WO2020177322A1 - 纺丝的方法和装置 - Google Patents

纺丝的方法和装置 Download PDF

Info

Publication number
WO2020177322A1
WO2020177322A1 PCT/CN2019/110820 CN2019110820W WO2020177322A1 WO 2020177322 A1 WO2020177322 A1 WO 2020177322A1 CN 2019110820 W CN2019110820 W CN 2019110820W WO 2020177322 A1 WO2020177322 A1 WO 2020177322A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil bath
liquid medium
tank
temperature
storage tank
Prior art date
Application number
PCT/CN2019/110820
Other languages
English (en)
French (fr)
Inventor
邓杭军
周贵阳
俞孟飞
王国伟
Original Assignee
浙江新和成特种材料有限公司
绍兴裕辰新材料有限公司
浙江新和成股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江新和成特种材料有限公司, 绍兴裕辰新材料有限公司, 浙江新和成股份有限公司 filed Critical 浙江新和成特种材料有限公司
Publication of WO2020177322A1 publication Critical patent/WO2020177322A1/zh

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins

Definitions

  • the invention belongs to the field of production methods of chemical textile products, and specifically relates to a production method and production equipment of fiber materials, and more specifically, to a resin with a higher glass transition temperature, especially a production method of polyarylene sulfide fiber And device.
  • Polyarylene sulfide (PAS) resin has excellent heat resistance, shielding properties, chemical resistance, electrical insulation, humidity and heat resistance and other properties suitable for engineering plastics.
  • PAS polyarylene sulfide
  • PPS polyphenylene sulfide
  • PPS fiber is a new type of special plastic fiber, which is made of polyphenylene sulfide resin (PPS) using conventional melt spinning methods, and then post-processing at high temperature. It can be made of filaments, monofilaments, Yarn, staple fiber, etc. Short fiber can be obtained by crimping and cutting after stretching. Short fiber properties: strength 2.65 ⁇ 3.08 cN/dtex, elongation 25% ⁇ 35%, melting point 285°C, excellent thermal stability and flame retardancy , Oxygen index value 34-35, strength retention rate at 200 °C 60%, no change in elongation at break; chemical resistance second only to polytetrafluoroethylene (PTFE) fiber; good textile processing performance.
  • the products are mainly used for the filtration of high-temperature flue gas and special heating media, drying belts in the paper industry, cable coatings and fire-resistant fabrics, etc.
  • the woven fabric can be used to make advanced fire-fighting clothing.
  • the excellent performance of PPS itself also puts forward new requirements for the current fiber forming process.
  • Most synthetic fibers such as polyamides, polyesters and polyolefins, have a low glass transition temperature during the production process, so the temperature is usually set at 60-80°C during the oil bath drawing process.
  • the glass transition temperature of PPS is relatively high.
  • the temperature is usually set between 90 and 98°C.
  • the liquid medium in the oil bath is heated in the oil bath low tank, and then transferred to the oil bath by a pump, and then returned to the oil bath low tank for recycling.
  • tank valve to adjust the level of liquid in the oil bath.
  • this model has problems: 1. Because the glass transition temperature of PPS is high, the heating temperature needs to be above 90 °C, and such high temperature liquid medium is pumped from the low tank to the oil bath tank. In the middle, when water or mixed solvents are used as the medium, cavitation is prone to occur, and usually causes the temperature fluctuation of the liquid medium in the oil bath to exceed ⁇ 3°C; 2. When driving or parking, it is necessary to use a pump or The valve introduces or draws a large amount of high temperature liquid medium into or out of the oil bath, which is inefficient and uneconomical.
  • Reference 1 discloses a drafting bath heating device, including a drafting bath having a water inlet and a water outlet, a pipe, and an oil boiler, an oil bath, and a water pump.
  • the oil boiler is connected to the oil bath through the pipe to form one Closed circulating oil circuit, said closed oil circuit contains heat conduction oil; said oil bath is connected to the water inlet and outlet of the drafting bath through a pipe, and the water pump draws the water in the oil bath through the pipe. Extend the water in the bath to transfer.
  • it adopts the method of separating the oil bath and the drafting bath to make the temperature in the drafting bath more uniform and convenient for the drafting, it is still necessary to heat the water and transport it through a water pump, and inject the hot water directly Oil bath.
  • Reference 2 discloses an oil bath tow drawing device, which includes a front drafting machine roller device, a rear drafting machine roller device, and an intermediate heating device.
  • the intermediate heating device is set on the front drafting machine. Between the roller device and the roller device of the rear drafting machine, the intermediate heating device is an oil bath. The two ends of the oil bath are respectively provided with dipping rollers.
  • the dipping roller is correspondingly provided with a guide roller and the front drafting machine roller device , The roller device of the rear drafting machine is connected; this device can prevent the tow from sticking to each other, facilitate the subsequent tow to split and stack and crimp, facilitate disassembly and maintenance, and can also reduce the generation of waste silk. But it does not involve circulation and transportation as a heating medium.
  • the technical problem to be solved by the present invention is how to maintain uniform heating during fiber drawing in the resin spinning or resin fiber drawing process that requires high temperature heating.
  • the heating temperature is precisely controllable, to avoid the damage of the quality of the fiber in the oil bath due to the high temperature transmission of the heating medium, and to avoid the problem of insufficient utilization of the heating medium caused by the drastic change of the heating medium flow when the equipment is started or stopped .
  • the present invention also relates to how to provide a method for producing high-quality spun fibers, especially polyarylene sulfide spun fibers.
  • the present invention first provides a resin spinning method, including:
  • the fiber formed by the resin or its composition is introduced into the liquid medium of the oil bath,
  • the liquid medium flows from the oil bath storage tank into the oil bath tank, and the liquid medium flowing out of the oil bath tank flows into the low temperature tank,
  • the temperature of the liquid medium in the oil bath storage tank is higher than the temperature of the liquid medium in the cryogenic tank
  • the present invention also provides an oil bath device for resin spinning, including:
  • the oil bath tank, oil bath storage tank and low temperature tank are connected by pipelines and valves.
  • the glass transition temperature of the resin is 85°C or higher, and preferably the resin is a polyarylene sulfide resin.
  • the device further comprising a delivery pump to deliver a liquid medium, the liquid medium being sent from the cryogenic tank to the oil bath storage tank by the delivery pump in.
  • the oil bath storage tank has a heating device to heat the liquid medium, and the liquid medium is heated by the heating device in the oil bath storage tank. Heating, preferably the liquid medium is heated to above 90°C.
  • the heating temperature of the liquid medium in the oil bath storage tank is easy to control, and can flow into the oil bath at a stable flow rate through the valve, which can avoid the influence of the heat convection in the oil bath on the quality of the fiber. Moreover, the temperature in the oil bath can be controlled more accurately by controlling the flow rate or flow rate of the hot liquid medium flowing into the oil bath.
  • the low-level tank in the present invention may not heat the liquid medium or only perform proper preheating (The temperature does not exceed 80°C), therefore, the low-level tank in the prior art is also called a low-temperature tank in the present invention.
  • the low temperature liquid medium is transported from the low temperature tank through the pump, which avoids the high temperature loss of the pump when the pump is used to transport the high temperature medium in the traditional process; at the same time, the heating efficiency is increased, so that a large amount of high temperature liquid medium can be transferred in a short time. It is possible to introduce an oil bath.
