CN105401254B - A kind of high-strength and high-modulus polyformaldehyde fibre and its two-step method hot-drawn preparation method - Google Patents
A kind of high-strength and high-modulus polyformaldehyde fibre and its two-step method hot-drawn preparation method Download PDFInfo
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- CN105401254B CN105401254B CN201510703758.6A CN201510703758A CN105401254B CN 105401254 B CN105401254 B CN 105401254B CN 201510703758 A CN201510703758 A CN 201510703758A CN 105401254 B CN105401254 B CN 105401254B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- 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
- D01D5/08—Melt spinning methods
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- 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
- D01D5/08—Melt spinning methods
- D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
A kind of high-strength and high-modulus polyformaldehyde fibre and its two-step method hot-drawn preparation method, belong to polyformaldehyde fibre technical field.Acetal resin is uniformly dried afterwards with glucitols material mixing, heating melting, the mass fraction of glucitols material in the mixture is 0.2~0.3wt.%；The polyformaldehyde melt of melting is sprayed after measuring pump-metered by spinning head；The melt of ejection, which carries out blowing hot-air, makes melt Slow cooling；Fiber after cooling carries out obtaining as-spun fibre after one-level hot-rolling drawing-off, winding after the boundling that oils, and wherein heat roller temperature is 50~80 DEG C, and hot-rolling draft ratio is 1.2~2.5 times；As-spun fibre places 4~24h at room temperature, its internal stress is reached balance；Reach that the as-spun fibre of interior stress balance carries out multistage low speed high drafting using hot-rolling and both obtains finished product polyformaldehyde fibre.Polyformaldehyde fibre performance of the present invention is more preferable, fault of construction is reduced, and especially tensile strength and modulus is increased dramatically.Technical process is simple, the reduction of easily-controlled operation, production cost.
Description
Technical field
The present invention relates to a kind of high-strength and high-modulus polyformaldehyde fibre and its two-step method hot-drawn preparation method, especially melt spinning
Technique, belongs to polyformaldehyde fibre technical field.
Background technology
Acetal resin is as one of three big general-purpose plastics in the world at present, with excellent physical and mechanical properties and chemistry
Stability, especially copolymerized methanal, it is made with a small amount of dioxolanes or ethylene oxide polymerization by metaformaldehyde, contained on main chain
A small amount ofUnit, can prevent it from thermally decomposing, so as to improve the heat endurance of copolymerized methanal, make its processing temperature
Degree scope broaden, at present its commercially portion it is very big, considerably beyond acefal homopolymer resin.
With developing rapidly for process industry art, the purposes of acetal resin is more and more wider, and production capacity constantly expands,
Vehicles Collected from Market is badly in need of the production capacity of digestion polyformaldehyde, while to excavate the more purposes of acetal resin, produces more poly- first
Aldehyde product.
Because the crystallinity of polyformaldehyde is higher, crystalline rate very fast, and its fusing point and heat decomposition temperature are closer to, and are caused
Its process window is very narrow, and this brings difficulty to the process of polyformaldehyde.Melting spinning is carried out especially with acetal resin
When silk prepares polyformaldehyde fibre, processing technology difficulty is high.But research is found, polyformaldehyde fibre not only has being permitted for acetal resin
Many advantages can also increase new advantage because of its fibre structure, for example：Intensity height, modulus height, high abrasion resistance, dimensional stability
Good, acid-fast alkali-proof, weather-proof etc., cannot be only used for textiles for general use and can be additionally used in the fields such as military project and marine industry.Therefore having must
The characteristic of polyformaldehyde in itself is utilized, high-performance polyformaldehyde fibre is produced by changing its crystal property and process, makes
Its advantage is fully used.
