CN110330754A - Primary film, polyacrylonitrile film, polyacrylonitrile-radical C film and preparation method - Google Patents
Primary film, polyacrylonitrile film, polyacrylonitrile-radical C film and preparation method Download PDFInfo
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- CN110330754A CN110330754A CN201910718868.8A CN201910718868A CN110330754A CN 110330754 A CN110330754 A CN 110330754A CN 201910718868 A CN201910718868 A CN 201910718868A CN 110330754 A CN110330754 A CN 110330754A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
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Abstract
The present invention relates to a kind of primary film, polyacrylonitrile film, polyacrylonitrile-radical C films.The technical solution mainly used are as follows: the primary film is after polyacrylonitrile solution to be formed to the liquid stream of film-form, then obtained film after processing is formed to the liquid stream of film-form；Wherein, the cross-sectional shape of the primary film is generally rectangular；The ratio between the cross-sectional width of primary film and tranverse sectional thickness are greater than 50.Present invention is mainly used for the polyacrylonitrile-based carbon fibres for preparing film-form, i.e. polyacrylonitrile-radical C film；When using the polyacrylonitrile-radical C film as reinforced phase, the ratio of reinforced phase in the composite can not only be significantly improved, and reinforced phase can be evenly distributed in the composite, and then improve the performance of carbon fibre composite.
Description
Technical field
It is thin more particularly to a kind of primary film, polyacrylonitrile the present invention relates to a kind of polyacrylonitrile fibre technical field
Film, polyacrylonitrile-radical C film and preparation method.
Background technique
Polyacrylonitrile-based carbon fibre is a kind of inorfil of phosphorus content high 90%, with high specific strength, high ratio modulus
Etc. excellent performance, the composite material using it as reinforcing fiber is answered in fields such as aerospace, new energy extensively
With.
In carbon fibre composite, the content of carbon fiber has the function of determining to the performance of composite material.And it is round
The volume accounting of the carbon fiber in section in the composite is below 60%.
In order to improve the content of polyacrylonitrile-based carbon fibre in the composite, anisotropic cross sectional shape can be prepared (that is, non-
Circular section shape) polyacrylonitrile-based carbon fibre.But the inventors found that: general odd-shaped cross section (e.g., triangle
Shape, it is polygonal, diesis, multi-leaf-shaped etc.) polyacrylonitrile-based carbon fibre be unevenly distributed in the composite, be easy to cause
The fluctuation of composite property.
Summary of the invention
In view of this, the present invention provides a kind of primary film, polyacrylonitrile film, polyacrylonitrile-radical C film and preparation side
Method, main purpose are to make polyacrylonitrile-based carbon fibre in film-form, when using polyacrylonitrile-radical C film as reinforced phase, no
It is only capable of improving the ratio of reinforced phase in the composite, and reinforced phase can be evenly distributed in the composite.
In order to achieve the above objectives, present invention generally provides following technical solutions:
On the one hand, the embodiment of the present invention provides a kind of primary film, which is characterized in that the primary film is by poly- third
After alkene nitrile solution forms the liquid stream of film-form, then the liquid stream of film-form is formed the film obtained after processing；Wherein, described
The cross-sectional shape of primary film is generally rectangular；The ratio between the cross-sectional width of primary film and tranverse sectional thickness are greater than 50.
Preferably, the light transmittance of the primary film is greater than or equal to 60%.
Preferably, between the average pore size at the surface structure of the primary film and the average pore size at core structure
Deviation is within 10%；
Preferably, it is no more than at the surface structure for the shortest distance between film outer profile on film cross section
At 1/5 position of tranverse sectional thickness；It is most short between cross sectional centroid on film cross section at the core structure
Distance is no more than at 1/5 position of tranverse sectional thickness.
On the other hand, the embodiment of the present invention provides a kind of preparation method of primary film comprising following steps:
1) polyacrylonitrile solution is prepared；
2) polyacrylonitrile solution is made to form the liquid stream of film-form；
3) processing is formed to the liquid stream of film-form, obtains primary film；
Wherein, the section of the as-spun fibre is generally rectangular；The ratio between cross-sectional width and section thickness of primary film
Greater than 50；
Preferably, the light transmittance of the primary film is greater than or equal to 60%；
Preferably, the polyacrylonitrile polymer in the polyacrylonitrile solution includes polyacrylonitrile homopolymer, polyacrylonitrile
The mixture of one or both of copolymer；
Preferably, the liquid stream of polyacrylonitrile solution formation film-form is made using extrusion molding or the tape casting；
Preferably, processing is formed to the liquid stream of film-form using solvent evaporation method or coagulating bath forming process, obtained just
Raw film.
Preferably, the step 3) specifically: make forming processing of the liquid stream of the film-form Jing Guo coagulating bath, obtain just
Raw film；Wherein, the coagulating bath includes the non-solvent and solvent that mass ratio is 1:0~2:8；Preferably, the non-solvent and
The mass ratio of solvent is 1:0~3:7, further preferably 9:1~4:6, more preferably 8:2~4:6；And/or the coagulating bath
Temperature be -50 DEG C~70 DEG C, preferably -20 DEG C~5 DEG C；And/or stop of the liquid stream of the film-form in the coagulating bath
Time is 1-150s.
Preferably, the non-solvent formic acid in the coagulating bath, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform,
Isobutanol, isoamyl alcohol, butanediol, benzyl alcohol, carbon tetrachloride, toluene, acetone, water, any one or several of dioxane mix
Close object.