  • Figure 1 Diagram of an oil bath used in polyarylene sulfide spinning or fiber drawing in the prior art
  • Figure 2 A diagram of an oil bath used for polyarylene sulfide spinning or fiber drawing in the present invention.
  • the left is the top view
  • the right is the front view
  • the first aspect of the present invention relates to a resin spinning method.
  • the type of resin there is no particular limitation on the type of resin as long as the glass transition temperature of the resin is 85°C or higher, preferably 90°C or higher.
  • the first aspect of the present invention is particularly suitable for spinning polyarylene sulfide resins and their compositions. More specifically, in some specific embodiments of the present invention, it relates to a method for stretching polyarylene sulfide fibers in an oil bath.
  • the repeating unit of the chain structure of polyarylene sulfide is -[-Ar-S-]- or a polymer with such repeating unit fragments.
  • the main chain structure of the molecule has an aryl group and a sulfide structure.
  • a collective term for a type of polymer This type of polymer has a series of excellent properties; such as excellent heat resistance, chemical resistance, radiation resistance, flame retardancy, excellent mechanical and electrical properties, and dimensional stability.
  • the polyarylene sulfide suitable for the present invention is not particularly limited, and may be various polyarylene sulfide generally suitable for spinning in the field.
  • the polyarylene sulfide of the present invention is not limited and can be selected from polyphenylene sulfide, polyarylene sulfide sulfone, polyarylene sulfide ketone, polyarylene sulfide nitrile, polyarylene sulfide amide, polyarylene sulfide A mixture of any one or more of ether sulfone amide, polyarylene sulfide ketone amide, or polyphenylene sulfide copolymer in any ratio.
  • the weight average molecular weight of the polyarylene sulfide resin that can be used in the present invention is not particularly limited. In some preferred embodiments, it can be 2.0 ⁇ 10 4 or more, 4.0 ⁇ 10 4 or more, 6.0 ⁇ 10 4 or more, and is usually 10.1 ⁇ 10 4 or less.
  • the polyarylene sulfide described in the present invention can also be used in conjunction with other resins to form a composition according to any needs, such as having compatibility with polyarylene sulfide Polyamide, polyimide or phenolic resin, etc.
  • the polyarylene sulfide of the present invention may also contain no more than 40% of other resin based on the total mass of the mixture or composition.
  • the polyarylene sulfide described in the present invention may also use fillers as reinforcing components, and these fillers may be inorganic particles, chopped fibers, and the like.
  • these fillers may be inorganic particles, chopped fibers, and the like.
  • chopped fibers it may be organic fibers or inorganic fibers, such as glass fibers, carbon fibers, and the like.
  • the polyarylene sulfide in the present invention may also contain various functional additives.
  • the functional auxiliary agent can be selected from one or more of antioxidants, antistatic agents, softeners, brighteners, light stabilizers, dyes or matting agents.
  • the spinning involved in the present invention can be carried out with the help of usual spinning or extrusion equipment in this field, and organic solvents can be used or used when necessary.
  • the optional organic solvents in the present invention are dimethyl sulfoxide, sulfolane, diphenyl sulfone, N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, cyclohexanone, and tetrachloride A mixture of at least one or more of ethane. In a preferred embodiment, these organic solvents may not be used in the present invention.
  • the polyarylene sulfide or its composition is spun by melting or by means of solvent.
  • polyarylene sulfide or its composition is extruded from a spinneret by heating to form fibers.
  • the polyarylene sulfide resin or its composition used as the spinning raw material can be mixed with optional additives and added to the extruder for blending and extrusion.
  • Extrusion of the polyarylene sulfide resin or its composition can use an extruder that usually processes polyarylene sulfide resin in the art. It is not particularly limited, but from the viewpoint of extrusion efficiency, a screw extruder is preferably used, and a twin screw extruder is more preferably used for extrusion.
  • each section of the extruder is set to 150-250°C in the first zone, 180-300°C in the second zone, and 180-350°C in the third zone, and the temperature of the extruder outlet die is 190-320°C, preferably 250- 300°C.
  • the extrusion rate is 0.1-2 m/s, preferably 0.5-1 m/s.
  • fibers are prepared through a spinneret or an extruder die, and these fibers are introduced into an oil bath through a pulling roller for further stretching.
  • the fiber is drawn by one or more draft rollers set in the oil bath, and the fiber is immersed in the liquid medium in the oil bath.
  • the liquid medium is not particularly limited, and includes various solvents and substances used for fiber surface treatment.
  • the solvent it can be selected from various solvents with a boiling point above 85°C, preferably above 90°C.
  • it can be selected from one or more of water, NMP, DMF, DMSO, DMAc or triethylene glycol;
  • water or an aqueous phase blending solvent is a blending solvent of water and one or more of NMP, DMF, DMSO, DMAc, triethylene glycol, etc., more preferably water.
  • the surface treatment substance is not particularly limited, and various commercially available substances for treating the fiber surface, such as finishing agents, can be used.
  • the temperature of the liquid medium in the oil bath is not particularly limited as long as the temperature is above the glass transition temperature Tg of the stretched polyarylene sulfide or its composition. In some specific embodiments of the present invention, the temperature of the liquid medium in the oil bath is above 90°C, preferably above 95°C.
  • the oil bath also has a heating device. Since the temperature of the liquid medium is higher than the glass transition temperature of the stretched resin or resin composition, the above-mentioned fiber can be drawn and stretched in an oil bath.
  • the drawing speed of the drawing roller is not particularly limited. By setting different speeds of multiple drawing rollers, fibers with different stretching effects can be obtained. According to the required fiber fineness, the required draft can also be set The number of rollers. In the present invention, the fineness range of the fiber obtained by drawing by the drafting roll can be 0.8-6.0D, preferably 1.0-5.0D.
  • the fiber obtained after spinning or extrusion may be stretched in at least one of the above-mentioned oil baths.
  • multiple oil baths of the same or different may be provided.
  • the oil bath is provided with an inlet and an outlet for the liquid medium.
  • the liquid medium outlet of the oil bath is connected to the cryogenic tank through a valve and pipeline, and the liquid medium inlet of the oil bath is connected to the oil bath storage tank through a valve and pipeline.
  • the outlet and inlet valves control the flow rate of the liquid medium into or out of the oil bath, and thus can control the temperature of the liquid medium in the oil bath.
  • the outlet is set at the bottom of the oil bath, and the low-temperature liquid medium is discharged from the bottom of the oil bath through the cold and hot convection of the medium, for example, when the liquid medium flows into the oil bath from the oil bath storage tank.
  • the liquid level of the liquid medium in the oil bath exceeds the standard.
  • the outlet valve at the bottom of the oil bath is opened, and the liquid medium inlet valve of the oil bath can be closed at the same time.
  • the outlet is set above the standard line of the liquid medium in the oil bath and close to the standard line. When the liquid level of the liquid medium in the oil bath exceeds the standard line, the excess liquid medium It is automatically discharged from the outlet.
  • the oil bath can have one or more liquid medium outlets, which can be respectively arranged at the bottom and above the standard line of the liquid medium level of the oil bath.
  • the oil bath tank may also have one or more liquid medium inlets, and these liquid medium inlets may all be connected to one oil bath storage tank through a pipeline, or may be respectively connected to multiple oil bath storage tanks through a pipeline.
