CN101381898A - Fibrillation dissolving pulp, method for making same and applications - Google Patents
Fibrillation dissolving pulp, method for making same and applications Download PDFInfo
- Publication number
- CN101381898A CN101381898A CNA2008101991129A CN200810199112A CN101381898A CN 101381898 A CN101381898 A CN 101381898A CN A2008101991129 A CNA2008101991129 A CN A2008101991129A CN 200810199112 A CN200810199112 A CN 200810199112A CN 101381898 A CN101381898 A CN 101381898A
- Authority
- CN
- China
- Prior art keywords
- pulp
- fiber
- fibrillation
- acid
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a method for preparing fibrillation pulp. The method comprises the following steps: (1) pre-treating chopped fibers by a pre-treating agent; (2) Controlling the concentration of the chopped fibers to between 0.1 and 30 weight percent, and jordaning the chopped fibers in the jordaning equipment to obtain the pulp; and (3) dewatering and storing the pulp. The fibrillation pulp prepared by the method can be applied to friction materials, reinforcing materials, battery membranes, PCB base materials, honeycomb core materials or high-performance paper. The method has the advantages that with the method, the key technical problem in the fibrillation pulp preparing process is effectively solved, and the method is wider in application range; the method can effectively improve the preparing efficiency of the fibrillation pulp and save energy consumption; and by the concrete adjustment of process including the pre-treating agent, the pre-treating condition and the jordaning process, the fibrillation pulp meeting the service condition can be prepared according to the service requirement of products, so the method has larger flexibility.
Description
Technical field
The present invention relates to fiber pulping technique and paper technology, particularly a kind of fibrillation dissolving pulp and preparation method thereof and application.
Technical background
For some artificial fibres and synthetic fiber, fibrillation is meant fiber when being subjected to mechanical force, and the fiber top layer of otherwise smooth is damaged, and nano level fibril of fibrous inside or fibril bundle are exposed, invest on the main fibre, also has part to break away from fibrous body.The p-aramid fiber of fibrillation (PPTA) and polyparaphenylene's benzoxazole pulps such as (PBO) have kept not only that fiber is high temperature resistant, wear-resisting, high strength, low croop property, the excellent physical characteristic of electrical property, and dispersiveness with height, be a kind of very good composite, be widely used in rubber reinforcing material, substrate for printed circuit board, high-performance comb core, friction material and high-performance paper etc.The fibrillation dissolving pulp technology of preparing mainly contains Mechanical Method and straight forming method at present, and its key technology all is to control its original fiber degree, keeps certain fibre strength and solves scattering problem.
The patent No. is that the United States Patent (USP) of US5028372 proposes the p-aramid fiber gel that preparation earlier has certain orientation, again by some milling apparatus control pulp form and size; The patent No. is that the United States Patent (USP) of US2005028734 proposes para-aramid fiber and acrylic fiber mixing defibrination preparation sealing, friction material, and pulp preparation is used multistage mill defibrination; The patent No. is that the United States Patent (USP) of US532059 proposes to add poly N-vinyl-2-Pyrrolidone (PVP) in the p-aramid fiber polymerization system, the gel that preparation has certain orientation after the polymerization, PVP serves as discontinuous phase in gel, under certain shearing force, form easily that fibril is thin, the higher p-aramid fiber pulp of original fiber degree; The patent No. is that the Chinese invention patent proposition direct polycondensation of ZL02193843.3 prepares the p-aramid fiber pulp, forms high molecule liquid crystal attitude frozen glue body after the polymerization and obtain pulp after precipitating, pulverizing, washing; The patent No. prepares the p-aramid fiber pulp for the ZL02136979.8 Chinese invention patent proposes to adopt semicontinuous direct polycondensation method, the method is to add molecular weight less than 40000 polyvinylpyrrolidone in the p-aramid fiber polymerization system, extrude again and contain high molecule liquid crystal attitude frozen glue body, be incubated pulp preparation technologies such as slaking, making beating; The patent No. is that the Chinese invention patent of ZL02138112.7 proposes to adopt precipitation method to prepare the p-aramid fiber pulp, the p-aramid fiber resin that will have certain inherent viscosity dissolves in the concentrated sulfuric acid fully makes slurries, directly separates out Fanglun slurry cake in solidification liquid, under high degree of agitation.The method of above patent disclosure all belongs to pulp straight forming method, though shortened the preparation technology of pulp, but still has the solvent recovery problem, and this method can't fine control fibril form, and pulp intensity is relatively poor.
