CN102071493B - Method for preparing thermotropic liquid crystal polyarylester fiber - Google Patents
Method for preparing thermotropic liquid crystal polyarylester fiber Download PDFInfo
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- CN102071493B CN102071493B CN2011100224831A CN201110022483A CN102071493B CN 102071493 B CN102071493 B CN 102071493B CN 2011100224831 A CN2011100224831 A CN 2011100224831A CN 201110022483 A CN201110022483 A CN 201110022483A CN 102071493 B CN102071493 B CN 102071493B
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Abstract
The invention relates to a method for preparing thermotropic liquid crystal polyarylester fiber, in particular to a method for spinning high molecular weight thermotropic liquid crystal polyarylester doped with low molecular weight thermotropic liquid crystal polyarylester, which comprises the processes of raw material drying, fused spinning and post treatment. The method provided by the invention is characterized in that 1 to 15 wt percent of low molecular weight thermotropic liquid crystal polyarylester is contained in the spinning raw materials, and the rest materials are the high molecular weight thermotropic liquid crystal polyarylester, wherein the logarithmic viscosity number of the high molecular weight thermotropic liquid crystal polyarylester is 3.54 to 3.98 dL/g, and the logarithmic viscosity number of the low molecular weight thermotropic liquid crystal polyarylester is 2.58 to 2.90 dL/g. The method provided by the invention can be used for preparing the polyarylester fiber with excellent performance such as high-temperature resistance, self fire resistance, high intensity, high modulus and the like. When being adopted, the method provided by the invention has the characteristics that the fiber forming and forming performance of the thermotropic liquid crystal polyarylester can be effectively improved, and the production cost is reduced.
Description
Technical field
The present invention relates to a kind of thermotropic liquid crystal polyarylate fiber preparation method, particularly relate to a kind of HMW thermotropic liquid crystal polyarylate fiber preparation method that is mixed with low molecular weight thermotropic liquid crystal polyarylate.
Background technology
The thermotropic liquid crystal polyarylate is the one type of TLCP that after 20th century, the mid-1970s was with the liquid crystal polyamide, grows up.With thermotropic liquid crystal polyarylate heating and melting and when being in anisotropic liquid crystal state and flowing through spinneret orifice owing to receive shear action; The rigid macromolecule of polyarylate main chain is orientated; This high orientation texture can be good at keeping after leaving spinneret orifice; Thereby the gained undrawn yarn has just had more stable orientation texture; Need not first break draft or low power drawing-off, after heat treatment, the reasons such as the further raising of regularity that further polymerization and orientation unit take place between strand cause the intensity of fiber and modulus to improve greatly.Owing to have groups such as phenyl ring, ester bond in the molecular backbone; The thermotropic liquid crystal polyarylate can be prepared high-strength and high-modulus; Or even the liquid crystal fiber of the strong superelevation mould of superelevation; Can be applicable to the reinforcing material of heating line in optical fiber, communication cable, special electric wire, the heating blanket, can make protective clothing, protective cover, protective plate, protection walls, safety cap and high temperature resistance and high strength protective gloves etc.In addition, also can make the filtering material of high temperature resistant acid-proof, alkali prevention.That this fiber has is in light weight, intensity is high, moisture-proof is warm, abrasion performance, makes good operation performance behind the cable, can replace the steel wire cable also to can be used as the material that fishing net also can be used as the sports articles for use.But there is above group in the liquid crystal main chain just; Cause the thermotropic liquid crystal polyarylate often to have very high glass transition temperature and higher relatively melt temperature; The process window temperature of polyarylate is generally narrower in addition, and in very little temperature range, its viscosity takes place significantly to change; The precision of spinning equipment etc. is required high, these defectives have just influenced the spinning preparation of thermotropic liquid crystal polyarylate.
