CN109943906A - A kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof - Google Patents
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof Download PDFInfo
- Publication number
- CN109943906A CN109943906A CN201711393409.4A CN201711393409A CN109943906A CN 109943906 A CN109943906 A CN 109943906A CN 201711393409 A CN201711393409 A CN 201711393409A CN 109943906 A CN109943906 A CN 109943906A
- Authority
- CN
- China
- Prior art keywords
- spinning
- polyparaphenylene
- dry
- benzo dioxazole
- elongation rate
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Landscapes
- Artificial Filaments (AREA)
Abstract
The present invention relates to a kind of high elongation rate polyparaphenylene benzo dioxazole fibers and preparation method thereof, belong to high-performance fiber preparation technical field.High elongation rate polyparaphenylene benzo dioxazole fiber of the present invention is prepared for polyparaphenylene's benzo dioxazole polymer of 15-35dL/g as raw material, and by the spinning mode of dry-jet wet-spinning using intrinsic viscosity；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, elongation at break 3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3.Pbo fiber of the invention has high elongation rate, and the equally excellent equilibrium of other indexs, has more excellent shellproof and impact resistance, especially suitable for ballistic area, has filled up domestic blank, and be suitable for industrial-scale production.
Description
Technical field
The present invention relates to a kind of polyparaphenylene's benzo dioxazole fibers and preparation method thereof, and more specifically, the present invention relates to
And a kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof, belong to high-performance fiber preparation technical field.
Background technique
Polyparaphenylene's benzo dioxazole (PBO) fiber is invented by United States Air Force material laboratory, and Dow company participates in
It develops, Japanese Dongyang spinning company realizes industrialized production the nineties in last century.Currently, Dongyang spinning company trade name on the market
For Zylon®Pbo fiber have AS(conventional) and HM(high model) two kinds of models.The tensile strength of AS type pbo fiber therein and
Modulus is respectively 5.8GPa and 180GPa, density 1.54g/cm3, limit oxygen index (LOI) value 68,650 DEG C of thermal decomposition temperature, respectively
Item performance indicator is very excellent.Therefore, pbo fiber is considered as the new of the advanced configurations composite material such as Aeronautics and Astronautics and military affairs
Generation super fiber obtains in the special industries textiles such as aerospace industry, fire-entry suit and the ballistic protective clothing in the U.S. and Japan
Using.
The ballistic performance of composite material mainly determines by fiber therein, with the raising of fibre property, ballistic performance with
Raising.The excellent mechanical performance of pbo fiber can assign composite material light high-strength characteristic, and can meet simultaneously resistance to
The performance requirement of high temperature is a kind of ideal bullet resistant material.In addition, pbo fiber when being hit fiber can fibrillation, mainly
Longitudinally there is tearing phenomenon along fiber and absorbs a large amount of impact kinetic energies；Meanwhile this tearing effect is played prevents crack propagation again
Effect, therefore, the impact resistance of pbo fiber is very excellent.It is reported that the impact maximum load and energy absorption of pbo fiber
It is much higher than aramid fiber and carbon fiber, has been applied in shellproof shock resistance energy-absorbing material field, such as manufactures airframe, shellproof
Clothing, bulletproof halmet etc..
For shellproof fiber other than needing intensity and modulus with higher, it is also necessary to which high elongation percentage needs fibre
Dimension has good toughness.The researcher of the shellproof aspect in the U.S. has done many work in terms of ballistic fiber evaluation, wherein
Cunniff and Auerbach proposes the standard of evaluation ballistic fiber, and Phoenix and Portwal thereby establish fiber later
Judgment criteria theoretical formula can assess the performance of ballistic fiber using the normalized form.From formula it is found that compared to fiber
The elongation of modulus, ballistic fiber plays a crucial role ballistic performance, before not significantly affecting fiber modulus
The elongation for putting raising fiber is conducive to improve its ballistic performance.This is because the longitudinal elongation deformation before fiber destruction is advantageous
In the certain energy of absorption, while so that fiber is longitudinally generated tearing energy and preventing crack propagation well.It is contemplated that PBO is fine
The fibrillation tieed up under longitudinal large deformation effect can further absorb impact energy, preferably play bulletproof effect.
State Intellectual Property Office discloses the patent of invention of the preparation method of pbo fiber: Publication No. CN1644772A, name
The referred to as invention of " preparation method of polyparaphenylene's benzo dioxazole fiber "；Publication No. CN102943316A, entitled " one kind
The invention of the technique for producing polyparaphenylene's benzo dioxazole pbo fiber ".This two pieces disclosure of the invention preparation method of pbo fiber,
But the method for not referring to production high elongation rate pbo fiber.In addition, United States Patent (USP) US6,268,301B1, it is entitled
The invention of " Ballisitic-resistant article and process for making the same " refers to PBO
Application of the fiber in shellproof impact resistance field.But there is not the relevant report of high elongation rate pbo fiber and preparation method thereof also.
Summary of the invention
Present invention seek to address that the not high problem of polyparaphenylene's benzo dioxazole fibrous fracture elongation in the prior art, mentions
For a kind of high elongation rate polyparaphenylene benzo dioxazole fiber, which has compared with high elongation at tear, thus has more excellent
Different shellproof and impact resistance, especially suitable for ballistic area, and the fiber is suitble to industrial-scale production.
In order to achieve the above-mentioned object of the invention, specific technical solution is as follows:
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, it is characterised in that: the high elongation rate polyparaphenylene benzo two
Oxazole fiber using intrinsic viscosity for 15-35dL/g polyparaphenylene's benzo dioxazole polymer as raw material, and pass through dry-jet wet-spinning
Spinning mode be prepared；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-
5.8GPa, elongation at break 3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
There are two types of the tensile strength of fiber is usual: one kind referring to the tensile strength of monofilament (single fiber), and another kind is
The tensile strength of beam yarn (or multifilament).As its name suggests, beam yarn refers to mass of fibers, that is, one come out from multiple spinneret orifices
Bundle fiber.It is broken normally due to had differences between monofilament, and when test between monofilament inconsistent, the tensile strength of beam yarn is low
In the tensile strength of monofilament.It is more to use beam yarn tensile strength in terms of the industrial application of fiber, it is used in scientific research single more
The tensile strength of silk.Signified tensile strength of fiber refers both to the tensile strength of beam yarn in the present invention.