The patent No. is after the United States Patent (USP) of US5171402 proposes to adopt papermaking refining equipment commonly used to p-aramid fiber staple fiber defibrination, and dewatering after by the turbulent flow wet milk wet pulp being disperseed stores again; The patent No. is that the Japanese patent of invention of JP2000-273788A1 proposes to prepare p-aramid fiber pulp below 10ml with the staple fiber of p-aramid fiber by the mill defibrination; The patent No. is that the United States Patent (USP) of US6436236 proposes to add sulfonated polyaniline in p-aramid fiber spinning system, cut off the preparation staple fiber after the spinning, this moment, sulfonated polyaniline served as discontinuous phase in fiber, prepared pulp easily and saved refining energy consumption with the refining equipment of string; The patent No. is that the Chinese invention patent of ZL0329083.3 proposes to utilize mechanical cutter that the aramid fiber leftover pieces are cut to fibre length 0.1～10mm, be dispersed in the suspension that becomes 0.1～5.0% concentration in the water, again by single disc refiner defibrination 30～1800s, again with trough-style pulp beater making beating preparation in 0.5～5.0 hour pulp; The patent No. is that the Chinese invention patent of the ZL20061025779.8 waste silk that proposes to utilize fire-resistant high-performance organic fibers such as aramid fiber and pbo fiber, weaving, braiding leftover bits and pieces, leftover pieces etc. are raw material, through cutting into the staple fiber that length is 2～10mm, after making fiber in water, form 0.1～8% suspension equably by means of dispersants such as CATION and anion Compositional type high molecular surfactants, pump in mulser or the double plate mill with the flow of 2～10t/h and to grind the preparation pulp through row.Because the para-aramid fiber rigidity is bigger, prepare pulp with Mechanical Method, mechanical force does not often form when enriching the fibrillation structure just serious to fibre cutting at fiber, perhaps can keep under the mechanical force of certain fibre length, fibril, main fibre winding occur seriously, be difficult to realize disperseing.Adopt Mechanical Method to control pulp length and original fiber degree simultaneously than difficulty.
Summary of the invention
In order to solve the shortcoming and defect that above-mentioned prior art exists, primary and foremost purpose of the present invention is to provide a kind of fiber that makes to produce sufficient fibrillation, effectively improves the preparation method of the fibrillation dissolving pulp of fibrillation effect and reduction refining energy consumption.
Another object of the present invention is to provide a kind of fibrillation dissolving pulp by method for preparing.
A further object of the present invention is to provide the application of above-mentioned fibrillation dissolving pulp.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of fibrillation dissolving pulp comprises following operating procedure:
(1) adopt pretreating agent that staple fiber is carried out preliminary treatment;
(2) staple fiber is controlled at the concentration of 0.1～30%w.t., carries out defibrination, obtain pulp with refining equipment;
(3) pulp dehydration, storage.
Between step (1) and step (2), can add following steps: pretreated staple fiber water flushing to neutral, is removed pretreating agent.
Described staple fiber comprises PPTA (PPTA) fiber, polyparaphenylene's benzoxazole (PBO) fiber, tencel fiber, polyacrylonitrile (PAN) fiber etc.
Described pretreating agent is sulfuric acid (H
2SO
4), nitric acid (HNO
3), hydrochloric acid (HCl), NaOH (NaOH), chlorosulfonic acid (ClSO
3H), fluosulfonic acid (FSO
3H), inorganic acid solution of polyphosphoric acids or potassium permanganate etc.
The pretreating agent of described PPTA fiber can be 10～90% aqueous sulfuric acid, 10～90% aqueous solution of nitric acid, 30～70% sodium hydrate aqueous solutions, 10～90% chlorosulfonic acid N-Methyl pyrrolidone solution, fluosulfonic acid N-Methyl pyrrolidone solution of 10～90% etc.; Wherein, the PPTA pulp (reinforcing material, comb core etc.) that the preparation original fiber degree is lower, fiber requires to keep certain intensity more preferably is sulfuric acid or nitric acid, and concentration of treatment is 10～40%, processing time 10～30min; For the PPTA pulp (friction material, battery diaphragm etc.) of the higher or complete fibrillation of preparation original fiber degree, more preferably be sulfuric acid or nitric acid, concentration of treatment is 40～90%, processing time 30s～15min.
The pretreating agent of described pbo fiber can be 10～90% aqueous sulfuric acid (can add 0.1～5% potassium permanganate), 10～90% aqueous solution of nitric acid, 30～70% sodium hydrate aqueous solutions, 10～90% chlorosulfonic acid N-Methyl pyrrolidone solution, fluosulfonic acid N-Methyl pyrrolidone solution of 10～90% etc.Wherein, more preferably pretreating agent has 10～90% aqueous sulfuric acid (can add 0.1～5% potassium permanganate) and nitric acid, and the processing time is 30s～30min.
The pretreating agent of described tencel fiber can be 10～80% aqueous hydrochloric acid solutions and 0.1～20% sodium hydrate aqueous solution; Preferred 0.1～20% sodium hydrate aqueous solution, the processing time is 30s～5min (wherein, tencel fiber directly adds sodium hydrate aqueous solution in pulping process).
The pretreating agent of described PAN fiber can be 10～80% aqueous hydrochloric acid solutions and 0.1～20% sodium hydrate aqueous solution; Preferred 10～80% aqueous hydrochloric acid solutions, the processing time is 0.5～72hr.
Above-mentioned various fiber pretreating agent is not limited to listed content, can select other different pretreating agents for use according to fiber properties and pulp final use, comprises sulfuric acid (H
2SO
4), nitric acid (HNO
3), hydrochloric acid (HCl), NaOH (NaOH), chlorosulfonic acid (ClSO
3H), fluosulfonic acid (FSO
3H), inorganic acid solution of polyphosphoric acids, potassium permanganate etc.
Described refining equipment is a kind of in mill, trough-style pulp beater, the vertical fiberizer (PFI).
