CN107761185B - A kind of process control method for pbo fiber production - Google Patents
A kind of process control method for pbo fiber production Download PDFInfo
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- CN107761185B CN107761185B CN201711155695.0A CN201711155695A CN107761185B CN 107761185 B CN107761185 B CN 107761185B CN 201711155695 A CN201711155695 A CN 201711155695A CN 107761185 B CN107761185 B CN 107761185B
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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Abstract
The invention discloses a kind of process control methods for pbo fiber production, with polyphosphoric acids, phosphorus pentoxide, 4,6 diamino resorcin hydrochlorates and terephthalic acid (TPA) are raw material, pbo fiber is made in degassed, prepolymerization, rear polymerization, spinning, terephthalic acid (TPA) puts into production respectively at raw material mixing, prepolymerization, rear polymerization three phases, in production process, ensure that the terephthalic acid (TPA) mole summation put into three times is equal to the mole of 4,6 diamino resorcin hydrochlorates put into raw material mix stages.The method of the present invention coordinates the polymerization for completing pbo fiber in such a way that above-mentioned TPA feeds intake for more times, the solution presasure of TPA when the initial stage of reducing feeds intake, shorten mixing early period, degassing and prepolymerized process time, is conducive to the performance for improving follow-up pbo fiber product.
Description
Technical field
The present invention is a kind of process control method for pbo fiber production, and in particular to polyparaphenylene's Benzo-dioxazole
（PBO）The control method of fibrous polymer technique productions belongs to special polymer material polymerization field.
Background technology
Polyparaphenylene's Benzo-dioxazole（PBO）Fiber is tensile strength highest in current all high-performance organic fibres, is drawn
Modulus highest is stretched, the highest extraordinary organic fiber of thermal stability is known as " super fiber of 21 century ".Since it is with excellent
Comprehensive mechanical property, therefore by extensive with extraordinary bridge cable rope, shellproof anti-ballistic materials are that space flight and aviation and national defence are high
One of important special material in new technical field.
Wolfe in 1981 et al. first reported the synthesis of PBO materials, it is by 4,6-diaminoresorcinol hydrochloride
（DAR）And terephthalic acid (TPA)（TPA）Monomer is in polyphosphoric acids（PPA）Polycondensation in solution system and be made.In building-up process, first
Increase the activity of 4,6-diaminoresorcinol by removing HCl, then adds P2O5The concentration in PPA is controlled, in 120-
210 DEG C of temperature range temperature-programmed reactions, gradually form liquid crystalline phase during the reaction, finally obtain high relative molecular mass
Polymer.The method substantially reduces reaction time, but since dissolubilities of the TPA in PPA is extremely low, need to grind TPA and refine
Processing, to increase its dissolubility in PPA solvents, finally again by the PBO/PPA solution of certain concentration by doing obtaining for spray-wet spinning
To pbo fiber.
The same also existing patent document CN102943316A that PBO polymerizations are carried out using the above method（A kind of production is poly-
To the technique of penylene Benzo-dioxazole pbo fiber, 2013.02.27）, the patent using conventional material proportion, by
Liquid crystal characteristic is presented in polymerization process solution after PBO, and viscosity is high, to use double-screw reactor, then passes through spinneret
Spinning is carried out, although solving the king-sized defect of solution viscosity in rear polymerization process using double-screw reactor, whole
Problems with is still remained in a PBO preparation processes：
（1）Since dissolubilities of the TPA in PPA is relatively low, such as grinding refinement mode of not adopting an effective measure is to TPA materials
It is handled.
（2）Degassing in the early stage is when feeding intake, just will entire whole process two kinds of monomers DAR and TPA in molar ratio 1：0.97-1.05 is straight
Whole additions are connect, since dissolubilities of the TPA in PPA is relatively low, TPA powders are in solid-state undissolved state, material mixing and stirring
Difficulty, a large amount of powders are easy to be flushed on top layer mixing kettle inner wall when DAR removes HCl, and monomer equimolar is caused to be lost than proportioning
Weighing apparatus, and degassing prepolymerization time is caused significantly to extend.
（3）TPA is added by the way of disposably feeding intake, causes reaction TPA early period dissolving degree of difficulty to increase, takes off HCl
When easily cause two monomer equivalents proportioning it is unbalance, to cause the problems such as molecular weight is not high, and molecular weight distribution is wider.
Invention content
Since existing pbo fiber production technology uses 4,6- diamino resorcin hydrochlorates（DAR）And terephthalic acid (TPA)
（TPA）The mode once to feed intake is produced, and is asked although solution viscosity is big when polymerizeing after being solved by double-screw reactor
Topic, but do not consider the low influence caused by prepolymerization and subsequent product quality of TPA dissolubilities, for this purpose, the present invention provides
A kind of process control method for pbo fiber production, this method uses more feeding modes of TPA, respectively in production process
Mixing, prepolymerization, rear polymerization procedure fed intake in proportion and coordinate the polymerization for completing pbo fiber, reduce initial stage
The solution presasure of TPA when feeding intake shortens mixing early period, degassing and prepolymerized process time, is conducive to improve follow-up PBO fibres
Tie up the performance of product.