Currently preferred, the intrinsic viscosity of polyparaphenylene's benzo dioxazole polymer raw material is 25-32dL/g.
A kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber, it is characterised in that:
Synthesis and dry-jet wet-spinning spinning process including polyparaphenylene's benzo dioxazole polymer, during the spinning process, spinning speed
Degree is 40-200m/min, and the diameter of spinneret orifice is 0.10-0.25mm, and guide roller and drafting machine velocity ratio are 1.01-1.05:
1, tension≤500cN between drawing-off and washing, tension≤300cN between multistage rotating cylinder roller in washing procedure.
Currently preferred, specific step is as follows for the synthesis of polyparaphenylene's benzo dioxazole polymer:
A, prepolymerization
Prepare terephthalic acid (TPA) (PTA), 4,6- diamino resorcin hydrochlorate (DAR), polyphosphoric acids (PPA) and five oxidations two
Phosphorus (P2O5)；
Wherein: the molar ratio of terephthalic acid (TPA) and 4,6- diamino resorcin hydrochlorate is 1.0-1.02；
By in the dry degassing kettle of above-mentioned material investment, 10-15h is reacted in degassing under the conditions of 50-110 DEG C of temperature；Then de-
1-5h is reacted at 120-150 DEG C in bubble kettle, obtains the PBO prepolymer that solid content is 10-15%；
B, rear polymerization
PBO prepolymer obtained in step A is delivered in twin-screw extrusion reaction machine by metering pump, at 150-200 DEG C
Post-polymerization is carried out, residence time of the material in Screw Extrusion reaction machine is 5-30min, obtains being dissolved in polyphosphoric acids/five
Two phosphorus dicyandiamide solutions are aoxidized, and intrinsic viscosity is the PBO polymer of 15-35dL/g.
It is currently preferred, the dry-jet wet-spinning spinning include solidification, extraction, washing, alkali cleaning, neutralization, drying, oil and
Winding steps.
Specific step is as follows for the dry-jet wet-spinning spinning:
Polyphosphoric acids/phosphorus pentoxide dicyandiamide solution PBO polymer will be dissolved in directly as spinning solution, after filtering by counting
Pump-metered is measured, is sprayed from the spinneret orifice on spinneret；The hole count of spinneret be greater than 100 holes, aperture 0.10-0.25mm, out
By the air layer of 8-20mm after spinneret orifice, into coagulating bath, coagulating bath is phosphate aqueous solution, most of more in tow at this time
Polyphosphoric acid, which has hydrolyzed, to be extracted, and the wet yarn containing phosphoric acid is become, and wet yarn goes to the drafting machine of multistage rotating cylinder roller by guide roller,
The draw ratio of tow is controlled between 15-30；Wet yarn enters the washing procedure using multistage rotating cylinder roller later, further removes residual
The phosphoric acid deposited, it is then dry by hot-rolling drying machine, dry yarn is obtained, dry yarn is wound after oiling with up- coiler, winding speed 40-
200m/min, guide roller and drafting machine velocity ratio are 1.01-1.05:1, tension≤500cN between drawing-off and washing, washing
Tension≤300cN between multistage rotating cylinder roller in process.
Currently preferred, in dry-jet wet-spinning spinning process, the coagulating bath is the phosphoric acid water that mass concentration is 0-20%
Solution.
Currently preferred, in dry-jet wet-spinning spinning process, the temperature of the coagulating bath is 10-30 DEG C.
Currently preferred, in dry-jet wet-spinning spinning process, the drying temperature of the hot-rolling drying machine is 100-250
℃。
Currently preferred, in dry-jet wet-spinning spinning process, between the drawing-off and washing tension≤50cN.
Currently preferred, in dry-jet wet-spinning spinning process, between the multistage rotating cylinder roller in the washing procedure
Power≤100cN.
Bring advantageous effects of the present invention:
1, the present invention is made fracture using the spinning mode of dry-jet wet-spinning and is stretched by the PBO polymer of selection specific feature viscosity number
Long rate is 3.5-4.5%, and high elongation rate polyparaphenylene's benzo dioxazole (PBO) fiber of same excellent equilibrium of other indexs, this
Pbo fiber has more excellent shellproof and impact resistance, especially suitable for ballistic area, has filled up domestic blank, and suitable
For industrial-scale production.
2, currently preferred, the intrinsic viscosity of polyparaphenylene's benzo dioxazole polymer raw material is 25-32dL/g.
Pbo fiber is prepared using polyparaphenylene's benzo dioxazole polymer raw material within the scope of the intrinsic viscosity, can be more conducive to obtain
High elongation rate polyparaphenylene's benzo dioxazole fiber.
3, the invention also discloses the preparation methods of high elongation rate polyparaphenylene's benzo dioxazole fiber, in dry-jet wet-spinning
Spinning process in spinning speed be 40-200m/min, the diameter of spinneret orifice is 0.10-0.25mm, guide roller and drafting machine speed
Degree ratio is 1.01-1.05:1, tension≤500cN between drawing-off and washing, between the multistage rotating cylinder roller in washing procedure
Tension≤300cN obtains a kind of high elongation rate polyparaphenylene's benzo dioxazole fiber suitable for industrial-scale production, should
Pbo fiber has more excellent shellproof and impact resistance.
4, currently preferred, using the synthetic method of specific polyparaphenylene's benzo dioxazole polymer, wherein in advance
Polymerization uses specific PTA/DAR molar ratio, specific reaction temperature and reaction time, and obtaining solid content is 10-15%'s
PBO prepolymer, rear polymerization also use specific process parameter control, form specific polyparaphenylene's benzo dioxazole polymerization
The synthetic method of object and specific technological parameter system.The narrower polyparaphenylene's benzo two of molecular weight distribution can be made in this way
Oxazoline polymer uses polyparaphenylene's benzo dioxazole polymer to be easier to prepare the polyparaphenylene of high elongation rate for raw material
Benzo dioxazole fiber.
