CN109778342A - A kind of native staining method of polyparaphenylene's benzo dioxazole fiber - Google Patents
A kind of native staining method of polyparaphenylene's benzo dioxazole fiber Download PDFInfo
- Publication number
- CN109778342A CN109778342A CN201711121959.0A CN201711121959A CN109778342A CN 109778342 A CN109778342 A CN 109778342A CN 201711121959 A CN201711121959 A CN 201711121959A CN 109778342 A CN109778342 A CN 109778342A
- Authority
- CN
- China
- Prior art keywords
- tpa
- pigment
- pbo
- polyparaphenylene
- ppa
- 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)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to a kind of native staining methods of polyparaphenylene's benzo dioxazole fiber, belong to polymer fiber staining technique field.Part reaction monomers, pigment and polyphosphoric acids are configured to pigment/TPA/PPA slurries by the present invention, it is reacted in a manner of in-situ polymerization with prepolymer in rear polymerization process, solve the problems, such as that pbo fiber dyeing is difficult, achieve the purpose that pbo fiber dyes, the step of simplifying pbo fiber dyeing, is prepared for the higher coloured pbo fiber of dyefastness.
Description
Technical field
The present invention relates to a kind of colouring methods of fiber, it is more particularly related to a kind of polyparaphenylene's benzo two
The native staining method of oxazole fiber belongs to polymer fiber staining technique field.
Background technique
Pbo fiber is the abbreviation of polyparaphenylene's benzo dioxazole fiber.The had 5.8GPa tensile strength of the fiber and
The main performance index such as 280GPa modulus, 68 limited oxygen index LOI value and 650 DEG C of decomposition temperature, belong at present it is organic and
Inorfil performance most, specific strength is about 12-14 times of steel, and specific modulus is 1.4 times of steel, and specific gravity is 1.54-
1.56g/cm3Only the 1/5 of steel.Due to its superior performance, comes out from one and be considered as the advanced knot such as aerospace and military affairs
The super fiber of new generation of structure composite material.United States Patent (USP) introduction, pbo fiber are using 4,6-diaminoresorcinol hydrochloride
(DAR) it is then made by fiber spinning from crystalline state with terephthalic acid (TPA) (TPA), the progress solution polycondensation in polyphosphoric acids (PPA).
State Intellectual Property Office disclosed a Publication No. CN102943316A in 2013.02.27 days, and entitled " one
The invention of the technique that kind produces polyparaphenylene's benzo dioxazole pbo fiber ".This method are as follows: be proportionally added into original in degassing kettle
Material is de-gassed, and is then transferred to progress pre-polymerization deaeration in mixing kettle, is transferred to storage tank, will be stored up by HYDRAULIC CONTROL SYSTEM
It polymerize after being carried out in prepolymer indentation twin-screw in batch can, then filters spinning.The technology feeding operation is easy, to equipment precision
It is of less demanding, and heavy polymer and high performance pbo fiber can be obtained.
The pbo fiber being typically prepared is the color of polymer itself, golden yellow or yellowish-brown.And in order to meet fiber not
Same application field needs to dye pbo fiber, due to not having active group, fiber table on the macromolecular structure of pbo fiber
Face is smooth, and direct staining can be very difficult.
Summary of the invention
Present invention seek to address that problem of the prior art, provides a kind of native staining of polyparaphenylene's benzo dioxazole fiber
Method.By the method for this native staining, fiber is dyed in the rear polymerization of PBO, to solve the prior art
The difficult problem of middle pbo fiber dyeing.