Fibrillation dissolving pulp by method for preparing can be according to the fibrillation structure of pulp final use design pulp, and its average length is 0.1～6mm, and Canadian Standard Freeness is 10～800ml.Wherein,, fiber lower for original fiber degree requires to keep the pulp of certain intensity, its trunk fiber (being former staple fiber) keeps the cylinder bodily form, the surface is tens fibrillating fibres to hundreds of nanometers with diameter, the trunk average fiber length is 2～6mm, Canadian Standard Freeness is 300～800ml, as Fig. 3 C.The pulp of or complete fibrillation higher for original fiber degree, be tens to form mainly to the fibrillating fibre of hundreds of nanometers by diameter, the fraction not fiber of abundant fibrillation still keeps several microns diameter, average fiber length is 0.1～2mm, Canadian Standard Freeness is 10～300ml, as Fig. 3 F.
Fibrillation dissolving pulp by method for preparing can be applicable to prepare chemical products such as friction material, reinforcing material, battery diaphragm, PCB base material, comb core or high-performance paper.
The mechanism of action of the present invention is: but the fiber of fibrillation has typical skin-core structure, sandwich layer is height-oriented orderly multiple fibrillar structure, by Van der Waals force and hydrogen bonded, fiber can form abundant fibrillation structure between the fibrous inside molecule.But since in the fibrocortex big uncoiling of molecule chain along whole fiber axis to height-oriented and be evenly distributed, be wrapped in sandwich layer, make the fibrillation of fiber have certain difficulty.Therefore, utilize chemical treatment, comprise sulfuric acid, nitric acid, NaOH etc., before making beating, to a certain degree dissolve swelling down or destroy cortex, make fiber become soft,, help fiber and produce sufficient fibrillation again in conjunction with suitable mechanical force.Than directly handling, can effectively improve the fibrillation effect and reduce refining energy consumption with Mechanical Method.
Sulfuric acid (H
2SO
4), nitric acid (HNO
3), hydrochloric acid (HCl), NaOH (NaOH), chlorosulfonic acid (ClSO
3H), fluosulfonic acid (FSO
3H) equal solvent differs widely to the action intensity of fiber, and wherein, it is the highest that 60%～90% the concentrated sulfuric acid is handled intensity, and control does not with great difficulty destroy core structure, thereby influences the final strength of pulp.The salt acid molecule enters the sandwich layer weakness zone easily, destroys fibre strength, and fiber ruptures when being subjected to mechanical force easily, is unfavorable for preparing the pulp that needs keep certain fibre length.Therefore, should wait selected as required pulp length, original fiber degree and requirement of strength according to the kind and the pulp practical use of fiber when selecting finishing agent for use.As for tencel fiber, adopt alkali treatment with respect to acid treatment, can keep the intensity of fiber itself better; For PPTA (PPTA) fiber and polyparaphenylene's benzoxazole (PBO) fiber, because it has the rigid macromolecule structure, intermolecular arrangement is tight when becoming fine, common solvent is difficult to invasion, select pretreatment of fiber such as the higher sulfuric acid of concentration, nitric acid, potassium permanganate inorganic acid solution, controlling the processing time well destroys it in the cortex scope, help the height fibrillation of these two kinds of fibers.
The present invention has following advantage and beneficial effect with respect to prior art: (1) the present invention makes fibrocortex that certain hydrolysis or the effect of dissolving swelling partly take place by preliminary treatment, make its surface have certain polar group when destroying cortex, make fiber become soft, (see Fig. 3 B through the pulp that will produce height fibrillation behind the identical mechanical treatment easilier again, C), effectively improve preparation efficiency, the saving energy consumption of fibrillation dissolving pulp; (2) the present invention can comprise pretreating agent, pretreatment condition and refining process by the adjusting of concrete technology, prepares the fibrillation dissolving pulp that satisfies its service condition according to the product instructions for use, and its flexibility is bigger; (3) the invention provides a kind of comprehensive fibrillation dissolving pulp manufacturing technology, the employing present technique can effectively solve the key technical problem in the fibrillation dissolving pulp manufacturing technique, as control the pulp original fiber degree, keep certain fibre strength and solve scattering problem, make the technology scope of application of the present invention wider, can prepare chemical products such as friction material, reinforcing material, battery diaphragm, PCB base material, comb core and high-performance paper.
Description of drawings
Fig. 1 is the process chart of Comparative Examples.
Fig. 2 is a process chart of the present invention.
Fig. 3 is the electromicroscopic photograph of product of the present invention; A-Comparative Examples 1 p-aramid fiber pulp; B-embodiment 1 p-aramid fiber pulp; C-embodiment 5 p-aramid fiber pulps; D-embodiment 6 p-aramid fiber pulps; The PBO pulp of E-embodiment 12 preparations.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
At first pulp water retention value sign and pulp water retention value assay method are described as follows:
The pulp water retention value characterizes: reflect the swollen degree of fiber and the degree of fiber fibrillation to a certain extent.