Preferably, the solvent in the coagulating bath is the solvent that can dissolve polyacrylonitrile, preferably dimethyl sulfoxide, two
Methylformamide, dimethyl acetamide, lithium chloride solution, ionic liquid, sodium thiocyanate solution, any in liquor zinci chloridi
Kind.
Preferably, the step 2) specifically: polyacrylonitrile solution is extruded into the liquid stream of film-form using extrusion die；Its
In, the extruding aperture of the extrusion die is generally rectangular, any one of slit shape, class dog bone shape；Preferably, described to squeeze
The mean breadth of the extruding aperture of mold is 1~300 μm, preferably 4~200 μm out.
In another aspect, the embodiment of the present invention also provides a kind of polyacrylonitrile film, wherein the cross of the polyacrylonitrile film
Cross sectional shape is generally rectangular；The ratio between the cross-sectional width of polyacrylonitrile film and tranverse sectional thickness are greater than 50.Wherein, described
The deviation between the average pore size at average pore size and core structure at the surface structure of polyacrylonitrile film is within 10%；
Preferably, the thickness of the polyacrylonitrile film is less than 1mm；Preferably, the polyacrylonitrile film is by above-mentioned primary film
It is made.
In another aspect, the preparation method of above-mentioned polyacrylonitrile film, which comprises the steps of:
It prepares primary film: primary film is prepared using the preparation method of primary film described in any of the above embodiments；
Post-processing: the primary film is post-processed, polyacrylonitrile film is obtained；
Preferably, the post-processing includes being washed to primary film, drawing-off, oiling, be dried, and obtains polypropylene
Nitrile film；
It is further preferred that the post-processing includes being washed, water-bath drawing-off, being dried at heat to the primary film
Reason, vapor drawing-off, oiling treatment, obtain polyacrylonitrile film.
In another aspect, the embodiment of the present invention also provides a kind of polyacrylonitrile-radical C film, wherein the polyacrylonitrile-based carbon
The cross-sectional shape of film is generally rectangular；The ratio between the cross-sectional width of polyacrylonitrile film and tranverse sectional thickness are greater than 50；
Wherein, the polyacrylonitrile-radical C film with a thickness of 0.5~150 μm, in the range of preferably 1~10 μm, further preferred 3
~8 μm；Preferably, the width of the polyacrylonitrile-radical C film is 1-10m；Or the width of the polyacrylonitrile-radical C film is
25 μm~1m, preferably 1mm~20cm, further preferably 5mm~100mm；Preferably, the polyacrylonitrile-radical C film
Longitudinal tensile strength is 2.2-4.5GPa；
Preferably, the average pore size at the polyacrylonitrile-radical C film surface structure and the average pore size at core structure
Between deviation within 10%；
Preferably, the polyacrylonitrile-radical C film is made of above-mentioned polyacrylonitrile film.
In another aspect, the preparation method of above-mentioned polyacrylonitrile-radical C film includes the following steps:
Above-mentioned polyacrylonitrile film is heat-treated, polyacrylonitrile-radical C film is obtained；Preferably, the heat treatment
Include:
Pre-oxidation: 185~400 DEG C at a temperature of, to the polyacrylonitrile film carry out pre-oxidation treatment, obtain pre- oxygen
Change film；
Low-temperature carbonization: 400~1000 DEG C at a temperature of, to the pre-oxidation film carry out low-temperature carbonization processing, obtain
Low-temperature carbonization film；
High temperature cabonization: 1100~3000 DEG C at a temperature of, to the low-temperature carbonization film carry out high temperature cabonization, gathered
Acrylonitrile group C film.
Compared with prior art, primary film of the invention, polyacrylonitrile film, polyacrylonitrile-radical C film and preparation side
Method at least have it is following the utility model has the advantages that
1. the embodiment of the present invention provides a kind of primary film, which is substantially that cross section is rectangle and horizontal
The polyacrylonitrile-radical as-spun fibre of the film-form of the ratio between cross-sectional width and tranverse sectional thickness greater than 50；It can be with using the primary film
Prepare polyacrylonitrile-radical C film, i.e., the polyacrylonitrile-based carbon fibre that section is generally rectangular, entirety is in film-form；With this
When polyacrylonitrile-radical C film prepares composite material as reinforced phase, the ratio of reinforced phase in the composite can not only be significantly improved
Example, and reinforced phase can be evenly distributed in the composite, and then improve the performance of carbon fibre composite.
Further, the light transmittance of primary film provided in an embodiment of the present invention is greater than or equal to 60%；The light transmittance
Not only structure is uniform for primary film, and has elasticity, convenient for the processing such as subsequent progress drawing-off, to obtain the uniform polypropylene of structure
Nitrile film and polyacrylonitrile-radical C film.
2. the embodiment of the present invention provides a kind of preparation method of primary film, especially by the composition of control coagulating bath, coagulate
Admittedly the conditions such as the temperature bathed make the light transmittance of the primary film of forming be greater than or equal to 60%, so that primary film as far as possible
Structure is uniform, and there is elasticity, handled convenient for subsequent progresss drawing-off etc., thus obtain the uniform polyacrylonitrile film of structure and
Polyacrylonitrile-radical C film.