In order to achieve the above-mentioned object of the invention, specific technical solution is as follows:
A kind of native staining method of polyparaphenylene's benzo dioxazole fiber, it is characterised in that: comprise the following steps that:
A, according to the needs dyed in fiber, by pigment, part polyphosphoric acids (PPA) and part terephthalic acid (TPA) in kettle with slurry
(TPA) under the conditions of 40-95 DEG C of temperature, mixing is configured to concentration of the pigment in TPA/PPA slurries greater than 0, is less than
Pigment/TPA/PPA slurries equal to 20%；
B, by whole 4,6-diaminoresorcinol hydrochlorides (DAR), phosphorus pentoxide (P2O5), remaining terephthalic acid (TPA)
(TPA) it is added in degassing kettle with remaining polyphosphoric acids (PPA), degassing reaction 8-12h under the conditions of 40-120 DEG C of temperature；
Then 1-5h is reacted in deaeration in deaeration kettle, obtains PBO prepolymer；
C, pigment/TPA/PPA slurries and PBO prepolymer are delivered by flow proportional simultaneously by twin-screw by precision metering pump
Extrusion reaction machine carries out post-polymerization and dyeing, guarantees that material residence time in twin-screw extrusion reaction machine is 5-
30min obtains post-consumer polymer；
D, the post-consumer polymer that step C is obtained is pumped into filament spinning component spinning by accurate spinning measuring, slurry precursor is by leading
It stretches, solidifies disk, coagulating bath, alkali cleaning, multi-stage water wash, is dried to obtain coloured pbo fiber.
In step A of the present invention, it is described be mixed evenly after to stir 10-48h under vacuum conditions spare.
In step B of the present invention, the inherent viscosity of the PBO prepolymer is 5-20dl/g.
In step B of the present invention, it is described then in deaeration kettle deaeration react reaction condition be 120-150 DEG C of temperature,
Absolute pressure in vacuum degree 100-2000PaA(kettle).
In step C of the present invention, wherein entering pigment/TPA/PPA slurries and the PBO pre-polymerization in twin-screw extrusion reaction machine
The flow of object is the proportion of pigment in guarantee polymer, with 4,6-diaminoresorcinol hydrochloride in polymerization process
(DAR): terephthalic acid (TPA) (TPA) is 1:0.99-1.01 to calculate.
Ratio between each raw material of the present invention is state of the art, using conventional ratio.
Spinning process of the present invention is state of the art, and specific steps can refer to Publication No. in background technique
CN102943316A, the invention of entitled " a kind of technique for producing polyparaphenylene's benzo dioxazole pbo fiber ".
Pigment in the present invention can be inorganic pigment: such as cobalt blue, cobalt green, siderochrome are black, iron oxide red is acidproof, high temperature resistant face
Material, is also possible to organic pigment: azo pigments, phthalein blueness pigment etc..
Bring advantageous effects of the present invention:
Part reaction monomers, pigment and polyphosphoric acids are configured to pigment/TPA/PPA slurries by the present invention, in rear polymerization process
In reacted in a manner of in-situ polymerization with prepolymer, solve the problems, such as that pbo fiber dyeing is difficult, reached pbo fiber dye
The purpose of color simplifies the step of pbo fiber dyes, is prepared for the higher coloured pbo fiber of dyefastness.
Specific embodiment
Embodiment 1
A kind of native staining method of polyparaphenylene's benzo dioxazole fiber, comprises the following steps that:
A, according to the needs dyed in fiber, by pigment, part polyphosphoric acids and part terephthalic acid (TPA) 40 in kettle with slurry
DEG C temperature under the conditions of, be mixed be configured to concentration of the pigment in TPA/PPA slurries be 3% pigment/TPA/PPA slurries；
B, by whole 4,6-diaminoresorcinol hydrochlorides, phosphorus pentoxide, remaining terephthalic acid (TPA) and remaining more
Polyphosphoric acid is added in degassing kettle, degassing reaction 8h under the conditions of 40 DEG C of temperature；Then 1h is reacted in deaeration in deaeration kettle, obtains
To PBO prepolymer；
C, pigment/TPA/PPA slurries and PBO prepolymer are delivered by flow proportional simultaneously by twin-screw by precision metering pump
Extrusion reaction machine carries out post-polymerization and dyeing, guarantees that material residence time in twin-screw extrusion reaction machine is 5min, obtains
To post-consumer polymer；
D, the post-consumer polymer that step C is obtained is pumped into filament spinning component spinning by accurate spinning measuring, it is fine obtains coloured PBO
Dimension.