Pulp water retention value assay method: the wet pulp dregs of rice 30g that gets mass dryness fraction 10%w.t., pack in the cloth bag, the centrifuge that places industrial pulp water retention value to measure carries out centrifugal dehydration 2min, deviates from the free water in the slurry, take out slurry then, place the measuring cup of known weight to weigh.Put into the dry 6h of baking oven then and reach constant weight, take by weighing weight.
m
1-wet pulp quality after centrifugal, g; m
2-oven dry stock weight, g
Below the fiber pretreatment condition of each embodiment select with reference to table 1.
Comparative Examples 1
With 15g p-aramid fiber staple fiber (
Length 2～4mm, diameter 15 μ m), with PFI defibrination, refining concentration 10%, the defibrination spacing is 2mm, defibrination revolution 10000 changes, and the preparation pulp, technical process is seen Fig. 1, and the pulp performance sees Table 2, and the pulp pattern is seen Fig. 3 A.
Embodiment 1
With 15g p-aramid fiber staple fiber (
Length 2～4mm, diameter 15 μ m), soaking 8min with the sulfuric acid of 70% concentration, soaking concentration is 0.1%w.t..After having soaked fiber is taken out, extremely neutral with flushing with clean water.Adopt PFI mill defibrination, refining concentration 10%, the defibrination spacing is 2mm, defibrination revolution 10000 changes, the preparation pulp, technical process is seen Fig. 2, the pulp performance sees Table 2.
The water retention value of present embodiment pulp is 104.2%, exceeds 8.2 percentage points than the pulp of Comparative Examples 1, reacts the original fiber degree of present embodiment pulp from the side and wants high than the pulp of Comparative Examples 1, and comparatively ideal effect is played in preliminary treatment.The present embodiment pulp is seen Fig. 3 B, and with Comparative Examples 1 pulp contrast (seeing Fig. 3 A), the original fiber degree of present embodiment pulp is high, and the fiber trunk suffers destruction to a certain degree, and Comparative Examples 1 pulp trunk is kept perfectly, and fibril is less and shorter.
Embodiment 2
Present embodiment pulp preparation technology is identical with embodiment 1, and difference is that used preliminary treatment sulfuric acid concentration is 10%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Embodiment 3
Present embodiment pulp preparation technology is identical with embodiment 1, and difference is that used preliminary treatment sulfuric acid concentration is 60%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Present embodiment pulp preparation technology is identical with embodiment 1, and difference is that used preliminary treatment sulfuric acid concentration is 80%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Embodiment 5
Present embodiment pulp preparation technology is identical with embodiment 1, and difference is that used refining equipment is a mill, and technical process is seen Fig. 2, and the pulp performance sees Table 2.Its pulp form is seen Fig. 3 C, and mainly containing diameter in the pulp is the tens fibril compositions to hundreds of nanometers, and also having part is several microns fibril bundle of abundant fibrillation
Present embodiment pulp preparation technology is identical with embodiment 1, and difference is that used preliminary treatment sulfuric acid concentration is 90%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.The water retention value of present embodiment pulp is 110.6%, than the pulp water retention value height of embodiment 1.The pulp pattern is seen Fig. 3 D, and the trunk fiber has serious splitting phenomenon, destroy seriously, and original fiber degree is not as the pulp of embodiment 1.
With 15g p-aramid fiber staple fiber (
Length 2～4mm, diameter 15 μ m), with the nitric acid dousing 8min of 60% concentration, soaking concentration is 0.1%w.t..After having soaked fiber is taken out, extremely neutral with flushing with clean water.The making beating of employing slot type, the preparation pulp, technical process is seen Fig. 2, the pulp performance sees Table 2.
Embodiment 8
Present embodiment pulp preparation technology is identical with embodiment 4, and difference is that used preliminary treatment concentration of nitric acid is 10%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Present embodiment pulp preparation technology is identical with embodiment 4, and difference is that used preliminary treatment concentration of nitric acid is 80%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Present embodiment pulp preparation technology is identical with embodiment 4, and difference is that used preliminary treatment concentration of nitric acid is 90%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
With 15g p-aramid fiber staple fiber (
Length 2～4mm, diameter 15 μ m), with the soaking with sodium hydroxide 36hr of 50% concentration, soaking concentration is 0.1%w.t..After having soaked fiber is taken out, extremely neutral with flushing with clean water.Adopt the mill defibrination to prepare pulp, technical process is seen Fig. 2, and the pulp performance sees Table 2.The Canadian freedom of present embodiment pulp is 60ml, and water retention value is 310.3%, has higher original fiber degree.
Comparative Examples 2
With 15g PBO staple fiber (
Length 2～4mm, diameter 15 μ m), with PFI defibrination, refining concentration 10%, the defibrination spacing is 2mm, defibrination revolution 10000 changes, and the preparation pulp, technical process is seen Fig. 1, the pulp performance sees Table 2.
Embodiment 12
With 15g PBO staple fiber (
Length 2～4mm, diameter 15 μ m), with being dissolved with 1.5%KMnO
4(with respect to H
2SO
4) 50% sulfuric acid treatment 3min.After having soaked fiber is taken out, extremely neutral with flushing with clean water.Adopt PFI mill defibrination, refining concentration 10%, the defibrination spacing is 2mm, and 10000 transformations of ownership of defibrination revolution are equipped with pulp, and technical process is seen Fig. 2, and the pulp performance sees Table 2.The pulp form is seen Fig. 3 E, and the water retention value of present embodiment pulp is 109.7%, exceeds 19.4 percentage points than Comparative Examples 2 pulps, reacts the original fiber degree of present embodiment pulp from the side and wants high than Comparative Examples 2 pulps, and pretreating agent plays comparatively ideal effect.