3. the embodiment of the present invention provides a kind of polyacrylonitrile film and preparation method thereof, the polyacrylonitrile film is by above-mentioned
Primary film is prepared, and therefore, the structure of the polyacrylonitrile film of the embodiment of the present invention is uniform, better performances.
4. the embodiment of the present invention provides a kind of polyacrylonitrile-radical C film and preparation method thereof, the polyacrylonitrile-radical C film
It is formed by above-mentioned polyacrylonitrile film preparation, therefore, the structure of the polyacrylonitrile-radical C film of the embodiment of the present invention is uniform, property
It can be preferably；And when preparing composite material as reinforced phase using the polyacrylonitrile-radical C film, reinforced phase can not only be significantly improved and existed
Ratio in composite material, and reinforced phase can be evenly distributed in the composite, and then improve the performance of carbon fibre composite.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is distribution of the polyacrylonitrile-radical C film of the embodiment of the present invention preparation as reinforced phase in the composite
Schematic diagram；
Fig. 2 is distribution of the circular cross-section polyacrylonitrile-based carbon fibre in the prior art as reinforced phase in the composite
Schematic diagram.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Specific embodiment, structure, feature and its effect applied according to the present invention is described in detail such as in attached drawing and preferred embodiment
Afterwards.In the following description, what different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.In addition, one or more
Special characteristic, structure or feature in a embodiment can be combined by any suitable form.
On the one hand, the embodiment of the present invention provides a kind of primary film, the primary film be polyacrylonitrile solution is formed it is thin
After membranaceous liquid stream, then the liquid stream of film-form is formed the film obtained after processing；Wherein, the primary film is transversal
Face is generally shaped like rectangle；The ratio between the cross-sectional width of primary film and tranverse sectional thickness are greater than 50.
Film in the application is either macroscopic film, is also possible to microcosmic film；Wherein, the cross section of macroscopic film
Width is greater than 1m；The width of the cross section of microcosmic film is less than 1m.
Here, the fiber of microcosmic film (primary film, polyacrylonitrile film, polyacrylonitrile-radical C film) and the prior art
(as-spun fibre, polyacrylonitrile fibre, polyacrylonitrile carbon fiber) difference is: the section of prior art as-spun fibre is substantially in round
Shape or other general anisotropic approach.And the film of the application be substantially cross section be rectangle, cross-sectional width and cross section
The ratio between thickness is greater than 50, and whole is in the fiber of film-form.
Here, " width of cross section " the i.e. width of film, refers to the overlapped length of film upper and lower surface；It is " thin
The thickness of film " the i.e. thickness of film refers to: the average distance of film upper and lower surface.
Primary film refers to that polyacrylonitrile solution is preliminarily formed with film morphology, and the polyacrylonitrile in the film morphology can
To be that can be gel state in curdled appearance, it can also be and be partially in solidification state or gel state.Preferably, primary film
In gel state.
Preferably, in order to obtain structural behaviour, mechanical property good polyacrylonitrile film and polyacrylonitrile-radical C film: this
The light transmittance for the primary film that inventive embodiments provide is greater than or equal to 60%.If the transmitance of primary film is lower than 60%,
Its structural homogeneity is poor.Here, so-called light transmittance, which refers to, tests light transmittance obtained, test using light transmittance tester
When optical source wavelength be 500 ± 10nm.
Preferably, between the average pore size at the surface structure of the primary film and the average pore size at core structure
Deviation is within 10%；This means that the structure of the as-spun fibre is uniform.
It is no more than cross section at the surface structure for the shortest distance between film outer profile on film cross section
At 1/5 position of thickness；At the core structure not for the shortest distance between cross sectional centroid on film cross section
At position more than the 1/5 of tranverse sectional thickness.
Here, the test method of the average pore size of the surface structure and core structure of as-spun fibre is:
1, first with the dry as-spun fibre of freeze-drying, dry as-spun fibre sample is obtained；
2, the cross-sectional image that as-spun fibre is obtained using transmission electron microscope or scanning electron microscope etc., can before test
To carry out metal spraying processing to as-spun fibre sample, or other are carried out to as-spun fibre it can increase observing effect but do not change solidifying
Gu the pre-treatment of the original pattern of silk；
3, coagulated yarn micro image is handled using image processing software, obtains the pore-size distribution of different zones.Choosing
It selects at the 1000nm inwards of as-spun fibre surface, diameter is representative region of the border circular areas of 200nm as surface structure area,
The hole of the first two major diameter is removed when calculating the average pore size at surface structure, and calculating, to reduce error.Select as-spun fibre
Transversal cross-section center of gravity diameter is representative region of the border circular areas of 200nm as core structure, is calculated flat at inner layer structure
Equal aperture, when calculating, removes the hole of the first two major diameter, to reduce error.
On the other hand, the embodiment of the invention provides the preparation method of above-mentioned primary film, specifically comprise the following steps:
1) polyacrylonitrile solution is prepared.
Here, the polyacrylonitrile in polyacrylonitrile solution refers to: polyacrylonitrile homopolymer, using acrylonitrile as main component
One or both of polyacrylonitrile copolymer mixture.
The molecular chain conformation of polymer is not particularly limited, the smaller polyacrylonitrile film obtained of molecular weight and poly- third
The mechanical property of alkene itrile group C film is poorer, therefore polyacrylonitrile molecular weight preferably 100,000 or more.The molecular weight the big obtained
The mechanical property of polyacrylonitrile film and polyacrylonitrile-radical C film is better, but the polyacrylonitrile of macromolecule in a solvent molten
Solution property is poor, therefore the upper limit of polyacrylonitrile molecular weight is not particularly limited, as long as polyacrylonitrile can be dissolved in solvent i.e.