Embodiment 2
A kind of native staining method of polyparaphenylene's benzo dioxazole fiber, comprises the following steps that:
A, according to the needs dyed in fiber, by pigment, part polyphosphoric acids and part terephthalic acid (TPA) 95 in kettle with slurry
DEG C temperature under the conditions of, be mixed be configured to concentration of the pigment in TPA/PPA slurries be 20% pigment/TPA/PPA slurry
Liquid；
B, by whole 4,6-diaminoresorcinol hydrochlorides, phosphorus pentoxide, remaining terephthalic acid (TPA) and remaining more
Polyphosphoric acid is added in degassing kettle, degassing reaction 12h under the conditions of 120 DEG C of temperature；Then 5h is reacted in deaeration in deaeration kettle,
Obtain PBO prepolymer；
C, pigment/TPA/PPA slurries and PBO prepolymer are delivered by flow proportional simultaneously by twin-screw by precision metering pump
Extrusion reaction machine carries out post-polymerization and dyeing, guarantees that material residence time in twin-screw extrusion reaction machine is 30min,
Obtain post-consumer polymer；
D, the post-consumer polymer that step C is obtained is pumped into filament spinning component spinning by accurate spinning measuring, it is fine obtains coloured PBO
Dimension.
Embodiment 3
A kind of native staining method of polyparaphenylene's benzo dioxazole fiber, comprises the following steps that:
A, according to the needs dyed in fiber, pigment, part polyphosphoric acids and part terephthalic acid (TPA) are existed in kettle with slurry
Under the conditions of 67.5 DEG C of temperature, it is mixed and is configured to pigment/TPA/PPA that concentration of the pigment in TPA/PPA slurries is 10%
Slurries；
B, by whole 4,6-diaminoresorcinol hydrochlorides, phosphorus pentoxide, remaining terephthalic acid (TPA) and remaining more
Polyphosphoric acid is added in degassing kettle, degassing reaction 10h under the conditions of 80 DEG C of temperature；Then 3h is reacted in deaeration in deaeration kettle,
Obtain PBO prepolymer；
C, pigment/TPA/PPA slurries and PBO prepolymer are delivered by flow proportional simultaneously by twin-screw by precision metering pump
Extrusion reaction machine carries out post-polymerization and dyeing, guarantees that material residence time in twin-screw extrusion reaction machine is
17.5min obtains post-consumer polymer；
D, the post-consumer polymer that step C is obtained is pumped into filament spinning component spinning by accurate spinning measuring, it is fine obtains coloured PBO
Dimension.
Embodiment 4
A kind of native staining method of polyparaphenylene's benzo dioxazole fiber, comprises the following steps that:
A, according to the needs dyed in fiber, by pigment, part polyphosphoric acids and part terephthalic acid (TPA) 55 in kettle with slurry
DEG C temperature under the conditions of, be mixed be configured to concentration of the pigment in TPA/PPA slurries be 8% pigment/TPA/PPA slurries；
B, by whole 4,6-diaminoresorcinol hydrochlorides, phosphorus pentoxide, remaining terephthalic acid (TPA) and remaining more
Polyphosphoric acid is added in degassing kettle, degassing reaction 9h under the conditions of 100 DEG C of temperature；Then deaeration is reacted in deaeration kettle
2.5h obtaining PBO prepolymer；
C, pigment/TPA/PPA slurries and PBO prepolymer are delivered by flow proportional simultaneously by twin-screw by precision metering pump
Extrusion reaction machine carries out post-polymerization and dyeing, guarantees that material residence time in twin-screw extrusion reaction machine is 21min,
Obtain post-consumer polymer；
D, the post-consumer polymer that step C is obtained is pumped into filament spinning component spinning by accurate spinning measuring, it is fine obtains coloured PBO
Dimension.
Embodiment 5
On the basis of examples 1 to 4:
In step, it is described be mixed evenly after to stir 10h under vacuum conditions spare.
In stepb, the inherent viscosity of the PBO prepolymer is 5dl/g.
In stepb, reaction condition described and then that deaeration is reacted in deaeration kettle is 120 DEG C of temperature, vacuum degree
100PaA。
In step C, wherein entering pigment/TPA/PPA slurries and PBO prepolymer stream in twin-screw extrusion reaction machine
Amount is the proportion of pigment in guarantee polymer, with 4,6-diaminoresorcinol hydrochloride in polymerization process: to benzene
Dioctyl phthalate is 1:0.99 to calculate.
The pigment can be inorganic pigment and be also possible to organic pigment.