  • the inlet can be as close as possible to the middle of the oil bath, or the inlet can be set as a movable inlet through regular reciprocating The movement transports the high-temperature liquid medium uniformly to all parts of the oil bath, or when there are multiple inlets, each inlet can be evenly distributed in different parts of the oil bath.
  • the oil bath can also have other auxiliary settings, such as liquid medium agitators, heat preservation equipment, etc.
  • the cryogenic liquid medium in the oil bath is introduced into the cryogenic bath through valves and pipes.
  • the cryogenic bath may be located below the oil bath, which is usually also called a low-level bath.
  • the cryogenic tank contains used or excess liquid medium, which has a relatively low temperature relative to the liquid medium in the oil bath.
  • the temperature of the liquid medium in the cryogenic tank can be maintained at 20 to 80°C, preferably 60 to 80°C.
  • a heat preservation device or a temperature heating device can be installed in the cryogenic tank, so that the temperature of the liquid medium is maintained within the above-mentioned temperature range. If the temperature is too low, it will cost money to transfer the cryogenic liquid medium to the oil bath storage tank through a subsequent pump. More energy is used for reheating, and if the temperature is too high, it is inevitable to use the pump to transfer high-temperature liquid medium, which may increase the loss of the pump.
  • the oil bath storage tank needs to be supplemented with liquid medium.
  • the low temperature liquid medium in the low temperature tank is transported to the oil bath storage tank through the pipeline through the pump, and It is heated to 90°C or higher in an oil bath storage tank, preferably 95°C or higher.
  • the arrangement of the oil bath storage tank avoids the direct heating of the liquid medium to a high temperature above 90°C in the low-level tank (corresponding to the low-temperature tank of the present invention) in the traditional design, and then the high-temperature liquid medium is directly heated by the pump. Defects caused by adding to the oil bath. On the one hand, it can avoid the use of pumps to transfer high-temperature liquid media, which avoids the mechanical loss of the pump. On the other hand, the liquid media transferred by the pump is input into the oil bath storage tank, and the oil bath storage tank plays a buffering role.
  • the problem of unstable and difficult-to-control liquid medium transmission caused by the start and stop of the secondary pump can also avoid the occurrence of cavitation caused by the transmission of high-temperature liquid medium.
  • the oil bath storage tank can be used as a buffer to avoid such transient liquid medium flow instability. Through the valve of the oil bath storage tank, the high temperature liquid medium can be delivered to the oil bath at a stable flow rate at any time. Therefore, the temperature of the liquid medium in the oil bath can be controlled more accurately. In a preferred embodiment of the present invention, the temperature fluctuation of the liquid medium in the oil bath can be controlled within ⁇ 1°C by the above method.
  • the second aspect of the present invention relates to an oil bath device for resin spinning, and the selection of the resin is the same as the first aspect of the present invention.
  • the device includes:
  • Oil bath oil bath storage tank and low temperature tank.
  • the resin fiber is processed by the liquid medium in the oil bath.
  • the liquid medium flows from the oil bath storage tank into the oil bath tank, and the liquid medium flowing out from the oil bath tank flows into the low temperature tank.
  • the existing process of using an oil bath for fiber drawing is shown in Figure 1.
  • the liquid medium in the oil bath has a certain temperature, its function is to stretch the raw silk in the groove to achieve a certain size, and use the liquid medium in the oil bath to protect The surface of the polymer prevents it from causing a large number of defects during stretching and is not conducive to subsequent processing.
  • the liquid medium heated in the low tank (corresponding to the low temperature tank of the present invention) can be pumped into the oil bath with a pump, and in the oil bath. Open the valve at one end to return the excess liquid medium to the lower tank for reuse. Through such an internal circulation method, it can be ensured that the tow in the oil bath is always below the liquid level, and the heating and stretching can be performed normally.
  • the prior art usually heats the liquid medium in the low-level tank, and then directly sends the hot liquid medium into the oil bath through the oil pump.
  • a resin with a higher glass transition temperature such as polyarylene sulfide resin fiber
  • the liquid medium in the cryogenic tank is transported to the oil bath using a pump
  • the liquid medium is first transported to the oil bath storage tank and heated in the oil bath storage tank to
  • the temperature required in the oil bath is the same or slightly higher, for example, above 90°C.
  • the oil bath in the device of the present invention includes at least one drafting roller for drawing and drawing the resin fiber tow.
  • the fiber is located below the liquid level of the liquid medium in the oil bath, the temperature of the liquid medium in the oil bath is above 90°C, and the oil bath is provided with an inlet and an outlet for the liquid medium and corresponding valves.
  • the settings of the inlet and outlet are the same as the first aspect of the present invention.
  • the temperature of the liquid medium in the oil bath decreases, it can be adjusted by flowing into the high temperature liquid medium and flowing out of the low temperature liquid medium.
  • the low-temperature liquid medium flows into the low-temperature tank through the valve and the pipeline. At this time, the temperature in the low-temperature tank is maintained at 20-80°C, instead of heating the medium directly above 90°C in the low-temperature tank as in the prior art.
  • an oil bath storage tank is added to the upper part of the oil bath tank.
  • the liquid medium in the low temperature tank can still be preheated to 20 ⁇ 80°C or 20 ⁇ 60°C or 20 ⁇ 50°C or 20 ⁇ 40°C (lower than the temperature of the liquid medium required in the oil bath), and pumped to the oil bath storage tank, then heated to above 90°C in the oil bath storage tank, and then introduced oil In the bath, the liquid medium reflux part can still be controlled by the valve to return to the cryogenic tank for internal circulation to achieve recycling.
  • the volume of the oil bath is set to 300L, and the solvent used is set to water.
  • the method shown in Figure 1 was used to add a liquid medium (a mixture of water and finishing agent) to the lower tank and heat it directly. After the temperature of the liquid medium in the lower tank reached 98°C, the The liquid medium is pumped into the oil bath tank by a water pump. The maximum flow rate of the water pump is 16m 3 /h and the power is 4Kw. The temperature of the liquid medium in the oil bath tank is maintained stable through circulation.
  • a liquid medium a mixture of water and finishing agent
  • the temperature of the liquid medium in the low-temperature tank (the same composition as the liquid medium in the control group) is controlled to 70°C, while the temperature of the liquid medium in the oil bath tank is controlled to 98°C.
  • the water pump used from the tank to the oil bath storage tank is the same as the control group.
  • the oil bath storage tank directly drains the liquid medium to the oil bath tank through valve control, and also uses circulation to maintain temperature stability.
  • the target temperature of the oil bath is set to 95°C, and the time of filling the oil bath with the liquid medium in different methods and the fluctuation of the liquid medium temperature after filling are respectively counted. The results are shown in the following table.
  • the time for the oil bath tank to fill the liquid level can be greatly shortened, which speeds up the operation speed when starting and stopping; in addition, during normal production, the temperature fluctuation is also greatly reduced compared with the control group. It has great advantages in improving the stability of the overall spinning process and the quality of the fiber.
  • the technical scheme of the present invention can be used in the production of polyarylene sulfide fiber in industry.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