5, present invention employs specific dry-jet wet-spinning spinning process, wherein using a series of specific technological parameter controls
System, forms specific technological parameter system.About aperture, air layer, draw ratio, winding speed (spinning speed), speed in this method
While elongation can be increased substantially than the control with tension, its tensile strength is improved, spinning process is also more stable.
6, currently preferred, in dry-jet wet-spinning spinning process, the coagulating bath is the phosphoric acid that mass concentration is 0-20%
Aqueous solution.Currently preferred, in dry-jet wet-spinning spinning process, the temperature of the coagulating bath is 10-30 DEG C.In conjunction with the present invention
Low power stretch, molecule chain-unfolding less sufficiently may will cause the insufficient situation of phosphoric acid washing in fiber, use temperature
Degree is 10-30 DEG C, and mass concentration is the phosphate aqueous solution of 0-20% to reduce coagulation result, and process of setting is too fast, fiber dense skin
Layer can prevent the phosphoric acid of fibrous inside from spreading into external coagulating bath after being formed.
7, the present invention further defines the drying temperature of hot-rolling desiccant and optimizes tension force parameter, more favorably
In obtaining high elongation rate, and other have excellent performance balanced polyparaphenylene's benzo dioxazole fiber.
Specific embodiment
Embodiment 1
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 15-35dL/g is raw material, and the spinning mode system for passing through dry-jet wet-spinning
It is standby to form；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, extension at break
Rate is 3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
This product and other basic mechanical performances for being used for shellproof high-performance fiber product are shown in Table 1.
Several basic mechanical performances for shellproof high-performance fiber of table 1 compare
Embodiment 2
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 15dL/g is raw material, and is prepared by the spinning mode of dry-jet wet-spinning
At；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, and elongation at break is
3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
Preferably, the intrinsic viscosity of polyparaphenylene's benzo dioxazole polymer raw material is 25dL/g.
Embodiment 3
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 35dL/g is raw material, and is prepared by the spinning mode of dry-jet wet-spinning
At；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, and elongation at break is
3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
Preferably, the intrinsic viscosity of polyparaphenylene's benzo dioxazole polymer raw material is 32dL/g.
Embodiment 4
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 25dL/g is raw material, and is prepared by the spinning mode of dry-jet wet-spinning
At；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, and elongation at break is
3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
Preferably, the intrinsic viscosity of polyparaphenylene's benzo dioxazole polymer raw material is 28.5dL/g.
Embodiment 5
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 19dL/g is raw material, and is prepared by the spinning mode of dry-jet wet-spinning
At；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, and elongation at break is
3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
Preferably, the intrinsic viscosity of polyparaphenylene's benzo dioxazole polymer raw material is 30dL/g.
Embodiment 6
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 15-35dL/g is raw material, and the spinning mode system for passing through dry-jet wet-spinning
It is standby to form；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, extension at break
Rate is 3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
A kind of preparation method of above-mentioned high elongation rate polyparaphenylene benzo dioxazole fiber, including polyparaphenylene's benzo two are disliked
The synthesis of azoles polymer and dry-jet wet-spinning spinning process, during the spinning process, spinning speed 40m/min, the diameter of spinneret orifice
For 0.10mm, guide roller and drafting machine velocity ratio are 1.01:1, the tension 100cN between drawing-off and washing, in washing procedure
Multistage rotating cylinder roller between tension 200cN.
Embodiment 7
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 15-35dL/g is raw material, and the spinning mode system for passing through dry-jet wet-spinning
It is standby to form；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, extension at break
Rate is 3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
A kind of preparation method of above-mentioned high elongation rate polyparaphenylene benzo dioxazole fiber, including polyparaphenylene's benzo two are disliked
The synthesis of azoles polymer and dry-jet wet-spinning spinning process, during the spinning process, spinning speed 200m/min, the diameter of spinneret orifice
For 0.25mm, guide roller and drafting machine velocity ratio are 1.05:1, the tension 500cN between drawing-off and washing, in washing procedure
Multistage rotating cylinder roller between tension 300cN.
Embodiment 8
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 15-35dL/g is raw material, and the spinning mode system for passing through dry-jet wet-spinning
It is standby to form；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, extension at break
Rate is 3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
A kind of preparation method of above-mentioned high elongation rate polyparaphenylene benzo dioxazole fiber, including polyparaphenylene's benzo two are disliked
The synthesis of azoles polymer and dry-jet wet-spinning spinning process, during the spinning process, spinning speed 120m/min, the diameter of spinneret orifice
For 0.175mm, guide roller and drafting machine velocity ratio are 1.03:1, the tension 300cN between drawing-off and washing, in washing procedure
Multistage rotating cylinder roller between tension 250cN.
Embodiment 9
A kind of high elongation rate polyparaphenylene benzo dioxazole fiber, the high elongation rate polyparaphenylene benzo dioxazole fiber is with spy
Polyparaphenylene's benzo dioxazole polymer that property viscosity number is 15-35dL/g is raw material, and the spinning mode system for passing through dry-jet wet-spinning
It is standby to form；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-5.8GPa, extension at break
Rate is 3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
A kind of preparation method of above-mentioned high elongation rate polyparaphenylene benzo dioxazole fiber, including polyparaphenylene's benzo two are disliked
The synthesis of azoles polymer and dry-jet wet-spinning spinning process, during the spinning process, spinning speed 100m/min, the diameter of spinneret orifice
For 0.20mm, guide roller and drafting machine velocity ratio are 1.02:1, the tension 150cN between drawing-off and washing, in washing procedure
Multistage rotating cylinder roller between tension 280cN.
