CN104693348B - A kind of preparation method of carbon fibre precursor ternary polyacrylonitrile copolymer - Google Patents
A kind of preparation method of carbon fibre precursor ternary polyacrylonitrile copolymer Download PDFInfo
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- CN104693348B CN104693348B CN201510117462.6A CN201510117462A CN104693348B CN 104693348 B CN104693348 B CN 104693348B CN 201510117462 A CN201510117462 A CN 201510117462A CN 104693348 B CN104693348 B CN 104693348B
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Abstract
The present invention relates to the preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer; under nitrogen protective condition; acrylonitrile, itaconic acid, dispersant and water are mixed, is warming up to 60 75 DEG C, is added dropwise to initiator solution, acrylamide aqueous solution the most successively; clock reaction 3 24h after dropping; washing, de-single, filter; it is dried, to obtain final product.The present invention uses aqueous suspension polymerization method to be polymerized, and polymerization reaction heat is prone to get rid of, and polymerization temperature is easily controlled, and product mean molecule quantity is higher, narrow molecular weight distribution；Polyacrylonitrile copolymer prepared by the present invention can be effectively improved its thermal stability in the high temperature pre-oxidation stage, has certain actual application prospect.
Description
Technical field
The invention belongs to the preparation field of carbon fibre precursor copolymer, particularly to a kind of carbon fibre precursor ternary polyacrylonitrile
The preparation method of copolymer.
Background technology
Carbon fiber has high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, endurance, conduction, damping, heat transfer, anti-spoke
Penetrate a series of excellent properties such as little with proportion, be widely used in Aero-Space, military and national defense, environmental protection, medicine equipment and physical culture
The industries such as articles for use.
The macromolecular chain structure of HOPP nitrile is more regular, and degree of crystallinity is high, occurs with free radical mechanism when pre-oxidation cyclisation
Reaction, it is difficult to control, it is impossible to obtain carbon fiber of good performance.When preparing carbon fiber polyacrylonitrile-radical presoma, typically want
Ask acrylonitrile content more than 96%, be usually added into a small amount of vinyl monomer and carry out copolymerization with acrylonitrile.The one of copolymerization component selection
As require be: have similar reactivity ratio to acrylonitrile, be easily polymerized, stable spinning solution, good spinnability after polymerization, can be formed；
Can promote the pre-oxidation of precursor, after pre-oxidation, fibre structure is uniform；During carbonization, fault of construction is the fewest, and carbon yield is high.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer,
The present invention uses aqueous dispersion polymerization process to be polymerized, and polymerization reaction heat is prone to get rid of, and polymerization temperature is easily controlled, and product is put down
Average molecular weight is higher, narrow molecular weight distribution.
A kind of preparation method of the carbon fibre precursor ternary polyacrylonitrile copolymer of the present invention, including:
Under nitrogen protective condition, monomers acrylonitrile, itaconic acid (the second comonomer), dispersant and water are mixed, is warming up to
60-75 DEG C, it is added dropwise to initiator solution, acrylamide (the 3rd comonomer) aqueous solution the most successively, counts after dropping
Shi Fanying 3-24h (after being added dropwise to initiator and acrylamide, then reacts 3-24h), acrylonitrile polymer slurry, washing, de-
Single, filter, be dried, obtain ternary polyacrylonitrile copolymer；Wherein acrylonitrile, itaconic acid, the mass ratio of acrylamide are
96-99:0.5-3:0.5-1。
The protection of described nitrogen is that polymerisation pre-polymerization reaction generator vacuumizes, leads to nitrogen circulation 3 times, then adds polymer raw,
Logical nitrogen is kept in whole polymerization process.
Described dispersant is polyvinyl alcohol；Dispersant dosage is acrylonitrile, itaconic acid, the 0.5%-2.0% of acrylamide gross mass.
Described polyvinyl alcohol is one or more in polyvinyl alcohol 1755, polyvinyl alcohol 1788, polyvinyl alcohol 1799.
Described initiator is ammonium persulfate, and initiator amount is acrylonitrile, itaconic acid and the 0.2-2.0% of acrylamide gross mass.
Described acrylonitrile, itaconic acid and acrylamide account for the 20-33wt% of gross mass；Acrylonitrile, itaconic acid and acrylamide gross mass with
The ratio of water quality is 77%-80%；Water is deionized water.