Embodiment 6
On the basis of examples 1 to 4:
In step, it is described be mixed evenly after to stir 48h under vacuum conditions spare.
In stepb, the inherent viscosity of the PBO prepolymer is 20dl/g.
In stepb, reaction condition described and then that deaeration is reacted in deaeration kettle is 150 DEG C of temperature, vacuum degree
2000PaA。
In step C, wherein entering pigment/TPA/PPA slurries and PBO prepolymer stream in twin-screw extrusion reaction machine
Amount is the proportion of pigment in guarantee polymer, with 4,6-diaminoresorcinol hydrochloride in polymerization process: to benzene
Dioctyl phthalate is 1:1.01 to calculate.
The pigment can be inorganic pigment and be also possible to organic pigment.
Embodiment 7
On the basis of examples 1 to 4:
In step, it is described be mixed evenly after to stir 29h under vacuum conditions spare.
In stepb, the inherent viscosity of the PBO prepolymer is 12.5dl/g.
In stepb, reaction condition described and then that deaeration is reacted in deaeration kettle is 135 DEG C of temperature, vacuum degree
1050PaA。
In step C, wherein entering pigment/TPA/PPA slurries and PBO prepolymer stream in twin-screw extrusion reaction machine
Amount is the proportion of pigment in guarantee polymer, with 4,6-diaminoresorcinol hydrochloride in polymerization process: to benzene
Dioctyl phthalate is 1:1 to calculate.
The pigment can be inorganic pigment and be also possible to organic pigment.
Embodiment 8
On the basis of examples 1 to 4:
In step, it is described be mixed evenly after to stir 15h under vacuum conditions spare.
In stepb, the inherent viscosity of the PBO prepolymer is 19dl/g.
In stepb, reaction condition described and then that deaeration is reacted in deaeration kettle is 125 DEG C of temperature, vacuum degree
500PaA。
In step C, wherein entering pigment/TPA/PPA slurries and PBO prepolymer stream in twin-screw extrusion reaction machine
Amount is the proportion of pigment in guarantee polymer, with 4,6-diaminoresorcinol hydrochloride in polymerization process: to benzene
Dioctyl phthalate is 1:0.991 to calculate.
The pigment can be inorganic pigment and be also possible to organic pigment.
Embodiment 9
In the kettle with slurry of 50L, polyphosphoric acids (PPA) 13200 g is added, terephthalic acid (TPA) 810g, cobalt blue 540g, 40 is added
5h is stirred under the conditions of DEG C -80 DEG C, it is ensured that cobalt blue and terephthalic acid (TPA) are all infiltrated by PPA, are then vacuumized, and continue to stir 20h.
Concentration at this time with terephthalic acid (TPA) in slurries is 5.57%, and the concentration of cobalt blue is 3.71%.
88% that polyphosphoric acids (PPA) 42350g(is the total feeding quantity of polymerization is sequentially added in 200L degassing kettle), five oxidations
Two phosphorus (P2O5) 17700g, terephthalic acid (TPA) (TPA) 6707g(account for the 95% of TPA total amount of feeding), 4,6-diaminoresorcinol
Hydrochloride (DAR) 9000g seals degassing kettle, air in nitrogen displacement kettle.
Revolving speed is improved after being slowly stirred 1h under the conditions of 80 DEG C, is kept material temperature to be no more than 110 DEG C of degassing 10h, is then passed through
Delivery pump is transferred in deaeration kettle, is kept the temperature 120-150 DEG C of vacuum and is slowly stirred.The dynamic viscosity of PBO polymer fluid is at this time
1560Pas(110 DEG C), inherent viscosity 8.3dL/g.
PBO polymer fluid is matched with 42.6g/min, cobalt blue/TPA/PPA by slurries 3.72g/min by precision metering pump respectively
Flow be sent into double screw extruder, material residence time in twin-screw is 14min, and PBO polymer solids level is
12.5%, inherent viscosity 28.6dL/g.
According to Publication No. CN102943316A, a kind of entitled " work for producing polyparaphenylene's benzo dioxazole pbo fiber
Spinning process carries out PBO spinning in the invention of skill ", spins speed 50m/min, fiber number 115.5tex, the blue pbo fiber of preparation
(AS-PBO), wherein dye content is 2.3%, and the tensile strength of fiber is 32.6cN/dtex.