Embodiment 10
On the basis of embodiment 6-9:
Specific step is as follows for the synthesis of polyparaphenylene's benzo dioxazole polymer:
A, prepolymerization
Prepare terephthalic acid (TPA), 4,6- diamino resorcin hydrochlorate, polyphosphoric acids and phosphorus pentoxide；
Wherein: the molar ratio of terephthalic acid (TPA) and 4,6- diamino resorcin hydrochlorate is 1.0；
By in the dry degassing kettle of above-mentioned material investment, 10h is reacted in degassing under the conditions of 50 DEG C of temperature；Then in deaeration kettle
1h is reacted at 120 DEG C, obtains the PBO prepolymer that solid content is 10-15%；
B, rear polymerization
PBO prepolymer obtained in step A is delivered in twin-screw extrusion reaction machine by metering pump, is carried out at 150 DEG C
Post-polymerization, residence time of the material in Screw Extrusion reaction machine are 5min, obtain being dissolved in polyphosphoric acids/phosphorus pentoxide
Dicyandiamide solution, and intrinsic viscosity is the PBO polymer of 15-35dL/g.
Embodiment 11
On the basis of embodiment 6-9:
Specific step is as follows for the synthesis of polyparaphenylene's benzo dioxazole polymer:
A, prepolymerization
Prepare terephthalic acid (TPA), 4,6- diamino resorcin hydrochlorate, polyphosphoric acids and phosphorus pentoxide；
Wherein: the molar ratio of terephthalic acid (TPA) and 4,6- diamino resorcin hydrochlorate is 1.02；
By in the dry degassing kettle of above-mentioned material investment, 15h is reacted in degassing under the conditions of 110 DEG C of temperature；Then in deaeration kettle
5h is reacted at 150 DEG C, obtains the PBO prepolymer that solid content is 10-15%；
B, rear polymerization
PBO prepolymer obtained in step A is delivered in twin-screw extrusion reaction machine by metering pump, is carried out at 200 DEG C
Post-polymerization, residence time of the material in Screw Extrusion reaction machine are 30min, obtain being dissolved in polyphosphoric acids/five oxidations two
Phosphorus dicyandiamide solution, and intrinsic viscosity is the PBO polymer of 15-35dL/g.
Embodiment 12
On the basis of embodiment 6-9:
Specific step is as follows for the synthesis of polyparaphenylene's benzo dioxazole polymer:
A, prepolymerization
Prepare terephthalic acid (TPA), 4,6- diamino resorcin hydrochlorate, polyphosphoric acids and phosphorus pentoxide；
Wherein: the molar ratio of terephthalic acid (TPA) and 4,6- diamino resorcin hydrochlorate is 1.01；
By in the dry degassing kettle of above-mentioned material investment, 12.5h is reacted in degassing under the conditions of 80 DEG C of temperature；Then in deaeration kettle
3h is reacted at 135 DEG C, obtains the PBO prepolymer that solid content is 10-15%；
B, rear polymerization
PBO prepolymer obtained in step A is delivered in twin-screw extrusion reaction machine by metering pump, is carried out at 175 DEG C
Post-polymerization, residence time of the material in Screw Extrusion reaction machine are 17.5min, obtain being dissolved in polyphosphoric acids/five oxidations
Two phosphorus dicyandiamide solutions, and intrinsic viscosity is the PBO polymer of 15-35dL/g.
Embodiment 13
On the basis of embodiment 6-9:
Specific step is as follows for the synthesis of polyparaphenylene's benzo dioxazole polymer:
A, prepolymerization
Prepare terephthalic acid (TPA), 4,6- diamino resorcin hydrochlorate, polyphosphoric acids and phosphorus pentoxide；
Wherein: the molar ratio of terephthalic acid (TPA) and 4,6- diamino resorcin hydrochlorate is 1.012；
By in the dry degassing kettle of above-mentioned material investment, 13h is reacted in degassing under the conditions of 66 DEG C of temperature；Then in deaeration kettle
4.5h is reacted at 130 DEG C, obtains the PBO prepolymer that solid content is 10-15%；
B, rear polymerization
PBO prepolymer obtained in step A is delivered in twin-screw extrusion reaction machine by metering pump, is carried out at 189 DEG C
Post-polymerization, residence time of the material in Screw Extrusion reaction machine are 25min, obtain being dissolved in polyphosphoric acids/five oxidations two
Phosphorus dicyandiamide solution, and intrinsic viscosity is the PBO polymer of 15-35dL/g.
Embodiment 14
On the basis of embodiment 6-13:
Specific step is as follows for the dry-jet wet-spinning spinning:
Polyphosphoric acids/phosphorus pentoxide dicyandiamide solution PBO polymer will be dissolved in directly as spinning solution, after filtering by counting
Pump-metered is measured, is sprayed from the spinneret orifice on spinneret；The hole count of spinneret is greater than 100 holes, aperture 0.10mm, out spinneret orifice
Afterwards by the air layer of 8mm, into coagulating bath, coagulating bath is phosphate aqueous solution, and most of polyphosphoric acids in tow has been at this time
It is extracted through hydrolysis, becomes the wet yarn containing phosphoric acid, wet yarn goes to the drafting machine of multistage rotating cylinder roller by guide roller, controls tow
Draw ratio be 15；Wet yarn enters the washing procedure using multistage rotating cylinder roller later, further removes the phosphoric acid of remaining, then passes through
It is dry to cross hot-rolling drying machine, obtains dry yarn, dry yarn is wound after oiling with up- coiler, winding speed 40m/min, guide roller with lead
Stretching machine velocity ratio is 1.01:1, the tension 100cN between drawing-off and washing；Between multistage rotating cylinder roller in washing procedure
Power 200cN.