In described initiator solution, the mass ratio of initiator and water is 0.23:5-10；Acrylamide and the matter of water in acrylamide aqueous solution
Amount ratio is 0.23:5-10.
Described be warming up to 60-75 DEG C after, constant temperature 0.5-2h.
The time of described dropping initiator solution is 0.1-0.5h；The time of dropping acrylamide aqueous solution is 0.1-1h.
Described baking temperature is 50-60 DEG C, and the time is 12-24h.
The viscosity average molecular weigh of described ternary polyacrylonitrile copolymer is 300,000-45.8 ten thousand.
The feed postition of described second comonomer itaconic acid uses to add before initiator initiated polymerization starts and the most all adds,
After sonic oscillation 1～4h, using the method for progressively dropping continuously to add the 3rd comonomer, persistently dropping 1 hour is until the 3rd is single
Body is added dropwise to complete.
This patent employing itaconic acid and acrylamide carry out copolymerization with acrylonitrile and prepare polyacrylonitrile copolymer, improve polyacrylonitrile and spin
The hydrophily of silk stock solution and the compactness of strand, significantly improve its high-temperature thermal stability performance simultaneously.
The introducing of comonomer in the present invention, it is possible to improve the hydrophily of polyacrylonitrile spinning solution and the compactness of strand, can add
The cyclisation of the speed big molecule of linear polyacrylonitrile, makes HOPP nitrile be converted into ionic in the radical reaction of preoxidation process anti-
Should, relax the fiber very exothermic reaction when pre-oxidation, made exothermic reaction easily controllable, and provide oxygen to expand to fiber core
Dissipate and the molecular level passage of infiltration, substantially increase pre-oxidation and carbonization speed, make carbon fiber performance and carbonization rate all be carried
High.Meanwhile, the existence of comonomer hinders polar group cyano group and the formation of adjacent carbon atom hydrogen bond on macromolecular chain, reduces
The flexibility of polyacrylonitrile macromolecular chain, improves spinnability and the drawability energy of polyacrylonitrile copolymer.Particularly itaconic acid
Two carboxyls in molecule can cause polyacrylonitrile fibril to pre-oxidize by ionic mechanism, and efficiency of initiation is higher, can substantially drop
Low cyclisation temperature, makes exothermic peak broaden simultaneously, and rate of heat release reduces.Acrylamide comonomer can reduce the fusing point of polymer
And improve decomposition temperature, improve the spinnability of stoste.
Beneficial effect
(1) present invention uses aqueous suspension polymerization method to be polymerized, and polymerization reaction heat is prone to get rid of, and polymerization temperature is easily controlled,
Product mean molecule quantity higher (300,000～45.8 ten thousand), narrow molecular weight distribution；
(2) present invention has reaction yield height, and reaction system viscosity is low, easy temperature control system, constant product quality；
(3) polymerization slurry in the present invention is easily handled, and can save solvent recovery process；
(4) polyacrylonitrile polymer prepared by the present invention can be effectively improved its thermal stability in the high temperature pre-oxidation stage, has
Certain application prospect.
Accompanying drawing explanation
Fig. 1 is gel permeation chromatography (GPC) figure that in embodiment 1, polyacrylonitrile polymer records after dissolving；
Fig. 2 is resulting polymers nanometer particle size figure in embodiment 1；
Fig. 3 be in embodiment 2 polymerization temperature to copolymer conversion ratio and molecular weight effects figure；
Fig. 4 is the DSC figure of polymer in embodiment 3.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and not
For limiting the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art can
To make various changes or modifications the present invention, these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
Polymer reactor vacuumizes, logical nitrogen circulation 3 times, under the conditions of 35 DEG C by 22.31g acrylonitrile, 0.46g itaconic acid,
0.23g polyvinyl alcohol (1755) and 60g deionized water join in 5L glass reaction generator, logical nitrogen 30min, heat up
To 60 DEG C and constant temperature 0.5h at this temperature, then drip ammonium persulfate (0.23g/10gH2O) aqueous solution completing in 0.5h,
After initiator adds, same dropping mode is taked to add acrylamide (0.23g/7gH2O) aqueous solution completing in 1h.
