CN101205280B - Acrylonitrile copolymer as well as preparation and use thereof - Google Patents
Acrylonitrile copolymer as well as preparation and use thereof Download PDFInfo
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Abstract
The invention relates to an acrylonitrile-based copolymer and a preparation method as well as use thereof. In the molar ratio percent formula of the acrylonitrile-based copolymer, 74.3 percent to 89.3 percent of acrylonitrile monomers, 10.0 percent to 25.0 percent of second monomers and 0.45 percent to 0.7 percent of initiators are contained; the initiator is one of lithium alkyl, sodium alkyl, magnesium alkyl or strontium alkyl and the second monomer is one of the acrylic acid, methacrylic acid, methyl methacrylate, methacrylate or allylamine; the molar ratio of the acrylonitrile to the second monomer on the molecular chain of the acrylonitrile-based copolymer ranges from 3 to 1 to 7 to 1, and two monomer units on the molecular chain are arranged orderly. The degree of isotacticity of the triad on the molecular chain is larger than or equal to 50 percent, the molecular weight of the copolymer is larger than or equal to 20,000, the melting point is less than or equal to 220 DEG C and the thermal decomposition temperature is more than or equal to 280 DEG C. The templating polymerization technology is adopted in the preparation method of the acrylonitrile-based copolymer, and the copolymer can be used for adopting the melt processing method to prepare the high-strength polyacrylonitrile fiber or high-strength polyacrylonitrile membrane.
Description
Technical field
The present invention relates to a kind of acrylonitrile copolymer and manufacturing thereof and utilisation technology, be specially two kinds of orderly isotactic acrylonitrile copolymer and manufacture method thereof of monomeric units arrangement on a kind of molecular chain, and adopting this acrylonitrile copolymer melt-processed to prepare the method for high strength acrylic itrile group copolymer fibre and film, international monopoly Main classification number plan is Int.Cl.D01F 6/18 (2006.01).
Background technology
Polyacrylonitrile fibre (acrylic fibers) be most important weaving with polymeric fibre material it, polyacrylonitrile still is most important carbon fiber material simultaneously.But the decomposition temperature of polyacrylonitrile (250 ℃) is lower than its melting temperature (317 ℃), makes it just take place crosslinked and cyclisation without fusion when heating, therefore adopts solvent spinning processing method (dry method, wet method and dried wet method) to produce acrylic fiber always.The solvent spinning technical process is long, and has environmental pollution to some extent.Compare with solvent spinning technology, the melt-spinning technology energy consumption is low, environmental pollution is little, water saving, production efficiency height, range of product specification are many, it is the development trend of current production of chemical fibre, for example, 2006, the man-made fiber of China about 88.6% be adopt that melt-spinning technology produces (provide data computation according to Economy Prediction Dept of National Information Center, www.chinagateway.org.cn).The melt-spinning of polyacrylonitrile can make full use of existing melt-spinning technology and technology, enriches the kind of acrylic fibers product, enhances product performance.The employing melt-spinning technology is made acrylic fibers research direction that far-reaching academic theoretical value and broad prospect of application are arranged beyond doubt, but the melt-spinning of realizing polyacrylonitrile is lower than the problem of its melting temperature with regard to the decomposition temperature that must solve polyacrylonitrile, in other words, manage to make the decomposition temperature of polyacrylonitrile to bring up on its fusing point.
For elasticity, extensibility and dyeability and the oxidative stability etc. of improving polyacrylonitrile, second monomer in the conventional acrylic fibers, perhaps be used for making second monomer of the polyacrylonitrile of carbon fibre precursor, as methyl acrylate, vinyl acetate, methacrylic acid and methylene-succinic acid etc., the second monomeric content is usually below 5mol%, and this analog copolymer does not have melt-processable yet.For example, Chinese invention patent ZL91112764 and Chinese invention patent ZL94118476 disclose the composition and the technological method for processing of vinyl cyanide and methacrylonitrile copolymerization melt-processable polyacrylonitrile; Chinese invention patent ZL02136955 and Chinese invention patent ZL02136956 disclose employing vinyl cyanide and crotononitrile modification by copolymerization polyacrylonitrile, the novel process of preparation melt-processable polyacrylonitrile multipolymer.US5618901 discloses a kind of method that adopts vinyl cyanide and unsaturated olefin copolymerization melt-processable acrylonitrile copolymer.Because vinyl cyanide is different with the second monomeric reactivity ratio, that is to say the speed difference of these monomer generation copolymerizations, do not take special measure control vinyl cyanide and the ordered arrangement of second monomer on molecular chain in the described patent of invention document, thereby vinyl cyanide and the arrangement of second monomer on polymer molecular chain are at random, not having rule, is unregulated polymer.Though the vinyl cyanide and the second monomeric ratio may meet the demands in whole multipolymer, but certain or some segment at polymer molecular chain, two kinds of monomeric ratios and inequality in described two kinds of monomeric ratios and the multipolymer integral body, the distribution of described in other words two kinds of monomeric ratios on the whole segment of multipolymer is uneven, and second monomeric unit is for the elimination DeGrain of dipole effect between the cyano group.
Polyacrylonitrile fibre (acrylic fibers) is most important carbon fibre precursor material, owing to can only adopt the solvent spinning technology to prepare at present, resulting polymers is a unregulated polymer, so the performance of fiber and theoretical value differ greatly.As everyone knows, atactic polypropylene(APP) is an elastomerics, and isotactic polyprophlene is a kind of plastics with good physical mechanical property, can make uses such as fiber, film.Therefore taxis has very important influence to the performance of polyacrylonitrile fibre.The taxis acrylonitrile copolymer has relevant report, and how its structure prepares the taxis acrylonitrile based polymer and also caused attention both domestic and external as shown in Figure 2.For example, day disclosure special permission communique JP62282016 discloses a kind of novel method that adopts the radical polymerization of gamma-ray irradiation urea complex compound to prepare high normal polyacrylonitrile at low temperatures, but this method need be carried out under-78 ℃ and gamma-ray irradiation, reaction conditions is relatively harsher, and industry is difficult to carry out.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined has following 4:
1. design a kind of acrylonitrile copolymer, this acrylonitrile copolymer has the molecular chain and the taxis of regular arrangement, and melt-processable;
2. design a kind of preparation method of acrylonitrile copolymer; This preparation method can prepare the molecular chain with regular arrangement and the acrylonitrile copolymer of taxis, and cost is low, pollutes fewly, and technology is simple, and the conserve water resource is easy to industrializing implementation;
3. design a kind of purposes of acrylonitrile copolymer of the present invention, promptly under the situation that adds thermo-stabilizer, adopt melt-processed technology described acrylonitrile copolymer to be made the preparation method of high-intensity polyacrylonitrile fibre.
4. design the purposes of another kind of polyacrylonitrile base co-polymer of the present invention, promptly under the situation that adds thermo-stabilizer, adopt melt-processed technology described acrylonitrile copolymer to be made the preparation method of high-intensity polyacrylonitrile film.
