CN103304765A - Preparation method of wood liquefied product spinning solution - Google Patents
Preparation method of wood liquefied product spinning solution Download PDFInfo
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- CN103304765A CN103304765A CN2013102175171A CN201310217517A CN103304765A CN 103304765 A CN103304765 A CN 103304765A CN 2013102175171 A CN2013102175171 A CN 2013102175171A CN 201310217517 A CN201310217517 A CN 201310217517A CN 103304765 A CN103304765 A CN 103304765A
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Abstract
The invention provides a preparation method of a wood liquefied product spinning solution. The preparation method comprises the following steps of: mixing a solid-state wood biomass material which is difficult to dissolve with a polyhydric alcohol; liquefying a mixture into a solubilized wood material with reaction activity under an acidic catalysis condition; and adding a synthesizing agent to react under a certain condition to generate a spinning solution capable of being drew. According to the preparation method, the defects in a wood fiber material preparation technology are overcome and the utilization rate of the material is improved; the spinning solution is used for spinning a carbon fiber precursor so that the dependence on fossil fuel resources by a carbon fiber industry is relieved, the whole comprehensive utilization performance of wood is improved, and the additional values of the biomass material including the wood are greatly improved. Compared with an existing wood liquefaction technology, the preparation method disclosed by the invention has the characteristics of high liquefaction efficiency, low liquefaction temperature, no toxin and no harm, environmental friendliness, low fusion and spinning temperature range and the like, and spinning is easy and convenient to control.
Description
Technical field
The present invention relates to Wood liquefied technology, specifically, relate to a kind of preparation method of Wood liquefied spinning liquid.
Background technology
The agriculture and forestry biomass materials that with timber is representative derives from photosynthesis, and aboundresources is the unique natural materials that can regenerate naturally in the traditional material.Along with the exhaustion day by day of fossil resource, and complex process and the environmental pollution of fossil material extractive process, biomass resource becomes its important surrogate gradually.Because timber is the natural polymers of indissoluble, certain size has greatly limited the range of application of timber.Utilize Wood liquefied technology timber can be converted under the condition that some organism or catalyzer exist to have reactive behavior, mobile liquid, thereby use as industrial chemicals.By the liquefaction of timber, timber liquefied matter is modulated into spinning solution by chemical process, utilizes its spinning solution can further develop fibrosis material, synthetic adhesive and molding material etc.
Timber liquefied matter has unique character, and the modulation of itself and traditional biomass spinning solution has very big difference.Domestic once had adopt phenol to prepare the report of Wood liquefied spinning liquid as liquefying agent by the method for one-step synthesis, yet phenol has the intense stimulus smell, and building-up process used a large amount of formaldehyde etc. as compound agent, contaminative is bigger.Therefore, demand urgently developing a kind of environmentally friendly, the synthetic method of the Wood liquefied spinning liquid that liquefaction efficiency is high.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of Wood liquefied spinning liquid of novel environment friendly.
In order to realize the object of the invention, the preparation method of a kind of Wood liquefied spinning liquid of the present invention may further comprise the steps:
1) with obtaining wood powder after the timber pulverizing, wood powder is mixed according to weight ratio 1:1.5-6 with polyvalent alcohol, add an acidic catalyst, stir liquefaction down at 150 ℃-180 ℃, obtain timber liquefied matter stoste; 2) organic solvent that adds stoste weight 40%-60% in the above-mentioned stoste dilutes, then at 103 ℃ ± 2 ℃ preferred 12h of dry 8h-12h(down), the timber liquefied matter behind the moisture that is removed; 3) add the compound agent of liquefaction thing weight 20%-40% in the above-mentioned timber liquefied matter after, be heated to 100 ℃-120 ℃ from room temperature, the preferred 30min of isothermal reaction 30min-60min(), namely get Wood liquefied spinning liquid.
Wherein, the polyol blends that is mixed with by weight 7:3 as polyoxyethylene glycol and glycerol of the polyvalent alcohol that uses in the step 1); Polyoxyethylene glycol is PEG200-6000, and namely molecular-weight average is at one or more of 200 to 6000 polyoxyethylene glycol superpolymer.