Present embodiment pulp preparation technology is identical with embodiment 8, and difference is not add potassium permanganate in the used pretreating agent, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Present embodiment pulp preparation technology is identical with embodiment 8, and difference is to add 0.1% potassium permanganate in the used pretreating agent, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Present embodiment pulp preparation technology is identical with embodiment 8, and difference is to add 3% potassium permanganate in the used pretreating agent, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Present embodiment pulp preparation technology is identical with embodiment 8, and difference is to add 5% potassium permanganate in the used pretreating agent, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Embodiment 17
Present embodiment pulp preparation technology is identical with embodiment 8, and difference is that used preliminary treatment sulfuric acid concentration is 10%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Present embodiment pulp preparation technology is identical with embodiment 8, and difference is that used preliminary treatment sulfuric acid concentration is 90% sulfuric acid, and technical process is seen Fig. 2, and the pulp performance sees Table 2.Though the PBO pulp of this prepared has higher water retention value, in the preprocessing process, phenomenon appears being partly dissolved, boning in fiber.
With 15g PBO staple fiber (
), length 2～4mm, diameter 15 μ m, with the nitric acid dousing 8min of 50% concentration, soaking concentration is 0.1%w.t..After having soaked fiber is taken out, extremely neutral with flushing with clean water.Adopt PFI mill defibrination, refining concentration 10%, the defibrination spacing is 2mm, defibrination revolution 10000 changes, the preparation pulp, technical process is seen Fig. 2, the pulp performance sees Table 2.
Present embodiment pulp preparation technology is identical with embodiment 14, and difference is that used preliminary treatment concentration of nitric acid is 10%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Embodiment 21
Present embodiment pulp preparation technology is identical with embodiment 14, and difference is that used preliminary treatment concentration of nitric acid is 90%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Embodiment 22
With the 15gPBO staple fiber (
Length 2～4mm, diameter 15 μ m), soaking 10min with the chlorosulfonic acid (solvent is N-methyl-pyrrolidones) of 80% concentration, soaking concentration is 0.1%w.t..After having soaked fiber is taken out, extremely neutral with flushing with clean water.Adopt PFI mill defibrination, refining concentration 10%, the defibrination spacing is 2mm, defibrination revolution 10000 changes, the preparation pulp, the pulp performance sees Table 2.The water retention value of present embodiment pulp is 103.7%, exceeds 13.4 percentage points than Comparative Examples 2 pulps, reacts the original fiber degree of present embodiment pulp from the side and wants high than Comparative Examples 2 pulps, and pretreating agent plays comparatively ideal effect.
Comparative Examples 3
Get a certain amount of day silk staple fiber (
Length 2～4mm, diameter 15 μ m), use slot type making beating (concentration 1%w.t.) preparation pulp, the pulp performance sees Table 2.
Embodiment 23
Get a certain amount of day silk staple fiber (
Length 2～4mm, diameter 15 μ m), soak 8min with sodium hydroxide solution (sodium hydrate solid is a fiber oven-dry weight 2%), after having soaked fiber is taken out, use slot type making beating (concentration 1%w.t.) preparation pulp, the pulp performance sees Table 2.Present embodiment pulp original fiber degree is higher, and its water retention value is 420.9%.
Embodiment 24
Present embodiment pulp preparation technology is identical with embodiment 18, and difference is that used NaOH is fiber oven-dry weight 0.1%, and the pulp performance sees Table 2.
Embodiment 25
Present embodiment pulp preparation technology is identical with embodiment 18, and difference is that used NaOH is fiber oven-dry weight 5%, and the pulp performance sees Table 2.
Embodiment 26
Present embodiment pulp preparation technology is identical with embodiment 18, and difference is that used NaOH is fiber oven-dry weight 10%, and the pulp performance sees Table 2.
Embodiment 27
Present embodiment pulp preparation technology is identical with embodiment 18, and difference is that used NaOH is fiber oven-dry weight 20%, and the pulp performance sees Table 2.
Embodiment 28
Get 15g days silk staple fibers (
Length 2～4mm, diameter 15 μ m), soaking 8min with 20% sodium oxide molybdena, soaking concentration is 0.1%w.t, after having soaked fiber is taken out, and is extremely neutral with flushing with clean water.Adopt PFI mill defibrination, refining concentration 10%, the defibrination spacing is 2mm, defibrination revolution 10000 changes, the preparation pulp, technical process is seen Fig. 2, the pulp performance sees Table 2.
Embodiment 29
Present embodiment pulp preparation technology is identical with embodiment 20, and difference is that used NaOH is 10%, and the pulp performance sees Table 2.
Comparative Examples 4
Get 15g polyacrylonitrile (Shanghai Lanbang Industry Fibre Co., Ltd. produces, length 2～4mm, diameter 15 μ m), adopt PFI mill defibrination, refining concentration 10%, the defibrination spacing is 2mm, defibrination revolution 10000 changes, the preparation pulp, technical process is seen Fig. 1, the pulp performance sees Table 2.
