CN116003682A - Acrylonitrile copolymer and preparation method and application thereof - Google Patents
Acrylonitrile copolymer and preparation method and application thereof Download PDFInfo
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- CN116003682A CN116003682A CN202310179591.2A CN202310179591A CN116003682A CN 116003682 A CN116003682 A CN 116003682A CN 202310179591 A CN202310179591 A CN 202310179591A CN 116003682 A CN116003682 A CN 116003682A
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- acrylonitrile copolymer
- acrylonitrile
- polyacrylonitrile
- methacrylic acid
- methacrylate
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- 239000000178 monomer Substances 0.000 claims abstract description 54
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- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 6
- NHFBYYMNJUMVOT-UHFFFAOYSA-N methyl 2-bromo-2-phenylacetate Chemical group COC(=O)C(Br)C1=CC=CC=C1 NHFBYYMNJUMVOT-UHFFFAOYSA-N 0.000 claims description 6
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 5
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 5
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- WAKFRZBXTKUFIW-UHFFFAOYSA-M 2-bromo-2-phenylacetate Chemical compound [O-]C(=O)C(Br)C1=CC=CC=C1 WAKFRZBXTKUFIW-UHFFFAOYSA-M 0.000 description 1
- JKCOQORKEFKVAF-UHFFFAOYSA-N 3-(2-methoxyphenyl)-2-methylprop-2-enoic acid Chemical compound COC1=CC=CC=C1C=C(C)C(O)=O JKCOQORKEFKVAF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an acrylonitrile copolymer, a preparation method and application thereof. The technical scheme mainly adopted is as follows: a method for preparing an acrylonitrile copolymer, comprising the steps of: enabling acrylonitrile and comonomer to generate atom transfer radical copolymerization reaction to obtain acrylonitrile copolymer; wherein the comonomer is methacrylic acid modified phenolic derivative monomer or methacrylic acid modified terpene derivative monomer. The invention is mainly used for providing and preparing an acrylonitrile copolymer composed of phenol or terpenoid derivative monomer units and acrylonitrile units, wherein the weight average molecular weight of the acrylonitrile copolymer is 150000-250000, and the molecular weight distribution is 1.2-1.4. The acrylonitrile copolymer is used for preparing polyacrylonitrile fibers and polyacrylonitrile-based carbon fibers, and the tensile strength of the prepared polyacrylonitrile fibers can reach 910MPa.
Description
Technical Field
The invention relates to the technical field of acrylonitrile copolymers and polyacrylonitrile-based carbon fibers, in particular to an acrylonitrile copolymer and a preparation method and application thereof.
Background
Polyacrylonitrile-based carbon fibers (PAN) are an inorganic fibrous material with carbon element mass of more than 90%, and are increasingly becoming the first reinforcing material of advanced composite materials. The industrial carbon fiber is prepared by solid-phase carbonization of polymer organic fiber, and the PAN-based carbon fiber is a high-performance carbon fiber material prepared from PAN fiber raw materials through a series of solid-phase chemical reactions. The first step of preparing PAN-based carbon fiber is to prepare an acrylonitrile polymer, namely, mixing a certain proportion of acrylonitrile monomer, comonomer and solvent in solution, adding an initiator, heating and carrying out free radical polymerization reaction, and preparing the PAN polymer through a one-step method or a two-step method.
The acrylonitrile copolymer prepared by the existing free radical polymerization technology has two problems: (1) The molecular weight distribution of the acrylonitrile copolymer is more than 1.5, so that the mechanical property of the obtained polyacrylonitrile fiber is low (in the existing free radical polymerization, the concentration of the monomer at the early reaction stage is high, the molecular weight of the generated polymer is high, the concentration of the monomer at the later reaction stage is low, the molecular weight of the generated polymer is low, namely, the molecular weight gradually decreases along with the time of the reaction, and the molecular weight distribution of the acrylonitrile copolymer product is more than 1.5 at the end of the reaction); (2) An amount of azo or redox initiator is used, which is present as an impurity at the ends of the PAN polymer as a source of defects, degrading the mechanical properties of the PAN fiber.