The technical scheme that the present invention solves described the 1st technical problem is: design a kind of acrylonitrile copolymer, the prescription of this acrylonitrile copolymer is:
Acrylonitrile monemer 74.3～89.3mol%;
Second monomer, 10.0～25.0mol%;
Initiator 0.45～0.7mol%; Each component molar percentage sum is 100%;
Described initiator is a kind of in lithium alkylide, sodium alkyl, alkyl magnesium or the alkyl strontium; Described second monomer is a kind of in vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate or the allylamine; The vinyl cyanide and the second monomeric mol ratio are 3: 1～7: 1 on the described acrylonitrile copolymer molecular chain, and two monomeric units on the molecular chain are arranged in order, triad degree of isotacticity 〉=50% on the molecular chain, molecular weight of copolymer 〉=20000, fusing point≤220 ℃, heat decomposition temperature 〉=280 ℃.
The technical scheme that the present invention solves described the 2nd technical problem is: design a kind of preparation method of acrylonitrile copolymer, this preparation method adopts acrylonitrile copolymer prescription of the present invention and following technology:
Select for use material as template, place organic solution to soak a week, remove after reacting influential impurity with adsorptivity, vacuum drying, high purity nitrogen alternating permutation three times fills the nitrogen encapsulation, places in the moisture eliminator standby;
Pipette described mould material, be heated to 60 ℃, vacuumize, high purity nitrogen alternating permutation secondary fills under the nitrogen and is cooled to room temperature, vacuum condition adds organic solvent down, the submergence mould material adds the purified acrylonitrile monemer then, carry out the pre-assembling of monomer with the ultrasonic frequency of 20KHz vibration 30～60min after, drain steeping fluid, be cooled to room temperature;
Before initiator adds, earlier 10% mould material and second monomer that is loaded with acrylonitrile monemer is added in the reactor, stir, slowly drip the organic solvent that contains the described initiator of 0.2～2wt% of equitemperature, initiated polymerization, divide 3～6 droppings to add the remaining mould material and second monomer that is loaded with acrylonitrile monemer again, the drop rate of control initiator, initiator drips stopped reaction half an hour; Described polymeric reaction temperature is 0～70 ℃, and the initiator dropping time is 0.5～8h;
Product is filtered, and solid joins in the sodium nitrite solution of 2.0～10.0mol/L, after fully stirring, takes out the template that comes off and handle, and filters slurries, earlier with washed with de-ionized water 3 times, uses the methanol wash 3 times of 95wt% again, filters then, and oven dry promptly;
Described mould material is at least a in activated carbon fiber, carbon nanotube, carbon nano-tube fibre or the carbon nano pipe array material with high absorbability;
Described organic solvent is a kind of in hexanaphthene, normal hexane, normal heptane or the n-decane.
The technical scheme that the present invention solves described the 3rd technical problem is: design a kind of preparation method of polyacrylonitrile fibre, this preparation method adopts acrylonitrile copolymer of the present invention and following melt-processed technology:
1. interpolation thermo-stabilizer: adopt the mode of ground and mixed in described acrylonitrile copolymer, to add thermo-stabilizer by following mass ratio:
Acrylonitrile copolymer 92～99wt%;
Thermo-stabilizer 1～8wt%;
Described thermo-stabilizer is phthalate or toxilic acid Ester, and described phthalate material is a kind of in dibutyl phthalate, dihexyl phthalate, the dioctyl phthalate (DOP); Described toxilic acid Ester is maleic anhydride list lauryl alcohol ester, maleic anhydride list tetradecyl alcohol ester, maleic anhydride list hexadecanol ester, maleic anhydride list stearyl alcohol ester, a kind of in the two lauryl alcohol esters of maleic anhydride, the two tetradecyl alcohol esters of maleic anhydride, the two hexadecanol esters of maleic anhydride or the two stearyl alcohol esters of maleic anhydride.
2. melt-spinning: after the blend thorough drying with described thermo-stabilizer and acrylonitrile copolymer, join in the high-speed mixer and mix, join then and melt extrude spinning in the twin screw extruder, can prepare high-strength polypropylene nitrile fiber; Described spinning temperature is above 5～30 ℃ of the fusing point of described acrylonitrile copolymer, and at its below decomposition temperature 5～30 ℃.
The technical scheme that the present invention solves described the 4th technical problem is: design a kind of preparation method of polyacrylonitrile film, this preparation method adopts acrylonitrile copolymer of the present invention and following melt-processed technology:
1. interpolation thermo-stabilizer: adopt the mode of ground and mixed in described acrylonitrile copolymer, to add thermo-stabilizer by following mass ratio:
Acrylonitrile copolymer 92～99wt%;
Thermo-stabilizer 1～8wt%;
Described thermo-stabilizer is phthalate or toxilic acid Ester, and described phthalate material comprises a kind of in dibutyl phthalate, dihexyl phthalate, the dioctyl phthalate (DOP); Described toxilic acid Ester comprises maleic anhydride list lauryl alcohol ester, maleic anhydride list tetradecyl alcohol ester, maleic anhydride list hexadecanol ester, maleic anhydride list stearyl alcohol ester, a kind of in the two lauryl alcohol esters of maleic anhydride, the two tetradecyl alcohol esters of maleic anhydride, the two hexadecanol esters of maleic anhydride or the two stearyl alcohol esters of maleic anhydride.
2. fusion blown film: with the blend of described thermo-stabilizer and described acrylonitrile copolymer at 50～80 ℃ of down dry 2～24h, after the thorough drying, blend joined in the high-speed mixer mix, join in the twin screw extruder then and melt extrude, the material of extruding is cooled to below 80 ℃, behind blowing, cooling, insulation, subdivision, elimination static and winding process, can obtain high-intensity polyacrylonitrile film; Describedly melt extrude above 5～30 ℃ of the fusing point that temperature is described acrylonitrile copolymer, and at its below decomposition temperature 5～30 ℃.
Compared with prior art, acrylonitrile copolymer of the present invention has the molecular chain and the taxis of the regular arrangement of higher degree, the intensity height, melt-processable, and the polymerization technique advanced person of its preparation method, production technique is economized on water, environmental pollution is little, the production efficiency height, cost is lower, is easy to industrializing implementation; The polyacrylonitrile fibre smooth surface of making by the gained multipolymer, there is not tangible skin-core structure, the fibrous inside defective is few, tensile break strength is big, the fibre section structural changes is many, can prepare the fiber of multiple structures such as special crosssection, compound and hollow by changing spinning pack, adaptability is good, and production cost is relatively low; The polyacrylonitrile film surface of being made by the gained multipolymer is smooth, and defective is few, and is high temperature resistant, corrosion-resistant, good toughness, and intensity is big, and cost is low, has a good application prospect and economical, societal benefits.
Description of drawings
Fig. 1 arranges the structure of orderly acrylonitrile copolymer and this acrylonitrile copolymer preparation method for two monomeric units on taxis with higher degree of the present invention and the molecular chain and generates the process synoptic diagram that two monomeric units on taxis with higher degree and the molecular chain are arranged orderly acrylonitrile copolymer;
Fig. 2 has the molecular chain of regular arrangement of higher degree and the synoptic diagram of taxis structure for acrylonitrile copolymer of the present invention.