Embodiment 30
Get 15g polyacrylonitrile (Shanghai Lanbang Industry Fibre Co., Ltd. produce, length 2～4mm, diameter 15 μ m), with the salt acid soak of 50% concentration 1 hour, soaking concentration was 0.1%w.t..After having soaked fiber is taken out, extremely neutral with flushing with clean water.Adopt PFI mill defibrination, refining concentration 10%, the defibrination spacing is 2mm, defibrination revolution 10000 changes, the preparation pulp, technical process is seen Fig. 2, the pulp performance sees Table 2.Present embodiment pulp original fiber degree is higher, and its water retention value is 179.5%.
Embodiment 31
Present embodiment pulp preparation technology is identical with embodiment 24, and difference is that used preliminary treatment concentration of hydrochloric acid is 10%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Embodiment 32
Present embodiment pulp preparation technology is identical with embodiment 24, and difference is that used preliminary treatment concentration of hydrochloric acid is 80%, and technical process is seen Fig. 2, and the pulp performance sees Table 2.
Table 2 specific embodiment pulp performance
| Freedom (ml) | Water retention value (%) | |
| Comparative Examples 1 | 710 | 95.7 |
| Embodiment 1 | 678 | 104.2 |
| Embodiment 2 | 712 | 96.7 |
| Embodiment 3 | 693 | 98.6 |
| |
659 | 108.4 |
| Embodiment 5 | 49 | 342.8 |
| |
720 | 110.61 |
| |
603 | 131.4 |
| Embodiment 8 | 689 | 125.7 |
| |
583 | 134.9 |
| |
594 | 136.5 |
| |
60 | 310.3 |
| Comparative Examples 2 | 733 | 90.3 |
| Embodiment 12 | 670 | 109.7 |
| |
705 | 98.4 |
| |
694 | 98.3 |
| |
662 | 119.7 |
| |
653 | 126.4 |
| Embodiment 17 | 721 | 92.5 |
| |
645 | 115.3 |
| |
697 | 95.4 |
| |
719 | 91.7 |
| Embodiment 21 | 725 | 98.4 |
| Embodiment 22 | 693 | 103.7 |
| Comparative Examples 3 | 130 | 335.9 |
| Embodiment 23 | 71 | 420.9 |
| Embodiment 24 | 122 | 365.4 |
| Embodiment 25 | 66 | 421.5 |
| Embodiment 26 | 60 | 430.7 |
| Embodiment 27 | 57 | 433.8 |
| Embodiment 28 | 320 | 231.5 |
| Embodiment 29 | 323 | 222.7 |
| Comparative Examples 4 | 634 | 157.6 |
| Embodiment 30 | 576 | 179.5 |
| Embodiment 31 | 618 | 164.3 |
| Embodiment 32 | 553 | 185.9 |
Claims (9)
1, a kind of preparation method of fibrillation dissolving pulp is characterized in that comprising following operating procedure:
(1) adopt pretreating agent that staple fiber is carried out preliminary treatment;
(2) staple fiber is controlled at the concentration of 0.1～30%w.t., carries out defibrination, obtain pulp with refining equipment;
(3) pulp dehydration, storage.
2, the preparation method of fibrillation dissolving pulp according to claim 1 is characterized in that: add following steps between step (1) and step (2): pretreated staple fiber water flushing to neutral, is removed pretreating agent.
3, the preparation method of fibrillation dissolving pulp according to claim 1 is characterized in that: described staple fiber comprises Fanglun 1414, polyparaphenylene's benzoxazole fiber, tencel fiber or polyacrylonitrile fibre.
4, according to the preparation method of claim 1 or 3 described fibrillation dissolving pulps, it is characterized in that: described pretreating agent is the inorganic acid solution of sulfuric acid, nitric acid, hydrochloric acid, NaOH, chlorosulfonic acid, fluosulfonic acid, polyphosphoric acids or potassium permanganate.
5, the preparation method of fibrillation dissolving pulp according to claim 4 is characterized in that: described Fanglun 1414's pretreating agent is 10～90% aqueous sulfuric acid, 10～90% aqueous solution of nitric acid, 30～70% sodium hydrate aqueous solutions, 10～90% chlorosulfonic acid N-Methyl pyrrolidone solution or 10～90% fluosulfonic acid N-Methyl pyrrolidone solution;
The pretreating agent of described polyparaphenylene's benzoxazole fiber is 10～90% aqueous sulfuric acid, 10～90% aqueous solution of nitric acid, 30～70% sodium hydrate aqueous solutions, 10～90% chlorosulfonic acid N-Methyl pyrrolidone solution or 10～90% fluosulfonic acid N-Methyl pyrrolidone solution;
The pretreating agent of described tencel fiber is 10～80% aqueous hydrochloric acid solutions and 0.1～20% sodium hydrate aqueous solution;
The pretreating agent of described polyacrylonitrile fibre is 10～80% aqueous hydrochloric acid solutions and 0.1～20% sodium hydrate aqueous solution.