Can, usual polyacrylonitrile is below 1,500,000.
As long as polyacrylonitrile solvent can dissolve polyacrylonitrile, be not particularly limited, for example, can be dimethyl sulfoxide,
Dimethylformamide, dimethyl acetamide, dimethyl sulfoxide/lithium chloride, ionic liquid, sodium thiocyanate solution, liquor zinci chloridi
Equal single substances, are also possible to mixture.
2) polyacrylonitrile solution is made to form the liquid stream of film-form.
Here, the method that polyacrylonitrile solution forms the liquid stream of thin film shape can be through extrusion method, can also be
Using casting method, curtain coating drawing-off method also can be used；It is preferred that curtain coating drawing-off method.
The step mainly carries out in coagulating bath, if preparation is macroscopic film, needs to carry out film laterally and vertical
To drawing-off, longitudinal drawing-off is 0.7-12 times, lateral drawing-off is 0.65-3 times.If preparation be microcosmic film, only need to film into
Row longitudinal direction drawing-off, drafting multiple are 0.7-12 times.
Here, it is thin to obtain coming into being for film morphology by the orifice shapes for adjusting polyacrylonitrile solution extrusion die
Film.Polyacrylonitrile solution extrusion die mouth can have multiple apertures to combine, and can also only have single aperture.The orifice shapes of mold
It can be rectangle like, be also possible to slit, preferably class dog bone shape, the slit mean breadth in aperture is preferably 1~300 μm,
Further preferably 4~200 μm.
3) processing is formed to the liquid stream of film-form, obtains primary film.
Here, make the liquid stream of film-form can be by gelation or cured method make liquid stream enter in coagulating bath into
Row gelation or solidification can also make polyacrylonitrile liquid stream gelation or solidification in atmosphere；Preferably, make polyacrylonitrile liquid stream
Into progress gelation or solidification in coagulating bath.It is solidifying that the gelation process refers to that polymer solution is changed into from solution state
The process of colloidal state.The loss modulus of polymer solution is greater than storage modulus, and heretofore described gel state refers to that polymer is molten
Liquid its loss modulus in a certain transition process is equal to or less than state when storage modulus, but polymer solution still has part
There is no mutually separating.
For in the step, formation treatment process determines the structural homogeneity of primary film.It does not grow in the prior art
The polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre of film square shape；Basic reason is: the fiber of rectangular cross-sectional shape is not
Good drawing-off, and the fiber thickness that drawing-off goes out is uneven.
Therefore, the present inventor is put forward for the first time following technique, first more than or equal to 60% to prepare light transmittance
Raw film；So that the structure of the primary film is uniform, there is elasticity, to handle using subsequent drawing-off, to prepare knot
The uniform polyacrylonitrile film of structure, polyacrylonitrile-radical C film.Specifically, the formation treatment process is as follows:
Make the polyacrylonitrile liquid stream of film-form that processing be formed in coagulating bath.Wherein, the composition of coagulating bath can be
Polyacrylonitrile non-solvent and polyacrylonitrile solvent (here, polyacrylonitrile non-solvent is referred to as non-solvent, refer to insoluble depolymerization third
The solvent of alkene nitrile；Polyacrylonitrile solvent is referred to as solvent, refers to the solvent that can dissolve polyacrylonitrile).Wherein, with non-molten
Agent: the ratio of solvent=1:0~2:8 (mass percent) carries out mixing as coagulating bath.Preferably, the matter of non-solvent and solvent
Amount is than being 1:0~3:7, it is further preferred that the mass ratio of non-solvent and solvent is 9:1~4:6, it is still more preferably, non-
The mass ratio of solvent and solvent is 8:2~4:6.
Preferably, the non-solvent can be single substance, it is also possible to the mixture of different material；Such as it can be
Formic acid, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform, isobutanol, isoamyl alcohol, butanediol, benzyl alcohol, carbon tetrachloride, first
The mixture of one or more of benzene, acetone, water, dioxane.
Preferably, the polyacrylonitrile liquid stream of film-form is made to form gel in coagulating bath using the ingredient of coagulating bath and temperature
(gelation process refers to the process of that polyacrylonitrile solution is changed into gel state from solution state to the primary film of state.Polyacrylonitrile
The loss modulus of solution is greater than storage modulus.The gel state refers to polyacrylonitrile solution its loss in a certain transition process
Modulus be equal to or less than storage modulus when state, but polyacrylonitrile solution still have part there is no mutually separating).
The polyacrylonitrile liquid stream of film-form is set to form primary film using coagulating bath, the temperature of coagulating bath is higher than coagulating bath group
The fusing point divided, lower than the boiling point of coagulating bath component.The temperature selection of coagulating bath should have conducive to polyacrylonitrile solution in coagulating bath
It is easy to happen gelation process, preferably cryogenic conditions, is particularly preferred as -50 DEG C~70 DEG C, preferably -20 DEG C~5 DEG C.Solidify bath temperature
When degree is greater than 70 DEG C, polyacrylonitrile solution occurs mutually to separate in coagulating bath, so that primary film structure surface layer and endothecium structure
Difference is big, reduces film performance；Coagulation bath temperature is less than -50 DEG C, and energy consumption is high, in addition, coagulation bath temperature is too low, polyacrylonitrile is molten
Liquid drawdown in film forming process is deteriorated, and not easily passs through two-way drawing-off and improves film performance.