The present invention is achieved through the following technical solutions：A kind of process control method for pbo fiber production, the PBO
Terephthalic acid (TPA) in fiber production process be according to a certain percentage substep be added in mixing, prepolymerization, rear polymerization procedure, and
The 4,6- diamino resorcin hydrochloric acid being added in the mole summation for the terephthalic acid (TPA) being added in each step and mixing step
The ratio of the mole of salt is 0.97~1.05：1, specific process step is as follows：
A, mixing, degassing are put into mixing degassing kettle after heating polyphosphoric acids, then put into phosphorus pentoxide, 4,6-
Diamino resorcin hydrochlorate and terephthalic acid (TPA), are de-gassed；
B, prepolymerization, the material that step A is deaerated carry out prepolymerization, terephthaldehyde are added in pre-polymerization process
Acid obtains prepolymerization material；
Prepolymerization material and terephthalic acid (TPA) are sent into after screw reactor carries out and are polymerize, polymerize after obtaining by C, rear polymerization
Material；
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning,
The mole of the terephthalic acid (TPA) put into the step A：The mole of the terephthalic acid (TPA) put into step B：
Mole=5.0~8.5 of the terephthalic acid (TPA) used in step C：0.5~3.5：0.1~2.0.
In described step A, B, C, terephthalic acid (TPA) is first ground to be handled to 0.2~5 μm of grain size, then is come into operation,
Convenient for increasing the dissolubility of terephthalic acid (TPA) in the solution.
In the step A, polyphosphoric acids is heated to after 60~120 DEG C putting into again in mixing degassing kettle, when degassing, temperature
At 60~120 DEG C, vacuum degree control is controlled in 0~0.08Mpa, degassing time in 2~4h for control.In actual mechanical process, mix
Conjunction, degassing time can control within 4h.
In the step B, prepolymerization temperature is 120~150 DEG C, in pre-polymerization process, measures material in mixing degassing kettle
Temperature is 80~120 DEG C, and when viscosity is 100~300Pas, terephthalic acid (TPA) is added, to be measured to obtain object in mixing degassing kettle
When expecting that viscosity is 500~800Pas, stops prepolymerization, obtain prepolymerization material.
In pre-polymerization process, viscosity test can be carried out by rotational viscometer or falling ball viscometer, can quickly tested apparent
Viscosity does standard curve without test characteristic viscosity, has the characteristics that efficiently quick.
In the step C, the discharging speed of screw reactor is 100~400ml/min.
In the step D, the dynamic viscosity for controlling material before spinneret in spinning process is 900~1100Pas.
The step of dynamic viscosity of material is 900~1100Pas before spinneret in the control spinning process is as follows：
A, every 0.5~2h is sampled the material before spinneret,
B, the dynamic viscosity of sampling material is measured；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 900~1100Pas.
In the step b, the power of sampling material is tested using rotational viscometer, falling ball viscometer or vibrating type viscometer
Viscosity.
Compared with prior art, the present invention haing the following advantages and advantageous effect：
（1）The method of the present invention is by original primary TPA all put into respectively in degassing, prepolymerization and rear polymerization process
Through putting into production three times, during feeding intake, ensure that the molar ratio of DAR and TPA total amounts is 1：10.97~1.05, by the side of feeding intake
The change of formula, on the one hand, the solution pressures of TPA in the solution when can feed intake at the initial stage of reducing so that material system solid content drops
Low, stirring is more prone to feasible, and the case where avoiding the degassing of undissolved TPA powders from being flushed to kettle wall occurs, on the other hand, moreover it is possible to
Mixing early period, degassing and the process time in prepolymerization period is greatly improved, reaches the mesh for improving pbo fiber production efficiency
's.
（2）For the method for the present invention in TPA during feeding intake three times, the molar ratio by controlling the TPA put into every time is 5.0
~8.5：0.5~3.5：0.1~2.0, it realizes the reasonable control of each TPA input ratios, avoids causing two monomer equivalent of polycondensation
Proportioning it is unbalance, polymerizable molecular amount is not high, molecular weight distribution is wider the problems such as, be conducive to the property for improving follow-up pbo fiber product
Energy.
（3）The method of the present invention controls pre-polymerization process by the efficient quickly dynamic viscosity method test system extent of reaction
The reasonable addition time of middle TPA can not only shorten the process time by the efficient monitoring carried out to material system, moreover it is possible to so that
The consistency of product is greatly enhanced between different batches, it has been proved by practice that the method for the present invention prepolymerization time can
To control within 6~10h.
（4）The method of the present invention is 900~1100Pa by controlling the dynamic viscosity of material before spinneret in spinning process
In actual mechanical process, the mode of rotary viscosity method-inherent viscosity-molecular weight mapping can be used in s, forms quickly test and prison
The reactiveness of control system, in time adjustment polymerization and spinning technology parameter so that spinning rate be 4 times of conventional spinning rate with
On, it may ultimately reach 400~550m/min.
Specific implementation mode
The present invention is described in further detail with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, is put into after polyphosphoric acids is heated in mixing degassing kettle, then put into phosphorus pentoxide, 4,6- diamino
Resorcin hydrochlorate and terephthalic acid (TPA), are de-gassed；
B, prepolymerization, the material that step A is deaerated carry out prepolymerization, terephthaldehyde are added in pre-polymerization process
Acid obtains prepolymerization material；
Prepolymerization material and terephthalic acid (TPA) are sent into after screw reactor carries out and are polymerize, polymerize after obtaining by C, rear polymerization
Material；
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning.
In above-mentioned steps, the mole and step of the 4,6-diaminoresorcinol hydrochloride put into step A are only defined
The ratio of the terephthalic acid (TPA) mole summation put into rapid A, B, C is 1：0.97, it is accordingly required in particular to, it is noted that being thrown in step A
The mole of the terephthalic acid (TPA) entered：The mole of the terephthalic acid (TPA) put into step B：The terephthaldehyde used in step C
Mole=8.0 of acid：1.5：0.5.Remaining routinely gives birth to such as the input amount of material, response parameter and related process index
Production is selected and is controlled.