Influenceed by polyformaldehyde property itself, production technology and equipment etc., at present on preparing polyformaldehyde fibre
Relevant report it is very few, it is domestic then be even more few related fields researchs.Patent CN102677217A discloses a kind of modification
POM fibers and preparation method thereof, nono calcium carbonate modified rear and POM is blended, then by this mixture twin-screw extrusion,
Granulation, dries spinning again, although fiber mechanicses and thermal property have preferable raising, fiber surface made from the patent afterwards
Become coarse, strengthen with the interface interaction power such as cement, but because the addition of inorganic particulate, can be such that fiber is produced in drawing process
Raw stress concentration phenomenon, is easier to the defects such as lousiness or broken end occur；Patent CN101792938A discloses a kind of polyformaldehyde fibre
Novel preparation technology, polyformaldehyde fibre is prepared through multistage slow cooling and three-level different medium stretching, and fibre property is preferable, Gao Mo, height
By force, performance is stable, but its processing step is excessive, there is many uncontrollable factors in process of production, not easy to operate, and raw
Produce occupation area of equipment too big, its industrialized production is not utilized；Patent CN1504508 discloses a kind of by the contained oxidation of regulation
The ratio of alkene unit, controls the crystallization of polyformaldehyde, forms it into high intensity, the polyformaldehyde fibre of high-modulus, this is set from molecule
The polyformaldehyde that roofing control synthesis is adapted to spinning is counted, because the country also does polyformaldehyde base resin well at present, directly synthesis is spun
The technical difficulty of silk level polyformaldehyde is very big.
Patent CN102011201A discloses a kind of production method of the polyformaldehyde fibre with high fracture strength, in order to change
The crystallization situation of kind polyformaldehyde fibre obtains the polyformaldehyde fibre of high-module high-strength to be adapted to spinning and after-drawing, using slow cooling-
Quenching is pre-processed to as-spun fibre, and many at a slow speed multiplying power draft process of multistage, prepares polyformaldehyde fibre, but its work
Skill process is excessively complicated, not easy to operate, low production efficiency, and floor space is big, and production cost is high, is unfavorable for market competition；
In view of the deficiency of current polyformaldehyde fibre manufacturing process, it is necessary to have a kind of new process, this process
Production procedure is simple, easy to control, production equipment floor space is small, production cost is low, and energy consumption is small, be easily achieved industrialized production.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided a kind of high-strength and high-modulus polyformaldehyde fibre and its two-step method
Hot-drawn preparation method, this invention simple production process, easy to operate, occupation area of equipment are small, production cost is low, power consumption is few,
The fibre property of preparation is superior, Stability Analysis of Structures, and tensile strength and modulus are increased dramatically, and fault of construction is reduced.
The present invention relates to technique be melt-spinning technology, in order to improve at present production polyformaldehyde fibre it is technical not
Foot, the present invention prepares the polyformaldehyde fibre of high-strength and high-modulus using two-step method：The first step is by acetal resin and glucitols material
Melting is heated after well mixed, the mode then cooled down using ring blowing hot-air prepares as-spun fibre, second step is by as-spun fibre
Multistage low speed high drafting finished product fiber is carried out on hot-rolling.
A kind of high-strength and high-modulus polyformaldehyde fibre and its two-step method hot-drawn preparation method, are comprised the following steps that in the present invention：①
By acetal resin and glucitols material mixing it is uniform after in vacuum drying chamber dry a few hours, add screw extruder in
Heating melting, wherein glucitols material are as nucleator, and mass fraction in the mixture is 0.2~0.3wt.%；Melting
Polyformaldehyde melt through measure pump-metered after sprayed by spinning head；2. the melt that step sprays, which carries out blowing hot-air, makes melt slow
Cooling；3. the fiber after cooling down obtains as-spun fibre after carrying out one-level hot-rolling drawing-off, winding after the boundling that oils；4. as-spun fibre
4~24h is placed at room temperature, its internal stress is reached balance；5. reach that the as-spun fibre of interior stress balance is carried out using hot-rolling
Multistage low speed high drafting both obtains finished product polyformaldehyde fibre.
Step of the present invention in acetal resin 1. by adding the sorb that mass percent fraction is 0.2~0.3wt.%
Alcohols controls crystal property during polyformaldehyde melt cooling.The addition of glucitols material can be effectively reduced polyformaldehyde melt
Spherulite size during cooling, makes the more small spherocrystals of generation, while reducing the crystalline rate in polyformaldehyde fiber forming process.Institute of the present invention
It is dibenzal sorbitol class compound with Sorbitol Nucleator, its general structure is as follows：
R in formula1And R2The alkyl for being 4-8 for carbon number.