6, the preparation method of fibrillation dissolving pulp according to claim 5, it is characterized in that: the Fanglun 1414 that the preparation original fiber degree is lower, fiber requires to keep certain intensity, pretreating agent is sulfuric acid or nitric acid, concentration of treatment is 10～40%, processing time 10～30min; For the Fanglun 1414 of the higher or complete fibrillation of preparation original fiber degree, pretreating agent is sulfuric acid or nitric acid, and concentration of treatment is 40～90%, processing time 30s～15min;
The pretreating agent of the pretreating agent of described pbo fiber is 10～90% sulfuric acid or nitric acid, and the processing time is 30s～30min;
The pretreating agent of described tencel fiber is 0.1～20% sodium hydrate aqueous solution, and the processing time is 30s～5min.
The pretreating agent of described polyacrylonitrile fibre is 10～80% aqueous hydrochloric acid solutions, and the processing time is 0.5～72hr.
7, the preparation method of fibrillation dissolving pulp according to claim 1 is characterized in that: described refining equipment is a kind of in mill, trough-style pulp beater, the vertical fiberizer.
8, according to the fibrillation dissolving pulp of each described method preparation of claim 1～7, it is characterized in that: its average length is 0.1～6mm, and Canadian Standard Freeness is 10～800ml.
9, the fibrillation dissolving pulp according to each described method preparation of claim 1～7 is applied to prepare friction material, reinforcing material, battery diaphragm, PCB base material, comb core or high-performance paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101991129A CN101381898B (en) | 2008-10-14 | 2008-10-14 | Fibrillation dissolving pulp, method for making same and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101991129A CN101381898B (en) | 2008-10-14 | 2008-10-14 | Fibrillation dissolving pulp, method for making same and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101381898A true CN101381898A (en) | 2009-03-11 |
| CN101381898B CN101381898B (en) | 2011-08-17 |
Family
ID=40461944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101991129A Active CN101381898B (en) | 2008-10-14 | 2008-10-14 | Fibrillation dissolving pulp, method for making same and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101381898B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242408A (en) * | 2010-05-13 | 2011-11-16 | 上海兰邦工业纤维有限公司 | High-fibrillated polyacrylonitrile (PAN) pulp manufactured by spinning of water-plasticized melt colloid |
| CN102535241A (en) * | 2011-06-08 | 2012-07-04 | 王锡璐 | Poly p-phenylene terephthalamide aramid II pulp with high logarithm viscosity and high microfilament and preparation method thereof |
| CN103374817A (en) * | 2012-04-13 | 2013-10-30 | 上海拜邦材料科技有限公司 | Short fiber with microfiber structure, filter felt, and manufacturing method of filter felt |
| CN103966891A (en) * | 2014-04-23 | 2014-08-06 | 华南理工大学 | Method for preparing fiber pulp and prepared fiber pulp |
| JP2018070833A (en) * | 2016-11-02 | 2018-05-10 | 曙ブレーキ工業株式会社 | Friction material composition and friction material |
| CN108396581A (en) * | 2018-02-06 | 2018-08-14 | 深圳市新纶科技股份有限公司 | A kind of preparation method of fiber pulp and its fiber pulp of preparation |
| CN108790316A (en) * | 2018-04-16 | 2018-11-13 | 杭州协业超纤有限公司 | A kind of Compound Fabric and preparation method thereof of Tan Xier fibers and cotton gauze |
| CN112912564A (en) * | 2018-08-14 | 2021-06-04 | 杜邦安全与建筑公司 | High tensile strength paper suitable for use in electrochemical cells |
| CN113109204A (en) * | 2021-03-29 | 2021-07-13 | 杭州融凯盛科技有限公司 | Method for rapidly detecting pulp cellulose structure |
| CN114790652A (en) * | 2021-01-26 | 2022-07-26 | 中国科学院化学研究所 | Poly (p-phenylene benzobisoxazole) nano fiber and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1710196A (en) * | 2005-06-20 | 2005-12-21 | 华南理工大学 | Full-para-polyfiber amide paper, and its preparing method and use |
| CN100593594C (en) * | 2008-04-01 | 2010-03-10 | 上海依极科技有限公司 | Method for producing aramid fiber pulp by aramid fiber waste material |
-
2008
- 2008-10-14 CN CN2008101991129A patent/CN101381898B/en active Active
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242408A (en) * | 2010-05-13 | 2011-11-16 | 上海兰邦工业纤维有限公司 | High-fibrillated polyacrylonitrile (PAN) pulp manufactured by spinning of water-plasticized melt colloid |
| CN102535241A (en) * | 2011-06-08 | 2012-07-04 | 王锡璐 | Poly p-phenylene terephthalamide aramid II pulp with high logarithm viscosity and high microfilament and preparation method thereof |
| CN103374817A (en) * | 2012-04-13 | 2013-10-30 | 上海拜邦材料科技有限公司 | Short fiber with microfiber structure, filter felt, and manufacturing method of filter felt |
| CN103966891A (en) * | 2014-04-23 | 2014-08-06 | 华南理工大学 | Method for preparing fiber pulp and prepared fiber pulp |
| CN103966891B (en) * | 2014-04-23 | 2017-01-04 | 华南理工大学 | The preparation method of a kind of fiber pulp and the fiber pulp of preparation thereof |
