CN108219126B - Aramid fiber-based polyether polyol and preparation method thereof - Google Patents
Aramid fiber-based polyether polyol and preparation method thereof Download PDFInfo
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- CN108219126B CN108219126B CN201711350761.XA CN201711350761A CN108219126B CN 108219126 B CN108219126 B CN 108219126B CN 201711350761 A CN201711350761 A CN 201711350761A CN 108219126 B CN108219126 B CN 108219126B
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 127
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 40
- 229920000570 polyether Polymers 0.000 title claims abstract description 40
- 229920005862 polyol Polymers 0.000 title claims abstract description 37
- 150000003077 polyols Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004917 polyol method Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000004760 aramid Substances 0.000 claims abstract description 54
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 238000001465 metallisation Methods 0.000 claims abstract description 16
- 230000002950 deficient Effects 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 238000007670 refining Methods 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 90
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000004821 distillation Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 5
- 238000007380 fibre production Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
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- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 2
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 239000011496 polyurethane foam Substances 0.000 abstract description 2
- 239000012312 sodium hydride Substances 0.000 abstract description 2
- 229910000104 sodium hydride Inorganic materials 0.000 abstract description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 19
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 17
- 238000007599 discharging Methods 0.000 description 15
- 239000000835 fiber Substances 0.000 description 12
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- 239000000126 substance Substances 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 239000003365 glass fiber Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
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- 238000009270 solid waste treatment Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2633—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen the other compounds containing amide groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/5039—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyamides (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses aramid fiber-based polyether polyol and a preparation method thereof, wherein defective aramid fibers discharged in the production process of para-aramid fibers are refined to prepare defective aramid fiber powder; the aramid fiber powder or the aramid fiber product is activated by a metallization reagent, then is subjected to a hydroxyl alkylation reaction with EO, PO or a mixture of the EO and the PO, and after the reaction is finished, the aramid fiber-based polyether polyol is prepared by refining treatment. In the method, compared with sodium hydride, the metal sodium, sodium hydroxide and sodium methoxide used in the aramid fiber powder modified metallization reagent have the advantages of convenient use, less hydrogen generation and the like; the prepared aramid fiber-based polyether polyol is a low-viscosity liquid, has the basic characteristics of aramid fiber, has the flexibility and high reaction activity of polyether, can be used as a raw material of a coating, an adhesive, polyurethane foam or other materials, opens up a new application of the aramid fiber, realizes the resource utilization of defective low-molecular-weight aramid fiber powder in the production process of the aramid fiber, and changes waste into valuable.
Description
Technical Field
The invention relates to the technical field of graft modification of aramid fiber powder and low-molecular-weight defective aramid fiber powder generated in the production process of the aramid fiber powder, and particularly relates to aramid fiber-based polyether polyol and a preparation method thereof.
Background
Aramid fibers were born in the end of the 60's 20 th century and were originally known as materials for development in the universe and important strategic materials. After the end of a cold war, aramid fibers are gradually known as high-technical-content fiber materials for use in the civil field in large quantities. The aramid fibers have two varieties with practical values: the first is meta-aramid fiber with zigzag molecular chain arrangement, which is called aramid 1313; one is para-aramid fiber with linear molecular chain arrangement, called aramid 1414.
The para-aramid (PPTA) is synthesized by adopting a low-temperature polycondensation method, and monomers of p-phenylenediamine and paraphthaloyl chloride react as follows:
the production process comprises three stages of polymerization, filament spinning and tow spinning. In the first stage, the monomer is first spun into a dense fine-grained polymer powder (aramid powder) having the main thermal and chemical properties of para-aramid but not the reinforcing properties of yarn or pulp, which can be used to reinforce plastic components. The second stage dissolves the polymer in sulfuric acid to form a liquid crystal solution, which is then spun into fine filaments with 100% sub-crystalline structure and molecular chains parallel to the fiber axis, and this high-tropism distribution makes the filaments have various excellent characteristics. In the third stage, the yarns are subjected to wrinkling and finishing agent treatment to produce staple fibers; or cutting staple fiber into yarn, suspending the yarn in water, and performing fiberization treatment to obtain pulp.
