CN107217329A - A kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers - Google Patents
A kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers Download PDFInfo
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- CN107217329A CN107217329A CN201710506716.2A CN201710506716A CN107217329A CN 107217329 A CN107217329 A CN 107217329A CN 201710506716 A CN201710506716 A CN 201710506716A CN 107217329 A CN107217329 A CN 107217329A
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- China
- Prior art keywords
- preparation
- pulp
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- polyacrylonitrile
- polyurethane
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Paper (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers, its preparation has synthesized polyurethane solutions first, then with the N of polyacrylonitrile, N dimethylacetamide solutions are hybridly prepared into blending slurries, then by slurries injection dissolved with Ca (OH)2Coagulating bath in, acted in high speed shear and be passed through CO2, blending pulp is prepared using In-situ Precipitation.There is microcosmic phase separation using polyurethane and polyacrylonitrile in the present invention, nascent pulp is set to there is the substantial amounts of weak spot being evenly distributed, in the presence of shearing force, pulp is easy in the fracture of these weak spots or longitudinal splitting, realize fibrillation, thus gained pulp is smaller, evenly, and specific surface area is improved.
Description
Technical field
The present invention relates to a kind of preparation method of acrylic fibers pulp, and in particular to one kind uses In-situ Precipitation synthesis modification nitrile
The preparation method of synthetic fibre pulp fibers.
Background technology
Chemipulp (chemical-pulp), especially Fanglun slurry cake, are the ideal substitutes of asbestos, with glass fibre
And carbon fiber is competed in fields such as encapsulant, reinforcing material and friction materials.Polyacrylonitrile (PAN) pulp inherits PAN
The fine quality of fiber, with higher heat resistance and to the stability and fungus resistance of daylight, air and chemical reagent,
Relative low price, is expected in low side field fictitious hosts expensive Fanglun slurry cake and harmful asbestos fibre.
Specific surface area is an important evaluation index of pulp.The PAN pulp specific surface areas prepared with precipitation method are in 30-
70 m2Between/g, significantly larger than Fanglun slurry cake.There is patent report, by PPTA (PPTA) and poly- isophthalic
Two formyl m-phenylene diamine (MPD)s (PMIA) are blended, and due to there is microcosmic phase separation between polymer, more easily fibrillable are allowed to, so that effectively
Improve the specific surface area of pulp.
Therefore, the present invention is dissolved in DMA using polyurethane and polyacrylonitrile, utilizes both phases
Separation, prepares the higher PAN pulps of specific surface area.
The content of the invention
The present invention provides a kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers, effectively increases
The specific surface area of pulp, while reducing production cost.
The present invention is achieved by the following technical solutions：
A kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers, it is molten that its preparation has synthesized polyurethane first
Liquid, then the DMA solution with polyacrylonitrile be hybridly prepared into blending slurries, then by slurries injection dissolved with
Ca(OH)2Coagulating bath in, acted in high speed shear and be passed through CO2, blending pulp is prepared using In-situ Precipitation.
Comprise the following steps that：
（1）The preparation of polyurethane：
8-15 parts by weight dihydromethyl propionic acid powder is added into reaction bulb, adding 65-90 parts of DMAs makes
Dissolving, be warming up to 40-50 DEG C, be passed through nitrogen, start be added dropwise 8-15 parts of toluene di-isocyanate(TDI)s, dripped in 30 minutes
Finish, be warming up to 52-57 DEG C, insulation reaction 2-3 hours prepares polyurethane solutions；
（2）The preparation of mixed serum：
55-70 parts of polyacrylonitrile are placed in convection oven, it is standby in being dried 6-8 hours at 78-83 DEG C；By 110-150 parts of N,
N- dimethyl acetamides pour into three-necked bottle, and turn on agitator stirring adds 2-5 parts of lithium chlorides after after its dissolving completely, added dry
Dry good polyacrylonitrile, is put into water-bath and is heated to 78-83 DEG C of stirring fully dissolving, be cooled to after room temperature and add above-mentioned polyurethane
Solution, is mixed evenly；
（3）The preparation of solidification liquid：
Weigh 8-14 parts of Ca (OH)2Powder is added to the in the mixed solvent of DMA and water, is configured to Ca2+Concentration
For 0.04-0.06mol/L solution, ultrasonic disperse dissolves it；
（4）Under high speed shear effect, polyacrylonitrile/polyurethane mixed serum is injected in the above-mentioned solidification liquid prepared, cut
Cut after 1-5 minutes, be passed through CO2, after the completion of reaction, suction filtration is washed with deionized 2-4 times, centrifugal drying, obtains that pulp is blended.