Keeping reaction 24 hours at 60 DEG C, the polyacrylonitrile viscosity average molecular weigh of preparation is 3.4 × 10 simultaneously5G/mol, molecular weight divides
Cloth is 2.98.Above-mentioned polymer slurries is filtered, de-single, it is dried and prepares white particle sprills, recording copolymer conversion ratio is
87.7%.Under nitrogen atmosphere, DSC test (uses TA company of U.S. Q20 differential scanning calorimeter, with 5 DEG C/min's
Speed is risen to 310 DEG C from 30 DEG C), (prepared by same polymeric condition, viscous for its cyclisation initial temperature relatively HOPP nitrile
Average molecular weight 36.2 ten thousand) reduce by 30.2 DEG C；Cyclisation thermal discharge is 613.3J/g, and relatively polyacrylonitrile homopolymer thermal discharge adds
67.0J/g, the increase of cyclisation thermal discharge shows that cyclization degree improves.It is the spinning solution of 15wt% by solid content
(15gPAN/85gDMSO) through dry-jet wet spinning, the positive drawing-off of spinning head is 2.5 times, containing of one-level coagulating bath dimethyl sulfoxide (DMSO)
Amount is 70wt%, and temperature is 5 DEG C, and the content of two grades of coagulating bath dimethyl sulfoxide (DMSO)s is 60wt%, and temperature is 20 DEG C；One-level
Hot water (85 DEG C) drawing-off 1.8 times, two grades hot water (95 DEG C) drawing-off 2.8 times；Then carry out with 1.5wt% amino-modified silicone oil
Oil；150 DEG C of compacting by drying 1min；0.5Mpa vapours drawing-off 2.5 times；Secondary is carried out with 0.8wt% amino-modified silicone oil
Oiling, it is 1.18dtex that 150 DEG C of thermal finalizations prepare high-performance carbon fibre precursor fiber number, and intensity is 12.55cN/dtex.
Embodiment 2
Polymer reactor vacuumizes, logical nitrogen circulation 3 times, under the conditions of 35 DEG C by 22.54g acrylonitrile, 0.23g itaconic acid,
0.23g polyvinyl alcohol (1788) and 60g deionized water join in 5L glass reaction generator, logical nitrogen 30min, heat up
To 60 DEG C and constant temperature 0.5h at this temperature, then drip ammonium persulfate (0.23g/10gH2O) aqueous solution completing in 0.5h,
After initiator adds, same dropping mode is taked to add acrylamide (0.23g/7gH2O) aqueous solution completing in 1h.
Keeping reaction 24 hours at 60 DEG C, the polyacrylonitrile viscosity average molecular weigh of preparation is 3.8 × 10 simultaneously5G/mol, molecular weight divides
Cloth is 3.02.Above-mentioned polymer slurries is filtered, de-single, it is dried and prepares white particle sprills, recording copolymer conversion ratio is
89.1%.Under nitrogen atmosphere, DSC test (uses TA company of U.S. Q20 differential scanning calorimeter, with 5 DEG C/min's
Speed is risen to 310 DEG C from 30 DEG C), (prepared by same polymeric condition, viscous for its cyclisation initial temperature relatively HOPP nitrile
Average molecular weight 41.2 ten thousand) reduce by 32.7 DEG C；Cyclisation thermal discharge is 643.7J/g, and relatively polyacrylonitrile homopolymer thermal discharge adds
76.7J/g, the increase of cyclisation thermal discharge shows that cyclization degree improves.It is the spinning solution of 18wt% by solid content
(18gPAN/82gDMSO) through dry-jet wet spinning, the positive drawing-off of spinning head is 2.5 times, containing of one-level coagulating bath dimethyl sulfoxide (DMSO)
Amount is 70wt%, and temperature is 5 DEG C, and the content of two grades of coagulating bath dimethyl sulfoxide (DMSO)s is 60wt%, and temperature is 20 DEG C；One-level
Hot water (85 DEG C) drawing-off 1.8 times, two grades hot water (95 DEG C) drawing-off 2.8 times；Then carry out with 1.5wt% amino-modified silicone oil
Oil；150 DEG C of compacting by drying 1min；0.5Mpa vapours drawing-off 2.5 times；Secondary is carried out with 0.8wt% amino-modified silicone oil
Oiling, it is 1.21dtex that 150 DEG C of thermal finalizations prepare high-performance carbon fibre precursor fiber number, and intensity is 12.36cN/dtex.