In addition, atom transfer radical polymerization (Atom transfer radical polymerization, ATRP) is a promising controlled/"living" radical polymerization process, increasingly exhibiting features over traditional radical polymerization. When atom transfer radical polymerization is carried out, if the polymerized monomer is exhausted, the radical still keeps active, and when new monomer is added, the polymerization can be continued; the molecular weight of the polymerization product increases linearly with the conversion rate, and the molecular weight distribution is narrower; the end groups, composition, structure and molecular weight of the polymer are all controlled. Therefore, ATRP has the advantages of adjustable polymer microstructure, controllable polymerization degree and polydispersity, mild polymerization conditions, and the like, and is increasingly receiving attention.
Disclosure of Invention
In view of the above, the present invention provides an acrylonitrile copolymer, a preparation method and application thereof, and a main purpose of the present invention is to prepare an acrylonitrile copolymer with a narrow molecular weight distribution.
In order to achieve the above purpose, the present invention mainly provides the following technical solutions:
in one aspect, embodiments of the present invention provide a method for preparing an acrylonitrile copolymer, comprising the steps of: enabling acrylonitrile and comonomer to generate atom transfer radical copolymerization reaction to obtain acrylonitrile copolymer; wherein the comonomer is methacrylic acid modified phenolic derivative monomer or methacrylic acid modified terpene derivative monomer.
Preferably, the step of causing an atom transfer radical copolymerization reaction of acrylonitrile and a comonomer comprises: mixing a comonomer, acrylonitrile, a green solvent, an iron salt catalyst, an organic ligand and an ATRP initiator, and carrying out blue light induced iron catalyzed copolymerization reaction under the protection of inert gas to obtain the acrylonitrile copolymer.
Preferably, the comonomer is used in an amount of 0.1 to 5wt% based on the mass of acrylonitrile.
Preferably, the green solvent is one of cyclopentyl methyl ether, 2-methyltetrahydrofuran and tetraethylene glycol dimethyl ether.
Preferably, the mass ratio of the green solvent to the acrylonitrile is 1:1-2:1, preferably 1:1 to 1.5:1, and more preferably 1:1 to 1.2:1.
Preferably, the ferric salt catalyst is anhydrous ferric bromide; preferably, the anhydrous ferric bromide is used in an amount of 0.1 to 0.5wt%, preferably 0.1 to 0.4wt%, and more preferably 0.1 to 0.3wt% based on the mass of acrylonitrile.
Preferably, the organic ligand is tetrabutylammonium bromide; preferably, tetrabutylammonium bromide is used in an amount of 0.1 to 0.5wt%, preferably 0.1 to 4wt%, and more preferably 0.1 to 3wt% based on the mass of acrylonitrile.
Preferably, the ATRP initiator is methyl bromophenylacetate; preferably, the ATRP initiator is used in an amount of 0.1 to 1wt%, preferably 0.1 to 0.8wt%, and more preferably 0.2 to 0.8wt% based on the mass of acrylonitrile.
Preferably, the inert gas is argon.
Preferably, the blue light refers to light with a wavelength of 460-470 nm.
Preferably, the methacrylic acid modified phenolic derivative monomer is one or more of phenyl methacrylate, p-methylphenyl methacrylate, o-methoxyphenyl methacrylate, o-methoxy-p-formylphenyl methacrylate and o-dimethoxyphenyl methacrylate.
Preferably, the methacrylic acid modified terpene-derived monomer is (2-methyl-5-isopropyl) phenyl methacrylate.
Preferably, the methacrylic acid modified phenolic derivative monomer is prepared by the following steps: esterifying the phenol derivative with methacrylic anhydride to generate the methacrylic acid modified phenol derivative monomer; preferably, the phenol-based derivative includes: one or more of phenol, p-methylphenol, 2-methoxyphenol, 2-methoxy-4-formylphenol, 2, 6-dimethoxyphenol; the methacrylic acid modified phenolic derivative monomer is one or more of phenyl methacrylate, p-methylphenyl methacrylate, o-methoxyphenyl methacrylate, o-methoxy-p-formylphenyl methacrylate and o-dimethoxy phenyl methacrylate.
Preferably, the preparation steps of the methacrylic acid modified terpenoid derivative monomer are as follows: esterifying the terpenoid derivative with methacrylic anhydride to generate the methacrylic acid modified phenolic derivative monomer; preferably, the terpenoid derivative is 2-methyl-5-isopropyl phenol; the methacrylic acid modified terpenes derivative monomer is (2-methyl-5-isopropyl) phenyl methacrylate.
