CN102443873B - Aromatic copolyester liquid crystal fiber and its preparation method - Google Patents
Aromatic copolyester liquid crystal fiber and its preparation method Download PDFInfo
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- CN102443873B CN102443873B CN 201110283218 CN201110283218A CN102443873B CN 102443873 B CN102443873 B CN 102443873B CN 201110283218 CN201110283218 CN 201110283218 CN 201110283218 A CN201110283218 A CN 201110283218A CN 102443873 B CN102443873 B CN 102443873B
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Abstract
The invention discloses an aromatic copolyester liquid crystal fiber and a preparation method thereof, the fiber comprises the following groups, the logarithmic viscosity number is 3.98-5.94dl/g. The preparation method comprises the steps of raw material pretreating, drying, melt spinning, post-treating and the like. Nascent fiber is subjected to stable heating inert gas treatment containing nonionic substance after spinning, fiber is subjected to pretreatment of heating and immersing by an inorganic bittern solution, and a heat treatment is carried out. According to the invention, the high-molecular solid phase polycondensation of the product is complete, and the aromatic polyester high molecular chain is in a micro fiber structure with high order formed by a straight rigid chain, the strong interaction is existed between the molecules, thereby high tensile strength and modulus of the fiber can be endowed. The aromatic copolyester liquid crystal fiber has the characteristics of unique moisture and heat resistance performance, vibration attenuation performance, excellent acid and alkali resistance and wear resistance performances, and is more applicable under harsh environment. The fiber can be widely used for high performance composite material enhanced fiber, marine cable, optical cable reinforced member and the like.
Description
Technical field
The invention belongs to the high-performance fiber production technical field, relate to a kind of preparation method based on the thermotropic liquid crystal fiber on the petchem basis, more particularly relate to a kind of aromatic copolyester liquid crystal fiber and preparation method thereof.
Background technology
Early 1960s, du pont company is that raw material is through low-temperature polycondensation with p-benzoyl chlorine, the complete fragrant amide polymer (PBA) that the preparation contraposition replaces, find that simultaneously PBA can generate the liquid crystal polymer with good spinnability, this discovery so that the high mould lysotropic liquid crystal of high-temperature-resistant high fiber product come out, such as Kevlar series commodity.But the lysotropic liquid crystal fiber is because adopt the solution spinning, and there is the problem of solvent recovery simultaneously in the spinning technique more complicated.Therefore Thermotropic Liquid Crystal Fibers causes the interest that the various countries researcher is larger.
Aromatic polyester and long filament have been announced among the US-4347349A; high molecular building-up process has mainly been described; only introduced then about the preparation of long filament that under inert gas shielding melt to be stretched as fineness be the fibrous of 0.5tex; Technology for Heating Processing is 200 ℃ of lower 2h; 200～304 ℃ of lower 7h, 304 ℃ of lower 7h.Preferred 300～400 ℃ of lower melt spinnings, heat treatment 0.5～30h in 100～350 ℃ scope have been set forth under 250～450 ℃ among the US-4503005A.Introduced the melt spinning process of aromatic polyester fiber among the US-4743416A, by the Control Nozzle extrusion pressure at 3kgf/cm
2Or more than, promote fiber to have preferably orientation, give fiber higher strength and modulus.Although above report about the aromatic polyester fiber preparation method very early, but because aromatic polyester just produces crystallization under molten condition, and melt cooling is especially short hardening time, to such an extent as to make at short notice fiber have height-oriented being difficult to, so adopt above simple melt spinning Technology for Heating Processing, can not obtain the ideal tensile strength that its rigid structure should possess.
Summary of the invention
The purpose of this invention is to provide a kind of aromatic copolyester liquid crystal fiber and preparation method thereof, solved problems of the prior art, prepare high performance aromatic copolyester liquid crystal fiber.
The technical solution used in the present invention is that a kind of preparation method of aromatic copolyester liquid crystal fiber comprises preparation process: the operations such as pretreatment of raw material, drying, melt spinning and post processing below are detailed description and the explanation of each operating procedure:
1, the selection of raw material
The said aromatic copolyester liquid crystal fiber of the present invention comprises following construction unit, A in its raw molecule structure:
B:
Wherein to account for mass percent be that to account for percentage by weight be 20～70% to 10～70%, B to A.All the other structures do not limit, and are conventional structure.The logarithmic viscosity number of aromatic copolyester liquid crystal polymer is 2.5～5.94dl/g, preferred 3.98～5.94dl/g.Fracture strength (cN/dtex) is 12-20, and elongation at break (%) is 2.2-3.8.