Can therefore broadening process window temperature be perhaps added and is had a certain amount of high temperature additive or the low-melting point liquid crystal macromolecule reduces its viscosity, improve the spinning flowability and become one of the key factor that prepare thermotropic liquid crystal polyarylate fiber smoothly.In Chinese patent 200680046533 and patent 86106830, once mentioned and came the modification polyarylate with siloxanes; Or utilize silicone block copolymer to come the modification polyarylate, in the process of carrying out spinning, form the silicone block copolymer clad and give fiber unique excellent properties.And in this patent be made full use of low-molecular-weight thermotropic liquid crystal polyarylate in thermotropic liquid crystal polyarylate melting process since its molecular weight relatively low, good fluidity can effectively improve the effect of the rheological behaviour of system.And in the process of back the thermotropic liquid crystal polyarylate of these relatively low molecular weight polymerization reaction take place and cause its molecular weight to improve again, can not cause tangible influence to the performance of fiber.
Summary of the invention
The purpose of this invention is to provide a kind of thermotropic liquid crystal polyarylate fiber preparation method; The high viscosity thermotropic liquid crystal polyarylate that is mixed with low molecular weight thermotropic liquid crystal polyarylate spinning process particularly is provided, the present invention can prepare have high temperature resistant, from the polyarylate fiber of premium properties such as fire-retardant, high-strength and high-modulus.Utilize method of the present invention, can effectively improve the one-tenth fibre and the processability of thermotropic liquid crystal polyarylate, characteristics such as reduce production costs.
A kind of thermotropic liquid crystal polyarylate fiber preparation method of the present invention; Comprise spinning material drying, melt spinning and last handling process; The low molecular weight thermotropic liquid crystal polyarylate that contains 1-15wt% in the spinning material, all the other are HMW thermotropic liquid crystal polyarylate;
Wherein, the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.54～3.98dL/g;
The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.58～2.90dL/g.
As optimized technical scheme:
Wherein, aforesaid a kind of thermotropic liquid crystal polyarylate fiber preparation method, the dried moisture content of described spinning material is lower than 20ppm, preferred 10ppm or following.The dry employing of described spinning material vacuumize, the vacuumize temperature has just begun to be 80-160 ℃, is warming up to 110-190 ℃ after 1-2 hour, constant temperature 5-10 hour, guarantee that the moisture content of polyarylate is lower than 10ppm, exist otherwise in fiber, have bubble.
Aforesaid a kind of thermotropic liquid crystal polyarylate fiber preparation method, the screw rod heating-up temperature of described melt spinning is respectively: feed zone 220-250 ℃, melting zone 280-420 ℃, compressional zone 280-420 ℃, spin manifold temperature is consistent with the compressional zone temperature.
Aforesaid a kind of thermotropic liquid crystal polyarylate fiber preparation method, described post processing is for to heat-treat under vacuum state or under inert gas shielding, and heat treatment temperature is 250-300 ℃, and heat treatment time is 10-20 hour; 1～1.8 times of drafting multiple.
Aforesaid a kind of thermotropic liquid crystal polyarylate fiber preparation method; The whole process of described post processing is divided into a plurality of temperature sections distributions and carries out; Promptly under the following 30-40 of spinning temperature ℃ vacuum state, heat-treated 8-20 hour earlier; Do not carry out drawing-off, the molecular weight of thermotropic liquid crystal polyarylate is further improved; Under spinning temperature 10-20 ℃ then, under the protection of inert gas, heat-treated drafting multiple 1～1.2 3-20 hour; Perhaps be higher than spinning temperature 2-8 ℃ at spinning temperature at last, under inert gas shielding, heat-treat, drafting multiple is 1～1.2.
Because its viscosity pole was low when the thermotropic liquid crystal polyarylate reached a certain temperature section; This moment is the most favourable to the processing spinning, but temperature range is very narrow, restive; No matter be lower than this temperature or be higher than this temperature, (3-8 ℃) viscosity can obviously become big in very little variations in temperature.Therefore if guarantee in this temperature section, to carry out spinning, then very high to the requirement of spinning machinery.The thermotropic liquid crystal polyarylate that adds relatively low molecular weight because the lower and good fluidity of its molecular weight, can effectively improve the rheological behaviour of system, makes the broadening of processing temperature scope.Low-molecular-weight thermotropic liquid crystal polyarylate is formed identical with the used thermotropic liquid crystal polyarylate of spinning; And further polymerization can take place in low molecular weight thermotropic liquid crystal polyarylate in the process of fiber production processing and post processing; Its molecular weight significantly improves, and therefore can not cause tangible influence to fibre property.