一种纺丝的方法和装置。该方法和装置适用于具有较高玻璃化转变温度的聚芳硫醚纤维的生产，通过加入油浴储槽，能够保持纤维拉伸中受热均匀、且受热温度精确可控，避免由于加热介质的高温传输对于设备以及油浴槽中纤维的品质的损害，以及避免设备启动或停止时，开停车效率的降低以及加热介质流动的剧烈变动所导致的加热介质的利用率不充分的问题。

Description

纺丝的方法和装置 技术领域
本发明属于化工纺织产品的生产方法领域，具体涉及一种纤维材料的生产方法和生产设备，更具体而言，涉及具有较高玻璃化转变温度的树脂，尤其是聚芳硫醚纤维的生产方法和装置。
背景技术
聚芳硫醚(PAS)树脂具有优良的耐热性，屏蔽性，耐化学药品性，电绝缘性，耐湿热性等适合作为工程塑料的性质。作为聚芳硫醚的典型代表，聚苯硫醚(PPS)被广泛用于各种产品加工中。
其中，PPS纤维是一种新型特种塑料纤维，是由聚苯硫醚树脂(PPS)采用常规的熔融纺丝方法，然后在高温下进行后加工等即可制得，有长丝，单丝，纱线，短纤维等。拉伸后经过卷曲和切断可制得短纤维，短纤维性能：强度2.65～3.08厘牛/分特、伸长率25％～35％，熔点285℃，具有优异的热稳定性和阻燃性，氧指数值34～35，200℃时强度保持率为60％，断裂伸长无变化；耐化学性仅次于聚四氟乙烯(PTFE)纤维；有较好的纺织加工性能。制品主要用于高温烟道气和特殊热介质的过滤，造纸工业的干燥带以及电缆包胶层和防火织物等，其织布可以制作高级消防服装。
然而，PPS自身优异的性能也给目前对其纤维成型的工艺提出了新的要求。例如，在进行纺丝时，需要在油浴槽内对原丝纤维进行拉伸，以使其达到所需要的纤度，并且使分子链取向以增加纤维的强度。大多数的合成纤维，如聚酰胺，聚酯和聚烯烃等，在生产过程中，由于它们的玻璃化转变温度较低，因此在油浴拉伸过程中，温度通常设置为60～80℃。然而，PPS的玻璃化转变温度较高，原丝在油浴槽内进行加热拉伸时，温度通常设置为90～98℃之间。
通常，油浴槽的中的液体介质在油浴低位槽中进行加热，通过泵输送至油浴槽中，再回流至油浴低位槽进行循环使用，在开车或停车时，通过控制油浴槽回流至低位槽的阀门来调整油浴槽中液位的高低。在PPS纤维的生产过程中，这样的模式就出现了问题：1.由于PPS的玻璃化转变温度较高，加 热温度需要在90℃以上，而将如此高温的液体介质从低位槽抽至油浴槽中时，在使用水或者混合溶剂作为介质时，容易产生气蚀，且通常会导致油浴槽中液体介质的温度波动超过±3℃；2.开车或停车时，需在短时间内用泵或阀门将大量的高温液体介质引入或抽离油浴槽，效率低且不经济。
引用文献1公开了一种牵伸浴槽加热装置，包括具有进水口和出水口的牵伸浴槽、导管，还包括油锅炉、油浴槽和水泵，所述的油锅炉通过导管与油浴槽连接形成一个闭合的循环油路，所述的闭合油路内有导热油；所述的油浴槽通过导管分别与牵伸浴槽的进水口和出水口连接，所述的水泵通过导管将油浴槽的水和牵伸浴槽的水进行转移。尽管其采用了油浴槽和牵伸浴槽分离的方式，使得牵伸浴槽中的温度更加的均匀，方便牵伸的进行，但仍然需要将水加热后通过水泵将其输送，并将热水直接注入油浴槽。
引用文献2公开了一种油浴丝束拉伸装置，该装置包括前道牵伸机辊筒装置、后道牵伸机辊筒装置和中间加热装置，中间加热装置设置在前道牵伸机辊筒装置和后道牵伸机辊筒装置之间，中间加热装置为油浴槽，油浴槽的两端分别设置有浸渍辊，浸渍辊对应设置有一个导向辊与前道牵伸机辊筒装置、后道牵伸机辊筒装置相衔接；该装置可以防止丝束的相互粘结，方便后面的丝束分流堆叠卷曲，方便拆卸便于维修，也可以减少废丝的产生。但其并不涉及作为加热介质的循环和输送。
因此，尽管本领域中在纺丝拉伸工艺中处于稳定纤维拉伸时的温度，尝试了多种办法，但对于在纤维拉伸时加热装置的设置以及作为加热介质的循环设置仍然有进一步改进的余地。
引用文献：
引用文献1：CN202380141U
引用文献2：CN106757434A
发明内容
发明要解决的问题
针对上述本领域中在纺丝或纤维拉伸工艺中基本情况，本发明所要解决的技术问题在于对于需要高温加热的树脂纺丝或树脂纤维拉伸工艺中，如何保持纤维拉伸中受热均匀、且受热温度精确可控，避免由于加热介质的高温 传输对于油浴槽中纤维的品质的损害，以及避免设备启动或停止时，加热介质流动的剧烈变动所导致的加热介质的利用率不充分的问题。
此外，本发明也涉及如何提供一种生产高品质纺丝纤维、尤其是聚芳硫醚纺丝纤维的方法。
用于解决问题的方案
通过本发明发明人的大量研究，发现采用如下办法可以解决上述技术问题：
[1].本发明首先提供了一种树脂纺丝的方法，包括：
将树脂或其组合物形成的纤维引入油浴槽的液体介质中，
在所述液体介质中对所述纤维进行拉伸，
所述液体介质从油浴储槽中流入油浴槽，从油浴槽中流出的液体介质流入低温槽，
所述油浴储槽中的液体介质的温度高于所述低温槽中液体介质的温度，
[2].根据[1]所述的方法，所述液体介质通过输送泵被从所述低温槽送入所述油浴储槽中。
[3].根据[1]或[2]所述的方法，所述树脂的玻璃化转变温度为85℃以上，优选所述树脂为聚芳硫醚树脂。
[4].根据[1]～[3]任一项所述的方法，所述液体介质在所述油浴储槽中被加热，优选液体介质被加热到90℃以上。
[5].根据[1]～[4]任一项所述的方法，所述油浴槽中液体介质的温度为90℃以上；
[6].根据[1]～[5]任一项所述的方法，所述低温槽中的液体介质温度为20～80℃，优选60～80℃。
[7].进一步，本发明还提供了一种用于树脂纺丝的油浴装置，包括：
油浴槽，
油浴储槽，
低温槽，
所述油浴槽、油浴储槽和低温槽通过管路和阀门相连接。
[8].根据权利要求7所述的装置，其特征在于，所述树脂的玻璃化转变温度为85℃以上，优选所述树脂为聚芳硫醚树脂。
[9].根据[7]或[8]所述的装置，所述装置还包括输送泵以输送液体介质，所述液体介质通过输送泵被从所述低温槽送入所述油浴储槽中。
[10].根据[7]～[9]任一项所述的装置，所述油浴储槽具有加热装置以加热液体介质，所述液体介质在所述油浴储槽中通过加热装置被加热，优选液体介质被加热到90℃以上。
[11].根据[7]～[10]任一项所述的装置，所述油浴槽中还设置牵伸辊。
[12].根据[7]～[11]任一项所述的装置，所述装置中，液体介质从油浴储槽流入油浴槽，从油浴槽中流出的液体介质流入低温槽。
发明的效果
通过本发明上述方法的使用，在对聚芳硫醚的纺丝或纤维制备过程中可以获得如下的有益的技术效果：
1)本发明中，相对于现有的油浴槽设备，引入了独立的油浴储槽，在该油浴储槽中加热油浴用液体介质，加热后的液体介质通过阀门送入到油浴槽中，避免了由泵直接将热的液体介质送入到油浴槽中，因此，作为液体介质输送的缓冲容器，可以避免泵启停瞬间所导致热的液体介质的输送不稳定情况及气蚀的发生。