2, pretreatment of raw material
The aromatic copolyester liquid crystal is carried out the negative pressure High Temperature Pre process, extract raw material surface and inner small-molecule substance, wherein pretreatment temperature is 120～200 ℃, 2～12 hours processing times, and condition of negative pressure is-0.07～-0.1MPa.
3, heating and melting
Heating and melting step of the present invention is the multi-portion heating melting, and by melt-shaping, wherein melting divides multi-region through pretreated macromolecule, be 3～15 districts, preferred 3～8 districts, melt temperature is 285～360 ℃, melting time is 200～600s, and hauling speed is 800-2000m/min.
4, spinning process
Spinning uses resin after melting, spinning head ejection from fused spinning assembling parts, melt forms the melt thread after the spinning head ejection, and the air set moulding below spinning head, as-spun fibre is interior through one section stable atmosphere in the distance of distance spinning nozzle 0～50cm, this gas is nitrogen or helium, and pass through external heat, make the temperature of this atmosphere remain on 90～350 ℃, preferred 90～160 ℃, and in the distance of distance spinning nozzle 50～550cm, force cooling curing, force 15～28 ℃ of cooling curing temperature.
5, heat treatment process
Fiber is heat-treated by the heating dipping pretreatment of inorganic halide salting liquid again, and the heat treatment process fiber can be lax or tense situation, also can finish under anxiety+relaxation condition.Described heat treatment temperature is 200～320 ℃, and the processing time is 0.5～360 hour, and the time is 1-15 hour preferably.The heating atmosphere is under nitrogen or the vacuum condition, and vacuum is-0.05～0.1MPa.Fiber passed through first the dipping heating pretreatment of inorganic halide salting liquid before heat treatment step, treatment temperature is 50～120 ℃, and the processing time is 0.5～3h.Described inorganic halide salting liquid is alkali metal or alkaline earth metal halide salt, is sodium, potassium, calcium or magnesium salts, and concentration of salt solution is mass percent 5%～30%.
By the method, aromatic copolyester liquid crystal fiber generation solid state polycondensation improves molecular weight.The low-molecular material of the solid state polycondensation that heat treatment occurs is that medium accelerates to take away by decompression or inert gas, guarantee that solid phase polycondensation is the single direction reaction, avoid occuring reversible reaction, behind the heat treatment solid phase polycondensation, so that the aromatic polyester high molecular further increases, the amorphous phase system is further perfect towards the crystalline phase system, the aromatic polyester macromolecular chain is the orderly microfibrillar structure of rigid chain height of formation that stretches, and there is strong interaction force between the macromolecule, thereby given fiber very high TENSILE STRENGTH and modulus.
Liquid crystal fiber of the present invention has high DIMENSIONAL STABILITY, extremely low regain and good counter-bending fatigue and crocking resistance.This aromatic copolyester liquid crystal fiber Application Areas is very wide, can be used to the industries such as fishery, aviation, is used for making cable line, net rope, plastics reinforcing material, parachute line, various sporting equipment, gloves for protection etc.
The present invention is by selecting molecular structure, lower-molecular substance is extracted in pretreatment of raw material, and as-spun fibre taked the stable heated inert gas treatment that contains the nonionic material, fiber is the heating pretreatment of Salts in Synthetic Lubricants supersaturated solution by inorganic halide, carry out again high temperature negative pressure or inert gas shielding heat treatment, increase crystal, improve crystalline structure, promote that amorphous area changes to the crystalline region.By the present invention, the rigid chain that the aromatic polyester macromolecular chain is stretch forms high strength, high-modulus, structurally ordered little fibril supramolecular structure, and the stronger interaction of intermolecular existence, thus given fiber very high TENSILE STRENGTH and modulus.And the high temperature with uniqueness is done, damp and hot mechanical performance, high-strength and high-modulus, and low vibration attenuation performance and good acid and alkali-resistance, chemical-resistant reagent burn into abrasion resistance properties, fiber of the present invention is preferably to be used under adverse circumstances thereby give.
The present invention is described in detail below in conjunction with the specific embodiment.As known by the technical knowledge, the present invention can realize by other the embodiment that does not break away from its Spirit Essence or essential feature, so following embodiment is with regard to each side, all just illustrate, be not only, all within the scope of the present invention or the change that is equal in the scope of the present invention all be included in the invention.The equipment that the equipment of in the present invention all uses is conventional equipment or obtains through simply not needing to spend creative work.