Wherein, the in the mixed solvent DMA and the volume of water of described DMA and water
Than for 1-3:1.
Wherein, step（4）The high speed cleavage reaction time is 10-25 minutes.
The present invention has advantages below：
（1）The polyurethane used in the present invention in DMA, makes polyurethane with polyacrylonitrile energy co-dissolve
It is dispersed in polyacrylonitrile slurries, in precipitating forming process, dispersed phase polyurethane is similarly in the coagulating bath of flowing
Sheared and stretch and deform, due to two it is alternate there is microcosmic phase separation, nascent pulp is there is substantial amounts of be evenly distributed
Weak spot, in the presence of shearing force, pulp is easy to, in the fracture of these weak spots or longitudinal splitting, realize fibrillation, thus institute
Pulp it is smaller, evenly, specific surface area is improved.
（2）Ca (OH) is added in the present invention in solidification liquid2, when slurries inject solidification liquid, Ca2+Can be with polyurethane
Carboxyl react, produce complex compound, the CO being passed through afterwards2Gas dissociates generation CO in water3 2-, with polyurethane molecular chela
The Ca of conjunction2+Reaction, in-situ preparation CaCO3Particle is deposited in polyurethane segment, and the friction material prepared using the pulp is in reality
When border is applied, the CaCO in friction process3The carrying of matrix resin can be partly replaced, prevents the thermoplasticity of matrix resin to become
Shape, effectively increases the wearability of friction material, while reaching reduces cost, the effect of the hot stabilization of raising material.
Embodiment
A kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers, its preparation has synthesized poly- ammonia first
Ester solution, then the DMA solution with polyacrylonitrile be hybridly prepared into blending slurries, then slurries are injected
Dissolved with Ca (OH)2Coagulating bath in, acted in high speed shear and be passed through CO2, blending pulp is prepared using In-situ Precipitation.
Comprise the following steps that：
（1）The preparation of polyurethane：
15 parts by weight dihydromethyl propionic acid powder are added into reaction bulb, 90 parts of DMAs is added and is allowed to molten
Solution, is warming up to 45 DEG C, is passed through nitrogen, starts that 15 parts of toluene di-isocyanate(TDI)s are added dropwise, the completion of dropping in 30 minutes is warming up to 55
DEG C, insulation reaction 3 hours prepares polyurethane solutions；
（2）The preparation of mixed serum：
70 parts of polyacrylonitrile are placed in convection oven, it is standby in being dried 8 hours at 80 DEG C；By 150 parts of N, N- dimethylacetamides
Amine pours into three-necked bottle, and turn on agitator stirring adds 5 parts of lithium chlorides after after its dissolving completely, adds dried polyacrylonitrile,
It is put into water-bath and is heated to 80 DEG C of stirrings fully dissolving, is cooled to after room temperature and adds above-mentioned polyurethane solutions, be mixed evenly；
（3）The preparation of solidification liquid：
Weigh 14 parts of Ca (OH)2Powder is added to the in the mixed solvent of DMA and water, is configured to Ca2+Concentration is
0.04mol/L solution, ultrasonic disperse dissolves it；
（4）Under high speed shear effect, polyacrylonitrile/polyurethane mixed serum is injected in the above-mentioned solidification liquid prepared, cut
Cut after 3 minutes, be passed through CO2, after the completion of reaction, suction filtration is washed with deionized 4 times, centrifugal drying, obtains that pulp is blended.
Wherein, the in the mixed solvent DMA and the volume of water of described DMA and water
Than for 3:1.
Wherein, step（4）The high speed cleavage reaction time is 25 minutes.
Claims (4)
1. a kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers, it is characterised in that it is prepared first
Polyurethane solutions are synthesized, then the DMA solution with polyacrylonitrile is hybridly prepared into blending slurries, then
By slurries injection dissolved with Ca (OH)2Coagulating bath in, acted in high speed shear and be passed through CO2, prepared using In-situ Precipitation
Pulp is blended.