Embodiment 10
In the kettle with slurry of 50L, polyphosphoric acids (PPA) 10184g, terephthalic acid (TPA) (TPA) 810g, cobalt blue 578g, 40 is added
5h is stirred under the conditions of DEG C -80 DEG C, it is ensured that TPA is all infiltrated by PPA, is then vacuumized, and vacuum degree 0.096MPa continues to stir
20h.Concentration at this time with terephthalic acid (TPA) in slurries is 7%, and the concentration of cobalt blue is 5%.
96.29% that polyphosphoric acids (PPA) 46315g(is the total feeding quantity of polymerization is sequentially added in 200L degassing kettle), five
Two phosphorus (P2O5) 17700g is aoxidized, terephthalic acid (TPA) (TPA) 6918g(accounts for the 98% of TPA total amount of feeding), 4,6- diamino isophthalic
Diphenol hydrochloride (DAR) 9000g seals degassing kettle, air in nitrogen displacement kettle.
Revolving speed is improved after being slowly stirred 1h under the conditions of 80 DEG C, is kept material temperature to be no more than 110 DEG C of degassing 15h, is warming up to 120
DEG C reaction 10h, is then transferred to that deaeration is mixed to be criticized in kettle by delivery pump, keeps the temperature 110 DEG C of vacuum and is slowly stirred.PBO is poly- at this time
The dynamic viscosity for closing liquid is 350Pas(110 DEG C), inherent viscosity 15.5dL/g.
PBO polymer fluid is matched with 48.1g/min, cobalt blue/TPA/PPA by slurries 1.27g/min by precision metering pump respectively
Flow be sent into double screw extruder in, material in twin-screw the residence time be 4h.The PBO polymer fluid polymerizeing after screw rod
PBO polymer solids level is 12.5%, inherent viscosity 33.2dL/g.
According to Publication No. CN102943316A, a kind of entitled " work for producing polyparaphenylene's benzo dioxazole pbo fiber
Spinning process carries out PBO spinning in the invention of skill ", spins speed 55m/min, fiber number 112.2tex, the blue pbo fiber of preparation
(AS-PBO), wherein cobalt blue content is 1%, and the tensile strength of fiber is 36.3cN/dtex.
Embodiment 11
In the kettle with slurry of 50L, polyphosphoric acids (PPA) 14742g, terephthalic acid (TPA) (TPA) 810g, the black 648g of siderochrome is added,
5h is stirred under the conditions of 75 DEG C, it is ensured that TPA is all infiltrated by PPA, is then vacuumized, and vacuum degree 0.096MPa continues to stir
20h.Concentration at this time with terephthalic acid (TPA) in slurries is 5%, and the black concentration of siderochrome is 4%.
89.31% that polyphosphoric acids (PPA) 42958g(is the total feeding quantity of polymerization is sequentially added in 200L degassing kettle), five
Two phosphorus (P2O5) 17700g is aoxidized, terephthalic acid (TPA) (TPA) 6778g(accounts for the 96% of TPA total amount of feeding), 4,6- diamino isophthalic
Diphenol hydrochloride (DAR) 9000g seals degassing kettle, air in nitrogen displacement kettle.
Revolving speed is improved after being slowly stirred 1h under the conditions of 80 DEG C, is kept material temperature to be no more than 110 DEG C of degassing 15h, is warming up to 120
DEG C reaction 10h, is then transferred to that deaeration is mixed to be criticized in kettle by delivery pump, keeps the temperature 110 DEG C of vacuum and is slowly stirred.PBO is poly- at this time
The dynamic viscosity for closing liquid is 350Pas(110 DEG C), inherent viscosity 10.7dL/g.
PBO polymer fluid is matched with 45.6g/min, TPA/PPA by the flow of slurries 3.51g/min by precision metering pump respectively
It is sent into double screw extruder, material residence time in twin-screw is 4h.The PBO polymer fluid PBO polymerizeing after screw rod is poly-
Closing object solid content is 12.5%, inherent viscosity 31.4dL/g.