In another aspect, embodiments of the present invention provide an acrylonitrile copolymer, wherein the acrylonitrile copolymer contains disordered acrylonitrile units and copolymerized units; wherein the copolymerized units are methacrylic acid modified phenolic derivative monomer units; or the copolymerized units are methacrylic acid modified terpenoid derivative monomer units; preferably, the acrylonitrile copolymer has a weight average molecular weight of 150000-250000 and a molecular weight distribution of 1.2-1.4; preferably, the mass percentage of the copolymerized units in the acrylonitrile copolymer is 0.1-5wt%; preferably, the acrylonitrile copolymer is prepared by the preparation method of the acrylonitrile copolymer.
In yet another aspect, the use of the acrylonitrile copolymer described above in the preparation of polyacrylonitrile fibers, polyacrylonitrile-based carbon fibers.
In yet another aspect, an embodiment of the present invention provides a polyacrylonitrile fiber, wherein the polyacrylonitrile fiber is prepared from the above-mentioned acrylonitrile copolymer;
preferably, the acrylonitrile copolymer is prepared by a wet spinning or dry-jet wet spinning process.
Preferably, the tensile strength of the polyacrylonitrile fiber is 830-910MPa.
In still another aspect, an embodiment of the present invention provides a polyacrylonitrile-based carbon fiber, where the polyacrylonitrile-based carbon fiber is prepared from the polyacrylonitrile fiber described above;
preferably, the polyacrylonitrile-based carbon fiber is obtained after the polyacrylonitrile-based fiber is subjected to pre-oxidation and carbonization treatment.
Preferably, the tensile strength of the polyacrylonitrile-based carbon fiber is greater than or equal to 4GPa.
Compared with the prior art, the acrylonitrile copolymer, the preparation method and the application thereof have at least the following beneficial effects:
the embodiment of the invention provides an acrylonitrile copolymer and a preparation method thereof, in particular to a random acrylonitrile copolymer with molecular weight distribution of 1.2-1.4, which is prepared by adopting phenol or terpenoid derivative monomers and acrylonitrile as raw materials through ATRP reaction, wherein the molecular weight distribution is obviously narrower than that of the existing acrylonitrile copolymer containing itaconic acid and acrylonitrile monomer units (the preparation method provided by the invention is active polymerization, and the molecular weight of each chain is synchronously increased along with the lapse of reaction time, so that the molecular weight distribution of the acrylonitrile copolymer prepared by the embodiment of the invention is narrow), thereby being beneficial to improving the mechanical property of polyacrylonitrile fibers.
Further, the embodiment of the invention provides an acrylonitrile copolymer and a preparation method thereof, in particular, in the preparation process, low toxic substances such as cyclopentyl methyl ether, 2-methyltetrahydrofuran, tetraethyleneglycol dimethyl ether and the like are adopted as solvents, and the blue light irradiation iron-catalyzed ATRP polymerization reaction is carried out at room temperature.
In addition, the tensile strength of the polyacrylonitrile fiber prepared by the acrylonitrile copolymer can reach 910MPa, which is obviously higher than that of the existing polyacrylonitrile fiber prepared by itaconic acid and acrylonitrile copolymer.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram of the preparation equation of an acrylonitrile copolymer according to an embodiment of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset aim of the invention, the following detailed description refers to the specific implementation, structure, characteristics and effects according to the application of the invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "an embodiment" or "an embodiment" qualities are not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
On the one hand, the embodiment of the invention provides an acrylonitrile copolymer, a preparation method and application thereof, and mainly aims to solve the problem that the molecular weight distribution index of the acrylonitrile copolymer is larger than 1.5, and the mechanical property of a polyacrylonitrile fiber prepared from the acrylonitrile copolymer is low. The acrylonitrile copolymer is a disordered copolymer composed of acrylonitrile units and methacrylic acid modified phenolic derivative monomer units (or methacrylic acid modified terpene derivative monomer units). The disordered copolymer is used as a PAN fiber precursor, so that the mechanical property of the PAN fiber can be remarkably improved, and the invention is completed based on the discovery.