The specific embodiment
Embodiment 1
In the spinning technique method of aromatic copolyester fibre of the present invention, the logarithmic viscosity number of its Raw is 3.98dl/g, and pretreatment condition is negative pressure, is preliminary treatment under 120 ℃ the condition of negative pressure in temperature, and pressure is-0.09MPa that the processing time is 4h.Pretreated raw material is by melting spinning (equipment is prior art equipment, and following examples are identical), and melting divides 5 districts to carry out, and the melt temperature scope is 285～310 ℃, carries out spinning by the hauling speed of 1000m/min.As-spun fibre is interior through one section stable nitrogen atmosphere in the distance of distance spinning nozzle 0～20cm, makes its atmosphere temperature remain on 90 ℃ by external heat.With the reel silk fiber after the spinning under the environment of 60 ℃ of Nacl solution the dipping after, heat treatment 1h under relaxation condition, heat treatment temperature is 230 ℃.
Embodiment 2
In the spinning technique method of aromatic copolyester fibre of the present invention, the logarithmic viscosity number of its Raw is 4.20dl/g, and pretreatment condition is negative pressure, is preliminary treatment under 150 ℃ the condition of negative pressure in temperature, and pressure is-0.08MPa that the processing time is 4h.Pretreated raw material is by the melting spinning, and melting divides 5 districts to carry out, and the melt temperature scope is 305～320 ℃, carries out spinning by the hauling speed of 1200m/min.As-spun fibre is interior through one section stable nitrogen atmosphere in the distance of distance spinning nozzle 0～30cm, makes its temperature remain on 110 ℃ by external heat.With the reel silk after the spinning at Mgcl
2After flooding under the environment that solution is 70 ℃, heat treatment 2h under relaxation condition, heat treatment temperature is 250 ℃.
Embodiment 3
In the spinning technique method of aromatic copolyester fibre of the present invention, the logarithmic viscosity number of its Raw is 4.90dl/g, and pretreatment condition is negative pressure, is preliminary treatment under 160 ℃ the condition of negative pressure in temperature, and pressure is-0.095MPa that the processing time is 8h.Pretreated raw material is by the melting spinning, and melting divides 8 districts to carry out, and the melt temperature scope is 315～330 ℃, carries out spinning by the hauling speed of 1500m/min.As-spun fibre is interior through one section stable helium atmosphere in the distance of distance spinning nozzle 0～40cm, and heating makes its temperature remain on 120 ℃.With the reel silk after the spinning at Mgcl
2After soaking under the environment that solution is 70 ℃, heat treatment 3h under nervous condition, heat treatment temperature is 240 ℃.
Embodiment 4
In the spinning technique method of aromatic copolyester fibre of the present invention, the logarithmic viscosity number of its Raw is 5.40dl/g, and pretreatment condition is negative pressure, is preliminary treatment under 170 ℃ the condition of negative pressure in temperature, and pressure is-0.09MPa that the processing time is 12h.Pretreated raw material is by the melting spinning, and melting divides 8 districts to carry out, and the melt temperature scope is 315～340 ℃, carries out spinning by the hauling speed of 1200m/min.As-spun fibre is interior through one section stable nitrogen atmosphere in the distance of distance spinning nozzle 0～50cm, and heating makes its temperature remain on 130 ℃.With the reel silk fiber after the spinning at Cacl
2After soaking under the environment that solution is 70 ℃, heat treatment 4h under nervous condition, heat treatment temperature is 210 ℃.
Embodiment 5
In the spinning technique method of aromatic copolyester fibre of the present invention, the logarithmic viscosity number of its Raw is 5.94dl/g, and pretreatment condition is negative pressure, is preliminary treatment under 190 ℃ the condition of negative pressure in temperature, and pressure is-0.1MPa that the processing time is 20h.Pretreated raw material is by the melting spinning, melting divides 10 districts to carry out, the melt temperature scope is 330～360 ℃, and as-spun fibre is interior through one section stable nitrogen atmosphere in the distance of distance spinning nozzle 0～50cm, makes its temperature remain on 150 ℃ by external heat.With the reel silk fiber after the spinning after soaking under the environment of 80 ℃ of KBr solution, heat treatment 10h under relaxation condition, heat treatment temperature is 220 ℃.
Each spinning case fibre property table of table 1.