Embodiment
Further narrate the present invention below in conjunction with embodiment and accompanying drawing:
The acrylonitrile copolymer (abbreviation multipolymer) of the present invention's design, the vinyl cyanide on this copolymer molecule chain and the second monomeric mol ratio are 3: 1～7: 1, and have the molecular chain and the taxis (referring to Fig. 2) of regular arrangement, filling a prescription is:
Acrylonitrile monemer 74.3～89.3mol%;
Second monomer, 10.0～25.0mol%;
Initiator 0.45～0.7mol%; Each component molar percentage sum is 100%;
Described initiator is the alkali alkyl compound, a kind of as in lithium alkylide, sodium alkyl, alkyl magnesium or the alkyl strontium etc.; Described second monomer is a kind of in vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate or the allylamine.
Studies show that, when vinyl cyanide and the second monomeric mol ratio are 4: 1～5: 1, second monomer is for the elimination best results of dipole effect between the cyano group, vinyl cyanide and the optimal arrangement of second monomer should be per 4,5 acrylonitrile unit 1 second monomeric units at interval, and two kinds of monomeric arrangement modes as shown in Figure 1 on this moment copolymer molecule chain.The molecular chain and the taxis of the regular arrangement of the higher degree that multipolymer had of the present invention's design promptly comprise this structure.The molecular chain of the regular arrangement that multipolymer had of the present invention design and taxis are meant that vinyl cyanide and the second monomeric mol ratio are 3: 1～7: 1 on the acrylonitrile copolymer molecular chain, mol ratio is 4: 1～5: 1 preferably, and two monomeric units have the taxis of higher degree and arrange (referring to Fig. 2) in order.
The present invention has designed the preparation method of described acrylonitrile copolymer simultaneously, and this preparation method adopts acrylonitrile copolymer prescription of the present invention and following processing method:
At first select for use material as template, place organic solution to soak a week, remove reacting influential impurity with adsorptivity, as fatty dirt etc., make fiber surface " activation ", behind the vacuum drying, high purity nitrogen alternating permutation three times fills the nitrogen encapsulation, places in the moisture eliminator standby;
Pipette treated mould material, be heated to 60 ℃, vacuumize, alternately fill high purity nitrogen secondary, fill under the nitrogen and be cooled to room temperature, vacuum condition adds described organic solvent down, makes the described mould material of its submergence, adds formula ratio purified acrylonitrile monemer then, ultrasonic frequency oscillation treatment 30～60min with 20kHz, carry out monomeric pre-assembling, drain steeping fluid then, be cooled to room temperature;
In reactor, add aforesaid second monomer and the mould material that is loaded with acrylonitrile monemer in batches, the first mould material that is loaded with acrylonitrile monemer and second monomer with 10% is added in the reactor before initiator adds, stir, slowly drip the organic solvent that contains the described initiator of 0.2～2wt% of equitemperature, initiated polymerization, divide 3～6 addings with the remaining mould material and second monomer that is loaded with acrylonitrile monemer again, each adding 15～30%, the drop rate of control initiator, initiator drips stopped reaction half an hour; Described polymeric reaction temperature is 0～70 ℃, and the described initiator dropping time is 0.5～8h;
Products therefrom is filtered, solid is joined in the sodium nitrite solution of 2.0～10.0mol/L, firmly stir, processing comes off, after taking out template, filter slurries, use washed with de-ionized water 3 times earlier, use the 95wt% methanol wash again 3 times, remove salt, filter then, oven dry promptly;
Described mould material is that activated carbon fiber, carbon nanotube, carbon nano-tube fibre or carbon nano pipe array etc. have at least a in the material of high absorbability.If the adsorptivity of template is poor, monomer is difficult to obtain the high polymkeric substance of tacticity at the arrangement irregularity of template surface.
Described organic solvent is selected anionic polymerisation inert solvent for use, a kind of as in hexanaphthene, normal hexane, normal heptane or the n-decane etc.
The present invention has also developed the purposes of described multipolymer simultaneously.One of purposes is that design a kind ofly adopts multipolymer melt-processed of the present invention to prepare the method for high-strength polypropylene nitrile fiber, and to be that design is a kind of adopt multipolymer melt-processed of the present invention to prepare the method for high-strength polypropylene nitrile film to two of purposes.
The preparation method of polyacrylonitrile fibre of the present invention, adopt acrylonitrile copolymer of the present invention and following melt-processed technology:
1. interpolation thermo-stabilizer: adopt the mode of ground and mixed in described acrylonitrile copolymer, to add thermo-stabilizer by following mass ratio:
Acrylonitrile copolymer 92～99wt%;
Thermo-stabilizer 1～8wt%;
Described thermo-stabilizer is phthalate or toxilic acid Ester, and described phthalate material comprises a kind of in dibutyl phthalate, dihexyl phthalate, the dioctyl phthalate (DOP) etc.; Described toxilic acid Ester comprises maleic anhydride list lauryl alcohol ester, maleic anhydride list tetradecyl alcohol ester, maleic anhydride list hexadecanol ester, maleic anhydride list stearyl alcohol ester, a kind of in the two lauryl alcohol esters of maleic anhydride, the two tetradecyl alcohol esters of maleic anhydride, the two hexadecanol esters of maleic anhydride or the two stearyl alcohol esters of maleic anhydride;
2. melt-spinning: with blend dry 2～24h under 50～80 ℃ of temperature of described thermo-stabilizer and described acrylonitrile copolymer, thorough drying to remove moisture wherein, avoids producing in the product bubble; The exsiccant blend joined in the high-speed mixer mix, join then and melt extrude spinning in the twin screw extruder, can prepare high-strength polypropylene nitrile fiber.
Spinning equipment and processing parameter that melt-spinning process of the present invention is used except that spinning temperature, need not to do special adjustment, promptly are applicable to the requirement of prior art melt-spinning processing.
Spinning temperature of the present invention should be chosen in above 5～30 ℃ of the fusing point of described acrylonitrile copolymer, and at its below decomposition temperature 5～30 ℃; Spinning temperature is at its more than fusing point 10～25 ℃ preferably, selects in 10～25 ℃ of scopes below the decomposition temperature at it.Spinning temperature is low excessively, and the acrylonitrile copolymer fusion is incomplete, is difficult to make uniform fiber; Spinning temperature is too high, easily causes the decomposition of acrylonitrile copolymer.
The preparation method of polyacrylonitrile film of the present invention, adopt acrylonitrile copolymer of the present invention and following melt-processed technology:
1. interpolation thermo-stabilizer: the preparation method that this step process is same as described polyacrylonitrile fibre, do not give unnecessary details.
2. fusion blown film: with blend dry 2～24h under 50～80 ℃ of temperature of described thermo-stabilizer and described acrylonitrile copolymer, thorough drying to remove the moisture in the raw material, avoids producing in the product bubble; The exsiccant blend joined in the high-speed mixer mix, join in the twin screw extruder then and melt extrude, when the material of extruding is cooled to below 80 ℃, after operations such as blowing, cooling, insulation, subdivision, elimination static, rolling, can obtain the high-strength polyacrylonitrile film.
Used equipment and the processing parameter of fusion blown film process of the present invention except that melt extruding temperature, need not to do special adjustment, promptly is applicable to the requirement of prior art fusion blown film processing.