According to Publication No. CN102943316A, a kind of entitled " work for producing polyparaphenylene's benzo dioxazole pbo fiber
Spinning process carries out PBO spinning in the invention of skill ", spins speed 55m/min, fiber number 111.6tex, the brown pbo fiber of preparation
(AS-PBO) wherein the black content of siderochrome is 2.25%, and the tensile strength of fiber is 35.8N/dtex.
Embodiment 12
In the kettle with slurry of 50L, polyphosphoric acids (PPA) 14742g, terephthalic acid (TPA) (TPA) 810g, cobalt green 648g, 75 is added
5h is stirred under the conditions of DEG C, it is ensured that TPA is all infiltrated by PPA, is then vacuumized, vacuum degree 0.096MPa, continues to stir 20h.
Concentration at this time with terephthalic acid (TPA) in slurries is 5%, and the concentration of cobalt green is 4%.
89.31% that polyphosphoric acids (PPA) 42958g(is the total feeding quantity of polymerization is sequentially added in 200L degassing kettle), five
Two phosphorus (P2O5) 17700g is aoxidized, terephthalic acid (TPA) (TPA) 6778g(accounts for the 96% of TPA total amount of feeding), 4,6- diamino isophthalic
Diphenol hydrochloride (DAR) 9000g seals degassing kettle, air in nitrogen displacement kettle.
Revolving speed is improved after being slowly stirred 1h under the conditions of 80 DEG C, is kept material temperature to be no more than 110 DEG C of degassing 15h, is warming up to 120
DEG C reaction 10h, is then transferred to that deaeration is mixed to be criticized in kettle by delivery pump, keeps the temperature 110 DEG C of vacuum and is slowly stirred.PBO is poly- at this time
The dynamic viscosity for closing liquid is 350Pas(110 DEG C), inherent viscosity 10.3dL/g.
PBO polymer fluid is matched with 45.6g/min, TPA/PPA by the flow of slurries 3.51g/min by precision metering pump respectively
It is sent into double screw extruder, material residence time in twin-screw is 4h.The PBO polymer fluid PBO polymerizeing after screw rod is poly-
Closing object solid content is 12.5%, inherent viscosity 30.7dL/g.
According to Publication No. CN102943316A, a kind of entitled " work for producing polyparaphenylene's benzo dioxazole pbo fiber
Spinning process carries out PBO spinning in the invention of skill ", spins speed 55m/min, fiber number 111.5tex, the green pbo fiber of preparation
(AS-PBO) wherein cobalt green content is 2.25%, and the tensile strength of fiber is 36.4N/dtex.
Embodiment 13
Comparative experiments:
Using prepolymerization and rear polymerization technique, preparing polymer solids level is 12.5%, and inherent viscosity is the PBO of 31.4dL/g
Spinning solution, according to Shen according to Publication No. CN102943316A, entitled " a kind of production polyparaphenylene benzo dioxazole PBO is fine
Middle spinning process carries out PBO spinning in the invention of the technique of dimension ", spins speed 50m/min, fiber number 108.2tex, the stretching of fiber
Intensity is 37.1N/dtex.It is wound into 3 axis, the pbo fiber of every axis 500g respectively.By comparing the fiber number difference meter of dyeing front and back
Calculate the content of pigment after dyeing.
Above-mentioned 3 axis fibre number is recorded, then by fiber number 1,2,3.By pigment cobalt blue, siderochrome is black, cobalt green is matched respectively
At 5% slurries, No. 1 fiber is immersed in cobalt blue slurries respectively, No. 2 fibers are immersed in siderochrome black wash liquid, No. 3 fibers are soaked
In cobalt green slurries, for 24 hours, taking-up is drained for leaching, is dried in vacuum drying oven, is weighed fibre number, calculates the content of pigment in fiber,
Then the pigment content of fiber, degree of color uniformity and dyefastness compared with above-described embodiment 9-12 respectively.Wherein dyeing jail
Degree tests the fastness to rubbing of fibre bundle according to the method for GB/T3920-2008.
It can find out from table, 9-12 of the embodiment of the present invention is relative to comparative example, pigment content, uniformity coefficient and resistance to
Colorfastness to rubbing all has a clear superiority.