2)液体介质在油浴储槽中加热温度易于控制，并且，可以通过阀门能够以稳定流速流入到油浴槽中，能够避免油浴槽中由于热对流的加剧所导致对纤维的品质的影响。并且，通过控制流入油浴槽中的热的液体介质的流速或流量能够更精确的控制油浴槽中的温度。
3)与现有技术在低位槽中加热液体介质(与油浴槽中所预设处理温度接近或略高)不同，本发明中低位槽中可以不对液体介质进行加热或者是仅仅进行适当的预热(温度不超过80℃)，因此，本发明中也将现有技术中的低位槽称之为低温槽。从低温槽中将温度低的液体介质通过泵来进行输送， 避免了传统工艺中使用泵来输送高温介质时泵的高温损耗；同时也增加了加热的效率，使短时间内将大量高温液体介质引入油浴槽成为了可能。
附图说明
图1：现有技术中用于聚芳硫醚纺丝或纤维拉伸时油浴槽的示图；
图2：本发明中用于聚芳硫醚纺丝或纤维拉伸时油浴槽的示图。
以上图示中：左边是俯视图，右边是正视图。
具体实施方式
以下将对本发明所述的树脂纺丝方法及其设备进行详细说明。需要说明的是，除非特殊声明，本发明所使用的单位名称均为本领域通用的国际单位名称。此外，本发明以下出现的数值的点值或者数值范围均应当理解为包括了工业上允许的误差。
<本发明第一方面>
本发明的第一方面涉及一种树脂纺丝的方法，对于这样的树脂种类没有特别的限定，只要所述树脂的玻璃化转变温度为85℃以上，优选为90℃以上即可。本发明的第一方面尤其对聚芳硫醚树脂及其组合物的纺丝特别适用。更具体而言，在本发明一些具体的实施方案中，涉及一种在油浴槽中对聚芳硫醚纤维进行拉伸的方法。
聚芳硫醚或其组合物
聚芳硫醚(Polyarylene Sulfide，PAS)的链结构重复单元为-[-Ar-S-]-或具有此种重复单元片断的高分子聚合物，分子主链结构中以芳基和硫醚结构为主的一类高分子聚合物的统称。该类聚合物有一系列的优异性能；如优异的耐热性、耐化学腐蚀性、耐辐射、阻燃性、优良的力学、电学性能以及尺寸稳定性等。
对于适用于本发明的聚芳硫醚，没有特别的限定，可以是本领域通常适用于纺丝的各种聚芳硫醚。本发明所述的聚芳硫醚，不受限制的，可以选自 聚苯硫醚、聚芳硫醚砜、聚芳硫醚酮、聚芳硫醚腈、聚芳硫醚酰胺、聚芳硫醚砜酰胺、聚芳硫醚酮酰胺或聚苯硫醚的共聚物中的任一种或多种任意比例的混合物。
本发明可以使用的聚芳硫醚树脂的重均分子量没有特别的限定，在一些优选的实施方案中，可以为2.0×10 4以上、4.0×10 4以上、6.0×10 4以上，并且通常为10.1×10 4以下。
在一些具体的实施方案中，本发明所述的聚芳硫醚除了上述的聚合物以外，还可以根据任意需要，配合使用其他的树脂以形成组合物，例如具有与聚芳硫醚具有相容性的聚酰胺、聚酰亚胺或酚醛树脂等。优选的，本发明所述的聚芳硫醚除了聚芳硫醚本身以外，还可以包含不高于基于混合物或组合物总质量40％的其他树脂。
在另外一些具体的实施方案中，本发明所述的聚芳硫醚中还可以使用作为增强成分的填料，这些填料可以为无机颗粒、短切纤维等。对于短切纤维，其可以为有机纤维也可以为无机纤维，例如玻璃纤维、碳纤维等。
另外，不受限制的，本发明中的聚芳硫醚中，还可以包含各种功能性助剂。例如所述功能性助剂可以选自抗氧化剂、抗静电剂、柔顺剂、增白剂、光稳定剂、染料或哑光剂中的一种或多种。
纺丝
本发明所涉及的纺丝，可以借助本领域通常的纺丝或挤出设备而进行，在有必要的情况下可以借助或使用有机溶剂。
本发明中的可选的有机溶剂为二甲基亚砜、环丁砜、二苯砜、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基乙酰胺、环己酮和四氯乙烷中的至少一种或多种的混合。在优选的实施方案中，本发明可以不使用这些有机溶剂。
在一些具体的实施方案中，聚芳硫醚或其组合物通过熔融的方式或借助溶剂的方式进行纺丝。例如，聚芳硫醚或其组合物通过加热而被从喷丝板挤出以形成纤维。
在另外一些具体的情况下，作为纺丝原料的聚芳硫醚树脂或其组合物可 以与任选的添加剂进行混合，并被加入到挤出机中，进行共混挤出。聚芳硫醚树脂或其组合物的挤出，可以使用本领域通常加工聚芳硫醚树脂的挤出机。没有特别的限定，但从挤出效率考虑，优选使用螺杆挤出机，更优选使用双螺杆挤出机挤出。
挤出机中各段的温度设置为一区150-250℃，二区180-300℃，三区180-350℃，并且，挤出机出口模具的温度为190-320℃，优选为250-300℃。在本发明一些优选的实施方案中，挤出速率为0.1-2m/s，优选为0.5-1m/s。
油浴拉伸
上述纺丝中通过喷丝板或者挤出机模口制备得到纤维，这些纤维通过牵引辊被导入油浴槽中，进行进一步的拉伸。
通过设置在油浴槽中的一个或多个牵伸辊对纤维进行牵引，将纤维浸渍于油浴槽中的液体介质中。对于液体介质，没有特别的限定，其包括各种溶剂以及用于纤维表面处理的物质。对于溶剂，其可以选自沸点在85℃以上，优选为90℃以上的各种溶剂，通常根据需要，可以选自水、NMP、DMF、DMSO、DMAc或三甘醇的一种或多种；优选水或水相共混溶剂，所述水相共混溶剂为水和NMP、DMF、DMSO、DMAc、三甘醇等的一种或多种的共混溶剂，更优选水。对于表面处理的物质，没有特别限定，可以使用市售的各种用于处理纤维表面的物质，例如整理剂等。
对于油浴槽中液体介质的温度，只要其温度在所拉伸的聚芳硫醚或其组合物的玻璃化转变温度Tg以上，就没有特别的限定。在本发明一些具体的实施方案中，油浴槽中液体介质的温度在90℃以上，优选为95℃以上，任选的，油浴槽还具有加热装置。由于液体介质的温度高于所拉伸的树脂或树脂组合物的玻璃化转变温度，因此，上述纤维可以在油浴槽中被牵引和拉伸。对于牵引辊的牵引速度，没有特别的限定，通过对多个牵伸辊不同速率的设定，可以获得不同拉伸效果的纤维，根据所需的纤维纤度，也可以设定所需的牵伸辊的数量。本发明中，通过牵伸辊的拉伸，得到的纤维的纤度范围可以为0.8-6.0D，优选为1.0-5.0D。
本发明中，喷丝或挤出后得到的纤维，可以在至少一个上述的油浴槽中进行拉伸，在一些具体的实施方案中，可以设置相同或不同的多个油浴槽。
油浴槽中设置有液体介质的入口和出口。其中，油浴槽的液体介质的出口通过阀门、管路与低温槽相连接，油浴槽的液体介质入口通过阀门、管路与所述油浴储槽相连接。通过出口、入口的阀门控制液体介质流入或流出油浴槽的速率，并可以由此控制油浴槽中液体介质的温度。
在一些具体的实施方案中，所述出口被设置在油浴槽的底部，通过介质的冷热对流从底部将低温的液体介质排出油浴槽，例如当从油浴储槽流入油浴槽的液体介质造成油浴槽中液体介质的液面超出了标准，此时位于油浴槽底部的出口的阀门被打开，同时可以关闭油浴槽的液体介质入口阀门。
在另外一些具体的实施方案中，所述出口被设置在油浴槽液体介质的标准线之上、紧邻标准线处，当油浴槽中的液体介质液面超出了标准线时，则多余的液体介质自动从出口被排出。