Beneficial effect
The thermotropic liquid crystal polyarylate that adds relatively low molecular weight; The good fluidity because its molecular weight is lower; Can effectively improve the rheological behaviour of system; Make the broadening of processing temperature scope, it is narrow effectively to solve the process window temperature that runs into when spinning is carried out in the section of thermotropic liquid crystal polyarylate, to the high difficult problem of fibre spinning process equipment required precision.Utilize this method, on conventional spinning equipment, just can prepare the thermotropic liquid crystal polyarylate fiber of excellent performance.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The spinning material of HMW thermotropic liquid crystal polyarylate that will contain low molecular weight thermotropic liquid crystal polyarylate and the 99wt% of 1wt% carries out vacuumize; The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.58dL/g, and the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.84dL/g; It is 90 ℃ that the vacuumize temperature has just begun, and is warming up to 130 ℃ after 1 hour, constant temperature 10 hours, moisture content 12ppm.Carry out melt spinning then, the screw rod heating-up temperature of melt spinning is respectively: 250 ℃ of feed zones, 290 ℃ of melting zones, 290 ℃ of compressional zones, 290 ℃ of spin manifold temperatures.Carry out post processing behind the spinning moulding again, described post processing is for to heat-treat under inert gas shielding, and temperature is 275 ℃, and heat treatment time is 20 hours; 1.2 times of drafting multiples; Obtain thermotropic liquid crystal polyarylate fiber, intensity is 900MPa, and modulus is 30GPa, and the fiber logarithmic viscosity number is 4.02dL/g.
Embodiment 2
The spinning material of HMW thermotropic liquid crystal polyarylate that will contain low molecular weight thermotropic liquid crystal polyarylate and the 97.5wt% of 2.5wt% carries out vacuumize; The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.90dL/g, and the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.98dL/g; It is 90 ℃ that the vacuumize temperature has just begun, and is warming up to 190 ℃ after 1 hour, constant temperature 10 hours, moisture content 9ppm.Carry out melt spinning then, the screw rod heating-up temperature of melt spinning is respectively: 250 ℃ of feed zones, 293 ℃ of melting zones, 293 ℃ of compressional zones, 295 ℃ of spin manifold temperatures.Carry out post processing behind the spinning moulding again,, heat-treated under the vacuum state 20 hours, do not carry out drawing-off earlier at 260 ℃; At 290 ℃, heat-treat drafting multiple 1.1 then under the inert gas shielding; At 300 ℃, heat-treat under the inert gas shielding at last, drafting multiple is 1.1 times.Obtain thermotropic liquid crystal polyarylate fiber, intensity is 1.5GPa, and modulus is 45.4GPa, and its logarithmic viscosity number is 4.18dL/g.
Embodiment 3
The spinning material of HMW thermotropic liquid crystal polyarylate that will contain low molecular weight thermotropic liquid crystal polyarylate and the 95wt% of 5wt% carries out vacuumize; The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.90dL/g, and the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.98dL/g; It is 90 ℃ that the vacuumize temperature has just begun, and is warming up to 110 ℃ after 1 hour, 10 hours moisture content 12ppm of constant temperature.Carry out melt spinning then, the screw rod heating-up temperature of melt spinning is respectively: 220 ℃ of feed zones, 285 ℃ of melting zones, 285 ℃ of compressional zones, 286 ℃ of spin manifold temperatures.Carry out post processing behind the spinning moulding again, described post processing is for to heat-treat under inert gas shielding, and heat treatment temperature is 250 ℃, 1.2 times of drafting multiples; Obtain thermotropic liquid crystal polyarylate fiber, intensity is 903MPa, and modulus is 34.2GPa, and the fiber logarithmic viscosity number is 4.04dL/g.