Embodiment 2：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, is put into after polyphosphoric acids is heated in mixing degassing kettle, then put into phosphorus pentoxide, 4,6- diamino
Resorcin hydrochlorate and terephthalic acid (TPA), are de-gassed；
B, prepolymerization, the material that step A is deaerated carry out prepolymerization, terephthaldehyde are added in pre-polymerization process
Acid obtains prepolymerization material；
Prepolymerization material and terephthalic acid (TPA) are sent into after screw reactor carries out and are polymerize, polymerize after obtaining by C, rear polymerization
Material；
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning.
In above-mentioned steps, the mole and step of the 4,6-diaminoresorcinol hydrochloride put into step A are only defined
The ratio of the terephthalic acid (TPA) mole summation put into rapid A, B, C is 1：1, it is accordingly required in particular to, it is noted that put into step A
The mole of terephthalic acid (TPA)：The mole of the terephthalic acid (TPA) put into step B：The terephthalic acid (TPA) used in step C
Mole=6.5：3.0：0.5.Remaining as the input amount of material, response parameter and related process index routinely produce into
Row selection and control.
Embodiment 3：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, is put into after polyphosphoric acids is heated in mixing degassing kettle, then put into phosphorus pentoxide, 4,6- diamino
Resorcin hydrochlorate and terephthalic acid (TPA), are de-gassed；
B, prepolymerization, the material that step A is deaerated carry out prepolymerization, terephthaldehyde are added in pre-polymerization process
Acid obtains prepolymerization material；
Prepolymerization material and terephthalic acid (TPA) are sent into after screw reactor carries out and are polymerize, polymerize after obtaining by C, rear polymerization
Material；
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning.
In above-mentioned steps, the mole and step of the 4,6-diaminoresorcinol hydrochloride put into step A are only defined
The ratio of the terephthalic acid (TPA) mole summation put into rapid A, B, C is 1：1.05, it is accordingly required in particular to, it is noted that being thrown in step A
The mole of the terephthalic acid (TPA) entered：The mole of the terephthalic acid (TPA) put into step B：The terephthaldehyde used in step C
Mole=6.5 of acid：2.0：1.5, and, step A, in B, C, terephthalic acid (TPA) is first ground to be handled to 0.2 μm of grain size,
It comes into operation again.Remaining as the input amount of material, response parameter and related process index routinely production carry out selection and
Control.
Embodiment 4：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, is put into after polyphosphoric acids is heated in mixing degassing kettle, then put into phosphorus pentoxide, 4,6- diamino
Resorcin hydrochlorate and terephthalic acid (TPA), are de-gassed；
B, prepolymerization, the material that step A is deaerated carry out prepolymerization, terephthaldehyde are added in pre-polymerization process
Acid obtains prepolymerization material；
Prepolymerization material and terephthalic acid (TPA) are sent into after screw reactor carries out and are polymerize, polymerize after obtaining by C, rear polymerization
Material；
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning.
In above-mentioned steps, the mole and step of the 4,6-diaminoresorcinol hydrochloride put into step A are only defined
The ratio of the terephthalic acid (TPA) mole summation put into rapid A, B, C is 1：1.02, it is accordingly required in particular to, it is noted that being thrown in step A
The mole of the terephthalic acid (TPA) entered：The mole of the terephthalic acid (TPA) put into step B：The terephthaldehyde used in step C
Mole=7.5 of acid：1.0：1.5, and, step A, in B, C, terephthalic acid (TPA) is first ground to be handled to 5 μm of grain size, then
It comes into operation.Remaining is as routinely production is selected and controlled for the input amount of material, response parameter and related process index
System.
Embodiment 5：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, polyphosphoric acids is heated to after 60 DEG C putting into again in mixing degassing kettle, then put into phosphorus pentoxide, 4,
6- diamino resorcin hydrochlorates and terephthalic acid (TPA), are de-gassed, and control 60 DEG C, vacuum degree 0Mpa of degassing temperature, degassing
Time 4h.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 120 DEG C, to pre-polymerization process
It is monitored, it is 80 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 100Pas, terephthalic acid (TPA) is added again,
It is to be measured obtain mixing degassing kettle in material viscosity be 500Pas when, stop prepolymerization, obtain prepolymerization material.
Prepolymerization material and terephthalic acid (TPA) are sent into screw reactor by C, rear polymerization（It is 180 to preset reaction temperature
DEG C, rotating speed be 55 rpm）It polymerize after progress, the discharging speed for controlling screw reactor is 100ml/min, obtains post-consumer polymer
Material.
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning, in spinning process, need to control material before spinneret
Dynamic viscosity is 900Pas, and control mode is as follows：
A, the material before spinneret is sampled per 0.5h,
B, the dynamic viscosity of material is sampled using rotary viscosity measuring；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 900Pas, as shown in table 1 below.
The adjusting table of dynamic viscosity and screw reactor in 1 spinning process of table
In above-mentioned steps, the mole and step of the 4,6-diaminoresorcinol hydrochloride put into step A are defined
A, the ratio of the terephthalic acid (TPA) mole summation put into B, C is 1：0.99, it is accordingly required in particular to, it is noted that being put into step A
Terephthalic acid (TPA) mole：The mole of the terephthalic acid (TPA) put into step B：The terephthalic acid (TPA) used in step C
Mole=5.5：3.5：1.0, and, step A, in B, C, terephthalic acid (TPA) is first ground to be handled to 2.0 μm of grain size, then
It comes into operation.Remaining is as routinely production is selected and controlled for the input amount and related process index of material.
Embodiment 6：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, deaerate, polyphosphoric acids be heated to after 120 DEG C putting into again in mixing degassing kettle, then put into phosphorus pentoxide,
4,6-diaminoresorcinol hydrochloride and terephthalic acid (TPA), are de-gassed, and control 120 DEG C of degassing temperature, vacuum degree
0.08Mpa, degassing time 2h.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 150 DEG C, to pre-polymerization process
It is monitored, it is 120 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 300Pas, terephthalic acid (TPA) is added again,
It is to be measured obtain mixing degassing kettle in material viscosity be 800Pas when, stop prepolymerization, obtain prepolymerization material.