Specifically, the embodiment of the invention provides an acrylonitrile copolymer, wherein the acrylonitrile copolymer contains disordered acrylonitrile units and copolymerization units; wherein the copolymerized units are methacrylic acid modified phenolic derivative monomer units; or the copolymerized units are methacrylic acid modified terpenoid derivative monomer units; the weight average molecular weight of the acrylonitrile copolymer is 150000-250000, and the molecular weight distribution is 1.2-1.4; the mass percentage of the copolymerized units in the acrylonitrile copolymer is 0.1-5wt%.
Preferably, the acrylonitrile copolymer is prepared by copolymerization of acrylonitrile and one of phenyl methacrylate, p-methylphenyl methacrylate, o-methoxyphenyl methacrylate, o-methoxy-p-formylphenyl methacrylate, o-dimethoxyphenyl methacrylate and (2-methyl-5-isopropyl) phenyl methacrylate, and most preferably, one of phenyl methacrylate, p-methylphenyl methacrylate and o-methoxyphenyl methacrylate.
Wherein the weight average molecular weight and molecular weight distribution of the acrylonitrile copolymer can be quantitatively determined by gel chromatography (GPC). For example, a sample of the neat copolymer is dissolved in N, N-dimethylformamide containing lithium bromide and then analyzed with a GPC instrument equipped with a light scattering detector, a differential detector, a viscosity detector. From the obtained GPC spectra, the baseline and peak area integration intervals were selected, and the weight average molecular weight and molecular weight distribution of the acrylonitrile copolymer were calculated.
In the acrylonitrile copolymer, only the copolymerized units contain an oxygen element, and thus, the oxygen content in the copolymer can be measured by an elemental analyzer, and the mass percent of the copolymerized units in the copolymer can be calculated as follows.
X＝X O /X T ×100；
Wherein, X is the mass percent of the copolymerization unit in the acrylonitrile copolymer;
X O -oxygen content measurement in acrylonitrile copolymer,%;
X T -oxygen content in the copolymerized units,%;
preferably, the oxygen content X in the phenyl methacrylate monomer unit, the p-methylphenyl methacrylate monomer unit, the o-methoxyphenyl methacrylate monomer unit, the o-methoxy-p-formylphenyl methacrylate monomer unit, the o-dimethoxyphenyl methacrylate monomer unit, the (2-methyl-5-isopropyl) phenyl methacrylate monomer unit T 19.75, 18.18, 25.00, 29.09, 28.83, 14.68w, respectivelyt is as follows; see in particular table 1.
TABLE 1
On the other hand, the embodiment of the invention also provides a preparation method of the acrylonitrile copolymer, and the process flow of the preparation method is shown in the figure 1. Specifically, the preparation method of the acrylonitrile copolymer comprises the following steps:
enabling acrylonitrile and comonomer to generate atom transfer radical copolymerization reaction to obtain acrylonitrile copolymer; wherein the comonomer is methacrylic acid modified phenolic derivative monomer or methacrylic acid modified terpene derivative monomer. Specifically, a comonomer, acrylonitrile, a green solvent, an iron salt catalyst, an organic ligand and an ATRP initiator are mixed, and blue light irradiation (preferably, the blue light irradiation condition is that a sealed flask is placed in a box containing an LED lamp with the wavelength of 460-470nm and the power of 48 watts) is adopted under the protection of inert gas to perform blue light induced iron catalyzed copolymerization reaction, so that the acrylonitrile copolymer is obtained. The acrylonitrile copolymer prepared by the embodiment of the invention is used for preparing the polyacrylonitrile fiber and has the advantage of narrow molecular weight distribution, namely the molecular weight distribution of the acrylonitrile copolymer prepared by the embodiment of the invention is between 1.2 and 1.4, and the obtained polyacrylonitrile fiber has smaller crystal particles and higher fiber tensile strength. The molecular weight distribution of other prior acrylonitrile polymers is generally more than 1.5, and the obtained polyacrylonitrile fiber has large crystal particles and low fiber tensile strength.