Step 2) organic solvent that uses in is in dimethyl formamide, N,N-DIMETHYLACETAMIDE or the dimethyl sulfoxide (DMSO) etc. one or more.The preferred organic solvent that uses is dimethyl formamide (DMF).
The compound agent that uses in the step 3) is liquefaction diphenylmethanediisocyanate (MDI), i.e. one or more among the MDI of the MDI of carbodiimide modification, urethane-modified MDI or carbodiimide-urine ketoimine modification etc.
Among the aforementioned preparation method, an acidic catalyst that step 1) is used is sulfuric acid, hydrochloric acid or phosphoric acid, and add-on is the 3%-10% of polyvalent alcohol weight.Preferred working concentration is that 72% sulfuric acid is as catalyzer.
Among the aforementioned preparation method, the time that step 1) liquefies is 60min-90min.
Among the aforementioned preparation method, after in timber liquefied matter, adding compound agent, evenly be heated to 100 ℃-120 ℃ from room temperature through 30-60min in the step 3).
Among the aforementioned preparation method, step 1) is to cross the 20-80 order after timber is pulverized to obtain wood powder, also comprises before liquefaction reaction the withering step of wood powder.
Particularly, the preparation method of a kind of Wood liquefied spinning liquid of the present invention may further comprise the steps:
1) obtain wood powder after timber is pulverized, wood powder mixed according to weight ratio 1:1.5 with polyvalent alcohol, adding concentration be 72% sulfuric acid as catalyzer, 150 ℃ of 120rpm 60min that liquefy obtain timber liquefied matter stoste; 2) organic solvent that adds stoste weight 40% in the above-mentioned stoste dilutes, then at 105 ℃ of dry 12h down, the timber liquefied matter behind the moisture that is removed; 3) add the compound agent of liquefaction thing weight 20% in the above-mentioned timber liquefied matter after, evenly be heated to 120 ℃ from room temperature through 60min, isothermal reaction 30min namely gets Wood liquefied spinning liquid.
The present invention also provides the Wood liquefied spinning liquid of preparation according to the method described above.
The present invention also provides the application of Wood liquefied spinning liquid in synthon formed material, synthetic adhesive and molding material etc. by method for preparing.
The present invention further provides the carbon fiber and the activated carbon fiber precursor that are spun into by described Wood liquefied spinning liquid.
The preparation method of Wood liquefied spinning liquid provided by the invention, mix with polyvalent alcohol by the solid-state timber biological material with indissoluble, the solubilisate wood materials of liquefaction for having reactive behavior under the acid catalysis condition, but add the spinning solution that compound agent reacts the generation wire drawing under certain condition, have simple to operate, liquefaction efficiency is high, pollution-free, timber utilization rate advantages of higher, and improved existing spinning solution and polluted the problem high, that liquefaction efficiency is low.Simultaneously, spinning solution also can spin out the fiber of different diameter according to actual needs, and fiber has good elasticity, good processability.
The carbon fiber mean diameter of utilizing the synthetic spinning solution of the inventive method to spin out can reach 20-30 μ m, tensile strength 68-138MPa, tensile modulus 9.8-26GPa, elongation at break 3.52%-6.12%, its mechanical property is better than common phenolic fibre, has extraordinary toughness.
The invention solves the defective that exists in the lumber fibre formed material technology of preparing, improve raw-material utilising efficiency; Simultaneously, this spinning solution is used for being spun into carbon fibre precursor, thereby alleviates carbon fiber industry to the dependence of fossil resource, and the whole synthesis that improves timber utilizes performance, has greatly improved the added value of biological materials such as timber.Compare with existing Wood liquefied technology, the present invention has that liquefaction efficiency height, liquefaction temperature are low, nontoxic, environmental protection, low, the easy characteristics such as control that are easy to of spinning of spinning temperature scope.
Description of drawings
Fig. 1 prepares the technical process of Wood liquefied spinning liquid for embodiment of the invention 1-6.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.If do not specialize the conventional means that used technique means is well known to those skilled in the art among the embodiment, the raw materials used commercial goods that is.
Because length is limit, only exemplify the testing data of indivedual embodiment herein, those skilled in the art can understand with other embodiments of the invention and repeat following test, also can access identical or close conclusion (of pressure testing).