Of the present inventionly melt extrude above 5～30 ℃ of the fusing point that temperature should be chosen in described acrylonitrile copolymer, and at its below decomposition temperature 5～30 ℃; Melt extrude temperature preferably and be at its more than fusing point 10～25 ℃, select in 10～25 ℃ of scopes below the decomposition temperature at it.It is low excessively to melt extrude temperature, and the acrylonitrile copolymer fusion is incomplete, is difficult to make uniform thin film; It is too high to melt extrude temperature, easily causes the decomposition of acrylonitrile copolymer.
Copolymer method of the present invention at first will strictly be controlled the vinyl cyanide and the second monomeric additional proportion, makes its any moment in reaction, and the vinyl cyanide and the second monomeric ratio control are in the scope of prescription requirement and arts demand; Next adopts the template polymerization technology to prepare the high degree of isotacticity vinyl cyanide and the second monomeric multipolymer; Adopt in multipolymer the method that adds thermo-stabilizer once more, make that the isotactic acrylonitrile copolymer of two kinds of monomeric unit ordered arrangement has good heat-resistant on the molecular chain, can make acrylonitrile copolymer fiber or film by melt-processed technology.One of gordian technique in the copolymer method of the present invention is to have adopted described template polymerization technology.Template polymerization is meant the polyreaction that monomer is carried out in the presence of template, be a kind of by interactions such as hydrogen bond, static combination, Van der Waals force, crystallization envelopes, monomer can be constrained on the template, make these monomers carry out polymerization then, again new synthetic polymkeric substance is separated the polymerization process of relative molecular mass that thus can controlling polymers and distribution thereof, three-dimensional regularity, sequential structure etc. with template.Template polymerization has the reacting field effect, even polyreaction occurs in the certain space, thereby reaches the polymer size that qualification generates and the purpose of structure; Also have print effect, promptly utilize the interaction of acid, base groups, make growing chain, form the ion complex between polymer preferentially attached on the template, polymerization reaction take place, and the size of products therefrom and template and structure have " replicability ".Copolymer method of the present invention adopts described template polymerization technology, described these the two kinds of character of template polymerization technology have been utilized just, help acrylonitrile monemer and carry out spatial disposition by a graded, formation has the molecular chain of regular arrangement and the copolymer structure of taxis.Adopt the arrangement of template polymerization method control cyano group, also the generation of may command side reaction.Template polymerization itself is prior art (referring to Chinese invention patent CN 1786051A and CN 1663969A).
In the copolymer process of the present invention, monomeric rate of polymerization is proportional to reactivity ratio γ and this monomeric concentration [M], therefore will make that the second monomeric content is in 10～25mol% in the multipolymer, must make the second monomeric speed of reaction is 10～25% of vinyl cyanide.Under the vinyl cyanide and the second monomeric reactivity ratio fixed situation, the best approach that the molecular chain of control multipolymer carries out regular arrangement is the control second monomeric concentration.What the preparation process of acrylonitrile copolymer described in the present invention mainly adopted is the reinforced method of hunger-type, promptly polymerization velocity is greater than or equal to the interpolation speed of comonomer in this method, initiator adds polymerization system continuously, adding speed is kept rate of polymerization, grow sequence with this vinyl cyanide that prevents to form in the multipolymer, the sequence of comonomer distributes in the controlling polymers, forms uniform acrylonitrile copolymer with preparation.Specific practice is: be loaded with the mould material of vinyl cyanide with 10% and second monomer of formula ratio is added in the reactor before initiator adds, divide 3～6 droppings to add the remaining mould material and second monomer that is loaded with vinyl cyanide again, each add-on is 15～30%, and the initiator dropping time is 0.5～8h;
Multipolymer of the present invention is the vinyl cyanide and the second monomeric isotactic copolymer, and triad isotaxy (mm) ratio is more than 50% on the molecular chain, and molecular weight of copolymer is more than 20000; The fusing point of this acrylonitrile copolymer can be reduced to below 220 ℃, and thermolysis (cyclisation) temperature can be brought up to more than 280 ℃.
The present invention utilizes described multipolymer, in the presence of thermo-stabilizer, can prepare high-intensity polyacrylonitrile fibre or film by melt processing.Because except that spinning temperature, the preparation method of polyacrylonitrile fibre is same as prior art substantially, therefore, made polyacrylonitrile fibre kind is analogous to prior art, for example the cross section of fiber can be circle, trilateral and hollow shape etc., but fibre property is largely increased, and for example fiber does not have tangible skin-core structure, inner not tangible cavity, having physical strength preferably, is a kind of high-performance polyacrylonitrile fiber; As a same reason, made polyacrylonitrile film surface is smooth, and radiation hardness, corrosion-resistant, high temperature resistant has good toughness and intensity, also is a kind of high-performance polyacrylonitrile film.After tested, the fiber number of the polyacrylonitrile fibre that the embodiment of the invention is prepared is below 10dtex, and tensile break strength is more than 4.0cN/dtex, and extension at break is below 50%; The tensile strength of polyacrylonitrile film is more than 30MPa, and elongation at break is more than 35%.
The present invention does not address part and is applicable to prior art.
Below provide specific embodiments of the invention, but protection scope of the present invention is not subjected to the restriction of these specific embodiments:
Embodiment 1
With the polyacrylonitrile based activated carbon fiber selected for use as mould material, rub into bead after, place hexanaphthene to soak a week, remove reacting influential impurity, make fiber surface " activation ", vacuum drying, high purity nitrogen alternating permutation three times fills the nitrogen encapsulation, places in the moisture eliminator standby.Initiator adopts n-Butyl Lithium, and the Gilman preparation method in the conventional anionoid polymerization is adopted in its preparation.
Pipette the treated mould material of 200g, be heated to 60 ℃, vacuumize, alternately fill high purity nitrogen secondary, fill under the nitrogen and be cooled to room temperature, vacuum condition adds an amount of hexane solution down, the submergence mould material adds purified acrylonitrile monemer 235.9g (89.0mol%) then, carry out monomeric pre-assembling with the ultrasonic frequency of 20KHz vibration 60min after, drain steeping fluid, be cooled to room temperature.
In reactor, add mould material and the 4.5g second monomer methyl acrylate (10wt% of monomer total amount) that 43.6g is loaded with acrylonitrile monemer earlier, stir, beginning slowly drips the hexane solution 100mL that contains 1.6g (0.5mol%) n-Butyl Lithium of equitemperature, initiated polymerization, the mould material that is loaded with acrylonitrile monemer and the second monomer methyl acrylate with remainder divides three addings again, the drop rate of control initiator, initiator drips stopped reaction half an hour, total reaction times is 5h, and the second monomer methyl acrylate content of adding is 10.5mol%.
Product is filtered, solid is joined in the sodium nitrite solution that concentration is 4mol/L, firmly stir, carry out the template processing that comes off, after template is taken out with tweezers, dope filtration, use washed with de-ionized water 3 times earlier, use the 95wt% methanol wash again 3 times, remove salt etc., filter, oven dry can obtain having the molecular chain of regular arrangement and the acrylonitrile copolymer of taxis.