Embodiment 15
On the basis of embodiment 6-13:
Specific step is as follows for the dry-jet wet-spinning spinning:
Polyphosphoric acids/phosphorus pentoxide dicyandiamide solution PBO polymer will be dissolved in directly as spinning solution, after filtering by counting
Pump-metered is measured, is sprayed from the spinneret orifice on spinneret；The hole count of spinneret is greater than 100 holes, aperture 0.25mm, out spinneret orifice
Afterwards by the air layer of 20mm, into coagulating bath, coagulating bath is phosphate aqueous solution, and most of polyphosphoric acids in tow has been at this time
It is extracted through hydrolysis, becomes the wet yarn containing phosphoric acid, wet yarn goes to the drafting machine of multistage rotating cylinder roller by guide roller, controls tow
Draw ratio be 30；Wet yarn enters the washing procedure using multistage rotating cylinder roller later, further removes the phosphoric acid of remaining, then passes through
It is dry to cross hot-rolling drying machine, obtains dry yarn, dry yarn is wound after oiling with up- coiler, winding speed 200m/min, guide roller with
Drafting machine velocity ratio is 1.05:1, the tension 500cN between drawing-off and washing；Between multistage rotating cylinder roller in washing procedure
Tension 300cN.
Embodiment 16
On the basis of embodiment 6-13:
Specific step is as follows for the dry-jet wet-spinning spinning:
Polyphosphoric acids/phosphorus pentoxide dicyandiamide solution PBO polymer will be dissolved in directly as spinning solution, after filtering by counting
Pump-metered is measured, is sprayed from the spinneret orifice on spinneret；The hole count of spinneret is greater than 100 holes, aperture 0.175mm, out spinneret
By the air layer of 14mm behind hole, into coagulating bath, coagulating bath is phosphate aqueous solution, at this time most of polyphosphoric acids in tow
It has hydrolyzed and has been extracted, become the wet yarn containing phosphoric acid, wet yarn goes to the drafting machine of multistage rotating cylinder roller by guide roller, controls silk
The draw ratio of beam is 22；Wet yarn enters the washing procedure using multistage rotating cylinder roller later, further removes the phosphoric acid of remaining, then
It is dry by hot-rolling drying machine, dry yarn is obtained, dry yarn is wound after oiling with up- coiler, winding speed 120m/min, guide roller
It is 1.03:1 with drafting machine velocity ratio, the tension 300cN between drawing-off and washing；Between multistage rotating cylinder roller in washing procedure
Tension 250cN.
Embodiment 17
On the basis of embodiment 6-13:
Specific step is as follows for the dry-jet wet-spinning spinning:
Polyphosphoric acids/phosphorus pentoxide dicyandiamide solution PBO polymer will be dissolved in directly as spinning solution, after filtering by counting
Pump-metered is measured, is sprayed from the spinneret orifice on spinneret；The hole count of spinneret is greater than 100 holes, aperture 0.20mm, out spinneret orifice
Afterwards by the air layer of 19mm, into coagulating bath, coagulating bath is phosphate aqueous solution, and most of polyphosphoric acids in tow has been at this time
It is extracted through hydrolysis, becomes the wet yarn containing phosphoric acid, wet yarn goes to the drafting machine of multistage rotating cylinder roller by guide roller, controls tow
Draw ratio between 19；Wet yarn enters the washing procedure using multistage rotating cylinder roller later, further removes the phosphoric acid of remaining, so
It is dry by hot-rolling drying machine afterwards, dry yarn is obtained, dry yarn is wound after oiling with up- coiler, winding speed 100m/min, guiding
Roller and drafting machine velocity ratio are 1.02:1, the tension 150cN between drawing-off and washing；Multistage rotating cylinder roller in washing procedure it
Between tension 280cN.
Embodiment 17
On the basis of embodiment 6-13:
In dry-jet wet-spinning spinning process, the coagulating bath is the phosphate aqueous solution that mass concentration is 2%.
In dry-jet wet-spinning spinning process, the temperature of the coagulating bath is 10 DEG C.
In dry-jet wet-spinning spinning process, the drying temperature of the hot-rolling drying machine is 100 DEG C.
Tension 10cN in dry-jet wet-spinning spinning process, between the drawing-off and washing.
The tension 20cN between multistage rotating cylinder roller in dry-jet wet-spinning spinning process, in the washing procedure.
Embodiment 18
On the basis of embodiment 6-13:
In dry-jet wet-spinning spinning process, the coagulating bath is the phosphate aqueous solution that mass concentration is 20%.
In dry-jet wet-spinning spinning process, the temperature of the coagulating bath is 30 DEG C.
In dry-jet wet-spinning spinning process, the drying temperature of the hot-rolling drying machine is 250 DEG C.
Tension 50cN in dry-jet wet-spinning spinning process, between the drawing-off and washing.
The tension 100cN between multistage rotating cylinder roller in dry-jet wet-spinning spinning process, in the washing procedure.
Embodiment 19
On the basis of embodiment 6-13:
In dry-jet wet-spinning spinning process, the coagulating bath is the phosphate aqueous solution that mass concentration is 11%.
In dry-jet wet-spinning spinning process, the temperature of the coagulating bath is 20 DEG C.
In dry-jet wet-spinning spinning process, the drying temperature of the hot-rolling drying machine is 175 DEG C.
Tension 30cN in dry-jet wet-spinning spinning process, between the drawing-off and washing.
The tension 60cN between multistage rotating cylinder roller in dry-jet wet-spinning spinning process, in the washing procedure.
Embodiment 20
On the basis of embodiment 6-13:
In dry-jet wet-spinning spinning process, the coagulating bath is the phosphate aqueous solution that mass concentration is 19%.
In dry-jet wet-spinning spinning process, the temperature of the coagulating bath is 29 DEG C.
In dry-jet wet-spinning spinning process, the drying temperature of the hot-rolling drying machine is 190 DEG C.
Tension 19cN in dry-jet wet-spinning spinning process, between the drawing-off and washing.
The tension 99cN between multistage rotating cylinder roller in dry-jet wet-spinning spinning process, in the washing procedure.