The preparation of embodiment 1 Wood liquefied spinning liquid
Timber was ground the wood powder of 80 mesh sieve (mesh diameter 0.20mm), after the drying that the polyoxyethylene glycol (PEG400) of wood powder and its 1.5 times of weight and the polyol blends of glycerol (weight ratio of polyoxyethylene glycol and glycerol is 7:3) is mixed, add concentration simultaneously and be 72% sulfuric acid as catalyzer (sulfuric acid add-on be polyvalent alcohol weight 5%) in there-necked flask, place the oil bath of 150 ℃ of preheat value, install condensing works, start agitator (rotating speed 120rpm), carry out Wood liquefied, liquefying time 60min obtains timber liquefied matter stoste.
After adding 40% dimethyl formamide and dilute by timber liquefied matter stoste weight ratio, place air dry oven, 105 ℃ of dryings 12 hours are removed moisture.Add the timber liquefied matter weight ratio again and be the diphenylmethanediisocyanate (liquefied mdi) of 30% carbodiimide modification, evenly be heated to 120 ℃ from room temperature through 60min, can obtain having the timber polyvalent alcohol liquefied spinning liquid of wire-drawing performance at 120 ℃ of reaction 30min.The average fibre diameter of measuring its spinning is 24 μ m, and tensile strength is 76-94MPa, tensile modulus 16-22GPa, elongation at break 3.88%-4.82%.
The preparation of embodiment 2 Wood liquefied spinning liquids
Timber was ground the wood powder of 60 mesh sieve (mesh diameter 0.30mm), after the drying that the polyoxyethylene glycol (PEG1000) of wood powder and its 2 times of weight and the polyol blends of glycerol (weight ratio of polyoxyethylene glycol and glycerol is 7:3) is mixed, adding concentration simultaneously and be 72% sulfuric acid joins in the there-necked flask as catalyzer (sulfuric acid add-on be polyvalent alcohol weight 5%), place the oil bath of 150 ℃ of preheat value, install condensing works, start agitator (rotating speed 120rpm), carry out Wood liquefied, liquefying time 60min obtains the thing that liquefies.
After adding 40% N,N-DIMETHYLACETAMIDE and dilute by timber liquefied matter stoste weight ratio, place air dry oven, 105 ℃ of dryings 12 hours are removed moisture.Add the timber liquefied matter weight ratio again and be the diphenylmethanediisocyanate (liquefied mdi) of 30% carbodiimide modification, evenly be heated to 120 ℃ from room temperature through 60min, can obtain having the timber polyvalent alcohol liquefied spinning liquid of wire-drawing performance at 120 ℃ of reaction 30min.The average fibre diameter of measuring its spinning is 26 μ m, and tensile strength is 70-82MPa, tensile modulus 15-20GPa, elongation at break 4.12%-5.62%.
The preparation of embodiment 3 Wood liquefied spinning liquids
Timber was ground the wood powder of 40 mesh sieve (mesh diameter 0.20mm), after the drying that the polyoxyethylene glycol (PEG400) of wood powder and its 2 times of weight and the polyol blends of glycerol (weight ratio of polyoxyethylene glycol and glycerol is 7:3) is mixed, adding concentration simultaneously and be 72% sulfuric acid joins in the there-necked flask as catalyzer (sulfuric acid add-on be polyvalent alcohol weight 3%), place the oil bath of 150 ℃ of preheat value, install condensing works, start agitator (rotating speed 120rpm), carry out Wood liquefied, liquefying time 60min obtains the thing that liquefies.
Add after 40% dimethyl sulfoxide (DMSO) dilutes by timber liquefied matter stoste weight ratio, place air dry oven, 105 ℃ of dryings 12 hours are removed moisture.Add the timber liquefied matter weight ratio again and be the diphenylmethanediisocyanate (liquefied mdi) of 30% carbodiimide modification, evenly be heated to 120 ℃ from room temperature through 60min, can obtain having the timber polyvalent alcohol liquefied spinning liquid of wire-drawing performance at 100 ℃ of reaction 30min.The average fibre diameter of measuring its spinning is 30 μ m, and tensile strength is 68-79MPa, tensile modulus 9.8-14.2GPa, elongation at break 5.29%-6.12%.