1. melt-spinning technology heating process Zhong Ge areas design temperature is involved step in the present invention：Feeding section 60~
75 DEG C, 170~205 DEG C of compression section, 170~220 DEG C of metering section, 170~230 DEG C of head, 200~230 DEG C of spinning head.Polyformaldehyde
Resin is when heating-up temperature is less than 230 DEG C, and the mass fraction of decomposition is only 3wt.% or so；When temperature is higher than 230 DEG C, poly- first
Aldehyde starts rapid decomposition, therefore answers strict temperature control when preparing polyformaldehyde fibre, it is to avoid polyformaldehyde is decomposed into formaldehyde gas,
Influence the performance of polyformaldehyde finished fiber.
The present invention is in order to further improve the spinnability of acetal resin and improve the intensity and modulus of finished fiber, to spray
The silk gone out carries out blowing hot-air processing, it is preferred to use the device that can circulate continuous blowing hot-air carries out ring blowing hot-air so that from spinneret
The melt Slow cooling that plate sprays, and then its crystallinity and crystalline rate are controlled, while reducing the knot such as internal stress and skin-core structure
Structure defect.The length in hot blast area and the temperature in hot blast area are the key factors of crystal property when influenceing melt cooling, are related into
The performances such as the intensity and modulus of product fiber；It is spinneret to oiling that the part of blowing hot-air processing is carried out to the silk of ejection in the present invention
Roll spacing is 1/3 from before, and hot blast wind speed is 0.25~0.5m/s, and hot blast temperature is 60~155 DEG C, hot blast direction vertical fibers.
Fiber first passes through hot-rolling after the boundling that oils and carries out one-level drawing-off in the present invention, then winds again and nascent fibre is made
Dimension, so make it that fibre structure is stable through one-level drawing-off, and is less prone to during posterior drawing fault of construction.But drawing-off times
Rate is unsuitable too high, if multiple is too high, and not only the drafting multiple of fiber can also influence carrying for fibre strength during influence after-drawing
Rise.Heat roller temperature is 50~80 DEG C, and hot-rolling draft ratio is 1.2~2.5 times, preferably 1.5-2.0.
A kind of high-strength and high-modulus polyformaldehyde fibre of the present invention and its two-step method hot-drawn preparation method, its second step are multistage
The placed fiber reached after interior stress balance of low speed super drawing, the intensity for making fiber by high drafting increases, and fracture is stretched
Long rate reduction；Fiber is shaped by multistage drafting can also further lift the intensity of fiber, while fiber
Shrinkage factor can also be greatly lowered through multistage stretching.It should be improved as far as possible on the premise of the faults of construction such as micropore are occurred without
Drafting multiple makes its intensity reach maximum.Draw speed is 5~80m/min, and drafting multiple is 3.0~8.0 times, drawing-off series
For 2~4 grades, drawing temperature is 80-150 DEG C.
Feature of the present invention is as follows：Prepared in the present invention using two-step method hot-drawn in high-strength and high-modulus polyformaldehyde fibre, the first step
The crystal property in polyformaldehyde melt cooling process, reduction knot are controlled using a small amount of Sorbitol Nucleator and blowing hot-air is added
Brilliant degree and spherulite size, improve the spinnability of polyformaldehyde, then make fibre structure stable by hot-rolling one-level drawing-off, reduce follow-up draw
Fault of construction during stretching；Make polyformaldehyde fibre sizing in second step using multistage low speed high power hot-drawn and improve poly- first
The intensity and modulus of aldehyde fiber.By using the cold-drawn standby polyformaldehyde fibre of two-step method, its energy consumption is small, and easy to operate, equipment takes up an area face
Product is small, and the fibre strength and modulus of preparation are all very high.The polyformaldehyde finished fiber of preparation cannot be only used for cement enhancing, cable car rope
The sphere of lifes such as rope, it may also be used in the Ocean Fishery Field such as warship gun cover, fishing net.