Adopt nuclear magnetic resonance spectrometry and infrared spectroscopy test products obtained therefrom, the result shows that two kinds of monomers are pressed the feed ratio arrangement on the molecular chain of gained multipolymer, and the isotaxy degree of isotacticity of multipolymer is 52%; Differential scanning calorimeter and thermogravimetric analysis experimental result show that the fusing point of gained multipolymer is 189 ℃, and heat decomposition temperature is 311 ℃.
In exsiccant vinyl cyanide-methyl acrylate copolymer 100g, add dibutyl phthalate 3g as thermo-stabilizer, after ground and mixed is even, 200 ℃ melt extrude on the plunger spinning-drawing machine, make the rounded section nascent fibre, nascent fibre, after 90 ℃ of water-baths and 150 ℃ of steam baths stretch,, can obtain the acrylonitrile copolymer fiber of finished product at 150 ℃ of dryness finalizations.
Test shows: the fiber number of gained fiber is 3.2dtex, and tensile break strength is 5.3cN/dtex, and extension at break is 31%, and is best in quality.
Embodiment 2
Adopt the method identical to prepare mould material and normal-butyl magnesium initiator with embodiment 1.Only 224.7g (84.8mol%) vinyl cyanide replaces the 235.9g vinyl cyanide, with 64.1g (14.9mol%) methyl acrylate, replace the 45.2g methyl acrylate, 1.2g (0.3mol%) normal-butyl magnesium replaces the 1.6g n-Butyl Lithium, and other polymerization, treatment condition are identical with embodiment 1.
After tested, two kinds of monomers are pressed the feed ratio arrangement on the molecular chain of multipolymer, and the isotaxy degree of isotacticity is 51%.Differential scanning calorimeter and thermogravimetric analysis experimental result show that the fusing point of multipolymer is 184 ℃, and heat decomposition temperature is 312 ℃.
In exsiccant vinyl cyanide-methyl acrylate copolymer 100g, add the two lauryl alcohol ester 2.3g of maleic anhydride as thermo-stabilizer, after ground and mixed is even, 205 ℃ melt extrude on the plunger spinning-drawing machine, make the trilobal(cross) section nascent fibre, nascent fibre obtains finished fiber at 150 ℃ of dryness finalizations after 90 ℃ of water-baths and 150 ℃ of steam baths stretch.Test shows: the fiber number of gained fiber is 2.7dtex, and tensile break strength is 5.1cN/dtex, and extension at break is 33%.
Embodiment 3
As mould material, place normal heptane to soak a week multi-walled carbon nano-tubes fiber (external diameter 42 μ m, length 5mm) selected for use, remove reacting influential impurity, make material surface " activation ", vacuum drying, high purity nitrogen alternating permutation three times fills the nitrogen encapsulation, places in the moisture eliminator standby.
Pipette the treated mould material of 210g, being heated to 60 ℃ vacuumizes, alternately fill high purity nitrogen secondary, fill under the nitrogen and be cooled to room temperature, a certain amount of hexane solution of adding under the vacuum condition, submergence mould material, add purified acrylonitrile monemer 216.8g (81.8mol%) then, ultrasonic frequency vibration 45min with 20KHz carries out monomeric pre-assembling, drains steeping fluid, is cooled to room temperature.
In reactor, add mould material and the 7.7g second monomer methyl acrylate (10wt% of monomer total amount) that 42.7g is loaded with acrylonitrile monemer earlier, stir, beginning slowly drips the hexane solution 200mL that contains 0.6g (0.2mol%) n-Butyl Lithium of equitemperature, initiated polymerization, the remaining mould material that is loaded with acrylonitrile monemer and the second monomer methyl acrylate divide six addings, the drop rate of control initiator, initiator drips stopped reaction half an hour, total reaction times is 6.5h, and the second monomer methyl acrylate content of adding is 18.0mol%.
Product is filtered, and it is in the sodium nitrite solution of 6mol/L that solid adds concentration, firmly stirs, and processing comes off, template is taken out the back dope filtration with tweezers, uses washed with de-ionized water 3 times earlier, uses the 95wt% methanol wash again 3 times, remove salt etc., filter, oven dry promptly gets multipolymer.
Nuclear magnetic resonance spectrometry and infrared spectroscopy test result show that two kinds of monomers are pressed the feed ratio arrangement on the molecular chain of multipolymer, and the isotaxy degree of isotacticity is 57%.Differential scanning calorimeter and thermogravimetric analysis experimental result show that the fusing point of multipolymer is 181 ℃, and heat decomposition temperature is 298 ℃.
In exsiccant acrylonitrile methyl meth acrylat copolymer 2000g, add maleic anhydride list stearyl alcohol ester 20g as thermo-stabilizer, after ground and mixed is even, 220 ℃ melt extrude on Φ 20 single screw extrusion machines, make nascent fibre, nascent fibre obtains finished fiber at 150 ℃ of dryness finalizations after 90 ℃ of water-baths and 150 ℃ of steam baths stretch.Test shows: the fiber number of gained fiber is 2.5dtex, and tensile break strength is 4.4cN/dtex, and extension at break is 31%.
Embodiment 4
With the array of multi-walled carbon nanotubes of on silicon chip, growing selected for use (5cm * 5cm) as mould material, place n-decane to soak a week makes fiber surface " activation ", vacuum drying, high purity nitrogen alternating permutation three times fills the nitrogen encapsulation, places moisture eliminator interior standby.
Pipette the treated mould material of 220g, being heated to 60 ℃ vacuumizes, alternately fill high purity nitrogen secondary, fill under the nitrogen and be cooled to room temperature, a certain amount of n-heptane solution of adding under the vacuum condition, submergence mould material, add purified acrylonitrile monemer 231.6g (87.4mol%) then, ultrasonic frequency vibration 50min with 20KHz carries out monomeric pre-assembling, drains steeping fluid, is cooled to room temperature.
In reactor, add mould material and the 6.0g second monomer methyl acrylate (10wt% of monomer total amount) that 45.2g is loaded with acrylonitrile monemer earlier, stir, beginning slowly drips the n-heptane solution 300mL that contains 3.2g (0.8mol%) normal-butyl sodium of equitemperature, initiated polymerization, the mould material that is loaded with acrylonitrile monemer and the second monomer methyl acrylate with remainder divides five addings again, the drop rate of control initiator, initiator drips stopped reaction half an hour, total reaction times is 5.5h, and the second monomer methyl acrylate content of adding is 11.8mol%.
Product is filtered, and it is in the sodium nitrite solution of 5mol/L that solid adds concentration, firmly stirs, and processing comes off, template is taken out the back dope filtration with tweezers, uses washed with de-ionized water 3 times earlier, uses the 95wt% methanol wash again 3 times, remove salt etc., filter, oven dry promptly.
After tested, two kinds of monomers are pressed the feed ratio arrangement on the molecular chain of multipolymer, and the isotaxy degree of isotacticity is 65%.The fusing point of multipolymer is 208 ℃, and heat decomposition temperature is 339 ℃.