In another aspect, the embodiment of the present invention also provides a kind of polyacrylonitrile film, wherein the polyacrylonitrile film is cut
Face is generally shaped like rectangle；The ratio between cross-sectional width and section thickness of polyacrylonitrile film are greater than 50.Preferably, described poly- third
Alkene nitrile film is made of above-mentioned primary film.
In another aspect, the preparation method of above-mentioned polyacrylonitrile film, which comprises the steps of:
1) it prepares primary film: primary film is prepared using the preparation method of above-mentioned primary film；
2) it post-processes: the primary film being post-processed, polyacrylonitrile film is obtained；
Preferably, the post-processing includes being washed to primary film, drawing-off, oiling, be dried, and obtains polypropylene
Nitrile film.
It is further preferred that the post-processing includes being washed, water-bath drawing-off, being dried at heat to the primary film
Reason, vapor drawing-off, oiling treatment, obtain polyacrylonitrile film.
Preferably, the step of post-processing is as follows: washing step washs obtained film in a water bath；Water-bath drawing-off work
Sequence, by the drawing-off in a water bath of obtained film；Dry heat treatment procedure, is dried heat treatment for film；Vapor drawing-off work
Film is carried out drawing-off processing by sequence in vapor；Oil process, assigns protectiveness finish to film surface.Preferably, in shape
After polyacrylonitrile primary film, successively passes through washing step, water-bath drafting process, the process that oils and compacting by drying, obtain
To polyacrylonitrile thin film precursor.Increase solid carbon dioxide steam drafting process further preferably on the basis of previous process, do
Hot gas spring process.
Preferably, (washing step, water-bath drafting process, dry heat treatment procedure, vapor are led the postprocessing working procedures
Stretch process, the process that oils, oiling process, drying process, vapor draft process, dry heat drafting technique etc.) it can be according to technique
Optimize and revise implementation sequence.
Preferably, in above-mentioned post-processing step, longitudinal drafting multiple of the film in water-bath drafting process be preferably 1.2~
4 times, more preferably 2~3.5 times.
Preferably, dry heat treatment procedure can use known method in above-mentioned post-processing step, it is dry using hot-rolling
Dry or plate drying etc., drying temperature is chosen as 85~170 DEG C.
Preferably, in vapor draft process, carrying out longitudinal drawing-off to polyacrylonitrile film in above-mentioned post-processing step
Drafting multiple is preferably 1.5 times or more, more preferably 2 times or more.
Preferably, in bath after drawing-off, generating electrostatic, protective film surface, shadow in order to prevent in above-mentioned post-processing step
Continuous production is rung, oiling treatment preferably is carried out to the film after water-bath drawing-off.
Preferably, polyacrylonitrile molecule is easy to increase thin film mechanics along drawing-off direction orientations when increasing drafting multiple
Performance.Therefore, in the preparation process of polyacrylonitrile film, two-way drawing-off preferably is carried out to film.Specific drafting multiple according to
According to depending on the size of extrusion mould-outlet and final products.
In another aspect, the embodiment of the present invention also provides a kind of polyacrylonitrile-radical C film, wherein the polyacrylonitrile-based carbon
The cross sectional shape of film is generally rectangular；The ratio between cross-sectional width and section thickness of polyacrylonitrile film are greater than 50；
The thickness of polyacrylonitrile C film is smaller, and mechanical property is better, still, can reduce production efficiency.It is poly- in preparation
When acrylonitrile film, due to needing to be heat-treated in oxygen in post-processing, and oxygen element is needed from film surface to film
Inside diffusion.In order to avoid film surface and internal structure difference are excessive, the performance of polyacrylonitrile-radical C film, polypropylene are influenced
The thickness of itrile group C film is preferably in the range of 0.5~150 μm, further excellent in the range of further preferred 1~10 μm
Select 3~8 μm.The width of polyacrylonitrile-radical C film is unlimited, according to practical use, can pass through the orifice shapes size of mold mouth
It is adjusted jointly with subsequent technique, as the width of polyacrylonitrile-radical C film can be less than 10m.As the reinforcement of composite material,
The width of polyacrylonitrile-radical C film is preferably 25 μm~1m, further preferably 1mm~20cm, and more preferably 5mm~
100mm。
Preferably, the polyacrylonitrile-radical C film is made of above-mentioned polyacrylonitrile film.
In another aspect, the preparation method of above-mentioned polyacrylonitrile-radical C film includes the following steps:
Above-mentioned polyacrylonitrile film is heat-treated, polyacrylonitrile-radical C film is obtained；Preferably, the heat treatment
Include:
Pre-oxidation: 185~400 DEG C at a temperature of, to the polyacrylonitrile film carry out pre-oxidation treatment, obtain pre- oxygen
Change film；
Low-temperature carbonization: 400~1000 DEG C at a temperature of, to the pre-oxidation film carry out low-temperature carbonization processing, obtain
Low-temperature carbonization film；
High temperature cabonization: 1100~3000 DEG C at a temperature of, to the low-temperature carbonization film carry out high temperature cabonization, gathered
Acrylonitrile group C film.