Polyformaldehyde fibre performance of the present invention is more preferable, fault of construction is reduced, and especially tensile strength and modulus is significantly carried
Rise, and present invention process process is simple, easily-controlled operation is implemented, the larger reduction of production cost.
Specific embodiment
Raw materials used in following examples of the present invention is copolymerized methanal resin, and preferably its melt index is 2~54g/
10min, fusing point is 160~170 DEG C.Its structure isWherein n, m are greater than 1 natural number；Its
InThe mole percent level of ethoxy construction unit is 0.5~8.0mol%.Blowing hot-air is carried out to the silk of ejection
(especially ring blowing hot-air) processing part be from spinneret to oiling roller distance before 1/3.
Embodiment 1：Melt index is dried into 12h for 11g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.27wt.% sorbierite (R1=R2=carbon number be 6 alkyl) mixing after add screw extruder in melt heating,
Fully sprayed after melting through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature is set as：70 DEG C of feeding section,
170 DEG C of compression section, 200 DEG C of metering section, 220 DEG C of head, 220 DEG C of spinning head.Melt is carried out at blowing hot-air after being sprayed through spinneret
Reason, hot blast temperature is 140 DEG C, then obtains as-spun fibre, heat roller temperature by being wound after hot-rolling one-level drawing-off through the boundling that oils
For 70 DEG C, drafting multiple is 1.5 times.As-spun fibre is placed under conditions of constant temperature (room temperature) constant humidity after 12~24h, by
Draft speed is 20m/min, and drawing-off series is 4 grades, and total draft multiple is 8.0 times, under conditions of 120 DEG C of temperature of traction, cold
Drawing-off at a slow speed is carried out on roller, silk, finished product fiber is received.
Embodiment 2：Melt index is dried into 12h for 11g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.27wt.% sorbierite (R1=R2=carbon number be 6 alkyl) mixing after add screw extruder in melt heating,
Fully sprayed after melting through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature is set as：70 DEG C of feeding section,
170 DEG C of compression section, 200 DEG C of metering section, 220 DEG C of head, 220 DEG C of spinning head.Melt is carried out at blowing hot-air after being sprayed through spinneret
Reason, hot blast temperature is 155 DEG C, then obtains as-spun fibre, heat roller temperature by being wound after hot-rolling one-level drawing-off through the boundling that oils
For 80 DEG C, drafting multiple is 2.0 times.As-spun fibre is placed under conditions of constant temperature (room temperature) constant humidity after 12~24h, by
Draft speed is 20m/min, and drawing-off series is 4 grades, and total draft multiple is 6.0 times, under conditions of 150 DEG C of temperature of traction, cold
Drawing-off at a slow speed is carried out on roller, silk, finished product fiber is received.
Embodiment 3：Melt index is dried into 12h for 11g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.27wt.% sorbierite (R1=R2=carbon number be 6 alkyl) mixing after add screw extruder in melt heating,
Fully sprayed after melting through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature is set as：70 DEG C of feeding section,
190 DEG C of compression section, 200 DEG C of metering section, 210 DEG C of head, 220 DEG C of spinning head.Melt is carried out at blowing hot-air after being sprayed through spinneret
Reason, hot blast temperature is 60 DEG C, then obtains as-spun fibre by being wound after hot-rolling one-level drawing-off through the boundling that oils, heat roller temperature is
50 DEG C, drafting multiple is 1.5 times.As-spun fibre is placed under conditions of constant temperature (room temperature) constant humidity after 12~24h, by leading
Speed is stretched for 20m/min, drawing-off series is 3 grades, total draft multiple is 8.0 times, under conditions of 80 DEG C of temperature of traction, in chilling roller
Carry out drawing-off at a slow speed, receive silk, finished product fiber.