优选的是，油浴槽可以具有一个或多个液体介质出口，可以分别设置在底部以及油浴槽液体介质液面标准线之上。同样，油浴槽也可以具有一个或多个液体介质入口，这些液体介质入口可以均与一个油浴储槽通过管路相连，也可以分别与多个油浴储槽通过管路相连接。对于液体介质入口设置的位置，没有特别的限定，但从控制油浴槽中液体介质温度均衡的角度考虑，入口可以尽量靠近油浴槽的中部，或者将入口设置为位置可移动入口，通过规律的往复运动将高温液体介质均匀的输送到油浴槽各部分，或者当具有多个入口时，可将各个入口均匀分布于油浴槽的不同部位。
不受限制的，油浴槽还可以具有其他辅助设置，例如液体介质搅动器，保温设备等。
油浴槽中低温液体介质通过阀门和管道被引入低温槽中，在一些实施方案中所述低温槽位可以位于油浴槽的下方，通常也可以叫做低位槽。低温槽盛放使用过的或者多余出的液体介质，这些液体介质相对于油浴槽中的液体介质具有相对低的温度。在一些具体实施方案中，低温槽中液体介质的温度 可以维持在20～80℃，优选60～80℃。任选的，可以在低温槽中设置保温装置或者温度加热装置，使得其中液体介质温度维持在上述温度范围以内，温度太低，则经过后续泵将低温液体介质传送到油浴储槽时需要花费更多的能源进行再次加热，而温度太高，则不可避免的使用泵传输高温液体介质，有可能增加对泵的损耗。
当高温液体介质从油浴储槽中流入到油浴槽后，油浴储槽需要补充液体介质，此时，通过泵将低温槽中的低温液体介质经由管路输送到油浴储槽中，并在油浴储槽中加热到90℃以上，优选为95℃以上。
通过上述的液体介质的流动，实现液体介质的循环使用。
本发明中，通过油浴储槽的设置，避免了传统设计中在低位槽(与本发明的低温槽相对应)中直接加热液体介质到90℃以上的高温，然后通过泵将高温液体介质直接加入到油浴槽中所导致的缺陷。一方面，可以避免使用泵传输高温液体介质，这样避免了泵的机械损耗，另一方面，泵传输的液体介质输入到油浴储槽中，油浴储槽起到缓冲作用，可以避免在每次泵的启停瞬间所造成的液体介质的传输不稳、难以控制的问题，也可以避免由于高温液体介质的传送所导致的气蚀的发生。油浴储槽可以作为缓冲器避免这种瞬时的液体介质的流量不稳的情况，通过油浴储槽的阀门，使得在任意时刻均可以以稳定的流速将高温液体介质输送到油浴槽中，因此，可以更为精确的控制油浴槽中液体介质的温度。本发明优选的实施方案中，通过上述方法，可以将油浴槽中液体介质的温度波动控制在±1℃以内。
<本发明的第二方面>
本发明的第二方面涉及一种用于树脂纺丝的油浴装置，所述树脂的选择与本发明的第一方面相同。所述装置包括：
油浴槽，油浴储槽和低温槽。
通过油浴槽中的液体介质对树脂纤维进行处理。所述液体介质从油浴储槽流入油浴槽，从油浴槽中流出的液体介质流入低温槽。
现有的使用油浴槽进行纤维拉伸的工艺如示意图1中所示。典型地，在 涤纶或丙纶等纺丝过程中，油浴槽中液体介质具有一定的温度，其作用是将原丝在槽内进行拉伸以达到一定的纤度，并利用油浴槽中的液体介质保护聚合物的表面以防止其在拉伸时造成大量缺陷而不利于后续的加工。
由于在这里油浴加热所使用的温度较低，大约为60～80℃，因此可以用泵将在低位槽(与本发明低温槽对应)加热好的液体介质打入油浴槽，并在油浴槽的一端开启阀门将多余的液体介质回流至低位槽重复使用。通过这样内循环的方式，可以保证在油浴槽内的丝束一直处于液面以下，并且加热拉伸能够正常的进行。
因此，现有技术通常是在低位槽中对液体介质进行加热，进而通过油泵直接将热的液体介质送入油浴槽中。如上所述，对于这样的油浴槽的设计，如果直接用于玻璃化温度较高的树脂，如聚芳硫醚树脂纤维拉伸的时候，存在上文已经阐述过的问题，尤其的，如果在这样的低位槽中将液体介质加热到与油浴槽中所需的温度相同或略高的温度，并直接用泵吸将热的液体介质送入油浴槽中，通常会导致油浴槽中液体介质的温度波动超过±3℃。
本发明的装置中，相对于现有技术，在使用泵将低温槽中的液体介质输送到油浴槽之前，先将液体介质输送到油浴储罐中，并在油浴储槽中加热到与油浴槽中所需的温度相同或略高的温度，例如90℃以上。如图2所示，本发明的装置中油浴槽包括至少一个牵伸辊，用于树脂纤维丝束的拉伸和牵引。所述纤维位于油浴槽的液体介质液面以下，油浴槽中的液体介质的温度为90℃以上，并且油浴槽中设有液体介质的入口和出口以及相应的阀门。对于所述入口和出口的设置与本发明第一方面是相同的。
纤维拉伸过程中，如果油浴槽中的液体介质温度降低，可以通过流入高温液体介质和流出低温液体介质来进行调节。低温液体介质通过阀门和管路流入低温槽中，此时的低温槽中，维持温度在20～80℃，而不必像现有技术那样再次在低温槽中将介质直接加热到90℃以上。
在一些优选的实施方案中，在油浴槽的上部增加了一个油浴储槽，在生产过程中，可以依旧将低温槽中的液体介质预热至20～80℃或20～60℃或 20～50℃或20～40℃(低于油浴槽中所需的液体介质的温度)，并通过泵输送到油浴储槽中，之后在油浴储槽中进行加热至90℃以上，再引入油浴槽，液体介质回流部分依旧可以通过阀门控制回流至低温槽进行内循环从而实现循环使用。
通过这种上述装置的使用，可以避免直接用泵抽取高温液体，可以大大减少气蚀的发生，并且由于高温的加热在油浴储槽中进行，可以方便地对温度进行精确的控制并减少了能耗，经过检测，发现这样的装置可以对牵伸时油浴的温度控制在±1℃以内。利用这样的循环，纤维丝束的温度也能得到很好的控制，在牵伸过程中减少毛丝或断丝的产生。
实施例
以下，列举实例，对本发明进行更具体的说明，但本发明并不仅限于这些实例。
将油浴槽的体积设置为300L，所用溶剂设置为水。
在对照组中，采用图1所示的方式，在低位槽中加入液体介质(水和整理剂的混合物)，并直接进行加热，待低位槽中的液体介质温度达到98℃后，再将该液体介质通过水泵抽至油浴槽内，水泵最高流量为16m 3/h，功率4Kw，并通过循环维持油浴槽内液体介质温度的稳定。
在实验组中，采用图2所示的方式，低温槽的液体介质(与对照组中液体介质的组成相同)温度控制为70℃，而油浴储槽的液体介质温度控制为98℃，低温槽至油浴储槽所用水泵与对照组一致，油浴储槽通过阀门控制直接将液体介质引流至油浴槽，同样利用循环维持温度的稳定。
将油浴槽的目标温度设定为95℃，分别统计了不同方法将油浴槽充满液体介质的时间，以及在充满之后液体介质温度的波动情况，其结果如下表所示。
  对照组 实验组
充满时间 2min 40s
温度波动(℃/h) 2.58 0.87
可以发现，通过引入油浴储槽，可以将油浴槽充满液位的时间大大缩短，这加快了开停车时的操作速度；此外，在正常生产时，其温度波动也较对照组大大降低，这对提升整体纺丝过程的稳定性和纤维的品质均有较大的好处。
产业上的可利用性
本发明的技术方案可以在工业上用于聚芳硫醚纤维的生产。