Here, the methacrylic acid-modified phenol-derived monomer or methacrylic acid-modified terpene-derived monomer is a known compound or is prepared by a similar known method. For example, phenyl methacrylate is generally prepared by an esterification method in which methacrylic anhydride is heated with phenol in the presence of an azeotropic solvent such as 2-methyltetrahydrofuran in the presence of an esterification accelerator such as triethylamine, and then the esterification product methacrylic acid, water and solvent 2-methyltetrahydrofuran are removed, petroleum ether/ethyl acetate (volume ratio 90:10) is used as a mobile phase, impurities are removed by column chromatography, and petroleum ether/ethyl acetate solvent is evaporated to obtain a transparent and viscous liquid, namely phenyl methacrylate. The esterification reaction was stirred at 40℃for 24 hours at constant temperature.
Preferably, phenyl methacrylate, p-methylphenyl methacrylate, o-methoxyphenyl methacrylate, o-methoxy-p-formylphenyl methacrylate, o-dimethoxyphenyl methacrylate, 2, 6-dimethoxyphenol, terpene derivatives such as 2-methyl-5-isopropyl phenol are prepared by esterification reaction with methacrylic anhydride, respectively.
Preferably, in the copolymerization, the comonomer is generally used in an amount of 0.1 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.1 to 3% by weight, based on the mass of acrylonitrile.
ATRP initiators include haloalkanes, benzyl halides, α -bromoesters, α -haloketones, α -halonitriles, arylsulfonyl chlorides, azobisisobutyronitrile, methyl bromophenylacetate being preferred for use in the present invention.
In the copolymerization, the ATRP initiator capable of generating radicals is generally used in an amount of 0.1 to 1% by weight, preferably 0.1 to 0.8% by weight, more preferably 0.2 to 0.8% by weight, based on acrylonitrile.
The process of the present invention is generally carried out in the presence of a green solvent. Suitable green solvents are one of cyclopentyl methyl ether, 2-methyltetrahydrofuran and tetraethylene glycol dimethyl ether. The mass ratio of the green solvent to the acrylonitrile is 1:1-2:1, preferably 1:1-1.5:1, more preferably 1:1-1.2:1.
The ferric salt catalyst is anhydrous ferric bromide, and the dosage of the anhydrous ferric bromide is 0.1-0.5wt%, preferably 0.1-0.4wt%, and more preferably 0.1-0.3wt% of the acrylonitrile mass.
The organic ligand is tetrabutylammonium bromide; wherein the amount of tetrabutylammonium bromide is 0.1 to 0.5wt%, preferably 0.1 to 0.4wt%, more preferably 0.1 to 0.3wt% based on the mass of acrylonitrile.
The preparation method of the acrylonitrile copolymer is carried out under the atmosphere of inert gas, preferably argon, and the irradiation of blue light is carried out at room temperature, preferably at a temperature of 20-25 ℃, preferably blue light with a wavelength of 460-470 nm.
The weight average molecular weight of the acrylonitrile copolymer prepared by the method of the embodiment of the invention can be changed within a certain range. For example, the weight average molecular weight of the copolymer may be up to 250000, for example 150000-250000, preferably 150000-220000, more preferably 150000-200000. Such weight average molecular weight can be determined by Gel Permeation Chromatography (GPC).
The acrylonitrile copolymer prepared by the method provided by the embodiment of the invention has narrower molecular weight distribution. For example, the molecular weight distribution (weight average molecular weight to number average molecular weight ratio) of the acrylonitrile copolymer may be 1.2 to 1.4. Such molecular weight distribution can be determined by Gel Permeation Chromatography (GPC).
The acrylonitrile copolymer prepared by the method provided by the embodiment of the invention is suitable for preparing the polyacrylonitrile fiber. When the acrylonitrile copolymer is used for preparing the polyacrylonitrile fiber by a wet method or a dry-jet wet spinning method, the tensile strength of the fiber can reach 910MPa, which is obviously higher than that of the existing polyacrylonitrile fiber prepared from itaconic acid and acrylonitrile copolymer. Accordingly, the present invention further provides a polyacrylonitrile fiber prepared from the above-mentioned acrylonitrile copolymer of the present invention; wherein, the tensile strength of the polyacrylonitrile fiber can reach 910MPa.