Para-aramid (PPTA) is called poly-p-phenylene terephthalamide (PPTA) and is a novel material consisting of aromatic rings and amido bonds on a macromolecular main chain, amide groups and benzene rings form pi conjugation, the PPTA has high internal rotation energy, molecular chains are arranged in a planar rigid straight line shape, and the crystallinity is high; the covalent bond energy is very large, and the strength is very high; contains more polar groups, and has strong intermolecular interaction force, good rigidity and high modulus. PPTA has excellent performance, the maximum service temperature is 240 ℃, the Tg is more than 300 ℃, the decomposition temperature reaches 500 ℃, and the PPTA determines that the PPTA has better chemical corrosion resistance than other synthetic fibers, so the PPTA is often used for reinforcing composite materials. The specific strength of PPTA is 6 times that of steel wires and 3 times that of glass fibers; the modulus is 2-3 times of that of the steel wire or the glass fiber; the toughness is 2 times of that of the steel wire; but only about 20% of the weight of the steel wire. However, due to the excellent properties of PPTA, PPTA has poor solubility and fatigue resistance, poor light resistance, poor shearing performance and easy microfibrillation and splitting of fibers. Due to the chemical inertia and the smooth surface of the aramid fiber, the surface of the fiber is smooth and low in activity, and the fiber is not easy to be infiltrated by resin, so that the bonding performance of the fiber and the resin matrix interface is poor, and the interface shear strength is low.
PPTA is more and more emphasized by people because of having the advantages of high strength, high modulus, high temperature resistance, chemical corrosion resistance and the like, and is widely used in the fields of friction materials, special adhesives, coatings and the like, but because the molecule of PPTA has a skin-core structure, a plurality of benzene rings and carbonyl groups also exist in a chain structure, the 'conjugation effect' and 'steric hindrance' action between the benzene rings and the carbonyl groups are very strong, the surface lacks of the PPTA has chemical active groups, the PPTA has poor wettability and is difficult to process and form under normal conditions; therefore, the aramid fiber can be improved in interface combination with the composite material after being subjected to surface modification.
At present, the modification method for aramid fiber mainly comprises two methods of physical modification and chemical modification. The physical modification method comprises the following steps: surface coating method, plasma modification, high-energy ray radiation modification, ultrasonic dipping modification and the like. The chemical modification method is to introduce active functional groups such as-COOH, -OH, -C ═ O, -NH on the surface of the aramid fiber by chemical reaction2And the like, thereby forming a covalent bond with the composite material, improving the solubility and mechanical properties of the aramid fiber and enhancing the interface performance of the material. The following methods are mainly used: (1) and (3) copolymerization modification, wherein a third monomer is introduced into an aramid molecular chain to improve the performances of solubility, adhesive force and the like of the aramid fiber. (2) Surface etching, hydrolyzing amido bonds on molecular chains or destroying the crystallization state of the aramid fiber surface by using substances with strong oxidizing property, increasing the surface roughness and promoting the living of the fiber surfaceThe functional group enhances the wettability and the adhesiveness with the resin. Chemical etching of acid chloride (methacryloyl chloride), acid base (acetic anhydride), etc. is commonly used to treat aramid fibers. (3) The grafting reaction on the benzene ring, the ortho-para position of the benzene ring directly connected with the amino group in the aramid fiber has reactivity, and can generate H substitution reaction with some electrophilic substituent groups, and the grafting reaction on the benzene ring at present is mainly divided into nitration reduction reaction, chlorosulfonation reaction, Friedel-crafts reaction and the like. (4) H substitution on amide. In the aramid structure, because the steric hindrance of a benzene ring is high, a certain shielding effect is achieved on hydrogen atoms on amide, and an amide bond and the benzene ring form a two-conjugate system structure, so that the H on the amide functional group is relatively weak in reaction activity and not easy to replace, and the current activation methods mainly comprise two methods: one is isocyanate modification, isocyanate is used for replacing active hydrogen on amido bond, so that high-activity isocyanate group (-NCO) is introduced, and then the isocyanate group is reacted with water to be converted into amino; the other is metallization reaction, metal ions are formed by alkali metal salt or alkaline earth metal salt and dimethyl sulfoxide (DMSO), H on an amido group in PPTA is replaced by the obtained metal ions to form metallized aramid fiber, and finally the metallized aramid fiber is reacted with aliphatic or aromatic halogenated hydrocarbon to introduce reactive functional groups such as alkyl or epoxy groups; the interface strength of the modified composite material is improved.
During the polymerization and spinning process of PPTA, a certain amount of inferior aramid fiber can be generated due to factors such as raw materials, equipment, process and operation, and the like, and the method mainly comprises the following steps: 1) the crude product of the para-aramid oligomer is mainly from a polymerization reaction system, and the polymerized molecular weight of the aramid cannot meet the spinning requirement due to factors such as raw materials, operation or equipment, and is discharged in the form of waste (low molecular weight defective aramid powder) for solid waste treatment. 2) The pulp and the waste silk are mainly derived from the waste pulp and the waste silk generated in the spinning and short fiber processes. Because the aramid fiber has good temperature resistance, the burning is difficult, and the environment is easily polluted.
The para-aramid oligomer powder and the block material are light yellow, still have the basic characteristics of aramid fiber, such as high strength, high modulus, low density, high temperature resistance, wear resistance and chemical corrosion resistance, and have the characteristics of structure, such that the para-aramid oligomer powder and the block material are insoluble in common organic solvents, have inert surfaces and poor wettability, so that the processing performance of the para-aramid oligomer powder and the application of the para-aramid oligomer powder and the block material are limited.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide a preparation method of aramid fiber-based polyether polyol, which is characterized in that inferior-quality low-molecular-weight aramid fibers discharged in the production process of para-aramid fibers are used as raw materials to carry out hydroxyalkylation grafting modification to prepare liquid aramid fiber-based polyether polyol, so that the inferior-quality low-molecular-weight aramid fibers in the production process of aramid fibers are recycled, and waste materials are changed into valuable materials. The invention also aims to provide a method for preparing and obtaining the aramid-based polyether polyol by replacing defective aramid fiber with high-quality aramid fiber powder.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a preparation method of aramid fiber-based polyether polyol is characterized in that inferior aramid fibers discharged in a para-aramid fiber production process are refined to prepare inferior aramid fiber powder; activating aramid fiber powder with a metallizing reagent, carrying out a hydroxyl alkylation reaction with Ethylene Oxide (EO), Propylene Oxide (PO) or a mixture thereof, and refining after the reaction to prepare the aramid fiber polyether polyol.
The refining treatment comprises the following steps: stirring the low-molecular defective aramid fiber discharged from the aramid fiber production workshop and water in a container according to the mass ratio of 1:2-5, uniformly stirring, performing suction filtration, and continuously washing a filter cake for multiple times by using water until the filtrate is neutral; and drying the solid powder to constant weight, sieving the dried solid powder by a 40-mesh sieve, and filling the powder into a sealed bag for storage to obtain the refined aramid powder.
The preparation method of the aramid fiber-based polyether polyol comprises the steps of adding a metallization reagent and defective aramid fiber powder into a reaction kettle, and adding N2Replacing air in the reaction kettle, starting a stirrer, controlling the stirring speed to be 400-; then continuously dropwise adding metered EO/PO, controlling the reaction temperature to be 80-140 ℃, controlling the reaction time to be 3-8 h, after EO/PO addition, carrying out heat preservation reaction until the pressure in the kettle is kept unchanged, and carrying out reduced pressure steamingDistilling to recover the solvent, dissolving the crude product by dichloromethane, washing by a proper amount of water, and distilling under reduced pressure to recover the dichloromethane to obtain a brown viscous liquid.
The inferior aramid fiber powder is sampled in three stages in the aramid fiber polycondensation production process, and the molecular weight of the inferior aramid fiber powder is measured by an Ubbelohde viscometer: firstly, discharging at the initial stage of polycondensation reaction, and naming the aramid fiber with low molecular weight, wherein the molecular weight is about 2600; discharging the aramid fiber at the middle stage of the polycondensation reaction, and naming the aramid fiber as the aramid fiber with medium molecular weight, wherein the molecular weight is about 3000; and discharging at the later stage of the polycondensation reaction, and naming the aramid fiber with higher molecular weight, wherein the molecular weight is about 5200. The three molecular weight infrared spectrograms are similar; thermogravimetric analysis shows that the three aramid fibers have good heat resistance, less degradation is carried out within 500 ℃, the temperatures of the aramid fibers with low, medium and high molecular weights are 498, 540 and 550 ℃ respectively when the mass loss is 50%, and the defective aramid fibers still have good heat resistance. The defective aramid powder contained these three portions.
In the preparation process of the metallization reagent, the solvent can be dimethyl sulfoxide (DMSO) or dimethyl formamide (DMF), and the dosage is 40-70mL/g aramid fiber powder; the alkali metal or the compound thereof is metal sodium, sodium methoxide, sodium hydroxide or metal potassium, potassium methoxide and potassium hydroxide, the dosage of the alkali metal or the compound thereof is 0.2 to 0.6 percent of the total mass (the sum of the mass of the solvent, the mass of aramid fiber and the mass of EO) of the reactants, and the most suitable dosage of the alkali metal or the compound thereof is 0.3 to 0.4 percent of the total mass of the reactants. The alkali metal compound is preferably metallic sodium. Under the protection of nitrogen, adding a solvent DMSO or DMF into a reactor provided with a stirrer, a condenser and a thermometer, slowly adding a certain amount of alkali metal compound, slowly heating to 60-90 ℃ under stirring, reacting until the alkali metal compound is completely dissolved, and obtaining a dark brown clear solution as a metallization reagent.
In the process of the aramid fiber polyether polyol, a metallization reagent and a given amount of aramid fiber powder are added into a reaction kettle, and N2Replacing air in the reaction kettle for 3 times, starting a stirrer, controlling the stirring speed to be 400 plus materials at 500r/min, reacting for 1h at 60 ℃, discharging the air in the kettle, slowly heating to 110 ℃, and then stirring for reacting for 2 h; then continuously dropwise adding metered EO/PO, controlling the reaction temperature to be 80-140 ℃, controlling the reaction time to be 3-8 h, after the EO/PO is added, and carrying out heat preservation reaction until the pressure in the kettle is increasedAnd (3) distilling under reduced pressure to recover the solvent while keeping the temperature constant, dissolving the crude product by using dichloromethane, washing by using a proper amount of water, and distilling under reduced pressure to recover the dichloromethane to obtain a brown viscous liquid product.
In the method, the feeding ratio of EO or PO is m (EO or PO) and m (aramid fiber powder) is 1-5: 1, and the suitable feeding ratio is m (EO or PO) and m (aramid fiber powder) is 1.5-3: 1; the appropriate reaction temperature of the hydroxyalkylation reaction is 105-115 ℃, the reaction rate is slow when the reaction temperature is too low, the reaction pressure is high when the reaction temperature is too high, and the requirements on equipment and operation are high; the optimum reaction time is 4-5 h.
The aramid fiber polyether polyol obtained by the preparation method of the aramid fiber polyether polyol.
An aramid-based polyether polyol is prepared by the following method: adding a metallization reagent and defective aramid fiber powder or certified aramid fiber powder into a reaction kettle, and adding N2Replacing air in the reaction kettle, starting a stirrer, controlling the stirring speed to be 400-; and then continuously dropwise adding metered EO/PO, controlling the reaction temperature to be 80-140 ℃, reacting for 3-8 hours, after the EO/PO is added, carrying out heat preservation reaction until the pressure in the kettle is kept unchanged, carrying out reduced pressure distillation to recover the solvent, dissolving the crude product with dichloromethane, washing with a proper amount of water, and recovering the dichloromethane through reduced pressure distillation to obtain the product, namely the aramid fiber-based polyether polyol, which is brown viscous liquid.
Has the advantages that: the novel aramid fiber-based polyether polyol and the preparation method thereof take the para-aramid fiber and the inferior low-molecular-weight aramid fiber discharged in the production process as raw materials, and carry out hydroxyalkylation grafting modification under the activation of a metallization reagent to obtain low-viscosity liquid aramid fiber-based polyether polyol; compared with sodium hydride, the metal sodium, sodium hydroxide and sodium methoxide used in the aramid powder metallization reagent have the advantages of convenient use, less hydrogen generation and the like; the prepared aramid-based polyether has the basic characteristics of aramid, the flexibility and the high reaction activity of the polyether, can be used as a raw material of a coating, an adhesive, polyurethane foam or other materials, realizes the resource utilization of inferior-quality low-molecular-weight aramid powder in the production process of the aramid and changes waste into valuable; and opens up new application for aramid fiber application, and has good practicability.
Drawings
FIG. 1 is an infrared image of recovered refined aramid powder;
fig. 2 is a thermogravimetric diagram of recovered refined aramid powder.
Detailed Description
The invention will now be further illustrated by reference to specific examples, but is not limited to the examples given.
The raw material ethylene oxide in the examples is industrial grade, Yangzi oil chemical industry Co., Ltd; propylene oxide is technical grade, qilu petrochemical corporation; metal sodium, sodium hydroxide, dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone are analytically pure, Nanjing chemical reagent Co., Ltd; high purity nitrogen, purity 99.9%, Nanjing specialty gas works, Inc.; aramid fiber powder and chemical fiber. The hydroxyl value of the aramid-based polyether polyol in the examples was measured by GB/2008.3-89.
Example 1
Respectively adding 300g of dimethyl sulfoxide and 1.78g of metal sodium into a four-neck flask filled with nitrogen, controlling the stirring speed to be 300r/min, slowly heating to 80 ℃, after reacting for 2 hours, adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing a cover of the autoclave, replacing with nitrogen for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2 hours, introducing 20.64g of EO, maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 110-.
Example 2
Respectively adding 330g of dimethyl sulfoxide and 1.75g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to be 300r/min, slowly heating to 70 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down a cover of the autoclave, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2 hours, introducing 15.48g of EO, maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 100 plus of 110 ℃, reacting for 2.5 hours, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, performing reduced pressure distillation to recover dimethyl sulfoxide, dissolving the crude product with dichloromethane, washing with a proper amount of water for three times, and performing reduced pressure distillation to recover dichloromethane to obtain the low-viscosity aramid fiber-based polyether polyol black liquid with the hydroxyl value of 215 mgKOH/g.
Example 3
Respectively adding 330g of dimethylformamide and 3.0g of sodium hydroxide into a four-neck flask filled with nitrogen, controlling the stirring speed to be 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down a cover of the autoclave, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2 hours, introducing 10.32g of EO, maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 120-130 ℃, reacting for 2.5 hours, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, performing reduced pressure distillation to recover dimethylformamide, dissolving the crude product with dichloromethane, washing with a proper amount of water for three times, and performing reduced pressure distillation to recover dichloromethane to prepare the low-viscosity aramid fiber-based polyether polyol black liquid with the hydroxyl value of 193 mgKOH/g.
Example 4
Respectively adding 330g of dimethyl sulfoxide and 1.08g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down a cover of the autoclave, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2 hours, introducing 25.80g of EO, maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 100 plus of 110 ℃, reacting for 4 hours, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, performing reduced pressure distillation to recover dimethyl sulfoxide, dissolving the crude product with dichloromethane, washing with a proper amount of water for three times, and performing reduced pressure distillation to recover dichloromethane to obtain the low-viscosity aramid fiber-based polyether polyol black liquid, wherein the hydroxyl value is 187 mgKOH/g.
Example 5
Respectively adding 330g of dimethyl sulfoxide and 2.17g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to 300r/min, slowly heating to 90 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into a high-pressure kettle, simultaneously adding 6g of aramid fiber powder, screwing a cover of the high-pressure kettle, replacing with nitrogen for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2 hours, introducing 25.80g of EO, maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 110-120 ℃, reacting for 3 hours, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, carrying out reduced pressure distillation to recover dimethyl sulfoxide, dissolving the crude product with dichloromethane, washing with a proper amount of water for three times, and carrying out reduced pressure distillation to recover dichloromethane to obtain the low-viscosity aramid fiber-based polyether polyol black liquid with the hydroxyl value of 221 mgKOH/g.
Example 6
Respectively adding 300g of dimethyl sulfoxide and 1.04g of metal sodium into a four-neck flask filled with nitrogen, controlling the stirring speed to be 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down a cover of the autoclave, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2 hours, introducing 9.83g of PO (propylene oxide), maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 90-100 ℃, reacting for 2 hours, after the reaction is finished, cooling, opening an emptying valve, taking out a reactant, performing reduced pressure distillation to recover dimethyl sulfoxide, dissolving a crude product with dichloromethane, washing the crude product with a proper amount of water for three times, and performing reduced pressure distillation to recover dichloromethane to prepare the low-viscosity aramid fiber-based polyether polyol black liquid with the hydroxyl value of 329 mgKOH/g.
Example 7
Respectively adding 300g of dimethyl sulfoxide and 2.10g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to be 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down a cover of the autoclave, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2 hours, introducing 16.39g of PO, maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 120-130 ℃, reacting for 2.5 hours, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, performing reduced pressure distillation to recover dimethyl sulfoxide, dissolving the crude product with dichloromethane, washing with a proper amount of water for three times, and performing reduced pressure distillation to recover dichloromethane to prepare 294mgKOH/g of low-viscosity aramid fiber-based polyether polyol black liquid.
Example 8
Respectively adding 300g of dimethylformamide and 2.10g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to be 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down a cover of the autoclave, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2 hours, introducing 16.39g of PO (propylene oxide), maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 130-.
Example 9
Respectively adding 330g of dimethyl sulfoxide and 1.06g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down a cover of the autoclave, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2h, introducing 16.39g of PO (propylene oxide), maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 110 plus 120 ℃, reacting for 2.5h, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, performing reduced pressure distillation to recover dimethyl sulfoxide, dissolving the crude product with dichloromethane, washing with a proper amount of water for three times, and performing reduced pressure distillation to recover dichloromethane to obtain the low-viscosity aramid fiber-based polyether polyol black liquid with the hydroxyl value of 201 mgKOH/g.
Example 10
Respectively adding 330g of dimethyl sulfoxide and 2.11g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down the autoclave cover, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2h, introducing PO16.39g, maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 110 plus 120 ℃, reacting for 2.5h, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, performing reduced pressure distillation to recover dimethyl sulfoxide, dissolving the crude product with dichloromethane, washing with a proper amount of water for three times, and performing reduced pressure distillation to recover dichloromethane to obtain the low-viscosity aramid fiber-based polyether polyol black liquid with the hydroxyl value of 225 mgKOH/g.
Example 11
Respectively adding 330g of dimethylformamide and 2.07g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing a cover of the autoclave, replacing with nitrogen for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2h, introducing a mixture of EO and PO, wherein EO0.8g and PO9.0g are kept at the pressure of not more than 0.4MPa, controlling the reaction temperature to be 105-115 ℃, reacting for 2.5h, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, carrying out reduced pressure distillation to recover dimethylformamide, dissolving the crude product with dichloromethane, washing with water for three times in proper amount, and recovering dichloromethane by reduced pressure distillation to prepare the aramid fiber-based polyether polyol black liquid with the low viscosity of mg211 KOH/g.
Example 12
Respectively adding 330g of dimethyl sulfoxide and 1.38g of sodium metal into a four-neck flask filled with nitrogen, controlling the stirring speed to 300r/min, slowly heating to 80 ℃, reacting for 2 hours, and then discharging; adding the reacted feed liquid into an autoclave, simultaneously adding 6g of aramid fiber powder, screwing down an autoclave cover, performing nitrogen displacement for three times, controlling the stirring speed to be 500-600 r/min, heating to 110 ℃, reacting for 2h, introducing PO9.78g, maintaining the pressure to be not more than 0.4MPa, controlling the reaction temperature to be 110 plus 120 ℃, reacting for 2.0h, cooling after the reaction is finished, opening an emptying valve, taking out the reactant, performing reduced pressure distillation to recover dimethyl sulfoxide, dissolving the crude product with dichloromethane, washing with a proper amount of water for three times, and performing reduced pressure distillation to recover dichloromethane to obtain the low-viscosity aramid fiber-based polyether polyol black liquid with the hydroxyl value of 341 mgKOH/g.
Example 13
In the above examples, the recovery and refining process of the raw material aramid powder is as follows: collecting aramid fiber powder containing N-methyl pyrrolidone discharged in the production process; stirring the crude aramid fiber powder and water in a beaker according to the mass ratio of 1:2, filtering after stirring for 1h, and adding water into a filter cake according to the mass ratio of 1:3 for multiple times until the filtrate is neutral. And finally, pouring the filter cake into a clean evaporating dish, and putting the evaporating dish into an oven to dry the evaporating dish to constant weight. And (3) grinding the dried aramid fiber powder, sieving the powder by a 40-mesh sieve, and filling the powder into a sealing bag to obtain the aramid fiber powder.
0.125g of recovered and refined aramid powder dried to constant weight is dissolved in 25mL of 98% concentrated sulfuric acid, the viscosity of the aramid powder is measured in a constant temperature bath at (30 +/-0.05) DEG C in an Ubbelohde viscometer, and the molecular weight of the aramid powder is calculated according to the viscosity, and the result is shown in Table 1.
TABLE 1 eta for recovery of refined aramid powder]、MηAnd DPη
The viscosity-average molecular weights of the low, medium and high-grade aramid fibers measured by an Ubbelohde viscometer are 2606, 2903 and 5226 respectively, and the polymerization degrees are 11, 12 and 22 respectively. The structural properties of the low-grade aramid fiber and the middle-grade aramid fiber are similar, and the high-grade aramid fiber has large molecular weight, high crystallinity and better mechanical property.
The infrared spectrogram of the recovered and refined aramid powder is determined, and the result is shown in figure 1. The recovered refined aramid powder was subjected to TG analysis, and the results are shown in fig. 2. Through infrared and thermogravimetric analysis, infrared images of low-grade, medium-grade and high-grade aramid fibers are similar, heat resistance is good, degradation is low within 500 ℃, the temperature of the low-grade, medium-grade and high-grade aramid fibers is 498, 540 and 550 ℃ respectively when mass loss is 50%, and the fact that the aramid fibers are high in molecular weight and good in heat resistance is shown.
Claims (5)
1. A preparation method of aramid fiber-based polyether polyol is characterized in that inferior aramid fibers discharged in a para-aramid fiber production process are refined to prepare inferior aramid fiber powder; adding a metallization reagent and defective aramid fiber powder into a reaction kettle, and adding N2Replacing air in the reaction kettle, starting a stirrer, controlling the stirring speed to be 400-; continuously dropwise adding metered EO/PO, controlling the reaction temperature to be 80-140 ℃, reacting for 3-8 hours, after the EO/PO is added, carrying out heat preservation reaction until the pressure in the kettle is kept unchanged, carrying out reduced pressure distillation to recover the solvent, dissolving the crude product with dichloromethane, washing with a proper amount of water, and recovering the dichloromethane through reduced pressure distillation to obtain a brown viscous liquid; wherein the feeding proportion of EO or PO is m (EO or PO) and m (aramid fiber powder) is 1-5: 1;
the refining treatment of the defective aramid fiber comprises the following steps: stirring the low-molecular defective aramid fiber discharged from the aramid fiber production workshop and water in a container according to the mass ratio of 1:2-5, uniformly stirring, performing suction filtration, and continuously washing a filter cake for multiple times by using water until the filtrate is neutral; drying the solid powder to constant weight, sieving with a 40-mesh sieve, and packaging in a sealed bag for storage to obtain refined aramid powder;
the preparation process of the metallization reagent comprises the following steps: under the protection of nitrogen, adding a solvent DMSO or DMF into a reactor provided with a stirrer, a condenser and a thermometer, slowly adding a certain amount of alkali metal or a compound thereof, slowly heating to 60-90 ℃ under stirring, reacting until the alkali metal or the compound thereof is completely dissolved, and obtaining a dark brown clear solution as a metallization reagent, wherein the dosage of the solvent is 40-70mL/g of aramid fiber powder; the alkali metal or the compound thereof is selected from metallic sodium, sodium methoxide, sodium hydroxide or metallic potassium, potassium methoxide and potassium hydroxide, and the dosage of the alkali metal or the compound thereof is 0.2 to 0.6 percent of the total mass of the reactants.
2. The preparation method of the aramid-based polyether polyol as claimed in claim 1, wherein the feeding ratio of m (EO or PO) and m (aramid powder) is 1.5-3: 1.
3. The preparation method of the aramid-based polyether polyol as claimed in claim 1, wherein the EO/PO is continuously dropwise added and metered, and the reaction is carried out at 105-115 ℃ for 4-5 hours.
4. The aramid-based polyether polyol obtained by the method for producing an aramid-based polyether polyol according to any one of claims 1 to 3.
5. The aramid-based polyether polyol is characterized by being prepared by the following method:
refining inferior aramid fibers discharged in the production process of the para-aramid fibers to prepare inferior aramid fiber powder; adding a metallization reagent and defective aramid fiber powder into a reaction kettle, and adding N2Replacing air in the reaction kettle, starting a stirrer, controlling the stirring speed to be 400-; continuously dropwise adding metered EO/PO, controlling the reaction temperature to be 80-140 ℃, reacting for 3-8 hours, after the EO/PO is added, carrying out heat preservation reaction until the pressure in the kettle is kept unchanged, carrying out reduced pressure distillation to recover the solvent, dissolving the crude product with dichloromethane, washing with a proper amount of water, and recovering the dichloromethane through reduced pressure distillation to obtain the product of aramid fiber-based polyether polyol which is brown viscous liquid; wherein the feeding proportion of EO or PO is m (EO or PO) and m (aramid fiber powder) is 1-5: 1; the preparation process of the metallization reagent comprises the following steps: under the protection of nitrogen, adding a solvent DMSO or DMF into a reactor provided with a stirrer, a condenser and a thermometer, slowly adding a certain amount of alkali metal or a compound thereof, slowly heating to 60-90 ℃ under stirring, reacting until the alkali metal or the compound thereof is completely dissolved, and clarifying the solution in dark brown to obtain a metallization reagent; wherein the dosage of the solvent is 40-70mL/g aramid fiber powder; the alkali metal or the compound thereof is selected from metallic sodium, sodium methoxide, sodium hydroxide or metallic potassium, potassium methoxide and potassium hydroxide, and the dosage of the alkali metal or the compound thereof is 0.2 to 0.6 percent of the total mass of the reactants.
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