Prepolymerization material and terephthalic acid (TPA) are sent into screw reactor by C, rear polymerization（It is 180 to preset reaction temperature
DEG C, rotating speed be 60 rpm）It polymerize after progress, the discharging speed for controlling screw reactor is 400ml/min, obtains post-consumer polymer
Material.
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning, in spinning process, need to control material before spinneret
Dynamic viscosity is 1100Pas, and control mode is as follows：
A, the material before spinneret is sampled per 2h,
B, the dynamic viscosity of sampling material is measured using falling ball viscometer；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 1100Pas, as shown in table 2 below.
The adjusting table of dynamic viscosity and screw reactor in 2 spinning process of table
In above-mentioned steps, the mole and step of the 4,6-diaminoresorcinol hydrochloride put into step A are defined
A, the ratio of the terephthalic acid (TPA) mole summation put into B, C is 1：1.05, it is accordingly required in particular to, it is noted that being put into step A
Terephthalic acid (TPA) mole：The mole of the terephthalic acid (TPA) put into step B：The terephthalic acid (TPA) used in step C
Mole=5.5：3.5：1.0, and, step A, in B, C, terephthalic acid (TPA) is first ground to be handled to 0.8 μm of grain size, then
It comes into operation.Remaining is as routinely production is selected and controlled for the input amount and related process index of material.
Embodiment 7：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, polyphosphoric acids is heated to after 80 DEG C putting into again in mixing degassing kettle, then put into phosphorus pentoxide, 4,
6- diamino resorcin hydrochlorates and terephthalic acid (TPA), are de-gassed, and control 100 DEG C, vacuum degree 0.05Mpa of degassing temperature,
Degassing time 2.5h.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 125 DEG C, to pre-polymerization process
It is monitored, it is 100 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 200Pas, terephthalic acid (TPA) is added again,
It is to be measured obtain mixing degassing kettle in material viscosity be 600Pas when, stop prepolymerization, obtain prepolymerization material.
Prepolymerization material and terephthalic acid (TPA) are sent into screw reactor by C, rear polymerization（It is 180 to preset reaction temperature
DEG C, rotating speed be 65 rpm）It polymerize after progress, the discharging speed for controlling screw reactor is 300ml/min, obtains post-consumer polymer
Material.
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning, in spinning process, need to control material before spinneret
Dynamic viscosity is 1000Pas, and control mode is as follows：
A, the material before spinneret is sampled per 1h,
B, the dynamic viscosity of sampling material is measured using vibrating type viscometer；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 1000Pas, as shown in table 3 below.
The adjusting table of dynamic viscosity and screw reactor in 3 spinning process of table
In above-mentioned steps, the mole and step of the 4,6-diaminoresorcinol hydrochloride put into step A are defined
A, the ratio of the terephthalic acid (TPA) mole summation put into B, C is 1：1, it is accordingly required in particular to, it is noted that pair put into step A
The mole of phthalic acid：The mole of the terephthalic acid (TPA) put into step B：The terephthalic acid (TPA) used in step C rubs
You measure=6.0：2.0：2.0, and, step A, in B, C, terephthalic acid (TPA) is first ground to be handled to 1.2 μm of grain size, then is put into
It uses.Remaining is as routinely production is selected and controlled for the input amount and related process index of material.
Embodiment 8：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, deaerate, polyphosphoric acids be heated to after 100 DEG C putting into again in mixing degassing kettle, then put into phosphorus pentoxide,
4,6-diaminoresorcinol hydrochloride and terephthalic acid (TPA), are de-gassed, and control 105 DEG C of degassing temperature, vacuum degree
0.02Mpa, degassing time 3h.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 125 DEG C, to pre-polymerization process
It is monitored, it is 90 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 150Pas, terephthalic acid (TPA) is added again,
It is to be measured obtain mixing degassing kettle in material viscosity be 580Pas when, stop prepolymerization, obtain prepolymerization material.
Prepolymerization material and terephthalic acid (TPA) are sent into screw reactor by C, rear polymerization（It is 185 to preset reaction temperature
DEG C, rotating speed 50rpm）It polymerize after progress, the discharging speed for controlling screw reactor is 255ml/min, obtains post-consumer polymer material.
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning, in spinning process, need to control material before spinneret
Dynamic viscosity is 960Pas, and control mode is as follows：
A, the material before spinneret is sampled per 1.5h,
B, the dynamic viscosity of material is sampled using rotary viscosity measuring；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 960Pas, as shown in table 4 below.
The adjusting table of dynamic viscosity and screw reactor in 4 spinning process of table
In above-mentioned steps, the mole and step of the 4,6-diaminoresorcinol hydrochloride put into step A are defined
A, the ratio of the terephthalic acid (TPA) mole summation put into B, C is 1：1, it is accordingly required in particular to, it is noted that pair put into step A
The mole of phthalic acid：The mole of the terephthalic acid (TPA) put into step B：The terephthalic acid (TPA) used in step C rubs
You measure=6.0：1.8：2.0, and, step A, in B, C, terephthalic acid (TPA) is first ground to be handled to 0.5 μm of grain size, then is put into
It uses.Remaining is as routinely production is selected and controlled for the input amount and related process index of material.