2. a kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers according to claims 1,
Characterized in that, comprising the following steps that：
（1）The preparation of polyurethane：
8-15 parts by weight dihydromethyl propionic acid powder is added into reaction bulb, adding 65-90 parts of DMAs makes
Dissolving, be warming up to 40-50 DEG C, be passed through nitrogen, start be added dropwise 8-15 parts of toluene di-isocyanate(TDI)s, dripped in 30 minutes
Finish, be warming up to 52-57 DEG C, insulation reaction 2-3 hours prepares polyurethane solutions；
（2）The preparation of mixed serum：
55-70 parts of polyacrylonitrile are placed in convection oven, it is standby in being dried 6-8 hours at 78-83 DEG C；By 110-150 parts of N,
N- dimethyl acetamides pour into three-necked bottle, and turn on agitator stirring adds 2-5 parts of lithium chlorides after after its dissolving completely, added dry
Dry good polyacrylonitrile, is put into water-bath and is heated to 78-83 DEG C of stirring fully dissolving, be cooled to after room temperature and add above-mentioned polyurethane
Solution, is mixed evenly；
（3）The preparation of solidification liquid：
Weigh 8-14 parts of Ca (OH)2Powder is added to the in the mixed solvent of DMA and water, is configured to Ca2+Concentration
For 0.04-0.06mol/L solution, ultrasonic disperse dissolves it；
（4）Under high speed shear effect, polyacrylonitrile/polyurethane mixed serum is injected in the above-mentioned solidification liquid prepared, cut
Cut after 1-5 minutes, be passed through CO2, after the completion of reaction, suction filtration is washed with deionized 2-4 times, centrifugal drying, obtains that pulp is blended.
3. a kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers according to claims 2,
Characterized in that, described DMA and the in the mixed solvent DMA of water and the volume ratio of water
For 1-3:1.
4. a kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers according to claims 2,
Characterized in that, step（4）The high speed cleavage reaction time is 10-25 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710506716.2A CN107217329A (en) | 2017-06-28 | 2017-06-28 | A kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710506716.2A CN107217329A (en) | 2017-06-28 | 2017-06-28 | A kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers |
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| Publication Number | Publication Date |
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| CN107217329A true CN107217329A (en) | 2017-09-29 |
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| CN201710506716.2A Pending CN107217329A (en) | 2017-06-28 | 2017-06-28 | A kind of preparation method of use In-situ Precipitation synthesis modification acrylic fibers pulp fibers |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535445A (en) * | 2018-12-11 | 2019-03-29 | 上海洁晟环保科技有限公司 | A kind of preparation method and process units of polymer pulp |
| CN113882185A (en) * | 2021-12-03 | 2022-01-04 | 山东非金属材料研究所 | Preparation method of PBO (Poly-p-phenylene benzobisoxazole) fibrids for preparing pulp |
Citations (7)
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| US20080152855A1 (en) * | 2004-04-20 | 2008-06-26 | Fei Wang | Release layer for in-mold decoration |
| CN101283013A (en) * | 2005-08-17 | 2008-10-08 | 圣戈班柴恩纽克斯特性塑料公司 | Hydrolysis resistant cellular material, the composition and method for the production thereof |
| CN102071542A (en) * | 2011-02-22 | 2011-05-25 | 天津工业大学 | Method for preparing polymeric nano-micro fiber non-woven fabric |
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| CN103031617A (en) * | 2012-12-24 | 2013-04-10 | 中原工学院 | Carbon nanotube/polyurethane/polyacrylonitrile composite conductive fiber and preparation method thereof |
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| CN104593946A (en) * | 2008-05-29 | 2015-05-06 | 三井化学株式会社 | Mixed fiber spun bonded nonwoven fabric and use thereof |
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2017
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Patent Citations (7)
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| US20080152855A1 (en) * | 2004-04-20 | 2008-06-26 | Fei Wang | Release layer for in-mold decoration |
| CN101283013A (en) * | 2005-08-17 | 2008-10-08 | 圣戈班柴恩纽克斯特性塑料公司 | Hydrolysis resistant cellular material, the composition and method for the production thereof |
| CN104593946A (en) * | 2008-05-29 | 2015-05-06 | 三井化学株式会社 | Mixed fiber spun bonded nonwoven fabric and use thereof |
| CN102080269A (en) * | 2009-11-27 | 2011-06-01 | 日本韦琳株式会社 | Spinning apparatus, apparatus and process for manufacturing nonwoven fabric, and nonwoven fabric |
| CN102071542A (en) * | 2011-02-22 | 2011-05-25 | 天津工业大学 | Method for preparing polymeric nano-micro fiber non-woven fabric |
| CN103031617A (en) * | 2012-12-24 | 2013-04-10 | 中原工学院 | Carbon nanotube/polyurethane/polyacrylonitrile composite conductive fiber and preparation method thereof |
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Non-Patent Citations (2)
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|---|
| 刘永乐等: "PAN/PMIA 相容性研究及其共混浆粕的制备", 《合成纤维》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535445A (en) * | 2018-12-11 | 2019-03-29 | 上海洁晟环保科技有限公司 | A kind of preparation method and process units of polymer pulp |
| CN113882185A (en) * | 2021-12-03 | 2022-01-04 | 山东非金属材料研究所 | Preparation method of PBO (Poly-p-phenylene benzobisoxazole) fibrids for preparing pulp |
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Application publication date: 20170929 |