Comparative example 4：Melt index is dried into 12h for 11g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.27wt.% sorbierite (R1=R2=carbon number be 6 alkyl) mixing after add screw extruder in melt heating,
Fully sprayed after melting through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature is set as：70 DEG C of feeding section,
205 DEG C of compression section, 210 DEG C of metering section, 220 DEG C of head, 230 DEG C of spinning head.Melt is carried out at blowing hot-air after being sprayed through spinneret
Reason, hot blast temperature is 140 DEG C, then obtains as-spun fibre, heat roller temperature by being wound after hot-rolling one-level drawing-off through the boundling that oils
For 70 DEG C, drafting multiple is 3.0 times.As-spun fibre is placed under conditions of constant temperature (room temperature) constant humidity after 12~24h, by
Draft speed is 20m/min, and drawing-off series is 3 grades, and total draft multiple is 6.0 times, under conditions of 120 DEG C of temperature of traction, cold
Drawing-off at a slow speed is carried out on roller, silk, finished product fiber is received.
Embodiment 5：Melt index is dried into 12h for 11g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.3wt.% sorbierite (R1=R2=carbon number be 6 alkyl) mixing after add screw extruder in melt heating, fill
Divide after melting and sprayed through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature is set as：70 DEG C of feeding section, pressure
185 DEG C of contracting section, 200 DEG C of metering section, 210 DEG C of head, 210 DEG C of spinning head.Melt carries out blowing hot-air processing after being sprayed through spinneret,
Hot blast temperature is 120 DEG C, then obtains as-spun fibre by being wound after hot-rolling one-level drawing-off through the boundling that oils, heat roller temperature is 70
DEG C, drafting multiple is 1.5 times.As-spun fibre is placed under conditions of constant temperature (room temperature) constant humidity after 12~24h, by drawing-off
Speed is 20m/min, and drawing-off series is 3 grades, and total draft multiple is 6.0 times, enterprising in chilling roller under conditions of 90 DEG C of temperature of traction
Capable drawing-off at a slow speed, receipts silk, finished product fiber.
Embodiment 6：Melt index is dried into 12h for 2g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.2wt.% sorbierite (R1=R2=carbon number be 6 alkyl) mixing after add screw extruder in melt heating, fill
Divide after melting and sprayed through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature is set as：70 DEG C of feeding section, pressure
170 DEG C of contracting section, 200 DEG C of metering section, 220 DEG C of head, 220 DEG C of spinning head.Melt carries out blowing hot-air processing after being sprayed through spinneret,
Hot blast temperature is 140 DEG C, then obtains as-spun fibre by being wound after hot-rolling one-level drawing-off through the boundling that oils, heat roller temperature is 70
DEG C, drafting multiple is 1.5 times.As-spun fibre is placed under conditions of constant temperature (room temperature) constant humidity after 12~24h, by drawing-off
Speed is 20m/min, and drawing-off series is 4 grades, and total draft multiple is 8.0 times, under conditions of 120 DEG C of temperature of traction, in chilling roller
Carry out drawing-off at a slow speed, receive silk, finished product fiber.
Embodiment 7：Melt index is dried into 12h for 25g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.25wt.% sorbierite (R1Alkyl, R that=carbon number is 62=carbon number be 8 alkyl) mixing after add screw rod
Heating is melted in extruder, is fully sprayed after melting through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature
It is set as：70 DEG C of feeding section, 195 DEG C of compression section, 200 DEG C of metering section, 220 DEG C of head, 220 DEG C of spinning head.Melt is through spinneret
Blowing hot-air processing is carried out after ejection, hot blast temperature is 130 DEG C, is then obtained through the boundling that oils by being wound after hot-rolling one-level drawing-off
As-spun fibre, heat roller temperature is 80 DEG C, and drafting multiple is 2.0 times.As-spun fibre is placed on to the condition of constant temperature (room temperature) constant humidity
After lower 12~24h, by being 20m/min in draft speed, drawing-off series is 4 grades, and total draft multiple is 6.0 times, draws temperature
Under conditions of 120 DEG C, drawing-off at a slow speed is carried out in chilling roller, silk, finished product fiber is received.