Embodiment 9：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, 2300g polyphosphoric acids is heated to after 80 DEG C putting into again in mixing degassing kettle, then put into 901.4g five
Two phosphorus, 508.7g 4,6-diaminoresorcinols hydrochloride and 250.5g terephthalic acid (TPA)s are aoxidized, is de-gassed, control degassing
110 DEG C, vacuum degree 0.05Mpa, degassing time 2h of temperature.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 120 DEG C, to pre-polymerization process
It is monitored, it is 100 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 250Pas, 105.5g is added again to benzene
Dioctyl phthalate, it is to be measured obtain mixing degassing kettle in material viscosity be 700Pas when, stop prepolymerization, obtain prepolymer
Material.
Prepolymerization material and 25.8g terephthalic acid (TPA)s are sent into screw reactor by C, rear polymerization（Preset reaction temperature
For 180 DEG C, rotating speed 60rpm）It polymerize after progress, the discharging speed for controlling screw reactor is 350ml/min, is polymerize after obtaining
Material.
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning, in spinning process, need to control material before spinneret
Dynamic viscosity is 1050Pas, and control mode is as follows：
A, the material before spinneret is sampled per 1h,
B, the dynamic viscosity of sampling material is measured using falling ball viscometer；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 1050Pas, as shown in table 5 below.
The adjusting table of dynamic viscosity and screw reactor in 5 spinning process of table
In above-mentioned steps A, B, C, terephthalic acid (TPA) is first ground to be handled to 1.0 μm of grain size, then is come into operation, and is used
When, the mole of the 4,6-diaminoresorcinol hydrochloride put into rate-determining steps A be equal to put into step A, B, C to benzene
Dioctyl phthalate mole summation, and the mole of the terephthalic acid (TPA) put into step A：The terephthalic acid (TPA) put into step B
Mole：Mole=6.5 of the terephthalic acid (TPA) used in step C：2.7：0.8, remaining input amount and correlation such as material
Routinely production is selected and is controlled technic index.
Embodiment 10：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, 2300g polyphosphoric acids is heated to after 120 DEG C putting into again in mixing degassing kettle, then put into 901.4g
Phosphorus pentoxide, 508.7g 4,6-diaminoresorcinols hydrochloride and 268.5g terephthalic acid (TPA)s, are de-gassed, and control is de-
100 DEG C, vacuum degree 0.08Mpa, degassing time 3h of temperature degree.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 140 DEG C, to pre-polymerization process
It is monitored, it is 110 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 260Pas, 75.8g is added again to benzene two
Formic acid, it is to be measured obtain mixing degassing kettle in material viscosity be 660Pas when, stop prepolymerization, obtain prepolymer
Material.
Prepolymerization material and 37.5g terephthalic acid (TPA)s are sent into screw reactor by C, rear polymerization（Preset reaction temperature
For 180 DEG C, rotating speed 60rpm）It polymerize after progress, the discharging speed for controlling screw reactor is 310ml/min, is polymerize after obtaining
Material.
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning, in spinning process, need to control material before spinneret
Dynamic viscosity is 950Pas, and control mode is as follows：
A, the material before spinneret is sampled per 2h,
B, the dynamic viscosity of sampling material is measured using vibrating type viscometer；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 950Pas, as shown in table 6 below.
The adjusting table of dynamic viscosity and screw reactor in 6 spinning process of table
In above-mentioned steps A, B, C, terephthalic acid (TPA) is first ground to be handled to 1.5 μm of grain size, then is come into operation, and is used
When, the mole of the 4,6-diaminoresorcinol hydrochloride put into rate-determining steps A be equal to put into step A, B, C to benzene
Dioctyl phthalate mole summation, and the mole of the terephthalic acid (TPA) put into step A：The terephthalic acid (TPA) put into step B
Mole：Mole=7.0 of the terephthalic acid (TPA) used in step C：2.0：1.0, remaining input amount such as material and related work
Routinely production is selected and is controlled skill index.
Embodiment 11：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, 2300g polyphosphoric acids is heated to after 90 DEG C putting into again in mixing degassing kettle, then put into 901.4g five
Two phosphorus, 508.7g 4,6-diaminoresorcinols hydrochloride and 158.5g terephthalic acid (TPA)s are aoxidized, is de-gassed, control degassing
105 DEG C, 0~0.01Mpa of vacuum degree, degassing time 3h of temperature.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 150 DEG C, to pre-polymerization process
It is monitored, it is 100 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 300Pas, 155.8g is added again to benzene
Dioctyl phthalate, it is to be measured obtain mixing degassing kettle in material viscosity be 750Pas when, stop prepolymerization, obtain prepolymer
Material.
Prepolymerization material and 67.5g terephthalic acid (TPA)s are sent into screw reactor by C, rear polymerization（Preset reaction temperature
For 180 DEG C, rotating speed 60rpm）It polymerize after progress, the discharging speed for controlling screw reactor is 280ml/min, is polymerize after obtaining
Material.
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning, in spinning process, need to control material before spinneret
Dynamic viscosity is 1020Pas, and control mode is as follows：
A, the material before spinneret is sampled per 1h,
B, the dynamic viscosity of material is sampled using rotary viscosity measuring；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 1020Pas, as shown in table 7 below.
The adjusting table of dynamic viscosity and screw reactor in 7 spinning process of table
In above-mentioned steps A, B, C, terephthalic acid (TPA) is first ground to be handled to 0.2~5 μm of grain size, then is come into operation,
It is put into use, the mole of the 4,6-diaminoresorcinol hydrochloride put into rate-determining steps A is equal in step A, B, C
Terephthalic acid (TPA) mole summation, and the mole of the terephthalic acid (TPA) put into step A：The terephthaldehyde put into step B
The mole of acid：Mole=4.1 of the terephthalic acid (TPA) used in step C：4.0：1.9, remaining as material input amount and
Routinely production is selected and is controlled related process index.