Claims (6)
1. a kind of native staining method of polyparaphenylene's benzo dioxazole fiber, it is characterised in that: comprise the following steps that:
A, according to the needs dyed in fiber, by pigment, part polyphosphoric acids and part terephthalic acid (TPA) in 40- in kettle with slurry
Under the conditions of 95 DEG C of temperature, mixing is configured to concentration of the pigment in TPA/PPA slurries and is greater than 0, the face less than or equal to 20%
Material/TPA/PPA slurries；
B, by whole 4,6-diaminoresorcinol hydrochlorides, phosphorus pentoxide, remaining terephthalic acid (TPA) and remaining more
Polyphosphoric acid is added in degassing kettle, degassing reaction 8-12h under the conditions of 40-120 DEG C of temperature；Then deaeration is anti-in deaeration kettle
1-5h is answered, PBO prepolymer is obtained；
C, pigment/TPA/PPA slurries and PBO prepolymer are delivered by flow proportional simultaneously by twin-screw by precision metering pump
Extrusion reaction machine carries out post-polymerization and dyeing, guarantees that material residence time in twin-screw extrusion reaction machine is 5-
30min obtains post-consumer polymer；
D, the post-consumer polymer that step C is obtained is pumped into filament spinning component spinning by accurate spinning measuring, it is fine obtains coloured PBO
Dimension.
2. a kind of native staining method of polyparaphenylene's benzo dioxazole fiber according to claim 1, it is characterised in that:
In step, it is described be mixed evenly after to stir 10-48h under vacuum conditions spare.
3. a kind of native staining method of polyparaphenylene's benzo dioxazole fiber according to claim 1, it is characterised in that:
In stepb, the inherent viscosity of the PBO prepolymer is 5-20dl/g.
4. a kind of native staining method of polyparaphenylene's benzo dioxazole fiber according to claim 1, it is characterised in that:
In stepb, reaction condition described and then that deaeration is reacted in deaeration kettle is 120-150 DEG C of temperature, vacuum degree 100-
2000PaA。
5. a kind of native staining method of polyparaphenylene's benzo dioxazole fiber according to claim 1, it is characterised in that:
In step C, wherein the flow of the pigment/TPA/PPA slurries and PBO prepolymer that enter in twin-screw extrusion reaction machine is to protect
It demonstrate,proves in polymer in the case of the proportion of pigment, with 4,6-diaminoresorcinol hydrochloride in polymerization process: terephthalic acid (TPA) is
1:0.99-1.01 is calculated.
6. a kind of native staining method of polyparaphenylene's benzo dioxazole fiber according to claim 1, it is characterised in that:
The pigment can be inorganic pigment and be also possible to organic pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711121959.0A CN109778342A (en) | 2017-11-14 | 2017-11-14 | A kind of native staining method of polyparaphenylene's benzo dioxazole fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711121959.0A CN109778342A (en) | 2017-11-14 | 2017-11-14 | A kind of native staining method of polyparaphenylene's benzo dioxazole fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109778342A true CN109778342A (en) | 2019-05-21 |
Family
ID=66493521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711121959.0A Pending CN109778342A (en) | 2017-11-14 | 2017-11-14 | A kind of native staining method of polyparaphenylene's benzo dioxazole fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109778342A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323507A (en) * | 2022-09-05 | 2022-11-11 | 成都新晨新材科技有限公司 | Method for blending dyeing of PBO (Poly-p-phenylene benzobisoxazole) fibers |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3528247B2 (en) * | 1994-07-13 | 2004-05-17 | 東洋紡績株式会社 | Polybenzazole fiber and fiber cloth |
| CN1644772A (en) * | 2004-12-24 | 2005-07-27 | 东华大学 | Preparation of poly-p-phenylene benzodioxazole fibers |
| CN1665973A (en) * | 2002-06-26 | 2005-09-07 | 东洋纺织株式会社 | Polybenzazole fiber and use thereof |
| CN1890413A (en) * | 2003-12-11 | 2007-01-03 | 东洋纺织株式会社 | Polybenzazole fiber and article comprising the same |