Embodiment 8：Melt index is dried into 12h for 40g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.2wt.% sorbierite (R1Alkyl, R that=carbon number is 52=carbon number be 6 alkyl) mixing after add screw rod
Heating is melted in extruder, is fully sprayed after melting through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature
It is set as：70 DEG C of feeding section, 170 DEG C of compression section, 200 DEG C of metering section, 220 DEG C of head, 220 DEG C of spinning head.Melt is through spinneret
Blowing hot-air processing is carried out after ejection, hot blast temperature is 140 DEG C, is then obtained through the boundling that oils by being wound after hot-rolling one-level drawing-off
As-spun fibre, heat roller temperature is 70 DEG C, and drafting multiple is 1.5 times.As-spun fibre is placed on to the condition of constant temperature (room temperature) constant humidity
After lower 12~24h, by being 20m/min in draft speed, drawing-off series is 4 grades, and total draft multiple is 6.0 times, draws temperature
Under conditions of 100 DEG C, drawing-off at a slow speed is carried out in chilling roller, silk, finished product fiber is received.
Comparative example 9：Melt index is dried into 12h for 54g/10min acetal resin in 80 DEG C of vacuum drying chamber.
With 0.27wt.% sorbierite (R1=R2=carbon number be 6 alkyl) mixing after add screw extruder in melt heating,
Fully sprayed after melting through measuring pump-metered distribution by spinneret, heating process Zhong Ge areas temperature is set as：70 DEG C of feeding section,
170 DEG C of compression section, 200 DEG C of metering section, 210 DEG C of head, 210 DEG C of spinning head.Melt is carried out at blowing hot-air after being sprayed through spinneret
Reason, hot blast temperature is 140 DEG C, then obtains as-spun fibre, heat roller temperature by being wound after hot-rolling one-level drawing-off through the boundling that oils
For 70 DEG C, drafting multiple is 1.0 times.As-spun fibre is placed under conditions of constant temperature (room temperature) constant humidity after 12~24h, by
Draft speed is 20m/min, and drawing-off series is 3 grades, and total draft multiple is 6.0 times, under conditions of 120 DEG C of temperature of traction, cold
Drawing-off at a slow speed is carried out on roller, silk, finished product fiber is received.
Embodiment 10：Melt index is dried into 12h for 2g/10min acetal resin in 80 DEG C of vacuum drying chamber.
It is directly added into screw extruder and melts heating, is fully sprayed after melting through measuring pump-metered distribution by spinneret, it is heated
Cheng Zhongge areas temperature is set as：70 DEG C of feeding section, 170 DEG C of compression section, 200 DEG C of metering section, 220 DEG C of head, 220 DEG C of spinning head.
Melt carries out blowing hot-air processing after being sprayed through spinneret, hot blast temperature is 140 DEG C, is then led through the boundling that oils by hot-rolling one-level
Winding obtains as-spun fibre after stretching, and heat roller temperature is 70 DEG C, and drafting multiple is 2.0 times.As-spun fibre is placed on constant temperature (room
Temperature) under conditions of constant humidity after 12~24h, by being 20m/min in draft speed, drawing-off series is 4 grades, and total draft multiple is
6.0 times, draw under conditions of 120 DEG C of temperature, drawing-off at a slow speed is carried out in chilling roller, silk, finished product fiber is received.
The fibre property result as obtained by the above example of table 1.
Claims (8)
1. the two-step method hot-drawn preparation method of a kind of high-strength and high-modulus polyformaldehyde fibre, it is characterised in that comprise the following steps that：1. will
A few hours are dried after acetal resin and glucitols material mixing are uniform in vacuum drying chamber, adds in screw extruder and adds
Heat fusing, wherein glucitols material are as nucleator, and mass fraction in the mixture is 0.2~0.3wt.%；Melting
Polyformaldehyde melt is sprayed after measuring pump-metered by spinning head；2. the melt sprayed, which carries out blowing hot-air, makes melt Slow cooling；
3. the fiber after cooling down carries out obtaining as-spun fibre after one-level hot-rolling drawing-off, winding after the boundling that oils, and wherein heat roller temperature is
50~80 DEG C, hot-rolling draft ratio is 1.2~2.5 times；4. as-spun fibre places 4~24h at room temperature, reaches its internal stress
Balance；5. reach that the as-spun fibre of interior stress balance carries out multistage low speed high drafting using hot-rolling and both obtained finished product polyformaldehyde fibre
Dimension；
Part to the silk progress blowing hot-air processing of ejection is spinneret to before oiling roller distance 1/3, and hot blast wind speed is 0.25
~0.5m/s, hot blast temperature is 60~155 DEG C, hot blast direction vertical fibers.