Embodiment 4
The spinning material of HMW thermotropic liquid crystal polyarylate that will contain low molecular weight thermotropic liquid crystal polyarylate and the 85wt% of 15wt% carries out vacuumize; The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.90dL/g, and the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.54dL/g; It is 90 ℃ that the vacuumize temperature has just begun, and is warming up to 190 ℃ after 1 hour, constant temperature 10 hours, moisture content 10ppm.Carry out melt spinning then, the screw rod heating-up temperature of melt spinning is respectively: 250 ℃ of feed zones, 285 ℃ of melting zones, 285 ℃ of compressional zones, 285 ℃ of spin manifold temperatures.Carry out post processing behind the spinning moulding again, under 250 ℃ of vacuum environments, heat-treated 20 hours earlier, do not carry out drawing-off; At 270 ℃, heat-treat 1.1 times of drafting multiples then under the inert gas shielding; At 290 ℃, heat-treat 1.2 times of drafting multiples at last under the inert gas shielding.Obtain thermotropic liquid crystal polyarylate fiber, intensity is 752MPa, and modulus is 21.4GPa, and the fiber logarithmic viscosity number is 3.86dL/g.
Embodiment 5
The spinning material of HMW thermotropic liquid crystal polyarylate that will contain low molecular weight thermotropic liquid crystal polyarylate and the 99wt% of 1wt% carries out vacuumize; The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.58dL/g, and the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.98dL/g; It is 90 ℃ that the vacuumize temperature has just begun, and is warming up to 130 ℃ after 1 hour, 5 hours constant temperature of constant temperature 10 hours, moisture content 11ppm.Carry out melt spinning then, the screw rod heating-up temperature of melt spinning is respectively: 240 ℃ of feed zones, 290 ℃ of melting zones, 290 ℃ of compressional zones, 290 ℃ of spin manifold temperatures.Carry out post processing behind the spinning moulding again.Described post processing is for to heat-treat under inert gas shielding, and heat treatment temperature is 300 ℃, and heat treatment time is 20 hours; 1.8 times of drafting multiples.Obtain thermotropic liquid crystal polyarylate fiber at last, intensity is 852MPa, and modulus is 37GPa, and the fiber logarithmic viscosity number is 4.02dL/g.
Embodiment 6
The spinning material of HMW thermotropic liquid crystal polyarylate that will contain low molecular weight thermotropic liquid crystal polyarylate and the 95wt% of 5wt% carries out vacuumize; The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.58dL/g, and the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.98dL/g; It is 90 ℃ that the vacuumize temperature has just begun, and is warming up to 130 ℃ after 1 hour, constant temperature 12 hours, moisture content 10ppm.Carry out melt spinning then, the screw rod heating-up temperature of melt spinning is respectively: 240 ℃ of feed zones, 290 ℃ of melting zones, 290 ℃ of compressional zones, 290 ℃ of spin manifold temperatures.Carry out post processing behind the spinning moulding again,, heat-treated under the vacuum environment 20 hours, do not carry out drawing-off earlier at 250 ℃; At 270 ℃, heat-treat 1.1 times of drafting multiples then under the inert gas shielding; At 290 ℃, heat-treat 1.2 times of drafting multiples at last under the inert gas shielding.Obtain thermotropic liquid crystal polyarylate fiber, intensity is 998MPa, and modulus is 39.2GPa, and the fiber logarithmic viscosity number is 4.09dL/g.
Embodiment 7
The spinning material of HMW thermotropic liquid crystal polyarylate that will contain low molecular weight thermotropic liquid crystal polyarylate and the 95wt% of 5wt% carries out vacuumize; The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.65dL/g, and the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.90dL/g; It is 90 ℃ that the vacuumize temperature has just begun, and is warming up to 130 ℃ after 1 hour, constant temperature 12 hours, moisture content 11ppm.Carry out melt spinning then, the screw rod heating-up temperature of melt spinning is respectively: 240 ℃ of feed zones, 289 ℃ of melting zones, 289 ℃ of compressional zones, 290 ℃ of spin manifold temperatures.Carry out post processing behind the spinning moulding again, described post processing is under inert gas shielding, and heat treatment temperature is 278 ℃, 1.6 times of drafting multiples; Obtain thermotropic liquid crystal polyarylate fiber, intensity is 884MPa, and modulus is 36.3GPa, and the fiber logarithmic viscosity number is 4.00dL/g.