Claims (12)

  1. 一种树脂纺丝的方法，其特征在于，包括：
    将树脂或其组合物形成的纤维引入油浴槽的液体介质中，
    在所述液体介质中对所述纤维进行拉伸，
    所述液体介质从油浴储槽中流入油浴槽，从油浴槽中流出的液体介质流入低温槽，
    所述油浴储槽中的液体介质的温度高于所述低温槽中液体介质的温度。
  2. 根据权利要求1所述的方法，其特征在于，所述液体介质通过输送泵被从所述低温槽送入所述油浴储槽中。
  3. 根据权利要求1或2所述的方法，其特征在于，所述树脂的玻璃化转变温度为85℃以上，优选所述树脂为聚芳硫醚树脂。
  4. 根据权利要求1～3任一项所述的方法，其特征在于，所述液体介质在所述油浴储槽中被加热，优选液体介质被加热到90℃以上。
  5. 根据权利要求1～4任一项所述的方法，其特征在于，所述油浴槽中液体介质的温度为90℃以上；
  6. 根据权利要求1～5任一项所述的方法，其特征在于，所述低温槽中的液体介质温度为20～80℃，优选60～80℃。
  7. 一种用于树脂纺丝的油浴装置，其特征在于，包括：
    油浴槽，
    油浴储槽，
    低温槽，
    所述油浴槽、油浴储槽和低温槽通过管路和阀门相连接。
  8. 根据权利要求7所述的装置，其特征在于，所述树脂的玻璃化转变温度为85℃以上，优选所述树脂为聚芳硫醚树脂。
  9. 根据权利要求7或8所述的装置，其特征在于，所述装置还包括输送泵以输送液体介质，所述液体介质通过输送泵被从所述低温槽送入所述油浴储槽中。
  10. 根据权利要求7～9任一项所述的装置，其特征在于，所述油浴储槽 具有加热装置以加热液体介质，所述液体介质在所述油浴储槽中通过加热装置被加热，优选液体介质被加热到90℃以上。
  11. 根据权利要求7～10任一项所述的装置，其特征在于，所述油浴槽中还设置牵伸辊。
  12. 根据权利要求7～11任一项所述的装置，其特征在于，所述装置中，液体介质从油浴储槽流入油浴槽，从油浴槽中流出的液体介质流入低温槽。
PCT/CN2019/110820 2019-03-01 2019-10-12 纺丝的方法和装置 WO2020177322A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910156589.7A CN109881271B (zh) 2019-03-01 2019-03-01 纺丝的方法和装置
CN201910156589.7 2019-03-01