In addition, regarding the above-described aspects of the present invention, it is to be noted that:
(1) For comonomer selection, the comonomer can be prepared from biological materials such as lignin and the like, so that the comonomer can be prepared from petrochemical product routes instead of the prior art, and sustainable development is promoted. The comonomer contains benzene ring, and when the comonomer is used for preparing carbon fiber, the carbon yield is high; copolymerization with acrylonitrile can form stable spinning solution, and has good spinnability; can promote the preoxidation reaction of the precursor, and the fiber structure after preoxidation is uniform.
(2) At present, ATRP is mainly carried out by polymerizing a single component, or by adding one component after polymerization, and then continuously polymerizing by adding the other component to form a block polymer. Unlike the prior art, the present invention adds two components simultaneously for the first time to form a random copolymer.
The invention is further illustrated by the following specific experimental examples:
first, the following is mainly explained:
determination of comonomer and acrylonitrile copolymerization conversion: when the conversion rate is measured by hydrogen nuclear magnetic spectrometry, chloroform is used as a solvent, the instrument is a Bruker Avance-300 spectrometer, the chemical displacement unit is ppm, and the proton signal of the solvent is used as a reference.
Determination of comonomer and acrylonitrile copolymer molecular weight and distribution: narrow and wide distribution Polystyrene (PS) standard sample solution preparation: 3.5 g of lithium bromide was weighed into a beaker containing 2 liters of dimethylformamide, the beaker was placed on a magnetic stirrer, stirred and dissolved for 12 hours, and vacuum-filtered three times using a vacuum pump, and the filtrate was used as a mobile phase of a gel chromatograph and a solvent for a standard sample and a sample. Taking a standard sample bottle matched with a gel chromatograph, recording the accurate weight of the PS polymer standard substance which is weighed into the standard sample bottle, opening a bottle cap, adding the accurate volume of the dimethyl formamide solvent containing lithium bromide by using a pipette, controlling the concentration of the PS polymer standard substance to be about 1mg/mL, and calculating the accurate concentration according to the weight of the PS polymer standard substance and the volume of the solvent. And (3) oscillating the glass bottle containing the solvent and the PS high molecular standard substance in a constant-temperature water bath at 50 ℃ of an oscillator for 30 minutes to enable the PS high molecular standard substance to be fully dissolved to form a homogeneous phase solution, so as to prepare the standard sample solution.
Sample solution preparation of Polyacrylonitrile (PAN) to be tested: accurately weighing a certain amount of PAN sample to be measured by using an electronic balance, adding the PAN sample to be measured into a sample bottle, adding a solvent with the same volume as that of a standard sample solution by using a liquid transfer device, controlling the concentration of the PAN sample to be measured to be about 1mg/mL, calculating the accurate concentration according to the weight of the PAN sample to be measured and the volume of the solvent, oscillating a glass bottle containing the solvent and the PAN sample to be measured in a constant-temperature water bath at 50 ℃ of an oscillator for 30 minutes, and fully dissolving the PAN sample to be measured into a homogeneous solution to prepare the PAN sample solution to be measured.
The detection method is established by using a narrow-distribution PS standard substance solution: the narrow-distribution PS standard substance solution was filtered by a syringe and a 0.2 μm filter membrane, and the filtrate was put into a sample bottle, put into a Markov Viscoteck autosampler, and a detection method was established according to the following experimental conditions.
Chromatograph: viscotek-GPC
Chromatographic column: malvern I-MBLMW-3078
Flow rate: 0.7ml/min
Temperature: 45 DEG C
Sample injection amount: 100 mu L
A detector: light scattering detector, differential detector, viscosity detector.
The detection method established by using the wide-distribution PS standard substance solution test comprises the following steps: and testing the sample solution of the PS standard substance with wide distribution by adopting the same flow as the analysis of the PS standard substance with narrow distribution, making a base line and an integral area on the obtained test curve, selecting the established detection method, calculating the molecular weight of the PS standard sample with wide distribution, and ensuring that the error between the calculated result and the standard value of the molecular weight of the PS standard substance with wide distribution is within +/-5 percent, thereby indicating that the established method is reliable.
PAN sample test to be tested: and testing the PAN sample solution to be tested by adopting the same flow as the wide-distribution PS standard substance analysis, making a base line and an integral area on the obtained test curve, and calculating to obtain the molecular weight and molecular weight distribution information of the PAN sample to be tested by adopting the established detection method.