2. according to the method for claim 1, it is characterised in that glucitols material is dibenzal sorbitol class compound, it is tied
Structure formula is as follows：
R in formula1And R2The alkyl for being 4-8 for carbon number.
3. according to the method for claim 1, it is characterised in that step 1. melt-spinning technology heating process Zhong Ge areas design temperature
For：60~75 DEG C of feeding section, 170~205 DEG C of compression section, 170~220 DEG C of metering section, 170~230 DEG C of head, spinning head 200
~230 DEG C.
4. according to the method for claim 1, it is characterised in that it is that use can circulate continuous blowing hot-air that 2. step, which carries out blowing hot-air,
Device carry out ring blowing hot-air.
5. according to the method for claim 1, it is characterised in that step 3. hot-rolling draft ratio 1.5-2.0.
6. according to the method for claim 1, it is characterised in that carry out multistage low speed high drafting using hot-rolling, wherein stretching speed
Spend for 5~80m/min, drafting multiple is 3.0~8.0 times, drawing-off series is 2~4 grades, drawing temperature is 80-150 DEG C.
7. according to the method for claim 1, it is characterised in that acetal resin is copolymerized methanal resin, its melt index is 2~
54g/10min, fusing point is 160~170 DEG C；Its structure isWherein n, m are greater than 1 nature
Number；WhereinThe mole percent level of ethoxy construction unit is 0.5~8.0mol%.
8. the high-strength and high-modulus polyformaldehyde fibre that any one method according to claim 1-7 is prepared.
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| CN106480535B (en) * | 2016-10-31 | 2019-01-15 | 江苏苏博特新材料股份有限公司 | A kind of method that melt spinning prepares polyformaldehyde fibre |
| KR20230174292A (en) * | 2017-07-14 | 2023-12-27 | 미츠비시 가스 가가쿠 가부시키가이샤 | Method for producing polyacetal fiber |
| CN107805850B (en) * | 2017-10-16 | 2020-06-19 | 唐山开滦化工科技有限公司 | High-strength high-modulus polyformaldehyde fiber and preparation method thereof |
| CN107938019B (en) * | 2017-10-16 | 2020-04-07 | 唐山开滦化工科技有限公司 | One-step forming preparation method of polyformaldehyde fibers |
| CN115262024A (en) * | 2022-08-11 | 2022-11-01 | 山东鲁化森萱新材料有限公司 | Intrinsic high-thermal-conductivity polyformaldehyde fiber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792938A (en) * | 2010-04-01 | 2010-08-04 | 东华大学 | Novel preparation technology of polyoxymethylene fiber |
| CN102011201A (en) * | 2010-12-15 | 2011-04-13 | 四川省纺织科学研究院 | Melt-spinning method for polyformaldehyde fibers |
| CN104499087A (en) * | 2014-12-23 | 2015-04-08 | 江苏苏博特新材料股份有限公司 | Preparation method of novel polyoxymethylene fibers |
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-
2015
- 2015-10-27 CN CN201510703758.6A patent/CN105401254B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792938A (en) * | 2010-04-01 | 2010-08-04 | 东华大学 | Novel preparation technology of polyoxymethylene fiber |
| CN102011201A (en) * | 2010-12-15 | 2011-04-13 | 四川省纺织科学研究院 | Melt-spinning method for polyformaldehyde fibers |
| CN104499087A (en) * | 2014-12-23 | 2015-04-08 | 江苏苏博特新材料股份有限公司 | Preparation method of novel polyoxymethylene fibers |
Non-Patent Citations (2)
| Title |
|---|
| High Efficiency Nucleating Agents of Polyoxymethylene;Ying Shu et al.;《Polymer-Plastics Technology and Engineering》;20061231;第45卷(第8期);摘要 * |
| 聚甲醛纤维的制备及其力学性能研究;文珍稀等;《合成纤维》;20110125(第1期);第24-27,54页 * |
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