The preparation of embodiment 4 Wood liquefied spinning liquids
Timber was ground the wood powder of 60 mesh sieve (mesh diameter 0.30mm), after the drying that the polyoxyethylene glycol (PEG400) of wood powder and its 4 times of weight and the polyol blends of glycerol (weight ratio of polyoxyethylene glycol and glycerol is 7:3) is mixed, adding concentration simultaneously and be 72% sulfuric acid joins in the there-necked flask as catalyzer (sulfuric acid add-on be polyvalent alcohol weight 10%), place the oil bath of 150 ℃ of preheat value, install condensing works, start agitator (rotating speed 120rpm), carry out Wood liquefied, liquefying time 60min obtains the thing that liquefies.
After adding 50% dimethyl formamide and dilute by timber liquefied matter stoste weight ratio, place air dry oven, 105 ℃ of dryings 12 hours are removed moisture.Add the timber liquefied matter weight ratio again and be 40% urethane-modified diphenylmethanediisocyanate (liquefied mdi), evenly be heated to 120 ℃ from room temperature through 60min, can obtain having the timber polyvalent alcohol liquefied spinning liquid of wire-drawing performance at 120 ℃ of reaction 30min.The average fibre diameter of measuring its spinning is 20 μ m, and tensile strength is 101-138MPa, tensile modulus 19-26GPa, elongation at break 3.52%-4.79%.
The preparation of embodiment 5 Wood liquefied spinning liquids
Timber was ground the wood powder of 80 mesh sieve (mesh diameter 0.30mm), after the drying that the polyoxyethylene glycol (PEG1000) of wood powder and its 6 times of weight and the polyol blends of glycerol (weight ratio of polyoxyethylene glycol and glycerol is 7:3) is mixed, adding concentration simultaneously and be 72% sulfuric acid joins in the there-necked flask as catalyzer (sulfuric acid add-on be polyvalent alcohol weight 10%), place the oil bath of 150 ℃ of preheat value, install condensing works, start agitator (rotating speed 120rpm), carry out Wood liquefied, liquefying time 60min obtains the thing that liquefies.
After adding 40% N,N-DIMETHYLACETAMIDE and dilute by timber liquefied matter stoste weight ratio, place air dry oven, 105 ℃ of dryings 12 hours are removed moisture.Add the timber liquefied matter weight ratio again and be the diphenylmethanediisocyanate (liquefied mdi) of 30% carbodiimide modification, evenly be heated to 120 ℃ from room temperature through 60min, can obtain having the timber polyvalent alcohol liquefied spinning liquid of wire-drawing performance at 120 ℃ of reaction 30min.The average fibre diameter of measuring its spinning is 22 μ m, and tensile strength is 82-110MPa, tensile modulus 18-24GPa, elongation at break 4.15%-5.02%.
The preparation of embodiment 6 Wood liquefied spinning liquids
Timber was ground the wood powder of 40 mesh sieve (mesh diameter 0.45mm), after the drying that the polyoxyethylene glycol (PEG400) of wood powder and its 4 times of weight and the polyol blends of glycerol (weight ratio of polyoxyethylene glycol and glycerol is 7:3) is mixed, adding concentration simultaneously and be 72% sulfuric acid joins in the there-necked flask as catalyzer (sulfuric acid add-on be polyvalent alcohol weight 10%), place the oil bath of 150 ℃ of preheat value, install condensing works, start agitator (rotating speed 120rpm), carry out Wood liquefied, liquefying time 60min obtains the thing that liquefies.
After adding 40% N,N-DIMETHYLACETAMIDE and dilute by timber liquefied matter stoste weight ratio, place air dry oven, 105 ℃ of dryings 12 hours are removed moisture.Add the timber liquefied matter weight ratio again and be the diphenylmethanediisocyanate (liquefied mdi) of 30% carbodiimide modification, evenly be heated to 120 ℃ from room temperature through 60min, can obtain having the timber polyvalent alcohol liquefied spinning liquid of wire-drawing performance at 120 ℃ of reaction 30min.The average fibre diameter of measuring its spinning is 26 μ m, and tensile strength is 77-91MPa, tensile modulus 12.6-16.8GPa, elongation at break 4.78%-5.62%.
The technical process of embodiment 1-6 as shown in Figure 1.