Claims (5)
1. thermotropic liquid crystal polyarylate fiber preparation method; Comprise spinning material drying, melt spinning and last handling process; It is characterized in that: contain the low molecular weight thermotropic liquid crystal polyarylate of 1-15wt% in the spinning material, all the other are HMW thermotropic liquid crystal polyarylate;
Wherein, the logarithmic viscosity number of described HMW thermotropic liquid crystal polyarylate is 3.54～3.98dL/g;
The logarithmic viscosity number of described low molecular weight thermotropic liquid crystal polyarylate is 2.58～2.90dL/g.
2. a kind of thermotropic liquid crystal polyarylate fiber preparation method according to claim 1 is characterized in that the dried moisture content of described spinning material is lower than 20ppm.
3. a kind of thermotropic liquid crystal polyarylate fiber preparation method according to claim 1; It is characterized in that the screw rod heating-up temperature of described melt spinning is respectively: feed zone 220-250 ℃, melting zone 280-420 ℃; Compressional zone 280-420 ℃, spin manifold temperature is consistent with the compressional zone temperature.
4. a kind of thermotropic liquid crystal polyarylate fiber preparation method according to claim 1; It is characterized in that; Described spinning temperature is 280-420 ℃; The whole process of described post processing is divided into three temperature sections carries out step by step, promptly earlier at the following 30-40 of spinning temperature ℃, under vacuum state, heat-treats 8-20 hour; Under spinning temperature 10-20 ℃ then, under inert gas shielding, to heat-treat, drafting multiple is 1～1.2 times; Perhaps be higher than spinning temperature 2-8 ℃ at spinning temperature at last, heat-treat in inert gas shielding, drafting multiple is 1～1.2.
5. a kind of thermotropic liquid crystal polyarylate fiber preparation method according to claim 1 is characterized in that described post processing is for to heat-treat under inert gas shielding, heat treatment temperature is 250-300 ℃, and heat treatment time is 10-20 hour; 1～1.8 times of drafting multiple.
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| CN103160953B (en) * | 2013-03-15 | 2016-06-08 | 武汉纺织大学 | A kind of short process making method of liquid crystal polyarylester raw nano fiber |
| CN104389045B (en) * | 2014-11-04 | 2016-05-18 | 黑龙江聚翔科技开发有限公司 | A kind of preparation method of Thermotropic Liquid Crystalline Copolyesters fiber |
| CN106591997B (en) * | 2016-12-23 | 2019-04-09 | 宁波海格拉新材料科技有限公司 | A method of improving thermotropic liquid crystal polyarylate fiber heat treatment efficiency |
| CN110184670B (en) * | 2019-05-21 | 2021-11-12 | 上海舟汉纤维材料科技有限公司 | Modified polyarylester spinning solution and spinning process |
| CN111101256A (en) * | 2019-12-27 | 2020-05-05 | 上海普利特化工新材料有限公司 | Liquid crystal polymer woven fabric and preparation method thereof |
| WO2024016304A1 (en) * | 2022-07-22 | 2024-01-25 | Ticona Llc | Stator winding for an electric power system |
| CN116063806A (en) * | 2022-12-31 | 2023-05-05 | 浙江威思康塑胶有限公司 | High-temperature wear-resistant sheath material and preparation method thereof |
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Application publication date: 20110525 Assignee: ZHEJIANG TRI-STAR SPECIAL TEXTILE CO., LTD. Assignor: Donghua University Contract record no.: 2015330000226 Denomination of invention: Method for preparing thermotropic liquid crystal polyarylester fiber Granted publication date: 20120620 License type: Common License Record date: 20150812 |
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