid and its one-step synthesis |
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| CN101074498A CN101074498A (en) | 2007-11-21 |
| CN101074498B true CN101074498B (en) | 2011-05-18 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2898126A4 (en) * | 2012-09-20 | 2016-07-27 | Graftech Int Holdings Inc | Carbon fibers derived from lignin |
| CN103014920B (en) * | 2012-12-17 | 2014-03-19 | 北京林业大学 | Wood carbon fiber precursor and preparation method thereof |
| CN103304765B (en) * | 2013-06-03 | 2015-06-24 | 北京林业大学 | Preparation method of wood liquefied product spinning solution |
| CN103469368A (en) * | 2013-09-06 | 2013-12-25 | 北京林业大学 | Wood carbon fiber precursor and preparation method thereof |
| CN104264259A (en) * | 2014-10-15 | 2015-01-07 | 钱景 | Graphene and salix psammophila regenerated cellulose blended fiber and preparation method thereof |
| CN104233492B (en) * | 2014-10-15 | 2016-01-06 | 钱景 | A kind of nanometer silver antimicrobial salix monogolica regenerated celulose fibre and preparation method thereof |
| CN105040162A (en) * | 2015-06-11 | 2015-11-11 | 天津科技大学 | Woody hollow fibers and preparation method of woody hollow active carbon fibers |
| CN105040157B (en) * | 2015-07-27 | 2017-08-08 | 北京林业大学 | A kind of preparation of wooden liquefied substance electrostatic spinning liquid and spinning process |
| CN108330569A (en) * | 2018-02-08 | 2018-07-27 | 北京林业大学 | A kind of lignin-base activated carbon fiber presoma and the preparation method and application thereof |
| CN109385889B (en) * | 2018-11-08 | 2021-05-07 | 银维康新材料科技(珠海)有限公司 | Antibacterial and anti-radiation fabric |
| CN111961222A (en) * | 2020-07-15 | 2020-11-20 | 天津科技大学 | Method for preparing gel elastomer based on wood liquefied product and gel elastomer |
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| CN1554724A (en) * | 2003-12-23 | 2004-12-15 | 中国林业科学研究院木材工业研究所 | Process for preparing liquefied wood phenolic adhesive |
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