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, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. the preparation method of a Wood liquefied spinning liquid is characterized in that, may further comprise the steps:
1) with obtaining wood powder after the timber pulverizing, wood powder is mixed according to weight ratio 1:1.5-6 with polyvalent alcohol, add an acidic catalyst, stir liquefaction down at 150 ℃-180 ℃, obtain timber liquefied matter stoste;
2) organic solvent that adds stoste weight 40%-60% in the above-mentioned stoste dilutes, then at 103 ℃ ± 2 ℃ dry 8h-12h down, the timber liquefied matter behind the moisture that is removed;
3) add the compound agent of liquefaction thing weight 20%-40% in the above-mentioned timber liquefied matter after, be heated to 100 ℃-120 ℃ from room temperature, isothermal reaction 30min-60min namely gets Wood liquefied spinning liquid;
Wherein, step 2) organic solvent that uses in is in dimethyl formamide, N,N-DIMETHYLACETAMIDE or the dimethyl sulfoxide (DMSO) one or more, and the compound agent that uses in the step 3) is liquefied mdi.
2. preparation method according to claim 1 is characterized in that, the polyol blends that the polyvalent alcohol that uses in the step 1) is mixed with by weight 7:3 as polyoxyethylene glycol and glycerol.
3. preparation method according to claim 2 is characterized in that, the employed polyoxyethylene glycol of preparation polyvalent alcohol is PEG200-6000.
4. preparation method according to claim 1 is characterized in that, an acidic catalyst that uses in the step 1) is sulfuric acid, hydrochloric acid or phosphoric acid, and add-on is the 3%-10% of polyvalent alcohol weight.
5. preparation method according to claim 1 is characterized in that, the time that step 1) liquefies is 60min-90min.
6. preparation method according to claim 1 is characterized in that, add compound agent in timber liquefied matter after, evenly is heated to 100 ℃-120 ℃ from room temperature through 30-60min in the step 3).
7. preparation method according to claim 1 is characterized in that, the liquefied mdi that uses in the step 3) is among the MDI of the MDI of carbodiimide modification, urethane-modified MDI or carbodiimide-urine ketoimine modification one or more.
8. preparation method according to claim 1 is characterized in that, in the step 1) is to cross the 20-80 order after timber is pulverized to obtain wood powder, also comprises before liquefaction reaction the withering step of wood powder.
9. preparation method according to claim 3 is characterized in that, may further comprise the steps:
1) obtain wood powder after timber is pulverized, wood powder mixed according to weight ratio 1:1.5 with polyvalent alcohol, adding concentration be 72% sulfuric acid as catalyzer, 150 ℃ of 120rpm 60min that liquefy obtain timber liquefied matter stoste;
2) organic solvent that adds stoste weight 40% in the above-mentioned stoste dilutes, then at 105 ℃ of dry 12h down, the timber liquefied matter behind the moisture that is removed;
3) add the compound agent of liquefaction thing weight 20% in the above-mentioned timber liquefied matter after, evenly be heated to 120 ℃ from room temperature through 60min, isothermal reaction 30min namely gets Wood liquefied spinning liquid.
10. according to the Wood liquefied spinning liquid of each described method preparation of claim 1-9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017791A (en) * | 2015-06-26 | 2015-11-04 | 北京林业大学 | Lignin-based carbon fiber precursor, and preparation method and application thereof |
| CN105040157A (en) * | 2015-07-27 | 2015-11-11 | 北京林业大学 | Preparation and spinning methods for wood liquefaction product electrospinning solution |
| 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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| CN101074498A (en) * | 2007-06-08 | 2007-11-21 | 北京林业大学 | Wood liquefied spinning liquid and its one-step synthesis |
| CN101135075A (en) * | 2007-10-11 | 2008-03-05 | 北京林业大学 | Wood liquefied carbide fiber, protofilament and preparation method thereof |
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| CN101074498A (en) * | 2007-06-08 | 2007-11-21 | 北京林业大学 | Wood liquefied spinning liquid and its one-step synthesis |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017791A (en) * | 2015-06-26 | 2015-11-04 | 北京林业大学 | Lignin-based carbon fiber precursor, and preparation method and application thereof |
| CN105040157A (en) * | 2015-07-27 | 2015-11-11 | 北京林业大学 | Preparation and spinning methods for wood liquefaction product electrospinning solution |
| 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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