| 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 |
| CN103726124A (en) * | 2014-01-03 | 2014-04-16 | 烟台泰和新材料股份有限公司 | Dope-dyed p-aramid filament yarn and preparation method thereof |
| WO2015159749A1 (en) * | 2014-04-14 | 2015-10-22 | 帝人株式会社 | Colored organic fiber, fabric and clothing and method for manufacturing fabric |
-
2017
- 2017-11-14 CN CN201711121959.0A patent/CN109778342A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3528247B2 (en) * | 1994-07-13 | 2004-05-17 | 東洋紡績株式会社 | Polybenzazole fiber and fiber cloth |
| CN1665973A (en) * | 2002-06-26 | 2005-09-07 | 东洋纺织株式会社 | Polybenzazole fiber and use thereof |
| CN1890413A (en) * | 2003-12-11 | 2007-01-03 | 东洋纺织株式会社 | Polybenzazole fiber and article comprising the same |
| CN1644772A (en) * | 2004-12-24 | 2005-07-27 | 东华大学 | Preparation 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 |
| CN103726124A (en) * | 2014-01-03 | 2014-04-16 | 烟台泰和新材料股份有限公司 | Dope-dyed p-aramid filament yarn and preparation method thereof |
| WO2015159749A1 (en) * | 2014-04-14 | 2015-10-22 | 帝人株式会社 | Colored organic fiber, fabric and clothing and method for manufacturing fabric |
Non-Patent Citations (1)
| Title |
|---|
| 吴大诚 等: "《合成纤维熔体纺丝》", 31 October 1980, 纺织工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115323507A (en) * | 2022-09-05 | 2022-11-11 | 成都新晨新材科技有限公司 | Method for blending dyeing of PBO (Poly-p-phenylene benzobisoxazole) fibers |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104499079B (en) | A kind of original liquid coloring is prepared the method for black polyester fiber | |
| CN102943316B (en) | Technology for producing poly(p-phenylene benzobisoxazole) (PBO) fibers | |
| CN104293116B (en) | A kind of photocuring 3 D-printing material and preparation method and application | |
| CN103255498B (en) | Method for preparing colored polyester fiber by coloring stock solution | |
| CN109778342A (en) | A kind of native staining method of polyparaphenylene's benzo dioxazole fiber | |
| CN113858720B (en) | Carbon fiber composite board and preparation method thereof | |
| CN105419461A (en) | UV (ultraviolet) offset metal ink and preparation method thereof | |
| CN104862826A (en) | Preparation method of PIPD/PBO (poly(dihydroxyphenylene pyridobisimidazole)/poly-p-phenylene ben-zobisthiazole) blend fiber | |
| CN102260932A (en) | Preparation method of polyparaphenylene benzobisoxazole (PBO) fiber | |
| US20240270906A1 (en) | Polyamide resin and preparation method therefor, composition, and fiber product | |
| CN101613892B (en) | Preparation method of poly(p-phenylene benzobisoxazole) composite fiber containing nano-TiO2 | |
| CN116623309B (en) | Polymer coloring method, spinning color paste, spinning solution and colored fiber | |
| CN104448277A (en) | Perfluoropolyether modified antifouling droplet-preventing copolyester and preparation method thereof | |
| CN202030686U (en) | Device for continuously preparing poly-p-phenylene terephthamide polymer | |
| CN113150266B (en) | Production system and production method of polyamide | |
| CN110724262B (en) | Ternary light-resistant liquid crystal copolymer containing oxazole structure and preparation and application thereof | |
| CN109778338B (en) | Production process for continuous polymerization spinning of poly (p-phenylene benzobisoxazole) fibers | |
| CN112724398A (en) | Production device and process for in-situ polymerization coloring graphene modified polyamide-6 slice | |
| CN112281244A (en) | Preparation method of stock solution dyed aramid 1414 fibers | |
| CN218372640U (en) | Screw extrusion device for preparing dyed PBO fibers | |
| CN110628164A (en) | Material for anesthesia machine and preparation method thereof | |
| CN105040465A (en) | Pigment dyeing liquor for dyeing superfine fibers and method for improving dyeing color depth of superfine fibers | |
| CN110093010A (en) | A kind of anti-shearing carbon fiber composite board | |
| CN109722903A (en) | A kind of polysulfone resin based composites carbon fiber and preparation method thereof | |
| CN113005582B (en) | Colorful spandex fiber and preparation method thereof |
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: 20190521 |