Embodiment 21
A kind of polyparaphenylene's benzo dioxazole fiber of high elongation rate, is polyparaphenylene's benzo of 15-35dL/g with intrinsic viscosity
Dioxazole polymer is raw material, and the specially treated in the spinning process for passing through dry-jet wet-spinning is prepared, polyparaphenylene's benzene
And it is 5.4-5.8GPa, elongation at break 3.5-4.5% that the specific targets of dioxazole fiber, which include: beam yarn tensile strength, is stretched
Modulus is 140-180GPa, density 1.53-1.54g/cm3。
The preparation method of polyparaphenylene's benzo dioxazole fiber of the high elongation rate, including polyparaphenylene's benzo dioxazole
(PBO) synthesis of polymer and dry-jet wet-spinning spinning process.
The synthetic method of polyparaphenylene's benzo dioxazole (PBO) polymer of the use, the specific steps are as follows:
A prepolymerization
Terephthalic acid (TPA) (PTA), 4,6-diaminoresorcinol hydrochloride (DAR), polyphosphoric acids (PPA), phosphorus pentoxide
(P2O5)；
Wherein: the molar ratio of PTA/DAR is 1.0-1.02；
By in the dry degassing kettle of above-mentioned material investment, 10-15h is reacted in degassing under the conditions of 50-110 DEG C of temperature；Then de-
1-5h is reacted at 120-150 DEG C in bubble kettle, obtains the PBO prepolymer that solid content is 10-15%；
It polymerize after B
Prepolymer obtained in step A is delivered in twin-screw extrusion reaction machine by metering pump, is carried out at 150-200 DEG C
Post-polymerization, residence time of the material in Screw Extrusion reaction machine are 5-30min, must be dissolved in PPA/P2O5Dicyandiamide solution, it is special
Property viscosity number be 15-35dL/g PBO polymer.
The dry-jet wet spinning process includes solidification, extraction, washing, alkali cleaning, neutralization, drying, oils, winding steps.
Specific step is as follows for the dry-jet wet-spinning:
PPA/P will be dissolved in obtained in above-mentioned steps B2O5The PBO polymer raw material of dicyandiamide solution is directly as spinning solution, warp
By being sprayed after metering pump accurate measurement from spinneret after filtering；The hole count of spinneret is greater than 100, aperture 0.10-0.25mm, out
Spin hole after by 8-20mm air layer, into coagulating bath, then through the solidification pipe of supersolidification disk center, from pipe under flow out, coagulate
Admittedly the temperature bathed is 10-30 DEG C, coagulating bath is the phosphate aqueous solution that mass concentration is 0-20%；Most of PPA in tow at this time
It has hydrolyzed and has been extracted, become the wet yarn containing phosphoric acid；Wet yarn goes to the drafting machine of multistage rotating cylinder roller by guide roller, controls silk
The draw ratio of beam is between 15-30；Wet yarn enters the washing procedure using multistage rotating cylinder roller later, further removes the phosphorus of remaining
Acid；Then dry by 150-250 DEG C of hot-rolling drying machine, obtain dry yarn；Dry yarn is wound after oiling with up- coiler, winding speed
For 40-200m/min.Guide roller and drafting machine velocity ratio are 1.01-1.05:1；Tension between drawing-off and alkali cleaning needs≤
500cN, preferably≤50cN；Wash the tension≤300cN, preferably≤100cN between roller.
The long yarn mechanical property of gained is shown in Table 2.
Claims (10)
1. a kind of high elongation rate polyparaphenylene benzo dioxazole fiber, it is characterised in that: the high elongation rate polyparaphenylene benzo
Dioxazole fiber is squirted for polyparaphenylene's benzo dioxazole polymer of 15-35dL/g as raw material, and by dry using intrinsic viscosity
The spinning mode of spinning is prepared；The beam yarn tensile strength of the high elongation rate polyparaphenylene benzo dioxazole fiber is 5.4-
5.8GPa, elongation at break 3.5-4.5%, stretch modulus 140-180GPa, density 1.53-1.54g/cm3。
2. a kind of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 1, it is characterised in that: described poly-
Intrinsic viscosity to penylene benzo dioxazole polymer raw material is 25-32dL/g.
3. a kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 1, feature
It is: synthesis and dry-jet wet-spinning spinning process including polyparaphenylene's benzo dioxazole polymer, during the spinning process, spinning speed
Degree is 40-200m/min, and the diameter of spinneret orifice is 0.10-0.25mm, and guide roller and drafting machine velocity ratio are 1.01-1.05:
1, tension≤500cN between drawing-off and washing, tension≤300cN between multistage rotating cylinder roller in washing procedure.
4. a kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 3, feature
Be: specific step is as follows for the synthesis of polyparaphenylene's benzo dioxazole polymer:
A, prepolymerization
Prepare terephthalic acid (TPA), 4,6- diamino resorcin hydrochlorate, polyphosphoric acids and phosphorus pentoxide；
Wherein: the molar ratio of terephthalic acid (TPA) and 4,6- diamino resorcin hydrochlorate is 1.0-1.02；
By in the dry degassing kettle of above-mentioned material investment, 10-15h is reacted in degassing under the conditions of 50-110 DEG C of temperature；Then de-
1-5h is reacted at 120-150 DEG C in bubble kettle, obtains the PBO prepolymer that solid content is 10-15%；
B, rear polymerization
PBO prepolymer obtained in step A is delivered in twin-screw extrusion reaction machine by metering pump, at 150-200 DEG C
Post-polymerization is carried out, residence time of the material in Screw Extrusion reaction machine is 5-30min, obtains being dissolved in polyphosphoric acids/five
Two phosphorus dicyandiamide solutions are aoxidized, and intrinsic viscosity is the PBO polymer of 15-35dL/g.