Add dioctyl phthalate (DOP) 5g as thermo-stabilizer in exsiccant acrylonitrile methyl meth acrylat copolymer 500g, fully evenly the back is standby 70 ℃ of following vacuum-dryings 8 hours for ground and mixed.The exsiccant blend joined in the high-speed mixer mix, join in the twin screw extruder then and melt extrude, each section temperature is respectively: 90-140-180-205 ℃.When the material of discharging is cooled to below 70 ℃, after operations such as blowing, cooling, insulation, subdivision, elimination static, rolling, promptly get high-strength polyacrylonitrile film of the present invention.Test shows: the tensile strength of gained film is 32.8MPa, and extensibility is 360%.
Embodiment 5
Adopt the method for embodiment 4 to prepare mould material.Pipette the treated mould material of 200g, being heated to 60 ℃ vacuumizes, alternately fill high purity nitrogen secondary, fill under the nitrogen and be cooled to room temperature, a certain amount of hexane solution of adding under the vacuum condition, submergence mould material, add purified acrylonitrile monemer 234.3g (88.4mol%) then, ultra-sonic oscillation 40min carries out monomeric pre-assembling, drains steeping fluid, is cooled to room temperature.
In reactor, add mould material and the 4.7g second monomer methyl acrylate (10wt% of monomer total amount) that 43.4g is loaded with acrylonitrile monemer earlier, stir, beginning slowly drips the hexane solution 300mL that contains 1.9g (11.0mol%) n-Butyl Lithium of equitemperature, initiated polymerization, the mould material that is loaded with acrylonitrile monemer and the second monomer methyl acrylate with remainder divides four addings again, the drop rate of control initiator, initiator drips stopped reaction half an hour, total reaction times is 4.5h, and the second monomer methyl acrylate content of adding is 11.0mol%.
Product is used washed with de-ionized water 3 times earlier, use the 95wt% methanol wash again 3 times, remove salt etc., filter, oven dry promptly gets multipolymer.
After tested, two kinds of monomers are pressed the feed ratio arrangement on the molecular chain of multipolymer, and the isotaxy degree of isotacticity of multipolymer is 58%.The fusing point of multipolymer is 205 ℃, and heat decomposition temperature is 336 ℃.
In exsiccant vinyl cyanide-methyl acrylate copolymer 500g, add maleic anhydride list lauryl alcohol to 8g as thermo-stabilizer, fully evenly back 75 ℃ of following vacuum-dryings 10 hours are standby for ground and mixed.The exsiccant blend joined in the high-speed mixer mix, join in the twin screw extruder then and melt extrude, each section temperature is respectively: 110-170-195-210 ℃.When the material of discharging is cooled to below 80 ℃, after operations such as blowing, cooling, insulation, subdivision, elimination static, rolling, promptly get high-strength polyacrylonitrile film of the present invention.Test shows: the tensile strength of gained film is 35.2MPa, and extensibility is 375%.
Embodiment 6
As mould material, place normal heptane to soak a week polyacrylonitrile radical active carbon fiber selected for use, make fiber surface " activation ", vacuum drying, high purity nitrogen alternating permutation three times fills the nitrogen encapsulation, places moisture eliminator interior standby.
Pipette the treated mould material of 240g, being heated to 60 ℃ vacuumizes, alternately fill high purity nitrogen secondary, fill under the nitrogen and be cooled to room temperature, a certain amount of n-heptane solution of adding under the vacuum condition, submergence mould material, add purified acrylonitrile monemer 229.8g (86.7mol%) then, ultrasonic frequency vibration 55min with 20KHz carries out monomeric pre-assembling, drains steeping fluid, is cooled to room temperature.
In reactor, add mould material and 5.6g second monomers methyl methacrylate (10wt% of monomer total amount) that 47.0g is loaded with acrylonitrile monemer earlier, stir, beginning slowly drips the n-heptane solution 100mL that contains 1.3g (0.4mol%) n-Butyl Lithium of equitemperature, initiated polymerization, the mould material that is loaded with acrylonitrile monemer and the second monomer methyl acrylate with remainder divides three addings again, the drop rate of control initiator, initiator drips stopped reaction half an hour, total reaction times is 3.5h, and the second monomer methyl acrylate content of adding is 12.9mol%.
Product is filtered, and it is in the sodium nitrite solution of 6mol/L that solid adds concentration, firmly stirs, and processing comes off, template is taken out the back dope filtration with tweezers, uses washed with de-ionized water 3 times earlier, uses the 95wt% methanol wash again 3 times, remove salt etc., filter, oven dry promptly.
After tested, the isotaxy degree of isotacticity of multipolymer is 59%.The fusing point of multipolymer is 202 ℃, and heat decomposition temperature is 326 ℃.
In exsiccant acrylonitrile methyl meth acrylat copolymer 500g, add maleic anhydride list stearyl alcohol to 9g as thermo-stabilizer, fully evenly back 75 ℃ of following vacuum-dryings 8 hours are standby for ground and mixed.The exsiccant blend joined in the high-speed mixer mix, join in the twin screw extruder then and melt extrude, each section temperature is respectively: 120-175-190-215 ℃.When the material of discharging is cooled to below 70 ℃, after operations such as blowing, cooling, insulation, subdivision, elimination static, rolling, promptly get high-strength polyacrylonitrile film of the present invention.Test shows: the tensile strength of gained film is 35.0MPa, and extensibility is 380%.
Embodiment 7
Adopt carbon nano-tube fibre to replace the activated carbon fiber among the embodiment 1 to prepare mould material.Surplus with embodiment 1.
Adopt nuclear magnetic resonance spectrometry and infrared spectroscopy test products obtained therefrom, the result shows that two kinds of monomers are pressed the feed ratio arrangement on the molecular chain of gained multipolymer, and the isotaxy degree of isotacticity of multipolymer is 56%; Differential scanning calorimeter and thermogravimetric analysis experimental result show that the fusing point of gained multipolymer is 192 ℃, and heat decomposition temperature is 310 ℃.
In exsiccant vinyl cyanide-methyl acrylate copolymer 100g, add dibutyl phthalate 3g as thermo-stabilizer, after ground and mixed is even, 200 ℃ melt extrude on the plunger spinning-drawing machine, make the rounded section nascent fibre, nascent fibre, after 90 ℃ of water-baths and 150 ℃ of steam baths stretch,, can obtain the acrylonitrile copolymer fiber of finished product at 150 ℃ of dryness finalizations.
Test shows: the fiber number of gained fiber is 3.0dtex, and tensile break strength is 5.4cN/dtex, and extension at break is 30%, and is best in quality.
Embodiment 8
Adopt carbon nano pipe array to replace the activated carbon fiber among the embodiment 1 to prepare mould material.Surplus with embodiment 1.
Adopt nuclear magnetic resonance spectrometry and infrared spectroscopy test products obtained therefrom, the result shows that two kinds of monomers are pressed the feed ratio arrangement on the molecular chain of gained multipolymer, and the isotaxy degree of isotacticity of multipolymer is 61%; Differential scanning calorimeter and thermogravimetric analysis experimental result show that the fusing point of gained multipolymer is 187 ℃, and heat decomposition temperature is 318 ℃.