Embodiment 12：
The present embodiment proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, 2300g polyphosphoric acids is heated to after 70 DEG C putting into again in mixing degassing kettle, then put into 901.4g five
Two phosphorus, 508.7g 4,6-diaminoresorcinols hydrochloride and 132.5g terephthalic acid (TPA)s are aoxidized, is de-gassed, control degassing
100 DEG C, 0~0.06Mpa of vacuum degree, degassing time 2h of temperature.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 130 DEG C, to pre-polymerization process
It is monitored, it is 85 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 150Pas, 158.2g is added again to benzene two
Formic acid, it is to be measured obtain mixing degassing kettle in material viscosity be 600Pas when, stop prepolymerization, obtain prepolymer
Material.
Prepolymerization material and 91.1g terephthalic acid (TPA)s are sent into screw reactor by C, rear polymerization（Preset reaction temperature
For 120 DEG C, rotating speed 55rpm）It polymerize after progress, the discharging speed for controlling screw reactor is 350ml/min, is polymerize after obtaining
Material.
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning, in spinning process, need to control material before spinneret
Dynamic viscosity is 910Pas, and control mode is as follows：
A, the material before spinneret is sampled per 0.5h,
B, the dynamic viscosity of sampling material is measured using falling ball viscometer；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until before spinneret material dynamic viscosity
To stop sampling after 910Pas, as shown in table 8 below.
The adjusting table of dynamic viscosity and screw reactor in 8 spinning process of table
In above-mentioned steps A, B, C, terephthalic acid (TPA) is first ground to be handled to 0.2~5 μm of grain size, then is come into operation,
It is put into use, the mole of the 4,6-diaminoresorcinol hydrochloride put into rate-determining steps A is equal in step A, B, C
Terephthalic acid (TPA) mole summation, and the mole of the terephthalic acid (TPA) put into step A：The terephthaldehyde put into step B
The mole of acid：Mole=3.4 of the terephthalic acid (TPA) used in step C：4.1：2.5, remaining input amount and phase such as material
Closing technic index, routinely production is selected and is controlled.
Comparative example 1：
This comparative example is using pbo fiber production technology disclosed in existing patent document CN102943316A, it is contemplated that benzene
The relatively low situation of dioctyl phthalate dissolubility in PPA, increases the pretreatment of terephthalic acid (TPA), and specific process step is as follows：
A, it deaerates, 2300g polyphosphoric acids is heated 60 minutes at 80 DEG C, subsequently into degassing kettle, add 508.7g
4,6- diamino resorcin hydrochlorates, 381.8g terephthalic acid (TPA)s（Terephthalic acid (TPA) such as embodiment 9, advance ground processing
To 1.0 μm of grain sizes, then come into operation.）It with 901.4g phosphorus pentoxides, deaerates in the kettle that deaerates, controls degassing temperature 110
DEG C, vacuum degree 0.05Mpa, degassing time 20h.
B, prepolymerization enters in mixing kettle after the completion of degassing, carries out prepolymerization and deaeration, and it is 120 DEG C to control mixing kettle,
Vacuum degree is 0~0.05Mpa, and prepolymerization is 10h with inclined heated plate, obtains prepolymerization material.
C, rear polymerization by the temperature rise of mixing kettle to 150 DEG C, then prepolymerization material is pressed into material-storage jar, by pre-polymerization
It closes material and is pressed into screw extruder by capableing of the hydraulic press of accurate control flow, control hydraulic press discharging speed is 80ml/
Min, prepolymerization material carry out post-polymerization in screw extruder, are filtering deaeration by filter, are obtaining post-consumer polymer
Material.
D, it post-processes, by post-consumer polymer material through spinning（150 DEG C of spinning temperature, 100 m/min of spinning speed）After processing
Pbo fiber is made.
Compare the pbo fiber production technology that above-described embodiment 9~12 is related to comparative example 1, difference is as shown in table 9 below.
Table 9
Above-described embodiment 9~12 is taken to be monitored with pbo fiber made from comparative example 1, fiber index parameter such as following table
Shown in 10.
Table 10
It is known that according to above-mentioned relatively content：
（1）PBO disclosed in the more existing patent document CN102943316A of pbo fiber production technology that the method for the present invention is related to
It for fibre manufacturing technique, is added by the suitable distribution of each stage terephthalic acid (TPA), mixing early period is greatly improved, takes off
Gas, the process time in prepolymerization period, the discharging speed polymerizeing after improving have and improve pbo fiber production efficiency and reduction
The advantage of production technology cost, every kilogram of pbo fiber production cost can be controlled in 1400~2000 yuan.
（2）PBO disclosed in the more existing patent document CN102943316A of pbo fiber production technology that the method for the present invention is related to
It is viscous by material power in the reasonable adjustment of each stage terephthalic acid (TPA) feed postition and spinning process for fibre manufacturing technique
The Reasonable Regulation And Control to related process parameters is spent, pbo fiber performance can be improved, by enhancing the indexs such as pbo fiber intensity, elongation
Situations such as characteristic ensures spinning efficiency on the basis of carrying high spinning rates, reduces fracture of wire.
Comparative example 2：
This comparative example proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, 2300g polyphosphoric acids is heated to after 80 DEG C putting into again in mixing degassing kettle, then put into 901.4g five
Two phosphorus, 508.7g 4,6-diaminoresorcinols hydrochloride and 285.5g terephthalic acid (TPA)s are aoxidized, is de-gassed, control degassing
100 DEG C, vacuum degree 0.08Mpa, degassing time 3h of temperature.
B, prepolymerization, the material that step A is deaerated carry out prepolymerization, control mixing degassing at a temperature of 145 DEG C
Temperature of charge obtains prepolymerization material for 120 DEG C, vacuum degree 0.096Mpa, prepolymerization time 8h in kettle.