5. a kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 3 or 4, special
Sign is: specific step is as follows for the dry-jet wet-spinning spinning:
Polyphosphoric acids/phosphorus pentoxide dicyandiamide solution PBO polymer will be dissolved in directly as spinning solution, after filtering by counting
Pump-metered is measured, is sprayed from the spinneret orifice on spinneret；The hole count of spinneret be greater than 100 holes, aperture 0.10-0.25mm, out
By the air layer of 8-20mm after spinneret orifice, into coagulating bath, coagulating bath is phosphate aqueous solution, most of more in tow at this time
Polyphosphoric acid, which has hydrolyzed, to be extracted, and the wet yarn containing phosphoric acid is become, and wet yarn goes to the drafting machine of multistage rotating cylinder roller by guide roller,
The draw ratio of tow is controlled between 15-30；Wet yarn enters the washing procedure using multistage rotating cylinder roller later, further removes residual
The phosphoric acid deposited, it is then dry by hot-rolling drying machine, dry yarn is obtained, dry yarn is wound after oiling with up- coiler, winding speed 40-
200m/min, guide roller and drafting machine velocity ratio are 1.01-1.05:1, tension≤500cN between drawing-off and washing；Washing
Tension≤300cN between multistage rotating cylinder roller in process.
6. a kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 5, feature
Be: in dry-jet wet-spinning spinning process, the coagulating bath is the phosphate aqueous solution that mass concentration is 0-20%.
7. a kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 5, feature
Be: in dry-jet wet-spinning spinning process, the temperature of the coagulating bath is 10-30 DEG C.
8. a kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 5, feature
Be: in dry-jet wet-spinning spinning process, the drying temperature of the hot-rolling drying machine is 100-250 DEG C.
9. a kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 5, feature
It is: tension≤50cN in dry-jet wet-spinning spinning process, between the drawing-off and washing.
10. a kind of preparation method of high elongation rate polyparaphenylene benzo dioxazole fiber according to claim 5, feature
It is: tension≤100cN between multistage rotating cylinder roller in dry-jet wet-spinning spinning process, in the washing procedure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711393409.4A CN109943906A (en) | 2017-12-21 | 2017-12-21 | A kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711393409.4A CN109943906A (en) | 2017-12-21 | 2017-12-21 | A kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109943906A true CN109943906A (en) | 2019-06-28 |
Family
ID=67004856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711393409.4A Pending CN109943906A (en) | 2017-12-21 | 2017-12-21 | A kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109943906A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110592706A (en) * | 2019-09-16 | 2019-12-20 | 浙江鼎龙科技有限公司 | Industrial production method of poly (p-phenylene-benzobisoxazole) fibers |
| CN111118669A (en) * | 2019-12-30 | 2020-05-08 | 中复神鹰碳纤维有限责任公司 | Preparation method of wear-resistant carbon fiber for high-tension winding |
| CN112760737A (en) * | 2021-01-27 | 2021-05-07 | 山东非金属材料研究所 | Preparation method of poly (p-phenylene-benzobisoxazole) fibers |
| CN112941657A (en) * | 2021-01-27 | 2021-06-11 | 山东非金属材料研究所 | Spinning forming method of poly (p-phenylene-benzobisoxazole) fibers |
| CN113105656A (en) * | 2021-04-06 | 2021-07-13 | 江苏沪江线业有限公司 | Preparation method of poly (p-phenylene-benzobisoxazole) fiber reinforced resin matrix composite material |
| CN114959936A (en) * | 2022-05-27 | 2022-08-30 | 成都新晨新材科技有限公司 | PBO fiber with oblate section and preparation method thereof |
| CN115044989A (en) * | 2022-06-07 | 2022-09-13 | 山东非金属材料研究所 | Dry-wet method forming method for PBO (Poly-p-phenylene benzobisoxazole) fibers |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295616A (en) * | 1992-01-21 | 1993-11-09 | Toray Ind Inc | Precursor for production of carbon fiber and its production |
| CN1155305A (en) * | 1994-08-05 | 1997-07-23 | 陶氏化学公司 | Method for preparing polybenzoxazole or polybenzothiazole fibers |
| CN1644772A (en) * | 2004-12-24 | 2005-07-27 | 东华大学 | Preparation of poly-p-phenylene benzodioxazole fibers |
| CN101323664A (en) * | 2008-07-24 | 2008-12-17 | 上海交通大学 | Preparation of polybenzoxazole |
| CN101568571A (en) * | 2006-07-31 | 2009-10-28 | 纳幕尔杜邦公司 | Polyarenazole microfilaments and process for making same |
| CN101824662A (en) * | 2010-04-28 | 2010-09-08 | 江苏振阳集团有限公司 | High-pressure spinning method for preparing poly (p-phenylenebenzobisoxazole) (PBO) fiber |
| CN102260932A (en) * | 2011-07-05 | 2011-11-30 | 深圳市中晟创新科技股份有限公司 | Preparation method of polyparaphenylene benzobisoxazole (PBO) fiber |
| CN102296376A (en) * | 2011-07-05 | 2011-12-28 | 深圳市中晟创新科技股份有限公司 | Production method of poly-p-phenylene benzodioxazole fibers |
| CN102943316A (en) * | 2012-11-30 | 2013-02-27 | 中蓝晨光化工研究设计院有限公司 | Technology for producing poly(p-phenylene benzobisoxazole) (PBO) fibers |
| CN103304817A (en) * | 2013-05-14 | 2013-09-18 | 徐州斯尔克纤维科技股份有限公司 | Preparation method of modified polybenzobisoxazole resin polymer |
| CN104862810A (en) * | 2015-05-18 | 2015-08-26 | 杨拯 | Method for producing PBO (poly-p-phenylene-benzobisoxazole) fibers |
-
2017