Publications (1)

Publication Number Publication Date
WO2020177322A1 true WO2020177322A1 (zh) 2020-09-10

Family

ID=66930337

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/110820 WO2020177322A1 (zh) 2019-03-01 2019-10-12 纺丝的方法和装置

Country Status (2)

Country Link
CN (1) CN109881271B (zh)
WO (1) WO2020177322A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109881271B (zh) * 2019-03-01 2021-02-19 绍兴裕辰新材料有限公司 纺丝的方法和装置
CN112921422B (zh) * 2021-01-20 2022-08-30 中国纺织科学研究院有限公司 一种牵伸丝用热箱

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB936758A (en) * 1960-06-01 1963-09-11 Monsanto Chemicals Method and apparatus for wet spinning polyacrylonitrile filaments
JPH04100916A (ja) * 1990-08-20 1992-04-02 Toray Ind Inc ポリフェニレンサルファイド繊維およびその製造方法
CN201883190U (zh) * 2010-11-10 2011-06-29 肇庆俊富纤网材料有限公司 油剂循环使用系统
CN202380141U (zh) * 2011-12-16 2012-08-15 杭州贝斯特化纤有限公司 牵伸浴槽加热装置
CN106757434A (zh) * 2016-12-02 2017-05-31 宁波大发化纤有限公司 一种油浴丝束拉伸装置
CN109881271A (zh) * 2019-03-01 2019-06-14 绍兴裕辰新材料有限公司 纺丝的方法和装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1337498C (en) * 1989-09-01 1995-11-07 Ephraim Broyer Thermal treatment of thermoplastic filaments
JP5001472B2 (ja) * 2010-09-21 2012-08-15 株式会社ゴーセン 超高分子量ポリオレフィン糸条とその製造方法及び延伸装置
CN102011202B (zh) * 2010-12-03 2015-11-18 西安航科等离子体科技有限公司 纤维丝束纺丝用水洗及热牵伸装置
CN203295671U (zh) * 2013-06-19 2013-11-20 宜宾丝丽雅股份有限公司 一种塑化槽用补充水供给装置
CN103726113A (zh) * 2013-12-25 2014-04-16 中国科学院化学研究所 新型的纤维牵伸热浴介质及其应用
CN206232857U (zh) * 2016-11-25 2017-06-09 中复神鹰碳纤维有限责任公司 改善槽内温度均一性的水牵槽

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB936758A (en) * 1960-06-01 1963-09-11 Monsanto Chemicals Method and apparatus for wet spinning polyacrylonitrile filaments
JPH04100916A (ja) * 1990-08-20 1992-04-02 Toray Ind Inc ポリフェニレンサルファイド繊維およびその製造方法
CN201883190U (zh) * 2010-11-10 2011-06-29 肇庆俊富纤网材料有限公司 油剂循环使用系统
CN202380141U (zh) * 2011-12-16 2012-08-15 杭州贝斯特化纤有限公司 牵伸浴槽加热装置
CN106757434A (zh) * 2016-12-02 2017-05-31 宁波大发化纤有限公司 一种油浴丝束拉伸装置
CN109881271A (zh) * 2019-03-01 2019-06-14 绍兴裕辰新材料有限公司 纺丝的方法和装置

Also Published As

Publication number Publication date
CN109881271A (zh) 2019-06-14
CN109881271B (zh) 2021-02-19

Similar Documents

Publication Publication Date Title
WO2020177322A1 (zh) 纺丝的方法和装置
JP5144641B2 (ja) 高分子量ポリ（α−オレフィン）溶液およびそれから作製される物品
CN104088031B (zh) 多功能锦纶6纤维及其制造方法
CN103088453B (zh) 熔体直纺涤纶活化工业丝的生产工艺
TWI519687B (zh) 消光聚醯胺５６纖維及其製造方法
CN102220659A (zh) 一种耐热聚苯硫醚纤维的制备方法
CN110499559B (zh) 一种高强度复合纱线和织物的制备方法
CN205223429U (zh) 分温区多通道在线热处理装置
WO2022247054A1 (zh) 一种凉感索弹纤维的生产方法
CN113737301A (zh) 一种聚乳酸产业用纤维纺丝牵伸卷绕联合机
US20140106167A1 (en) Method for hybrid dry-jet gel spinning and fiber produced by that method
CN105543988B (zh) 一种细旦缝纫线用涤纶工业丝及其加工设备
CN106400164A (zh) 一种多孔仿麻聚酯纤维及其制备方法
CN103757721B (zh) 一种聚酰胺酰亚胺纤维湿法一步纺丝工艺
CN106319678B (zh) 一种多孔超柔软仿毛聚酯纤维及其制备方法
CN108642584B (zh) 一种分纤母丝纺牵联合机
CN101984154B (zh) 拒水聚酯纤维的制备方法
CN110204889A (zh) 一种防静电连续长玻纤增强聚酰胺复合材料及其制备方法
CN109705543A (zh) 一种芳纶纤维改性长玻纤增强pet/ppo合金及其制备方法
CN113151918A (zh) 一种超高分子量聚乙烯有色纤维及其制备方法
CN106283262B (zh) 一种多孔聚酯纤维fdy丝及其制备方法
CN106400170B (zh) 一种多孔超柔软仿麻聚酯纤维及其制备方法
CN106544741B (zh) 一种提高超高分子量聚乙烯纤维性能的方法
CN116949598A (zh) 一种高强低缩pa6工业丝及其制备方法
CN106978635A (zh) 一种高强力低缩涤纶工业丝的加工工艺

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19918457

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19918457

Country of ref document: EP

Kind code of ref document: A1