Prepolymerization material and 96.3g terephthalic acid (TPA)s are sent into after screw reactor carries out and are polymerize, control spiral shell by C, rear polymerization
The discharging speed of bar reactor is 120ml/min, obtains post-consumer polymer material.
D, spinning, by post-consumer polymer material through spinning（200 DEG C of spinning temperature, spinning speed 180m/min）Pbo fiber is made.
In above-mentioned steps A, C, terephthalic acid (TPA) is first ground to be handled to 1.0 μm of grain size, then is come into operation, and is used
When, the mole of the 4,6-diaminoresorcinol hydrochloride put into rate-determining steps A be equal to put into step A, C to benzene two
Formic acid mole summation, and the mole of the terephthalic acid (TPA) put into step A：The terephthalic acid (TPA) used in step C rubs
You measure=7.5：2.5, remaining is as routinely production is selected and controlled for the input amount and related process index of material.
Comparative example 3：
This comparative example proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, 2300g polyphosphoric acids is heated to after 80 DEG C putting into again in mixing degassing kettle, then put into 901.4g five
Two phosphorus, 508.7g 4,6-diaminoresorcinols hydrochloride and 150.5g terephthalic acid (TPA)s are aoxidized, is de-gassed, control degassing
100 DEG C, vacuum degree 0.08Mpa, degassing time 3h of temperature.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 145 DEG C, to pre-polymerization process
It is monitored, it is 120 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 250Pas, 231.3g is added again to benzene
Dioctyl phthalate, it is to be measured obtain mixing degassing kettle in material viscosity be 650Pas when, stop prepolymerization, obtain prepolymer
Material.
Prepolymerization material is sent into after screw reactor carries out and is polymerize by C, rear polymerization, controls the discharging speed of screw reactor
Degree is 220ml/min, obtains post-consumer polymer material.
D, spinning, by post-consumer polymer material through spinning（200 DEG C of spinning temperature, spinning speed 255m/min）Pbo fiber is made.
In above-mentioned steps A, B, terephthalic acid (TPA) is first ground to be handled to 1.0 μm of grain size, then is come into operation, and is used
When, the mole of the 4,6-diaminoresorcinol hydrochloride put into rate-determining steps A be equal to put into step A, B to benzene two
Formic acid mole summation, and the mole of the terephthalic acid (TPA) put into step A：The terephthalic acid (TPA) put into step B rubs
You measure=1.0：1.5, remaining is as routinely production is selected and controlled for the input amount and related process index of material.
Compare the pbo fiber production technology that above-described embodiment 9~12 is related to comparative example 2,3, distinguishes such as the following table 11 institute
Show.
Table 11
Above-described embodiment 9~12 is taken to be monitored with pbo fiber made from comparative example 2,3, fiber index parameter is as follows
Shown in table 12.
Table 12
It is known that according to above-mentioned relatively content：
The pbo fiber production technology that the method for the present invention is related to is in raw material mix stages, prepolymerisation stage, rear polymerization stage point
The terephthalic acid (TPA) of proper range is added three times, then passes through the reasonable adjustment and spinning of each stage terephthalic acid (TPA) feed postition
Material dynamic viscosity has to the Reasonable Regulation And Control of related process parameters and improves pbo fiber production efficiency, reduces production work in the process
The characteristics of skill cost, enhancing pbo fiber properties of product, the arbitrary technology controlling and process for changing the wherein a certain stage（Such as, in comparative example 2
Reduce the addition of terephthalic acid (TPA) in prepolymerisation stage.）, the effect of the production technology can be impacted.
Comparative example 4：
This comparative example proposes a kind of process control method for pbo fiber production, the step of the process control method
It is as follows：
A, it deaerates, 2300g polyphosphoric acids is heated to after 80 DEG C putting into again in mixing degassing kettle, then put into 901.4g five
Two phosphorus, 508.7g 4,6-diaminoresorcinols hydrochloride and 300.5g terephthalic acid (TPA)s are aoxidized, is de-gassed, control degassing
100 DEG C, vacuum degree 0.08Mpa, degassing time 3h of temperature.
B, prepolymerization, the material that step A is deaerated carries out prepolymerization at a temperature of 145 DEG C, to pre-polymerization process
It is monitored, it is 120 DEG C to measure temperature of charge in mixing degassing kettle, and when viscosity is 250Pas, 40.5g is added again to benzene two
Formic acid, it is to be measured obtain mixing degassing kettle in material viscosity be 650Pas when, stop prepolymerization, obtain prepolymer
Material.
Prepolymerization material and 40.8g terephthalic acid (TPA)s are sent into after screw reactor carries out and are polymerize, control spiral shell by C, rear polymerization
The discharging speed of bar reactor is 300ml/min, obtains post-consumer polymer material.
D, spinning, spinning, by post-consumer polymer material through spinning（200 DEG C of spinning temperature, spinning speed 280m/min）PBO is made
Fiber.
In above-mentioned steps A, B, C, terephthalic acid (TPA) is first ground to be handled to 1.0 μm of grain size, then is come into operation, and is used
When, the mole of the 4,6-diaminoresorcinol hydrochloride put into rate-determining steps A be equal to put into step A, B, C to benzene
Dioctyl phthalate mole summation, and the mole of the terephthalic acid (TPA) put into step A：The terephthalic acid (TPA) put into step B
Mole：Mole=8.0 of the terephthalic acid (TPA) used in step C：1.0：1.0, remaining input amount such as material and related work
Routinely production is selected and is controlled skill index.
Compare the pbo fiber production technology that above-described embodiment 9~12 is related to comparative example 4, difference is as shown in table 13 below.