Claims (6)
1. the preparation method of an aromatic copolyester liquid crystal fiber, before spinning, needing it is characterized in that the aromatic copolyester liquid crystal polymer High Temperature Pre that reduces pressure is processed, extract raw material surface and inner small-molecule substance and residual synthon, wherein pretreatment temperature is 120～280 ℃, 2～12 hours processing times, condition of negative pressure is-0.07～-0.1MPa, and as-spun fibre is interior through one section stable atmosphere in the distance of distance spinning nozzle 0～50cm, this atmosphere is nitrogen or helium, and pass through external heat, make the temperature of this atmosphere remain on 90～350 ℃, and in the distance of distance spinning nozzle 50～550cm, force cooling curing, force 15～28 ℃ of cooling curing temperature;
Comprise following construction unit, A in the described aromatic copolyester liquid crystal fiber molecular structure:
Wherein A account for mass percent be 10～70%, B to account for percentage by weight be 20～70%, logarithmic viscosity number is 2.5～5.94dl/g, fracture strength is 12-20cN/dtex, elongation at break is 2.2-3.8%.
2. the preparation method of aromatic copolyester liquid crystal fiber according to claim 1, it is characterized in that passing through melt-shaping through pretreated macromolecule, wherein melting divides multi-region, be 3～15 districts, melt temperature is 285～360 ℃, melting time is 200～600s, and hauling speed is 800-2000m/min.
3. the preparation method of aromatic copolyester liquid crystal fiber according to claim 1, the fiber that it is characterized in that winding shaping need to pass through further heat treatment, heat treatment process is finished under fiber anxiety or relaxation condition, or finishes under anxiety+relaxation condition.
4. the preparation method of aromatic copolyester liquid crystal fiber according to claim 3, it is characterized in that described heat treatment temperature is 200～320 ℃, processing time is 0.5～360h, and the heating atmosphere is under nitrogen or the vacuum condition, vacuum is-0.05～-0.1MPa.
5. the preparation method of aromatic copolyester liquid crystal fiber according to claim 3 is characterized in that fiber before heat treatment step, passed through first the dipping heating pretreatment of inorganic halide salting liquid, and treatment temperature is 50～120 ℃, and the processing time is 0.5～3h.
6. the preparation method of aromatic copolyester liquid crystal fiber according to claim 5, it is characterized in that described inorganic halide salting liquid is alkali metal or alkaline earth metal halide salt, be in sodium, potassium, calcium or the magnesium salts one or more, concentration of salt solution is mass percent 5%～30%.
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| CN106592002A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Liquid crystal polyester fiber and preparation method thereof |
| CN106087177B (en) * | 2016-08-26 | 2018-06-08 | 四川省纺织科学研究院 | A kind of continuous solid phase polycondensation heat treatment method of liquid crystalline polyester fiber |
| EP3626868A4 (en) * | 2017-07-24 | 2020-06-10 | Kuraray Co., Ltd. | Liquid crystalline polyester fiber and method for producing same |
| CN107938014B (en) * | 2017-11-30 | 2020-04-28 | 中原工学院 | Preparation method of flame-retardant liquid crystal polyester fiber |
| CN107938013B (en) * | 2017-12-22 | 2019-07-23 | 江南大学 | A kind of preparation method of temperature response type liquid crystal fiber |
| CN110498760B (en) * | 2019-08-28 | 2023-06-23 | 东华大学 | Aromatic thermosetting liquid crystal fiber and preparation method thereof |
| 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 |
| CN111139547A (en) * | 2019-12-31 | 2020-05-12 | 上海普利特化工新材料有限公司 | Preparation method of wholly aromatic liquid crystal polyester nascent fiber |
| CN111364109B (en) * | 2020-01-20 | 2023-10-10 | 宁波海格拉新材料科技有限公司 | Fiber heat treatment reaction device, heat treatment system and heat treatment method |
| CN111441139B (en) * | 2020-03-27 | 2022-07-05 | 四川东方绝缘材料股份有限公司 | Preparation method of liquid crystal polymer film |
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| US4743416A (en) * | 1984-12-10 | 1988-05-10 | Sumitomo Chemical Company, Limited | Melt spinning process of aromatic polyester |
| CA2073838A1 (en) * | 1992-07-14 | 1994-01-15 | Giuseppe Motroni | Thermotropic liquid crystal aromatic polyesters |
| US5945216A (en) * | 1998-09-10 | 1999-08-31 | Celanese Acetate Llc | Process for making high denier filaments of thermotropic liquid crystalline polymers and compositions thereof |
| CN1271110C (en) * | 2004-08-26 | 2006-08-23 | 复旦大学 | Solid phase polymerization preparation method of liquid crystal copolyester |
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