It, can be by being electrolysed to poly- third in order to increase the bond strength of matrix in polyacrylonitrile-radical C film and composite material
Alkene itrile group carbon film surface is handled.After electrolysis processing, in order to be conducive to subsequent service performance, starching can be carried out to C film
Processing.Sizing agent used in starching processing is selected according to the type of matrix in composite material.Treated poly- third for starching
Alkene nitrile C film is referred to carbon fiber prepreg technique and is prepared into polyacrylonitrile-radical C film prepreg.
Different from the prior art, for the application in above-mentioned heat treatment step, atmosphere is preferably the advance side of parallel fibers
To especially when macroscopic film.Only parallel film traffic direction, the exhaust gas for chemically reacting generation could smoothly be taken away,
Be conducive to atmosphere and uniformly contacted with film.
As depicted in figs. 1 and 2, using the polyacrylonitrile-radical C film of the embodiment of the present invention and the circular cross-section of the prior art
When polyacrylonitrile-based carbon fibre prepares composite material: base of the polyacrylonitrile-radical C film 12 as reinforcement in composite material 1
The distribution situation of body 11 is shown in Figure 1；The polyacrylonitrile-based carbon fibre 13 of circular cross-section is as reinforcement in composite material 1
Matrix 11 distribution situation it is shown in Figure 1.
Can be become apparent from by Fig. 1 and Fig. 2: the polyacrylonitrile-radical C film of preparation of the embodiment of the present invention can increase
The volume fraction of reinforcement in composite material, also increases the contact area of reinforcement and matrix, and it is strong effectively to promote interface cohesion
Degree promotes composite property.It is multiple being used to prepare since the polyacrylonitrile-radical C film of the embodiment of the present invention is film morphology
Before condensation material, the processing such as fibrillation, tentering is not needed, simplifies preparation composite technology.
It is further described below below by specific experiment embodiment:
Embodiment 1
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；It specifically includes as follows
Step:
1) prepared by primary film: using dimethyl sulfoxide as solvent, passing through solution using acrylonitrile and itaconic acid as comonomer
The method of polymerization prepares polyacrylonitrile solution, and polyacrylonitrile molecular weight is 200,000, and viscosity is 120Pa.s (here, the present embodiment
And following embodiments mainly illustrate so that viscosity average molecular weigh is 200,000, viscosity is the polyacryl-nitrile spinning fluid of 120Pa.s as an example, still
Without being limited thereto, any one polyacryl-nitrile spinning fluid is suitable for the present invention).By polyacrylonitrile solution from the extruding aperture of mold
It is extruded into the liquid stream of film-form, the liquid stream of film-form enters in coagulating bath after air layer, at the beginning of shaping polyacrylonitrile
Raw film.
Wherein, the cross sectional shape of the extruding aperture of mold is that (mean breadth of the extruding aperture is class dog bone shape
0.025mm)；The temperature control of coagulating bath is -17 DEG C, and the composition of coagulating bath is the dimethyl sulfoxide and water that mass ratio is 6:4, edge
The drafting multiple of film longitudinal direction is 4.
2) it prepares polyacrylonitrile film: primary film being washed using deionized water, after drawing-off processing；Again to water-bath
Film afterwards carries out oiling treatment, densification then is dried to film using dryer roll, and in high-temperature vapor
Longitudinal drawing-off is carried out to film, obtains polyacrylonitrile film.
3) it prepares polyacrylonitrile-radical C film: in temperature range being 185~400 DEG C by obtained polyacrylonitrile film
It is pre-oxidized in the air of temperature gradient, obtains pre-oxidation film.By obtained pre-oxidized fibers temperature be 400~1000
DEG C nitrogen atmosphere in carry out low-temperature carbonization, obtain low-temperature carbonization film.By low-temperature carbonization fiber maximum temperature be 1600 DEG C
Nitrogen atmosphere in carry out high temperature cabonization.Ammonium bisulfate solution is recycled to carry out electricity to the film after high temperature cabonization as electrolyte
Solution processing；Then the film after electrolysis washed, dried, starching processing obtains C film.Finally, being carried out to C film
Pre-impregnating process obtains polyacrylonitrile-radical C film prepreg tape.
Embodiment 2
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The temperature of coagulating bath is 8 DEG C, and the group of coagulating bath becomes the dimethyl acetamide and water that mass ratio is 7:3.
Other steps and embodiment 1 are consistent.
Embodiment 3
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The temperature of coagulating bath is -20 DEG C, and the ingredient of coagulating bath is methanol.
Other steps and embodiment 1 are consistent.
Embodiment 4
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The temperature of coagulating bath is 5 DEG C, and the ingredient of coagulating bath is ethyl alcohol.
Other steps and embodiment 1 are consistent.
Embodiment 5
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The temperature of coagulating bath is -18 DEG C, and the group of coagulating bath becomes the second alcohol and water that mass ratio is 9:1.
Other steps and embodiment 1 are consistent.
Embodiment 6
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The temperature of coagulating bath is 1 DEG C, and the ingredient of coagulating bath is water.
Other steps and embodiment 1 are consistent.
Embodiment 7
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The liquid stream of film-form after air layer without entering in coagulating bath；The temperature of coagulating bath is 10 DEG C, coagulating bath
Group becomes the dimethylformamide and water that mass ratio is 4:6.
Other steps and embodiment 1 are consistent.
Embodiment 8
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The liquid stream of film-form after air layer without entering in coagulating bath；The temperature of coagulating bath is 63 DEG C, coagulating bath
Group becomes the dimethylformamide and water that mass ratio is 6:4.
Other steps and embodiment 1 are consistent.
Embodiment 9
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The liquid stream of film-form after air layer without entering in coagulating bath；The temperature of coagulating bath is 70 DEG C, coagulating bath
Group becomes the dimethyl sulfoxide and water that mass ratio is 8:2.
Other steps and embodiment 1 are consistent.
Embodiment 10
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The temperature of coagulating bath is -50 DEG C, and the ingredient of coagulating bath is methanol.
Other steps and embodiment 1 are consistent.
Embodiment 11
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The temperature of coagulating bath is -10 DEG C, and the group of coagulating bath becomes the dimethyl sulfoxide that mass ratio is 5:4:1: water: methanol.
Other steps and embodiment 1 are consistent.
Embodiment 12
The present embodiment prepares a kind of primary film, polyacrylonitrile film and polyacrylonitrile-radical C film；Entire preparation step
In, it is as follows with the difference of embodiment 1:
The temperature of coagulating bath is 60 DEG C, and the group of coagulating bath becomes the dimethyl sulfoxide and water that mass ratio is 3:7.
Other steps and embodiment 1 are consistent.
Comparative example 1
Comparative example 1 prepares a kind of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre；Entire preparation step
In, it is as follows with the difference of embodiment 1:
Orifice diameter is used to carry out spinneret for 150 μm of 6K spinneret, other operations similarly to Example 1 obtain
Carbon fiber.
The step of other steps are with embodiment 1 is consistent.
Comparative example 2
Comparative example 2 prepares a kind of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre；Entire preparation step
In, it is as follows with the difference of embodiment 2:
Orifice diameter is used to carry out spinneret for 200 μm of 3K spinneret, other operations similarly to Example 1 obtain
Carbon fiber.
The step of other steps are with embodiment 2 are consistent.
Comparative example 3
Comparative example 3 prepares a kind of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre；Entire preparation step
In, it is as follows with the difference of embodiment 3:
Orifice diameter is used to carry out spinneret for 200 μm of 1K spinneret, other operations similarly to Example 1 obtain
Carbon fiber.
The step of other steps are with embodiment 3 are consistent.
Comparative example 4
Comparative example 4 prepares a kind of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre；Entire preparation step
In, it is as follows with the difference of embodiment 7:
Orifice diameter is used to carry out spinneret for 55 μm of 6K spinneret, other operations similarly to Example 1 obtain carbon
Fiber.
The step of other steps are with embodiment 7 are consistent.
Comparative example 5
Comparative example 5 prepares a kind of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre；Entire preparation step
In, it is as follows with the difference of embodiment 8:
Orifice diameter is used to carry out spinneret for 65 μm of 3K spinneret, other operations similarly to Example 1 obtain carbon
Fiber.
The step of other steps are with embodiment 8 are consistent.
Comparative example 6
Comparative example 6 prepares a kind of as-spun fibre, polyacrylonitrile fibre and polyacrylonitrile-based carbon fibre；Entire preparation step
In, it is as follows with the difference of embodiment 9:
Orifice diameter is used to carry out spinneret for 70 μm of 1K spinneret, other operations similarly to Example 1 obtain carbon
Fiber.
The step of other steps are with embodiment 9 are consistent.
The characterization result of the properity parameter of embodiment 1-12, the technological parameter of comparative example 1-6, prepared product is joined
It is shown in Table 1.
Table 1 is the structural behaviour parameter of embodiment 1-12, the technological parameter of comparative example 1-6, prepared product
It can be seen that compared with the polyacrylonitrile-based carbon fibre of circular cross-section from table 1, Fig. 1 and Fig. 2, the embodiment of the present invention
The polyacrylonitrile base film of preparation prepares composite material as reinforced phase, can significantly improve the ratio of reinforced phase in the composite
Example (up to 90%), and reinforced phase can be evenly distributed in the composite.
In addition, the uniformity of film parameter ginseng for preparing product described in embodiment 1- embodiment 12 is shown in Table 2.
Table 2 is the structural behaviour parameter list of film prepared by embodiment 1-12
It can clearly be seen that primary film, polyacrylonitrile film and the polypropylene of preparation of the embodiment of the present invention from table 2
The structural homogeneity of itrile group C film is preferable.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (10)
1. a kind of primary film, which is characterized in that the primary film be by polyacrylonitrile solution formed film-form liquid stream after,
The liquid stream of film-form is formed again the film obtained after processing；
Wherein, the cross-sectional shape of the primary film is generally rectangular；The cross-sectional width of primary film and cross section are thick
The ratio between degree is greater than 50.
2. primary film according to claim 1, which is characterized in that the light transmittance of the primary film is greater than or equal to
60%；
Preferably, the deviation between the average pore size at the surface structure of the primary film and the average pore size at core structure
Within 10%；
Preferably, it is no more than at the surface structure for the shortest distance between film outer profile on film cross section transversal
At 1/5 position of face thickness；It is the shortest distance between cross sectional centroid on film cross section at the core structure
At position no more than the 1/5 of tranverse sectional thickness.
3. the preparation method of primary film of any of claims 1 or 2, which comprises the steps of:
1) polyacrylonitrile solution is prepared；
2) polyacrylonitrile solution is made to form the liquid stream of film-form；
3) processing is formed to the liquid stream of film-form, obtains primary film；
Preferably, the polyacrylonitrile in the polyacrylonitrile solution includes polyacrylonitrile homopolymer, in polyacrylonitrile copolymer
One or two kinds of mixtures；
Preferably, the liquid stream of polyacrylonitrile solution formation film-form is made using extrusion molding or the tape casting；
Preferably, processing is formed to the liquid stream of film-form using solvent evaporation method or coagulating bath forming process, obtains coming into being thin
Film.
4. the preparation method of primary film according to claim 3, which is characterized in that the step 3) specifically: make institute
Forming processing of the liquid stream of film-form Jing Guo coagulating bath is stated, primary film is obtained；Wherein,
The coagulating bath includes the non-solvent and solvent that mass ratio is 1:0~2:8；Preferably, the matter of the non-solvent and solvent
Amount is than being 1:0~3:7, further preferably 9:1~4:6, more preferably 8:2~4:6；And/or
The temperature of the coagulating bath is -50 DEG C~70 DEG C, preferably -20 DEG C~5 DEG C；And/or
Residence time of the liquid stream of the film-form in the coagulating bath is 2-150s.
5. the preparation method of primary film according to claim 4, which is characterized in that
Non-solvent formic acid, glycerol, ethylene glycol, acetic acid, ethyl alcohol, methanol, chloroform, isobutanol, isoamyl in the coagulating bath
The mixture of one or more of alcohol, butanediol, benzyl alcohol, carbon tetrachloride, toluene, acetone, water, dioxane；And/or
Solvent in the coagulating bath is the solvent that can dissolve polyacrylonitrile, preferably dimethyl sulfoxide, dimethylformamide, two
The mixing of any one or more of methylacetamide, lithium chloride solution, ionic liquid, sodium thiocyanate solution, liquor zinci chloridi
Object.
6. the preparation method of primary film according to claim 3, which is characterized in that the step 2) specifically: use
Polyacrylonitrile solution is extruded into the liquid stream of film-form by extrusion die；
Wherein, the extruding aperture of the extrusion die is generally rectangular, any one of slit shape, class dog bone shape；
Preferably, the mean breadth of the extruding aperture of the extrusion die is 1~300 μm, preferably 4~200 μm.
7. a kind of polyacrylonitrile film, which is characterized in that the cross-sectional shape of the polyacrylonitrile film is generally rectangular；It is poly-
The ratio between the cross-sectional width of acrylonitrile film and tranverse sectional thickness are greater than 50；
Wherein, inclined between the average pore size at the surface structure of the polyacrylonitrile film and the average pore size at core structure
Difference is within 10%；
Preferably, the thickness of the polyacrylonitrile film is less than 1mm；
Preferably, the polyacrylonitrile film is made of primary film of any of claims 1 or 2.
8. the preparation method of polyacrylonitrile film as claimed in claim 7, which comprises the steps of:
It prepares primary film: primary film is prepared using the preparation method of the described in any item primary films of claim 3-6；
Post-processing: the primary film is post-processed, polyacrylonitrile film is obtained；
Preferably, the post-processing includes being washed to primary film, drawing-off, oiling, be dried, and it is thin to obtain polyacrylonitrile
Film；
It is further preferred that the post-processing includes being washed to the primary film, water-bath drawing-off, drying heat treatment, water
Steam drawing-off, oiling treatment obtain polyacrylonitrile film.
9. a kind of polyacrylonitrile-radical C film, which is characterized in that the cross-sectional shape of the polyacrylonitrile-radical C film is substantially
Rectangle；The ratio between the cross-sectional width of polyacrylonitrile film and tranverse sectional thickness are greater than 50；
Wherein, the polyacrylonitrile-radical C film with a thickness of 0.5~150 μm, in the range of preferably 1~10 μm, further
It is preferred that 3~8 μm；
Preferably, the width of the polyacrylonitrile-radical C film is 1~10m；Or the width of the polyacrylonitrile-radical C film is
25 μm~1m, preferably 1mm~20cm, further preferably 5mm~100mm；
Preferably, the longitudinal tensile strength of the polyacrylonitrile-radical C film is 2.2-4.5GPa；
Preferably, the average pore size at the average pore size at the surface structure of the polyacrylonitrile-radical C film and core structure it
Between deviation within 10%；
Preferably, the polyacrylonitrile-radical C film is made of polyacrylonitrile film as claimed in claim 7.
10. the preparation method of polyacrylonitrile-radical C film as claimed in claim 9, which comprises the steps of: to power
Benefit require 7 described in polyacrylonitrile film be heat-treated, obtain polyacrylonitrile-radical C film；
Preferably, described be heat-treated includes:
Pre-oxidation: 185~400 DEG C at a temperature of, to the polyacrylonitrile film carry out pre-oxidation treatment, obtain pre-oxidizing thin
Film；
Low-temperature carbonization: 400~1000 DEG C at a temperature of, to the pre-oxidation film carry out low-temperature carbonization processing, obtain low temperature
Carbonized film；
High temperature cabonization: 1100~3000 DEG C at a temperature of, to the low-temperature carbonization film carry out high temperature cabonization, obtain polypropylene
Itrile group C film.
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| CN113048494A (en) * | 2021-03-17 | 2021-06-29 | 浙江精功科技股份有限公司 | Carbon fiber carbonization production line exhaust purification handles and waste heat recovery utilizes system |
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