In exsiccant vinyl cyanide-methyl acrylate copolymer 100g, add dibutyl phthalate 3g as thermo-stabilizer, after ground and mixed is even, 200 ℃ melt extrude on the plunger spinning-drawing machine, make the rounded section nascent fibre, nascent fibre, after 90 ℃ of water-baths and 150 ℃ of steam baths stretch,, can obtain the acrylonitrile copolymer fiber of finished product at 150 ℃ of dryness finalizations.
Test shows: the fiber number of gained fiber is 2.8dtex, and tensile break strength is 5.7cN/dtex, and extension at break is 30%, and is best in quality.
Embodiment 9
Adopt the multi-walled carbon nano-tubes fiber production mould material among the carbon nano pipe array replacement embodiment 4, surplus with embodiment 4.
After tested, two kinds of monomers are pressed the feed ratio arrangement on the molecular chain of multipolymer, and the isotaxy degree of isotacticity is 68%.The fusing point of multipolymer is 188 ℃, and heat decomposition temperature is 341 ℃.
Add dioctyl phthalate (DOP) 5g as thermo-stabilizer in exsiccant acrylonitrile methyl meth acrylat copolymer 500g, fully evenly the back is standby 70 ℃ of following vacuum-dryings 8 hours for ground and mixed.The exsiccant blend joined in the high-speed mixer mix, join in the twin screw extruder then and melt extrude, each section temperature is respectively: 90-140-180-205 ℃.When the material of discharging is cooled to below 70 ℃, after operations such as blowing, cooling, insulation, subdivision, elimination static, rolling, promptly get high-strength polyacrylonitrile film of the present invention.Test shows: the tensile strength of gained film is 34.5MPa, and extensibility is 330%.
Comparative example 1
In reactor, add acrylonitrile monemer 237.4g (89.6mol%), methyl acrylate 43.0g (10mol%), be cooled to 0 ℃, slowly drip the hexane solution of the 1.3g n-Butyl Lithium of equitemperature then, initiated polymerization, stir, dripping initiator is stopped reaction after half an hour.
Product is filtered, and solid adds in the sodium nitrite solution of 4mol/L, firmly stirs, and successively water, methanol wash are filtered for several times, and oven dry promptly.
Nuclear magnetic resonance spectrometry and infrared spectroscopy test result show that multipolymer is a random copolymers.The fusing point of multipolymer is 208 ℃, and heat decomposition temperature is 301 ℃.
In exsiccant vinyl cyanide-methyl acrylate copolymer 100g, add dibutyl phthalate 3g as thermo-stabilizer, after ground and mixed is even, 215 ℃ melt extrude on the plunger spinning-drawing machine, make nascent fibre, nascent fibre obtains finished fiber at 150 ℃ of dryness finalizations after 90 ℃ of water-baths and 150 ℃ of steam baths stretch.Test shows: the fiber number of gained fiber is 3.3dtex, and tensile break strength is 2.8cN/dtex, and extension at break is 34%.
Comparative example 2
As template, other reaction raw materials and reaction conditions are with embodiment 4 with the array of multi-walled carbon nanotubes among the isotactic polypropylene fibre replacement embodiment 4.The isotaxy degree of isotacticity of multipolymer is 35%.The fusing point of multipolymer is 194 ℃, and heat decomposition temperature is 289 ℃.The polyacrylonitrile film stretching intensity of making is 26.5MPa, and extensibility is 290%.
Comparative example 3
Adopt with embodiment 1 in identical template preparation technology and initiator.Quantitatively pipette treated mould material, heating vacuumizes once more, alternately fills high purity nitrogen secondary, fills under the nitrogen to be cooled to room temperature, adds acrylonitrile monemer 500g and normal hexane mixed solution then, the submergence mould material, and 60min is at room temperature flooded in vibration.Drain steeping fluid, be cooled to 0 ℃, slowly drip the hexane solution of the 2.1g normal-butyl strontium of equitemperature then, initiated polymerization sways slightly, and dripping behind the initiator 50min is stopped reaction.
Product is filtered, and solid adds in the potassium hydroxide solution of 2mol/L, firmly stir, and the processing that comes off, template is taken out the back dope filtration with tweezers, and successively water, methanol wash are removed salt etc. for several times, filter, and oven dry is promptly.
Nuclear magnetic resonance spectrometry and infrared spectroscopy test result show that the isotaxy degree of isotacticity of polymkeric substance is 54%.Differential scanning calorimeter and thermogravimetric analysis experimental result show that the heat decomposition temperature of polymkeric substance is 251 ℃, do not have tangible fusing point, can not carry out melt-spinning or blown film.
Claims (7)
1. acrylonitrile copolymer, the prescription of this acrylonitrile copolymer is:
Acrylonitrile monemer 74.3～89.3mol%;
Second monomer, 10.0～25.0mol%;
Initiator 0.45～0.7mol%; Each component molar percentage sum is 100%;
Described initiator is a kind of in lithium alkylide, sodium alkyl, alkyl magnesium or the alkyl strontium; Described second monomer is a kind of in vinylformic acid, methacrylic acid, methyl methacrylate, methyl acrylate or the allylamine; The mol ratio of the acrylonitrile unit and second monomeric unit is 3: 1～7: 1 on this acrylonitrile copolymer molecular chain, and two monomeric units on the molecular chain are arranged in order, triad degree of isotacticity 〉=50% on the molecular chain, molecular weight of copolymer 〉=20000, fusing point≤220 ℃, heat decomposition temperature 〉=280 ℃;
Described acrylonitrile copolymer is prepared by following processing method: select for use the material with adsorptivity as template, place organic solution to soak a week, remove after reacting influential impurity, vacuum drying, high purity nitrogen alternating permutation three times fills the nitrogen encapsulation, places in the moisture eliminator standby;
Pipette described mould material, be heated to 60 ℃, vacuumize, high purity nitrogen alternating permutation secondary fills under the nitrogen and is cooled to room temperature, vacuum condition adds organic solvent down, the submergence mould material adds the purified acrylonitrile monemer then, carry out the pre-assembling of monomer with the ultrasonic frequency of 20KHz vibration 30～60min after, drain steeping fluid, be cooled to room temperature;
Before initiator adds, 10wt% is loaded with the mould material of acrylonitrile monemer in elder generation and second monomer of 10wt% is added in the reactor, stir, slowly drip the organic solvent that contains the described initiator of 0.2～2wt% of equitemperature, initiated polymerization, divide 3～6 droppings to add the remaining mould material and second monomer that is loaded with acrylonitrile monemer again, the drop rate of control initiator, initiator drips stopped reaction half an hour; Described polymeric reaction temperature is 0～70 ℃, and the initiator dropping time is 0.5～8h;
Product is filtered, and solid joins in the sodium nitrite solution of 2.0～10.0mol/L, after fully stirring, takes out the template that comes off and handle, and filters slurries, earlier with washed with de-ionized water 3 times, uses the methanol wash 3 times of 95wt% again, filters then, and oven dry promptly;
Described mould material is at least a in activated carbon fiber, carbon nanotube, carbon nano-tube fibre or the carbon nano pipe array material with high absorbability;
Described organic solvent is a kind of in hexanaphthene, normal hexane, normal heptane or the n-decane.