Embodiment 3
Polymer reactor vacuumizes, logical nitrogen circulation 3 times, under the conditions of 35 DEG C by 22.08g acrylonitrile, 0.69g itaconic acid,
0.23g polyvinyl alcohol (1799) and 60g deionized water join in 5L glass reaction generator, logical nitrogen 30min, heat up
To 60 DEG C and constant temperature 0.5h at this temperature, then drip ammonium persulfate (0.23g/10gH2O) aqueous solution completing in 0.5h,
After initiator adds, same dropping mode is taked to add acrylamide (0.23g/7gH2O) aqueous solution completing in 1h.
Keeping reaction 24 hours at 60 DEG C, the polyacrylonitrile viscosity average molecular weigh of preparation is 4.1 × 10 simultaneously5G/mol, molecular weight distribution
It is 2.98.Above-mentioned polymer slurries is filtered, de-single, it is dried and prepares white particle sprills, recording copolymer conversion ratio is 92.4%.
DSC test under nitrogen atmosphere (use U.S. TA company Q20 differential scanning calorimeter, with the speed of 5 DEG C/min by
30 DEG C rise to 310 DEG C) understand, (prepared by same polymeric condition, viscous equal molecule for its cyclisation initial temperature relatively HOPP nitrile
Measure 43.0 ten thousand) reduce by 35.6 DEG C；Cyclisation thermal discharge is 658.8J/g, and relatively polyacrylonitrile homopolymer thermal discharge adds 70.9J/g,
The increase of cyclisation thermal discharge shows that cyclization degree improves.By the spinning solution (22gPAN/78gDMSO) that solid content is 22wt%
Through dry-jet wet spinning, the positive drawing-off of spinning head is 2.5 times, and the content of one-level coagulating bath dimethyl sulfoxide (DMSO) is 70wt%, temperature
Being 5 DEG C, the content of two grades of coagulating bath dimethyl sulfoxide (DMSO)s is 60wt%, and temperature is 20 DEG C；One-level hot water (85 DEG C) drawing-off
1.8 times, two grades of hot water (95 DEG C) drawing-off 2.8 times；Then oil with 1.5wt% amino-modified silicone oil；150 DEG C are dried cause
Densification 1min；0.5Mpa vapours drawing-off 2.5 times；Carry out secondary with 0.8wt% amino-modified silicone oil to oil, 150 DEG C of thermal finalizations
Preparing high-performance carbon fibre precursor fiber number is 1.15dtex, and intensity is 12.26cN/dtex.
Claims (10)
1. a carbon fibre precursor preparation method for ternary polyacrylonitrile copolymer, including:
Under nitrogen protective condition, acrylonitrile, itaconic acid, dispersant and water are mixed, is warming up to 60-75 DEG C, drips the most successively
Add initiator solution, acrylamide aqueous solution, clock reaction 3-24h after dropping, washing, de-list, filter, be dried,
Obtain ternary polyacrylonitrile copolymer；Wherein acrylonitrile, itaconic acid, the mass ratio of acrylamide are 96-99:0.5-3:0.5-1；Point
Powder consumption is acrylonitrile, itaconic acid, the 0.5%-2.0% of acrylamide gross mass.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 1, it is characterised in that:
Described dispersant is polyvinyl alcohol.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 2, it is characterised in that:
Described polyvinyl alcohol is one or more in polyvinyl alcohol 1755, polyvinyl alcohol 1788, polyvinyl alcohol 1799.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 1, it is characterised in that:
Described initiator is ammonium persulfate, and initiator amount is acrylonitrile, itaconic acid and the 0.2-2.0% of acrylamide gross mass.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 1, it is characterised in that:
Described acrylonitrile, itaconic acid and acrylamide account for the 20-33wt% of gross mass；The total matter of acrylonitrile, itaconic acid and acrylamide
Amount is 77%-80% with the ratio of water quality；Water is deionized water.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 1, it is characterised in that:
In described initiator solution, the mass ratio of initiator and water is 0.23:5-10；Acrylamide and water in acrylamide aqueous solution
Mass ratio is 0.23:5-10.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 1, it is characterised in that:
Described be warming up to 60-75 DEG C after, isothermal reaction 0.5-2h.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 1, it is characterised in that:
The time of described dropping initiator solution is 0.1-0.5h；The time of dropping acrylamide aqueous solution is 0.1-1h.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 1, it is characterised in that:
Described baking temperature is 50-60 DEG C, and the time is 12-24h.
The preparation method of a kind of carbon fibre precursor ternary polyacrylonitrile copolymer the most according to claim 1, it is characterised in that:
The viscosity average molecular weigh of described ternary polyacrylonitrile copolymer is 300,000-45.8 ten thousand.
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