| CN109906261B (en) * | 2016-11-02 | 2021-08-13 | 曙制动器工业株式会社 | Friction material composition and friction material |
| JP2018070833A (en) * | 2016-11-02 | 2018-05-10 | 曙ブレーキ工業株式会社 | Friction material composition and friction material |
| US11209063B2 (en) | 2016-11-02 | 2021-12-28 | Akebono Brake Industry Co., Ltd. | Friction material composition and friction material |
| WO2018084218A1 (en) * | 2016-11-02 | 2018-05-11 | 曙ブレーキ工業株式会社 | Friction material composition and friction material |
| CN109906261A (en) * | 2016-11-02 | 2019-06-18 | 曙制动器工业株式会社 | Friction material composition and friction material |
| CN108396581B (en) * | 2018-02-06 | 2020-01-14 | 深圳市新纶科技股份有限公司 | Preparation method of fiber pulp and fiber pulp prepared by preparation method |
| CN108396581A (en) * | 2018-02-06 | 2018-08-14 | 深圳市新纶科技股份有限公司 | A kind of preparation method of fiber pulp and its fiber pulp of preparation |
| CN108790316B (en) * | 2018-04-16 | 2020-11-13 | 杭州协业超纤有限公司 | Composite cloth of tamsular fiber and all-cotton gauze and preparation method thereof |
| CN108790316A (en) * | 2018-04-16 | 2018-11-13 | 杭州协业超纤有限公司 | A kind of Compound Fabric and preparation method thereof of Tan Xier fibers and cotton gauze |
| CN112912564A (en) * | 2018-08-14 | 2021-06-04 | 杜邦安全与建筑公司 | High tensile strength paper suitable for use in electrochemical cells |
| US11078627B2 (en) | 2018-08-14 | 2021-08-03 | Dupont Safety & Construction, Inc. | High tensile strength paper suitable for use in electrochemical cells |
| CN112912564B (en) * | 2018-08-14 | 2022-06-10 | 杜邦安全与建筑公司 | High tensile strength paper suitable for use in electrochemical cells |
| CN114790652A (en) * | 2021-01-26 | 2022-07-26 | 中国科学院化学研究所 | Poly (p-phenylene benzobisoxazole) nano fiber and preparation method thereof |
| CN114790652B (en) * | 2021-01-26 | 2023-09-22 | 中国科学院化学研究所 | Poly (p-phenylene benzobisoxazole) nanofiber and preparation method thereof |
| CN113109204A (en) * | 2021-03-29 | 2021-07-13 | 杭州融凯盛科技有限公司 | Method for rapidly detecting pulp cellulose structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101381898B (en) | 2011-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101381898B (en) | Fibrillation dissolving pulp, method for making same and applications | |
| TW452615B (en) | Lyocell fibers, and compositions for making the same | |
| Li et al. | Dissolution of cellulose from different sources in an NaOH/urea aqueous system at low temperature | |
| EP2895653B1 (en) | Method of producing dissolving pulp, dissolving pulp and use of method | |
| BR112017023243B1 (en) | Dry blended product, and, processes for producing a dry blended product, for producing reinforced paper, tissue paper and/or packaging product and for producing a reinforced product | |
| CN103502529A (en) | High aspect ratio cellulose nanofilaments and method for production thereof | |
| EP0392559B1 (en) | Oriented, shaped articles of pulpable para-aramid/meta-aramid blends | |
| BRPI0621120A2 (en) | processes for making a para-aramid pulp, aramid pulp, paper, friction material and fluid sealing material | |
| CN113062141A (en) | Para-meta-aramid copolymerized fibrid-reinforced para-aramid paper and preparation process thereof | |
| EP4021946A1 (en) | Cellulose pretreatment | |
| EP0731859B1 (en) | Process for preparing para-aromatic polyamide paper and paper obtainable by the process | |
| Khadraoui et al. | Production of lignin-containing cellulose nanofibrils by the combination of different mechanical processes | |
| CN103732825A (en) | Method for producing papermaking feedstock, papermaking feedstock obtained thereby, and heat-resistant electrical insulation sheet material using the feedstock | |
| Tong et al. | Deep eutectic solvent pretreatment for green preparation of nanocellulose | |
| KR101256706B1 (en) | Aramid pulp and method for manufacturing the same | |
| Ngene et al. | Influence of Hollander beater refining on xylan extraction from hardwood paper pulp by cold caustic extraction and xylanase treatment | |
| CN102174753A (en) | Preparation method of wood pulp for long viscose fibers | |
| CN115029920A (en) | Preparation method of aramid nanofiber | |
| Fridrihsone et al. | Dissolution of various cellulosic materials and effect of regenerated cellulose on mechanical properties of paper | |
| CN111809428A (en) | High-speed cutting method for softwood pulp | |
| JP2020158912A (en) | Wet nonwoven fabric of short carbon fiber, and carbon fiber reinforced resin | |
| KR101071862B1 (en) | Aramid pulp and method for manufacturing the same | |
| CN110938885B (en) | Flame-retardant regenerated cellulose fiber and preparation method thereof | |
| KR20110049365A (en) | Method for manufacturing aramid pulp | |
| CN113502685B (en) | Polyacrylonitrile pulp, preparation method thereof and application thereof in preparation of carbon rod filter element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |