CN115976676A - Preparation method of polyarylate spun yarn by continuous polymerization and polyarylate spun yarn - Google Patents
Preparation method of polyarylate spun yarn by continuous polymerization and polyarylate spun yarn Download PDFInfo
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- CN115976676A CN115976676A CN202310071941.3A CN202310071941A CN115976676A CN 115976676 A CN115976676 A CN 115976676A CN 202310071941 A CN202310071941 A CN 202310071941A CN 115976676 A CN115976676 A CN 115976676A
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- 229920001230 polyarylate Polymers 0.000 title claims abstract description 154
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000000889 atomisation Methods 0.000 claims abstract description 47
- 238000009987 spinning Methods 0.000 claims abstract description 32
- 239000000155 melt Substances 0.000 claims abstract description 17
- 238000002074 melt spinning Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 63
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 238000010583 slow cooling Methods 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000004804 winding Methods 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 17
- 238000006640 acetylation reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 230000014759 maintenance of location Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 230000021736 acetylation Effects 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract 1
- 229920006253 high performance fiber Polymers 0.000 abstract 1
- 230000008719 thickening Effects 0.000 abstract 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 20
- 239000003595 mist Substances 0.000 description 18
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 238000006757 chemical reactions by type Methods 0.000 description 6
- 238000005917 acylation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 3
- 239000004299 sodium benzoate Substances 0.000 description 3
- 235000010234 sodium benzoate Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002493 climbing effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- -1 2,5-dihydroxyphenyl Chemical group 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a preparation method of polyarylate raw silk for continuous polymerization spinning and polyarylate raw silk, belonging to the field of high-performance fibers. In the preparation method provided by the invention, atomization prepolymerization and arc-shaped plate enhanced devolatilization are adopted, so that the prepolymerization speed is accelerated, the molecular weight of the polyarylate prepolymer is increased, and the uniformity of the polyarylate prepolymer is improved; then extruding and thickening by a double screw, and directly spinning a melt to obtain polyarylate primary yarn; the preparation of the full-flow oxygen-insulating seal furthest inhibits side reactions such as oxidation, branching and crosslinking, so that the melt spinning of the polyarylate spun yarn is stabilized, the polyarylate spun yarn with high uniformity and low chroma is obtained, and a solid foundation is provided for the preparation of the high-performance and high-quality polyarylate fiber.
Description
Technical Field
The invention relates to the technical field of preparation of high-performance polymers, in particular to a preparation method of polyarylate raw silk for continuous polymerization spinning and polyarylate raw silk.
Background
Polyarylate is a class of thermotropic liquid crystalline polymers that emerged in the mid 70's of the 20 th century behind lyotropic liquid crystalline polyamides (poly-paraphenylene terephthalamide, a polymer of aramid 1414). The polyarylate melt is subjected to shear force when flowing through a spinneret orifice, and a high degree of uniaxial orientation of the polyarylate main chain occurs. Due to the high rigidity of the polyarylate structure, the high uniaxial orientation can not be loosened after leaving the spinneret orifice, so that the orientation can be well maintained, the orientation is further developed under the action of nozzle drafting, and the prepared polyarylate raw silk does not need to be subjected to post-drafting to improve the orientation degree. After heat treatment, the crystallinity is further improved while the macromolecule end in the polyarylate fiber is further condensed, so that the tensile strength of the polyarylate fiber is greatly improved, and the high-strength and high-modulus polyarylate fiber is prepared. The high-strength high-modulus polyarylate fiber can be applied to the aerospace field such as satellites, airplanes, airships and the like, can be applied to optical fibers, communication cables, sports goods for reinforcing, and can be used as bulletproof materials, protective composite plates, safety helmets, high-temperature-resistant high-strength protective gloves and the like. In addition, the material can also be used as a filter material for resisting high temperature, acid and alkali. In recent years, polyarylate fibers have been widely used in 5G materials due to their low dielectric constant and dielectric loss.
However, in the prior art, batch polymerization synthesis is adopted when preparing the polyarylate raw material, and a melt prepared by polymerization is cooled and then cut into particles, and then the particles are subjected to a technical route of drying, melting and spinning molding. The liquid crystal fiber as claimed in claim 9 is prepared by pre-curing the liquid crystal oligomer and then melt-spinning the pre-cured liquid crystal oligomer as disclosed in the chinese patent application No. 201910803586.8. In short, there is a need in the art for obtaining polyarylate raw filaments or fibers by a process of granulating a polyarylate melt, drying, and then spinning. This technical route has the following inevitable drawbacks: 1. batch polymerization results in unstable polyarylate quality; 2. the sectional conversion technology has long route and long polymerization time, and side reaction is easy to generate in the long-time high-temperature polymerization process, so that the b value of the product is high; 3. in the process of re-melting after cooling, granulating and drying the melt, the polymer is easily degraded, the quality of the fiber is reduced, and the energy consumption is increased.
Disclosure of Invention
Aiming at the existing problems, the invention provides a preparation method of polyarylate raw silk for continuous polymerization spinning and polyarylate raw silk, so as to overcome the problems of unstable polyarylate quality, long and time-consuming polymerization route and high energy consumption caused by adopting the technical route in the prior art, thereby obtaining polyarylate raw silk with high stability and good uniformity, and providing a solid foundation for the quality stability of polyarylate fibers obtained by post-heat treatment of the raw silk.
In order to realize the purpose, the invention adopts the technical scheme that:
a method of preparing continuous polymer spun polyarylate raw filament comprising the steps of:
(1) Acetylation:
continuously adding a phenolic hydroxyl monomer, acetic anhydride and a catalyst into a reactor, performing acetylation reaction under the protection of inert gas at the temperature of 120-185 ℃, staying for 30-240 min, and obtaining an acetylated monomer after acetylation reaction;
wherein the molar ratio of the phenolic hydroxyl group-containing monomer to the acetic anhydride is 3:1-1:1;
(2) Atomization prepolymerization:
adding or not adding aromatic dicarboxylic acid monomer into the acetylated monomer obtained in the step (1), continuously conveying the acetylated monomer into a horizontal atomization reactor, and carrying out spray atomization and deacetylation under the protection of inert gas and the pressure of 0.12-0.36 Mpa to obtain polyarylate prepolymer; controlling the temperature inside the horizontal atomization reactor to be 170-320 ℃, and controlling the retention time to be 30-300 min;
the horizontal atomization reactor has a spraying atomization function and comprises an arc-shaped plate;
(3) Double-screw final polymerization extrusion:
continuously inputting the polyarylate prepolymer obtained in the step (2) into a double-screw extruder with the length-diameter ratio of 30-75; the reaction temperature in the double-screw extruder is 255-355 ℃, the retention time of the polyarylate melt in the double screws is 25-45 min, and the head pressure of the double-screw extruder is 6-10 MPa;
(4) Melt spinning:
carrying out melt spinning on the polyarylate melt obtained in the step (3) through a spinning box, a metering pump and a spinneret plate, and winding to obtain polyarylate primary yarns; wherein, the polyarylate is extruded by a spinneret orifice and then is subjected to ring slow cooling solidification, the ring slow cooling height is 100-380 mm, and the slow cooling temperature is 120-315 ℃.
The preparation method of the continuous polymerization spinning polyarylate raw silk, wherein the catalyst in the step (1) is one or more of carboxylate and complex of sodium, potassium, zinc, calcium, magnesium, titanium, tin and antimony.
The preparation method of the polyarylate raw silk of the continuous polymerization spinning comprises the step (2), wherein the horizontal atomization reactor is divided into 4-6 sections for temperature control.
In the method for preparing polyarylate as the raw yarn by continuous polymerization spinning, the middle end and the rear end of the horizontal atomization reactor in the step (2) are respectively provided with a rectifying device for removing a large amount of acetic acid generated by the reaction.
The preparation method of the polyarylate as-spun yarns comprises the following steps that (1) in the step (2), the arc plates are pushed along the axial center at an angle of 35-85 degrees, the distance between the arc plates is 35-120 mm, the axial pushing speed of the arc plates is 5-25 r/min, and the thickness of the melt on the arc plates is 0.8-4.2 mm;
in the preparation method of the polyarylate raw yarn by continuous polymerization spinning, in the step (3), the twin-screw extruder is provided with 8 to 12 temperature control sections, and the middle rear part of the twin-screw extruder is also provided with at least 2 devolatilization ports.
The method for preparing polyarylate continuous polymerization spun raw filaments as described above, wherein the winding speed in the step (4) is 500 to 1500m/min.
A polyarylate raw silk prepared by the above preparation method has a total fineness of 10 to 3600dtex and a CV value of not more than 10%.
The polyarylate raw silk as described above, wherein b-value of said polyarylate raw silk is not more than 8.
The polyarylate raw yarn, wherein the strength at break of said polyarylate raw yarn is 3 to 11cN/dtex.
The technical scheme has the following advantages or beneficial effects:
according to the preparation method of the polyarylate nascent silk of the continuous polymerization spinning, provided by the invention, homogenization prepolymerization is carried out through acetylation reaction in the monomer kettle, atomization injection in the horizontal atomization reactor and arrangement of the arc-shaped plate, so that the specific surface area of a polymer is increased, devolatilization is accelerated, the polymerization reaction speed is improved, the reaction time is shortened, and the polyarylate prepolymer has high uniformity; then connecting a double screw for final polymerization, directly spinning polyarylate primary yarns after rapid viscosity increasing and pressure stabilizing, and implementing closed non-oxidation continuous production in the whole process so as to avoid oxidation in the gap polymerization process; the prepolymerization adopts a horizontal atomization reactor, and the final polymerization adopts a double-screw reactor, so that the reaction speed is increased, the reaction temperature is reduced, the rod climbing effect caused by a vertical reaction kettle is avoided, and the side reaction is reduced; and the method is further beneficial to the stability and uniformity of the polymer spinning of the primary yarn, namely, the polyarylate primary yarn with high stability and good uniformity can be obtained, and a solid foundation is provided for the quality stability of the polyarylate fiber obtained by the post-heat treatment of the primary yarn.
Compared with the prior art for preparing the polymer and spinning the nascent silk in a sectional mode, the method has the advantages of continuous production, compact equipment, small occupied area, and obvious reduction of investment cost and production operation cost.
Drawings
The invention and its features, aspects and advantages will become more apparent from reading the following detailed description of non-limiting embodiments with reference to the accompanying drawings. Like reference symbols in the various drawings indicate like elements. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
FIG. 1 is a sectional view showing the overall structure of a horizontal atomization reactor provided in example 5 of the present invention.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited thereto.
Example 1: embodiment 1 of the present invention provides a method for preparing polyarylate as-spun yarn by continuous polymerization, comprising the steps of:
(1) Acetylation:
75wt% of p-hydroxybenzoic acid (HBA), 25wt% of 2-hydroxy-6-naphthoic acid (HNA), acetic anhydride (Ac) of 76% of the total amount of monomers 2 O) and catalyst zinc acetate accounting for 0.5 percent of the total amount of the monomers are continuously added into a reactor with a lower inlet and an upper outlet according to a certain flow rate, and acetylation reaction is carried out in inert gas flow, wherein the reaction temperature is 155 ℃, and the retention time is controlled to be 100min;
(2) Atomization prepolymerization:
conveying the acetylated monomers obtained in the step (1) to a horizontal atomization reactor at a certain flow rate, spraying, atomizing and removing acetic acid under the pressure of 0.24MPa to obtain polyarylate prepolymer; the pushing angle of the arc-shaped plates along the axial center is 60 degrees, the distance between the arc-shaped plates is 75mm, the axial pushing rotating speed of the arc-shaped plates is 15r/min, and the thickness of the melt on the arc-shaped plates is 2.6mm; the whole atomization reactor is divided into 5 sections to control the temperature, the temperature is respectively set at 180 ℃, 220 ℃, 250, 270 and 280 ℃, and the retention time is 120min. The horizontal atomization reactor is protected under inert gas.
(3) Reaction type double-screw final polymerization and pressure-stabilizing conveying:
continuously inputting the polyarylate prepolymer into a twin-screw with the length-diameter ratio of 65; 2 devolatilization ports are arranged at the middle rear part of the double screw, and the double screw is vacuumized, and the pressure is controlled to be 3KPa; the residence time of the polyarylate melt in the twin screw was about 32min and the head pressure was 8.5MPa.
(4) Metering of spinning box and slow cooling forming of lower strand silk of spinneret plate
Metering the polyarylate melt by a metering pump in a spinning box body, distributing and filtering the melt, spinning, and slowly cooling and solidifying under a spinneret plate; wherein the ring slow cooling height is 250mm, and the atmosphere temperature of the slow cooling area is 260 ℃.
(5) Winding of the nascent yarn
Oiling the solidified polyarylate raw silk and winding to obtain polyarylate raw silk, wherein the winding speed is 1500m/min.
Example 2:
(1) Acetylation:
54wt% of p-hydroxybenzoic acid (HBA), 24wt% of 4,4' -dihydroxybiphenyl (BP), acetic anhydride (Ac) accounting for 151% of the total amount of the monomers 2 O) and sodium acetate which is 0.8 percent of the total amount of the monomers and is used as a catalyst are continuously added into a reactor with a lower inlet and an upper outlet according to a certain flow rate, and acylation reaction is carried out under inert gas flow, wherein the reaction temperature is 185 ℃, and the retention time is controlled to be 240min.
(2) Atomization prepolymerization:
adding 16wt% of terephthalic acid (TPA) and 6wt% of isophthalic acid (IPA) into the acetylated monomer obtained in the step (1), conveying the acetylated monomer into a horizontal atomization reactor at a certain flow rate, spraying, atomizing and removing acetic acid under the pressure of 0.36MPa to obtain a polyarylate prepolymer; the pushing angle of the arc-shaped plates along the axial center is 85 degrees, the distance between the arc-shaped plates is 80mm, the axial pushing rotating speed of the arc-shaped plates is 23r/min, and the thickness of the melt on the arc-shaped plates is 1.2mm; the temperature of the whole atomization reactor is controlled in 6 sections, the temperature is respectively set at 190, 240, 260, 280, 300 and 310 ℃, and the residence time is 270min. The horizontal atomization reactor is protected under inert gas.
(3) Reaction type double-screw final polymerization and pressure-stabilizing conveying:
continuously inputting the polyarylate prepolymer into a double screw with the length-diameter ratio of 75, wherein the double screw is provided with 12 temperature control sections, and the temperatures are respectively set to 305, 315, 320, 325, 335, 340, 345, 350, 355 and 350 ℃; 3 devolatilization ports are arranged at the middle rear part of the double screw, and the double screw is vacuumized, and the pressure is controlled to be 8KPa; the residence time of the melt in the twin-screw was approximately 43min and the head pressure was 9.8MPa.
(4) Metering of spinning box and slow cooling forming of lower strand silk of spinneret plate
The polyarylate melt is metered by a metering pump in a spinning box body, and is subjected to slow cooling solidification under a spinneret plate after being distributed and filtered, wherein the ring slow cooling height is 350mm, and the atmosphere temperature in a slow cooling area is 315 ℃.
(5) Winding of as-spun yarn
Oiling and winding the solidified polyarylate spun yarn at the winding speed of 950m/min.
Example 3:
(1) Acetylation:
62 weight percent of p-hydroxybenzoic acid (HBA), 22 weight percent of bisphenol A (AP) and 181 percent of acetic anhydride (Ac) of the total monomer amount 2 O) and catalyst sodium benzoate/zinc acetate accounting for 0.1 percent of the total amount of the monomers are continuously added into a reactor from bottom to top at a certain flow rate, and acylation reaction is carried out in inert gas flow, wherein the reaction temperature is 130 ℃, and the retention time is controlled to be 30min.
(2) Atomizing and pre-polymerizing:
conveying the acetylated monomer obtained in the step (1) and 16wt% of terephthalic acid (TPA) to a horizontal atomization reactor at a certain flow rate, spraying and atomizing under the pressure of 0.12MPa, and removing acetic acid to obtain a polyarylate prepolymer; the pushing angle of the arc-shaped plates along the axial center is 35 degrees, the distance between the arc-shaped plates is 120mm, the axial pushing rotating speed of the arc-shaped plates is 25r/min, and the thickness of the melt on the arc-shaped plates is 4.0mm; the temperature of the whole atomization reactor is controlled in 4 sections, the temperature is respectively set at 170, 210, 250 and 290 ℃, and the retention time is 40min. The horizontal atomization reactor is protected under inert gas.
(3) Reaction type double-screw final polymerization and pressure-stabilizing conveying:
continuously inputting the polyarylate prepolymer into a double screw with the length-diameter ratio of 50, wherein the double screw is provided with 8 temperature control sections, and the temperatures are respectively set to 285, 290, 295, 300, 305, 310, 315 and 310 ℃; 2 devolatilization ports are arranged at the middle rear part of the double screw, and the double screw is vacuumized, and the pressure is controlled to be 6KPa; the residence time of the melt in the twin-screw was about 35min and the head pressure was 6MPa.
(4) Metering of spinning box and slow cooling forming of lower strand silk of spinneret plate
The polyarylate melt is metered by a metering pump in a spinning box body, and is subjected to slow cooling solidification under a spinneret plate after being distributed and filtered, wherein the ring slow cooling height is 100mm, and the atmosphere temperature in a slow cooling area is 200 ℃.
(5) Winding of the nascent yarn
Oiling and winding the solidified polyarylate nascent fiber at the winding speed of 600m/min.
Example 4:
embodiment 4 of the present invention provides a method for preparing polyarylate as-spun yarns by continuous polymerization, comprising the steps of:
(1) Acetylation:
69wt% of p-hydroxybenzoic acid (HBA), 20wt% of hexafluorobisphenol A (AF), and 88% of acetic anhydride (Ac) in the total amount of the monomers 2 O) and a catalyst sodium benzoate/magnesium acetate accounting for 0.9 percent of the total amount of the monomers are continuously added into a reactor from bottom to top at a certain flow rate, and acylation reaction is carried out in inert gas flow, wherein the reaction temperature is 120 ℃, and the retention time is controlled to be 220min.
(2) Atomizing and pre-polymerizing: :
conveying the acetylated monomer obtained in the step (1) and 10wt% of terephthalic acid (TPA) to a horizontal atomization reactor at a certain flow rate, spraying and atomizing under the pressure of 0.16MPa, and removing acetic acid to obtain a polyarylate prepolymer; the pushing angle of the arc-shaped plates along the axial center is 45 degrees, the distance between the arc-shaped plates is 50mm, the axial pushing rotating speed of the arc-shaped plates is 8r/min, and the thickness of the melt on the arc-shaped plates is 3.6mm; the temperature of the whole atomization reactor is controlled in 5 sections, the temperature is respectively set at 170, 200, 235, 275 and 290 ℃, and the retention time is 180min. The horizontal atomization reactor is protected under inert gas.
(3) Reaction type double-screw final polymerization and pressure-stabilizing conveying:
continuously inputting the polyarylate prepolymer into a double screw with the length-diameter ratio of 55; 2 devolatilization ports are arranged at the middle rear part of the double screw, and the double screw is vacuumized, and the pressure is controlled to be 16KPa; the residence time of the melt in the twin-screw was about 45min and the head pressure was 7.5MPa.
(4) Metering of spinning box and slow cooling forming of lower strand silk of spinneret plate
The polyarylate melt is metered by a metering pump in a spinning box body, and is subjected to slow cooling solidification under a spinneret plate after being distributed and filtered, wherein the ring slow cooling height is 150mm, and the atmosphere temperature of a slow cooling zone is 220 ℃.
(5) Winding of the nascent yarn
Oiling and winding the solidified polyarylate nascent fiber at the winding speed of 500m/min.
Example 5:
embodiment 5 of the present invention provides a method for preparing polyarylate as-spun yarns by continuous polymerization, comprising the steps of:
(1) Acetylation:
60wt% of p-hydroxybenzoic acid (HBA), 16wt% of Hydroquinone (HQ) and 122% of acetic anhydride (Ac) of the total amount of the monomers 2 O) and catalyst tin acetate accounting for 0.3 percent of the total amount of the monomers are continuously added into a reactor with a certain flow rate and a reactor with a lower inlet and an upper outlet, and acylation reaction is carried out under inert gas flow, wherein the reaction temperature is 180 ℃, and the retention time is controlled to be 160min.
(2) Atomization prepolymerization:
conveying the acetylated monomers obtained in the step (1) and 12wt% of terephthalic acid (TPA) and 12wt% of isophthalic acid (IPA) into a horizontal atomization reactor at a certain flow rate, and spraying, atomizing and removing acetic acid under the pressure of 0.30MPa to obtain a polyarylate prepolymer; the pushing angle of the arc-shaped plates along the axial center is 55 degrees, the distance between the arc-shaped plates is 35mm, the axial pushing rotating speed of the arc-shaped plates is 5r/min, and the thickness of the melt on the arc-shaped plates is 0.8mm; the temperature of the whole atomization reactor is controlled in 6 sections, the temperature is respectively set at 185, 235, 255, 285, 310 and 320 ℃, and the retention time is 300min. The horizontal atomization reactor is protected under inert gas.
(3) Reaction type double-screw final polymerization and pressure-stabilizing conveying:
continuously inputting the polyarylate prepolymer into a double screw with the length-diameter ratio of 35, wherein the double screw is provided with 8 temperature control sections, and the temperatures are respectively set to 300, 310, 320, 330, 340, 350 and 355 ℃; 2 devolatilization ports are arranged at the middle rear part of the double screw, and the double screw is vacuumized, and the pressure is controlled to be 1KPa; the residence time of the melt in the twin-screw was about 25min and the head pressure was 6.0MPa.
(4) Metering of spinning box and slow cooling forming of lower strand silk of spinneret plate
The polyarylate melt is metered by a metering pump in a spinning box body, and is subjected to slow cooling solidification under a spinneret plate after being distributed and filtered, wherein the ring slow cooling height is 380mm, and the atmosphere temperature in a slow cooling area is 305 ℃.
(5) Winding of the nascent yarn
And oiling and winding the solidified polyarylate nascent fiber at the winding speed of 750m/min.
Example 6:
embodiment 6 of the present invention provides a method for preparing polyarylate as-spun yarns by continuous polymerization, comprising the steps of:
(1) Acetylation:
55.6wt% of p-hydroxybenzoic acid (HBA), 29.3wt% of 2-hydroxy-6-naphthoic acid (HNA) and 10.0wt% of 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPOHQ), acetic anhydride (Ac) in a total amount of 116% of the monomers 2 O) and 0.4 percent of catalyst sodium benzoate/calcium acetate of the total amount of the monomers are continuously added into a reactor from bottom to top according to a certain flow rate, and acylation reaction is carried out in inert gas flow, wherein the reaction temperature is 160 ℃, and the retention time is controlled to be 60min.
(2) Atomizing and pre-polymerizing:
adding 5.1wt% of terephthalic acid (TPA) into the acetylated monomer obtained in the step (1), conveying the acetylated monomer to a horizontal atomization reactor at a certain flow rate, spraying, atomizing and removing acetic acid under the pressure of 0.28MPa to obtain a polyarylate prepolymer; the pushing angle of the arc-shaped plates along the axial center is 50 degrees, the distance between the arc-shaped plates is 60mm, the axial pushing rotating speed of the arc-shaped plates is 18r/min, and the thickness of the melt on the arc-shaped plates is 3.2mm; the temperature of the whole atomization reactor is controlled in 5 sections, the temperature is respectively set at 175, 225, 250, 270 and 285 ℃, and the residence time is 210min. The horizontal atomization reactor is protected under inert gas.
(3) Reaction type double-screw final polymerization and pressure-stabilizing conveying:
continuously inputting the polyarylate prepolymer into a double screw with the length-diameter ratio of 45, wherein the double screw is provided with 8 temperature control sections, and the temperatures are respectively set to be 280 ℃, 290, 295, 300, 305, 310 and 310 ℃; 2 devolatilization ports are arranged at the middle rear part of the double screw, and the double screw is vacuumized, and the pressure is controlled to be 4KPa; the residence time of the melt in the twin-screw was about 30min and the head pressure was 7.9MPa.
(4) Metering of spinning box and slow cooling forming of lower strand silk of spinneret plate
The polyarylate melt is metered by a metering pump in a spinning box body, and is subjected to slow cooling solidification under a spinneret plate after being distributed and filtered, wherein the ring slow cooling height is 350mm, and the atmosphere temperature of a slow cooling area is 120 ℃.
(5) Winding of the nascent yarn
The cured polyarylate as-spun yarn was oiled and wound up at a winding speed of 1150m/min.
Example 7:
polyarylate raw silk having a fineness of 1680dtex, a number of 480f (1680 dtex/480 f), and a fineness CV value of 3.6% was prepared by the method of example 1; the strength was 10.9cN/dtex, and the b value was 5.
One application area for the polyarylate raw filaments of example 1 after heat treatment includes high tensile cords.
Example 8:
polyarylate raw silk having a fineness of 1100dtex, a number of pieces of 360f (1100 dtex/360 f), and a fineness CV value of 5.8% was prepared by the method of example 2; the strength was 4.2cN/dtex, and the b value was 7.
The polyarylate as-spun yarn of example 2 is heat-treated and mainly applied to a special tire cord and the like.
Example 9:
polyarylate raw silk having a fineness of 360dtex, a number of 210f (360 dtex/210 f) and a fineness CV value of 8.3% was prepared by the method of example 3; the strength was 3.2cN/dtex, and the b value was 6.
The polyarylate raw silk of example 3 is subjected to heat treatment, and the application fields thereof are mainly safety protection materials, airship skins and the like.
Example 10:
polyarylate raw yarn having a fineness of 22dtex, a number of the filaments of 5f (22 dtex/5 f), and a fineness CV value of 4.1% was prepared by the method of the above example 4; the strength was 4.8cN/dtex, and the b value was 5.
The polyarylate raw silk of the embodiment 4 is mainly applied to a 5G copper clad laminate, a reinforcing material of a wire and a cable, and the like after being subjected to heat treatment.
Example 11:
a polyarylate raw yarn having a fineness of 480dtex, a number of 240f (480 dtex/240 f) and a fineness CV value of 4.8% was obtained by the method of the above example 5; the strength was 3.7cN/dtex, and the b value was 7.
The polyarylate raw yarn of example 5 is subjected to heat treatment, and the application field thereof is mainly a reinforcing material for an optical cable and the like.
Example 12:
polyarylate raw silk having a fineness of 3600dtex, a number of the filaments of 800f (3600 dtex/800 f) and a fineness CV value of 6.2% was prepared by the method of example 6; the strength was 8.9cN/dtex, the b value was 6.
A polyarylate raw yarn obtained in the above step 6 is cut into a short fiber having a cut length of 38 to 102mm by heat treatment, and is mainly used for a high-temperature felt.
Example 13:
the horizontal atomization reactor in the above embodiments 1 to 6 has the following specific structure:
as shown in fig. 1, the horizontal atomization reactor comprises a stirring cage 1 and a spraying device 2; the spraying device 2 is fixedly arranged on the stirring cage 1; the stirring cage 1 comprises a conveying pipe 11 with a closed cavity; the two ends of the conveying pipe 11 are respectively provided with a feeding hole 111 and a discharging hole 112; the feed inlet 111 and the discharge outlet 112 are communicated with the inner space and the outer space of the conveying pipe 11; the spraying device 2 is hermetically fixed at the feed inlet 111; the spraying device 2 comprises a plurality of spraying pipes 21; the spray pipe 21 extends into the conveying pipe through the feed opening 111.
When the horizontal atomization reactor provided by embodiment 5 of the invention works, polyarylate acetylated monomers are arranged in the spraying device 2, the polyarylate acetylated monomers can enter the conveying pipe 11 from the feed inlet 111 of the stirring cage 1 in a mist mode when the spraying device 2 works, the stirring cage 1 works, the mist of polyarylate acetylated monomers in the conveying pipe 11 is fully stirred, and the stirred polyarylate acetylated monomers finally flow out from the discharge outlet 112; the conveying pipe for providing a stirring field for the polyarylate acetylated monomers is provided with the closed cavity, and the closed cavity can control the environment of vacuum degree and nitrogen filling pressure, so that the polyarylate acetylated monomers can be fully stirred and mixed, ester exchange can be better completed, and the polyarylate prepolymer can be obtained.
In order to realize the complete mixing of the polyarylate acetylated monomers in the conveying pipe 11, in this embodiment, the stirring cage 1 further comprises a rotating shaft 12 and an arc-shaped plate 13; the rotating shaft 12 is arranged coaxially with the conveying pipe 11; the rotating shaft 12 is rotatably arranged in the conveying pipe 11; the arc-shaped plate 13 is arranged in the conveying pipe 11; the arc-shaped plate 13 is spirally fixed on the rotating shaft 12; all the blades of the stirring cage 13 are arranged along the axial direction of the rotating shaft 12. When the polyarylate acetylated monomers are stirred, the rotating shaft 12 needs to be rotated to drive the arc-shaped plate 13 to rotate, the polyarylate acetylated monomers enter the conveying pipe 11 from the feed port 111 in a mist form and are suspended in the conveying pipe 11, the arc-shaped plate 13 which continuously rotates can stir the air flow in the conveying pipe 11, so that the suspended polyarylate acetylated monomers in the mist form violently move to collide, and then the polyarylate acetylated monomers are fully contacted to complete ester exchange; the arc-shaped plate 13 is fixed on the rotating shaft 12 in a spiral manner, when the rotating shaft 12 rotates, the airflow in the conveying pipe 11 can be blown by the arc-shaped plate 13 towards one direction, and the direction of the airflow is the direction of the arrangement position of the discharge hole 112 on the conveying pipe 11; the outlet 112 has a vertically downward opening to facilitate the flow of fluid (the pressure inside the delivery tube 11 can be ensured by providing a check valve at the outlet 112, and the apparatus can produce part of the polyarylate purified monomer droplets while squeezing the polyarylate acetylation monomer gas; or the outlet 112 can be closed during the production process, and the outlet 112 can be opened to take out the liquid once after the compression of the liquid is completed).
The polyarylate acetylated monomers are fed into the feeding pipe 11 by the spraying device 2 in the form of mist, and since the mist of polyarylate acetylated monomers will sink under the action of gravity, in order to make the polyarylate acetylated monomers contact the arc plate 13 sufficiently, in this embodiment, the axis of the rotating shaft 12 is arranged horizontally; the outlet of the spray pipe 21 is arranged opposite to the rotating shaft 12; the spray pipe 21 is arranged vertically above the rotating shaft 12; outlets of all the spray pipes 21 are arranged along the axial direction of the rotating shaft 12; the discharge port 112 is disposed vertically below the rotary shaft 12. The polyarylate acetylated monomer mist is thrown vertically above the rotating shaft 12, the polyarylate acetylated monomer mist can sink under the action of gravity, and the arc-shaped plate 13 can contact the sunk polyarylate acetylated monomer mist when rotating around the rotating shaft 12, so that the polyarylate acetylated monomer mist is better mixed, and the ester exchange is facilitated; after the operation is completed, the rotation of the rotating shaft 12 is stopped, and the mist of the polyarylate acetylated monomers falls down by gravity and flows out from the outlet 112 located vertically below the rotating shaft.
In order to make the fog of the polyarylate acetylated monomers condense into liquid better and flow out from the discharge hole 112, the spacing distance between the arc-shaped plates 13 is different in the embodiment; the interval between the arc plates 13 is the largest near one end of the spray pipe 21 provided with the feed port 111; the interval between the arc plates 13 is minimum near one end of the spray pipe 21 provided with the discharge port 112; the distance between the adjacent arc plates 13 decreases from the inlet 111 to the outlet 112. When the rotating shaft 12 rotates, the polyarylate acetylated monomer mist is continuously pushed towards the discharge port 112, the space between the two arc plates 13 is continuously reduced, when the polyarylate acetylated monomer mist moves towards the discharge port 112, the polyarylate acetylated monomer mist in a unit space will be increased, the polyarylate acetylated monomer mist is easier to condense to form larger droplets, the droplets are easier to fall under the action of larger gravity, and finally move towards the discharge port 112 until the droplets flow out, the interval between the polyarylate acetylated monomer mist and the discharge port 13 is continuously reduced, so that the polyarylate acetylated monomer mist can be extruded into larger droplets in the rotating process of the rotating shaft 12 and finally flow out from the discharge port 112, the rotation of the rotating shaft 12 is not stopped, the mist needs to stand and completely drip, and the working efficiency of the device is improved.
In order to drive the rotating shaft 12 to rotate, as a preferable scheme, in the embodiment, the motor 3 for driving the rotating shaft is further included; the driving shaft of the motor 3 is coaxially arranged with the rotating shaft 12; the driving shaft of the motor 3 is fixedly connected with the rotating shaft 12. The mode of directly rotating the driving shaft through the motor 3 to drive the rotating shaft 12 to rotate has simple structure and easy installation and maintenance, and the rotating speed of the rotating shaft 12 can be directly controlled by controlling the rotating speed of the motor 3.
Because the rotating shaft 12 inside the conveying pipe 11 is working, the air inside is also agitated, if the air and the final solution of the polyarylate acetylated monomers flow out from the discharge port 112 together, the solution at the discharge port 112 is sprayed, which is not beneficial for collection, and in order to solve this drawback, in this embodiment, the conveying pipe 11 is further provided with a plurality of exhaust holes 113 for exhausting air; the exhaust hole 113 is arranged vertically above the rotating shaft 12; a check valve is arranged on the exhaust hole 113; the gas at the gas discharge hole 113 can flow only from the inside of the duct 11 to the outside of the duct 11. The air vent 113 can exhaust the air flow inside the conveying pipe 11, and on the other hand, the air inside the conveying pipe 11 can be sucked through the air vent 113 in advance to change the vacuum degree inside the conveying pipe 11, so that the reaction can be better carried out.
In conclusion, according to the preparation method of the polyarylate raw yarn for continuous polymerization spinning, provided by the invention, the homogenization pre-polymerization is carried out through the acetylation reaction in the monomer kettle, the atomization spraying in the horizontal atomization reactor and the arrangement of the arc-shaped plate, so that the specific surface area of the polymer is increased, the devolatilization is accelerated, the polymerization reaction speed is improved, the reaction time is shortened, and the polyarylate prepolymer has high uniformity; then connecting double screws for final polymerization, directly spinning polyarylate primary yarns after rapid viscosity increasing and pressure stabilizing, and implementing closed non-oxidation continuous production in the whole process so as to avoid oxidation in the gap polymerization process; the horizontal atomization reactor is adopted for prepolymerization, and the double-screw reactor is adopted for final polymerization, so that the reaction speed is increased, the reaction temperature is reduced, the rod climbing effect caused by a vertical reaction kettle is avoided, and the occurrence of side reaction is reduced; and the method is further beneficial to the stability and uniformity of the polymer spun raw silk, namely, the polyarylate raw silk with high stability and good uniformity can be obtained, and a solid foundation is provided for the stable quality of polyarylate fibers obtained by post-heat treatment of the raw silk.
Compared with the prior art for preparing the polymer and spinning the as-spun silk in a sectional manner, the invention has the advantages of continuous production, compact equipment, small occupied area, and obviously reduced investment cost and production and operation cost.
The above description is of the preferred embodiment of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, in that devices and structures not described in detail are understood to be implemented in a manner common in the art; it will be understood by those skilled in the art that various changes and modifications may be made, or equivalents may be modified, without departing from the spirit of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention, unless the content of the technical solution of the present invention is departed from.
Claims (10)
1. A method of making continuous polymer spun polyarylate raw filament comprising the steps of:
(1) Acetylation:
continuously adding a phenolic hydroxyl group-containing monomer, acetic anhydride and a catalyst into a reactor, performing acetylation reaction under the protection of inert gas at 120-185 ℃, staying for 30-240 min, and obtaining an acetylated monomer after acetylation reaction;
wherein the molar ratio of the phenolic hydroxyl group-containing monomer to the acetic anhydride is 3:1-1:1;
(2) Atomizing and pre-polymerizing:
adding or not adding aromatic dicarboxylic acid monomer into the acetylated monomer obtained in the step (1), continuously conveying the acetylated monomer into a horizontal atomization reactor, and carrying out spray atomization and deacetylation under the protection of inert gas and the pressure of 0.12-0.36 Mpa to obtain polyarylate prepolymer; controlling the temperature inside the horizontal atomization reactor to be 170-320 ℃, and controlling the retention time to be 30-300 min;
the horizontal atomization reactor has a spraying atomization function and comprises an arc-shaped plate;
(3) Double-screw final polymerization extrusion:
continuously inputting the polyarylate prepolymer obtained in the step (2) into a double-screw extruder with the length-diameter ratio of 30-75; the reaction temperature in the double-screw extruder is 255-355 ℃, the retention time of the polyarylate melt in the double screws is 25-45 min, and the head pressure of the double-screw extruder is 6-10 MPa;
(4) Melt spinning:
carrying out melt spinning on the polyarylate melt obtained in the step (3) through a spinning box, a metering pump and a spinneret plate, and winding to obtain polyarylate primary yarns; wherein, the polyarylate is extruded by a spinneret orifice and then is subjected to ring slow cooling solidification, the ring slow cooling height is 100-380 mm, and the slow cooling temperature is 120-315 ℃.
2. The method of preparing continuous polymer spun polyarylate raw yarn as claimed in claim 1, wherein the catalyst in the step (1) is one or more of carboxylate, complex of sodium, potassium, zinc, calcium, magnesium, titanium, tin and antimony.
3. The method of preparing continuous polymer spun polyarylate raw yarn as claimed in claim 1, wherein the temperature of the horizontal atomization reactor is controlled in 4 to 6 stages in step (2).
4. The method of preparing a continuous polymerization spun polyarylate raw yarn as claimed in claim 1, wherein the horizontal atomization reactor in the step (2) is provided at each of the middle end and the rear end with a rectifying device for removing a large amount of acetic acid generated by the reaction.
5. The method of preparing a continuous polymer spun polyarylate raw yarn as claimed in claim 1, wherein the advancing angle of the arc plate in the axial center in the step (2) is 35 to 85 °, the interval of the arc plates is 35 to 120mm, the rotating speed of the axial advancing of the arc plate is 5 to 25r/min, and the thickness of the melt on the arc plate is 0.8 to 4.2mm.
6. The method of preparing continuous polymer spun polyarylate raw yarn as claimed in claim 1, wherein in the step (3), the twin screw extruder is provided with 8 to 12 temperature control sections, and the middle rear portion of the twin screw extruder is further provided with at least 2 devolatilization ports.
7. The method of preparing continuous polymer spun polyarylate raw yarn as claimed in claim 1, wherein the winding speed in the step (4) is 500 to 1500m/min.
8. Polyarylate raw silk obtained by the method of any of claims 1 to 7, wherein the total fineness of the polyarylate raw silk is 10 to 3600dtex and the cv value is not more than 10%.
9. The polyarylate raw silk of claim 8, wherein said polyarylate raw silk has a b value of not more than 8.
10. The polyarylate raw yarn of claim 8, wherein the polyarylate raw yarn has a breaking strength of 3 to 11cN/dtex.
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| CN114106301A (en) * | 2021-12-22 | 2022-03-01 | 中原工学院 | High-performance liquid crystal high-molecular polymer and preparation method and application thereof |
| CN114134590A (en) * | 2021-12-30 | 2022-03-04 | 浙江甬川聚嘉新材料科技有限公司 | High-performance liquid crystal polyarylester fiber and preparation method and production equipment thereof |
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| EP0035895A2 (en) * | 1980-03-10 | 1981-09-16 | Celanese Corporation | Semi or fully continuous process for preparation of polyester by transesterification polymerization |
| EP0123377A2 (en) * | 1983-02-16 | 1984-10-31 | Amoco Corporation | Polycondensation process |
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| US20200370205A1 (en) * | 2018-11-29 | 2020-11-26 | Seyang Polymer | Method for manufacturing wholly aromatic liquid-crystalline polyester fiber with enhanced spinnability |
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