- 2017-12-21 CN CN201711393409.4A patent/CN109943906A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295616A (en) * | 1992-01-21 | 1993-11-09 | Toray Ind Inc | Precursor for production of carbon fiber and its production |
| CN1155305A (en) * | 1994-08-05 | 1997-07-23 | 陶氏化学公司 | Method for preparing polybenzoxazole or polybenzothiazole fibers |
| CN1644772A (en) * | 2004-12-24 | 2005-07-27 | 东华大学 | Preparation of poly-p-phenylene benzodioxazole fibers |
| CN101568571A (en) * | 2006-07-31 | 2009-10-28 | 纳幕尔杜邦公司 | Polyarenazole microfilaments and process for making same |
| CN101323664A (en) * | 2008-07-24 | 2008-12-17 | 上海交通大学 | Preparation of polybenzoxazole |
| CN101824662A (en) * | 2010-04-28 | 2010-09-08 | 江苏振阳集团有限公司 | High-pressure spinning method for preparing poly (p-phenylenebenzobisoxazole) (PBO) fiber |
| CN102260932A (en) * | 2011-07-05 | 2011-11-30 | 深圳市中晟创新科技股份有限公司 | Preparation method of polyparaphenylene benzobisoxazole (PBO) fiber |
| CN102296376A (en) * | 2011-07-05 | 2011-12-28 | 深圳市中晟创新科技股份有限公司 | Production method of poly-p-phenylene benzodioxazole fibers |
| CN102943316A (en) * | 2012-11-30 | 2013-02-27 | 中蓝晨光化工研究设计院有限公司 | Technology for producing poly(p-phenylene benzobisoxazole) (PBO) fibers |
| CN103304817A (en) * | 2013-05-14 | 2013-09-18 | 徐州斯尔克纤维科技股份有限公司 | Preparation method of modified polybenzobisoxazole resin polymer |
| CN104862810A (en) * | 2015-05-18 | 2015-08-26 | 杨拯 | Method for producing PBO (poly-p-phenylene-benzobisoxazole) fibers |
Non-Patent Citations (1)
| Title |
|---|
| 金俊弘等: "高性能PBO纤维的成型、性能改善及其应用研究", 《高分子通报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110592706A (en) * | 2019-09-16 | 2019-12-20 | 浙江鼎龙科技有限公司 | Industrial production method of poly (p-phenylene-benzobisoxazole) fibers |
| CN111118669A (en) * | 2019-12-30 | 2020-05-08 | 中复神鹰碳纤维有限责任公司 | Preparation method of wear-resistant carbon fiber for high-tension winding |
| CN112760737A (en) * | 2021-01-27 | 2021-05-07 | 山东非金属材料研究所 | Preparation method of poly (p-phenylene-benzobisoxazole) fibers |
| CN112941657A (en) * | 2021-01-27 | 2021-06-11 | 山东非金属材料研究所 | Spinning forming method of poly (p-phenylene-benzobisoxazole) fibers |
| CN112760737B (en) * | 2021-01-27 | 2022-09-20 | 山东非金属材料研究所 | Preparation method of poly (p-phenylene-benzobisoxazole) fibers |
| CN113105656A (en) * | 2021-04-06 | 2021-07-13 | 江苏沪江线业有限公司 | Preparation method of poly (p-phenylene-benzobisoxazole) fiber reinforced resin matrix composite material |
| CN114959936A (en) * | 2022-05-27 | 2022-08-30 | 成都新晨新材科技有限公司 | PBO fiber with oblate section and preparation method thereof |
| CN114959936B (en) * | 2022-05-27 | 2023-09-08 | 成都新晨新材科技有限公司 | Oblate cross-section PBO fiber and preparation method thereof |
| CN115044989A (en) * | 2022-06-07 | 2022-09-13 | 山东非金属材料研究所 | Dry-wet method forming method for PBO (Poly-p-phenylene benzobisoxazole) fibers |
| CN115044989B (en) * | 2022-06-07 | 2024-02-13 | 山东非金属材料研究所 | Dry-wet method forming method of PBO fibers |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109943906A (en) | A kind of high elongation rate polyparaphenylene benzo dioxazole fiber and preparation method thereof | |
| CN102146595B (en) | Method for preparing polyacrylonitrile carbon fiber protofilament by dry and wet methods | |
| CN101316956B (en) | Carbon fiber, process for production of polyacrylonitrile-base precursor fiber for carbon fiber production, and process for production of carbon fiber | |
| JP5722991B2 (en) | Carbon fiber manufacturing method and carbon fiber precursor fiber | |
| JP6194704B2 (en) | Carbon fiber bundle manufacturing method | |
| JP6020201B2 (en) | Carbon fiber bundle and method for producing the same | |
| KR20060074131A (en) | Method of preparing polyketone fibers and the polyketone fibers prepared by the method | |
| CN102260919B (en) | Method for homogenizing, solidifying and forming polyacrylonitrile precursor | |
| JP2007162144A (en) | Method for producing carbon fiber bundle | |
| US4409289A (en) | Cellulose-acrylonitrile polymer solutions, articles, and methods of making same | |
| CN104562270A (en) | Wet spinning method for improving acrylic fiber glossiness | |
| CN106591996A (en) | Preparation method of poly (p-phenylene terephthalamide) (PPTA) fiber with high elongation at break | |
| JP2010100970A (en) | Method for producing carbon fiber | |
| CN103122499B (en) | A kind of Splittable conjugate fiber and Superfine Fibre Fabric | |
| WO2020090597A1 (en) | Methods for producing carbon fiber precursor fiber and carbon fiber | |
| JP2011042893A (en) | Method for producing polyacrylonitrile-based fiber and method for producing carbon fiber | |
| JP2011017100A (en) | Method for producing carbon fiber | |
| CN110067040B (en) | High-strength elastic fiber, preparation method thereof and fabric | |
| CN115584573A (en) | T700-grade wet large-tow carbon fiber and preparation method and application thereof | |
| JPS61108713A (en) | Polyvinyl alcohol fiber having good fiber properties and its production | |
| JP2017137602A (en) | Manufacturing method of polyacrylonitrile fiber bundle | |
| JP2008280632A (en) | Method for producing precursor fiber bundle of carbon fiber | |
| TW202033850A (en) | Precursor fiber bundle production method, carbon fiber bundle production method, and carbon fiber bundle | |
| JP2010031418A (en) | Method for producing precursor fiber for carbon fiber | |
| JP2007321267A (en) | Method for producing polyacrylonitrile-based fiber and carbon fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190628 |