Table 13
Above-described embodiment 9~12 is taken to be monitored with pbo fiber made from comparative example 4, fiber index parameter such as following table
Shown in 14.
Table 14
It is known that according to above-mentioned relatively content：
The pbo fiber production technology that the method for the present invention is related to is in raw material mix stages, prepolymerisation stage, rear polymerization stage point
The terephthalic acid (TPA) of proper range is added three times, then passes through the reasonable adjustment and spinning of each stage terephthalic acid (TPA) feed postition
Material dynamic viscosity can improve fiber spinning rates to greatest extent to the Reasonable Regulation And Control of related process parameters in the process so that
Spinning rate is 4 times or more of conventional spinning rate, and flank speed can reach 400~550m/min, simultaneously, moreover it is possible to improve PBO
Fibre property reduces the generation of spinning fracture of wire.
The above is only presently preferred embodiments of the present invention, not does limitation in any form to the present invention, it is every according to
According to the technical spirit of the present invention to any simple modification, equivalent variations made by above example, the protection of the present invention is each fallen within
Within the scope of.
Claims (5)
1. a kind of process control method for pbo fiber production, it is characterised in that：Pair in the pbo fiber production process
Phthalic acid is that substep is added in mixing, prepolymerization, rear polymerization procedure according to a certain percentage, and is added in each step to benzene
The mole summation and the ratio of the mole for the 4,6- diamino resorcin hydrochlorates being added in mixing step of dioctyl phthalate be
0.97~1.05：1, specific process step is as follows：
A, mixing, degassing are put into mixing degassing kettle after heating polyphosphoric acids, then put into phosphorus pentoxide, 4,6- diaminos
Base resorcin hydrochlorate and terephthalic acid (TPA), are de-gassed；
B, prepolymerization, the material that step A is deaerated carry out prepolymerization, terephthalic acid (TPA) are added in pre-polymerization process, obtains
To prepolymerization material；
Prepolymerization material and terephthalic acid (TPA) are sent into after screw reactor carries out and are polymerize, obtain post-consumer polymer material by C, rear polymerization；
Pbo fiber is made through spinning in post-consumer polymer material by D, spinning,
The mole of the terephthalic acid (TPA) put into the step A：The mole of the terephthalic acid (TPA) put into step B：Step C
Mole=5.0~8.5 of the middle terephthalic acid (TPA) used：0.5~3.5：0.1~2.0,
In the step B, prepolymerization temperature is 120~150 DEG C, in pre-polymerization process, measures temperature of charge in mixing degassing kettle
It is 80~120 DEG C, when viscosity is 100~300Pas, is added terephthalic acid (TPA), to be measured to obtain material in mixing degassing kettle viscous
When degree is 500~800Pas, stops prepolymerization, obtains prepolymerization material,
In the step D, the dynamic viscosity for controlling material before spinneret in spinning process is 900~1100Pas, the control
The step of dynamic viscosity of material is 900~1100Pas before spinneret in spinning process is as follows：
A, every 0.5~2h is sampled the material before spinneret,
B, the dynamic viscosity of sampling material is measured；
C, according to the reaction temperature and rotating speed of dynamic viscosity adjusting screw rod reactor, until the dynamic viscosity of material is before spinneret
Stop sampling after 900~1100Pas.
2. a kind of process control method for pbo fiber production according to claim 1, it is characterised in that：The step
In rapid A, B, C, terephthalic acid (TPA) is first ground to be handled to 0.2~5 μm of grain size, then is come into operation.
3. a kind of process control method for pbo fiber production according to claim 1, it is characterised in that：The step
In rapid A, polyphosphoric acids is heated to after 60~120 DEG C putting into again in mixing degassing kettle, and when degassing, temperature is controlled 60~120
DEG C, vacuum degree control is controlled in 0~0.08Mpa, degassing time in 2~4h.
4. a kind of process control method for pbo fiber production according to claim 1, it is characterised in that：The step
In rapid C, the discharging speed of screw reactor is 100~400ml/min.
5. a kind of process control method for pbo fiber production according to claim 1, it is characterised in that：The step
In rapid B, the dynamic viscosity of sampling material is measured using rotational viscometer, falling ball viscometer or vibrating type viscometer.
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| 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 |
| CN113136033B (en) * | 2021-04-30 | 2022-08-19 | 成都新晨新材科技有限公司 | Control method of PBO (Poly-p-phenylene benzobisoxazole) prepolymerization process |
| CN114957663B (en) * | 2022-05-27 | 2023-08-25 | 成都新晨新材科技有限公司 | PBO polymer continuous polymerization control process, device and system thereof and computer readable storage medium |
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| CN1644772A (en) * | 2004-12-24 | 2005-07-27 | 东华大学 | Preparation of poly-p-phenylene benzodioxazole fibers |
| CN102094255A (en) * | 2010-12-23 | 2011-06-15 | 哈尔滨工业大学 | Method for industrial continuous polymerization of poly (p-phenylenebenzobisoxazole) (PBO) |
| 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 |
| CN104072771A (en) * | 2014-07-18 | 2014-10-01 | 四川宝利丰科技有限公司 | Preparation method of PBO |
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| CN1644772A (en) * | 2004-12-24 | 2005-07-27 | 东华大学 | Preparation of poly-p-phenylene benzodioxazole fibers |
| CN102094255A (en) * | 2010-12-23 | 2011-06-15 | 哈尔滨工业大学 | Method for industrial continuous polymerization of poly (p-phenylenebenzobisoxazole) (PBO) |
| 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 |
| CN104072771A (en) * | 2014-07-18 | 2014-10-01 | 四川宝利丰科技有限公司 | Preparation method of PBO |
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