2. acrylonitrile copolymer according to claim 1 is characterized in that the mol ratio of acrylonitrile unit and second monomeric unit is 4: 1～5: 1 on the described acrylonitrile copolymer molecular chain.
3. the preparation method of the described acrylonitrile copolymer of claim 1, it adopts following technology:
Select for use material as template, place organic solution to soak a week, remove after reacting influential impurity with adsorptivity, vacuum drying, high purity nitrogen alternating permutation three times fills the nitrogen encapsulation, places in the moisture eliminator standby;
Pipette described mould material, be heated to 60 ℃, vacuumize, high purity nitrogen alternating permutation secondary fills under the nitrogen and is cooled to room temperature, vacuum condition adds organic solvent down, the submergence mould material adds the purified acrylonitrile monemer then, carry out the pre-assembling of monomer with the ultrasonic frequency of 20KHz vibration 30～60min after, drain steeping fluid, be cooled to room temperature;
Before initiator adds, the mould material and 10wt% second monomer that earlier 10wt% are loaded with acrylonitrile monemer are added in the reactor, stir, slowly drip the organic solvent that contains the described initiator of 0.2～2wt% of equitemperature, initiated polymerization, divide 3～6 droppings to add the remaining mould material and second monomer that is loaded with acrylonitrile monemer again, the drop rate of control initiator, initiator drips stopped reaction half an hour; Described polymeric reaction temperature is 0～70 ℃, and the initiator dropping time is 0.5～8h;
Product is filtered, and solid joins in the sodium nitrite solution of 2.0～10.0mol/L, after fully stirring, takes out the template that comes off and handle, and filters slurries, earlier with washed with de-ionized water 3 times, uses the methanol wash 3 times of 95wt% again, filters then, and oven dry promptly;
Described mould material is at least a in activated carbon fiber, carbon nanotube, carbon nano-tube fibre or the carbon nano pipe array material with high absorbability;
Described organic solvent is a kind of in hexanaphthene, normal hexane, normal heptane or the n-decane.
4. the preparation method of a polyacrylonitrile fibre, this preparation method adopts the technology of described acrylonitrile copolymer prescription of claim 1 and following melt-processed:
(1). add thermo-stabilizer: adopt the mode of ground and mixed in described third rare itrile group multipolymer, to add thermo-stabilizer by following mass ratio:
Acrylonitrile copolymer 92～99wt%;
Thermo-stabilizer 1～8wt%;
Described thermo-stabilizer is phthalate or toxilic acid Ester, and described phthalate material is a kind of in dibutyl phthalate, dihexyl phthalate, the dioctyl phthalate (DOP); Described toxilic acid Ester is maleic anhydride list lauryl alcohol ester, maleic anhydride list tetradecyl alcohol ester, maleic anhydride list hexadecanol ester, maleic anhydride list stearyl alcohol ester, a kind of in the two lauryl alcohol esters of maleic anhydride, the two tetradecyl alcohol esters of maleic anhydride, the two hexadecanol esters of maleic anhydride or the two stearyl alcohol esters of maleic anhydride.
(2). melt-spinning: after the blend thorough drying with described thermo-stabilizer and acrylonitrile copolymer, join in the high-speed mixer and mix, join then and melt extrude spinning in the twin screw extruder, can prepare high-strength polypropylene nitrile fiber; Spinning temperature is above 5～30 ℃ of the fusing point of described acrylonitrile copolymer, and at its below decomposition temperature 5～30 ℃.
5. the preparation method of polyacrylonitrile fibre according to claim 4 is characterized in that described spinning temperature is above 10～25 ℃ of the fusing point of described acrylonitrile copolymer, and at its below decomposition temperature 10～25 ℃.
6. the preparation method of a polyacrylonitrile film, this preparation method adopts the technology of described acrylonitrile copolymer prescription of claim 1 and following melt-processed:
(1). add thermo-stabilizer: adopt the mode of ground and mixed in described third rare itrile group multipolymer, to add thermo-stabilizer by following mass ratio:
Acrylonitrile copolymer 92～99wt%;
Thermo-stabilizer 1～8wt%;
Described thermo-stabilizer is phthalate or toxilic acid Ester, and described phthalate material comprises a kind of in dibutyl phthalate, dihexyl phthalate, the dioctyl phthalate (DOP); Described toxilic acid Ester comprises maleic anhydride list lauryl alcohol ester, maleic anhydride list tetradecyl alcohol ester, maleic anhydride list hexadecanol ester, maleic anhydride list stearyl alcohol ester, a kind of in the two lauryl alcohol esters of maleic anhydride, the two tetradecyl alcohol esters of maleic anhydride, the two hexadecanol esters of maleic anhydride or the two stearyl alcohol esters of maleic anhydride.
(2). fusion blown film: with blend dry 2～24h under 50～80 ℃ of temperature of described thermo-stabilizer and described acrylonitrile copolymer, after the thorough drying, blend joined in the high-speed mixer mix, join in the twin screw extruder then and melt extrude, the material of extruding is cooled to below 80 ℃, behind blowing, cooling, insulation, subdivision, elimination static and winding process, can obtain high-intensity polyacrylonitrile film; Melt extrude temperature and be above 5～30 ℃ of the fusing point of described acrylonitrile copolymer, and at its below decomposition temperature 5～30 ℃.
7. the preparation method of polyacrylonitrile film according to claim 6 is characterized in that described above 10～25 ℃ of the fusing point that temperature is described acrylonitrile copolymer that melt extrudes, and at its below decomposition temperature 10～25 ℃.
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| CN102718923B (en) * | 2012-06-26 | 2014-06-11 | 华南理工大学 | Method for preparing stable nano spherical polyacrylonitrile latex particles |
| CN103483611B (en) * | 2013-10-11 | 2015-08-12 | 苏州柯莱美高分子材料科技有限公司 | Preoxidised polyacrylonitrile film, heat insulation graphite film, conductive graphite film and preparation method |
| CN104710565B (en) * | 2015-03-17 | 2017-01-11 | 东华大学 | Preparation method of ternary polyacrylonitrile copolymer |
| CN108159898A (en) * | 2015-12-11 | 2018-06-15 | 天津工业大学 | The method that thermally induced phase separation prepares polyacrylonitrile-radical microporous barrier |
| WO2019003914A1 (en) * | 2017-06-28 | 2019-01-03 | 東レ株式会社 | Production method for carbon fiber precursor fibers and production method for carbon fibers |
| CN108588886A (en) * | 2018-04-27 | 2018-09-28 | 芜湖天科生物科技有限公司 | A kind of conducting polypropylene nitrile fiber and preparation method thereof |
| KR20210148160A (en) * | 2019-03-29 | 2021-12-07 | 토요잉크Sc홀딩스주식회사 | Dispersant, dispersion, resin composition, mixture slurry, electrode membrane, and non-aqueous electrolyte secondary battery |
| TWI762414B (en) | 2021-08-25 | 2022-04-21 | 臺灣塑膠工業股份有限公司 | Method for producing carbon fibers |
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| CN104479088B (en) * | 2014-12-10 | 2017-01-25 | 郑州轻工业学院 | Method for preparing thermosetting polyurethane acrylate nano array by virtue of template in situ polymerization |
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