Determination of the oxygen content of the comonomer and acrylonitrile copolymer: the acrylonitrile copolymer is pyrolyzed under high temperature in the presence of a catalyst, oxygen in phenol or terpenoid derivative monomers is completely converted into carbon monoxide, and the response value of the carbon monoxide is measured by a thermal conductivity cell (TCD) detector to obtain the oxygen element content of the copolymer.
The elemental analyzer is Vario EL cube, elementar, germany;
working mode: an oxygen measurement mode; cracking tube temperature: 1050 ℃; catalyst: platinum carbon; helium flow: 200mL/min; a detector: TCD.
Measurement of tensile Strength of Polyacrylonitrile fiber: the measurement of the tensile strength of the polyacrylonitrile fiber is carried out according to the method for testing the tensile property of high-strength fiber filaments of GB/T19975-2005, model of tensile machine: instron model 5943/1 KN.
Example 1
This example prepared an acrylonitrile copolymer as follows:
step 1) preparation of phenyl methacrylate:
37 g of phenol, 100 ml of 2-methyltetrahydrofuran and 60 ml of triethylamine are added in sequence to a 250 ml round-bottomed flask and stirred uniformly, then 65 ml of methacrylic anhydride are added, the solution is heated to 40℃and stirred at constant temperature for 24 hours. The methacrylic acid in the organic phase was extracted with saturated sodium bicarbonate solution and the process was repeated three times. Removing water in an organic phase by using anhydrous magnesium sulfate, removing a 2-methyltetrahydrofuran solvent by filtering and rotary evaporation, removing impurities by using petroleum ether/ethyl acetate (volume ratio of 90:10) as a mobile phase by using column chromatography, and evaporating the petroleum ether/ethyl acetate solvent to remove the impurities to obtain transparent viscous liquid, namely phenyl methacrylate.
Step 2) copolymerizing phenyl methacrylate and acrylonitrile to prepare an acrylonitrile copolymer:
20 mg of tetrabutylammonium bromide and 20 mg of ferric bromide are sequentially added into a 100 ml round bottom flask containing 10 g of tetraethyleneglycol dimethyl ether, 0.2 g of phenyl methacrylate, 10 g of acrylonitrile and 60 microliters of bromophenylacetate are added, the air above the flask is replaced by high-purity argon for 15 minutes, the flask is sealed and placed in a box containing an LED lamp with the wavelength of 460-470nm and the power of 48W, the stirring speed in the flask is 90 revolutions per minute, and after 16 hours of polymerization time, the polymerization reaction is finished, and the acrylonitrile copolymer is obtained. The conversion was determined by hydrogen spectrometry, the molecular weight and molecular weight distribution were determined by gel chromatography, and the content of oxygen element in the copolymer was analyzed by an elemental analyzer.
Example 2
This example produces an acrylonitrile copolymer, and the specific production steps are as follows from example 1: the tetraethylene glycol dimethyl ether solvent of example 1 was replaced with a cyclopentyl methyl ether solvent.
The remaining steps were the same as in example 1.
Example 3
This example produces an acrylonitrile copolymer, and the specific production steps are as follows from example 1: the tetraethylene glycol dimethyl ether solvent in example 1 was replaced with a 2-methyltetrahydrofuran solvent.
The remaining steps were the same as in example 1.
Example 1, example 2 and example 3 the conversion and molecular weight distribution of phenyl methacrylate and acrylonitrile in three different solvents under otherwise identical experimental conditions are shown in Table 2.
Table 2 shows the copolymerization reaction conversion and molecular weight distribution of phenyl methacrylate and acrylonitrile in three solvents
Note that: the feed ratio in Table 2 is the mass percentage of phenyl methacrylate, acrylonitrile, methyl bromophenylacetate, anhydrous ferric bromide, tetrabutylammonium bromide in the solution in order.
Example 4
This example produces an acrylonitrile copolymer, and the specific production steps are as follows from example 1: the polymerization time was set to 20 hours.
The remaining steps were the same as in example 1.
Example 5
This example prepared an acrylonitrile copolymer as follows:
step 1) preparation of p-methylphenyl methacrylate:
36 g of p-methylphenol, 100 ml of 2-methyltetrahydrofuran and 52 ml of triethylamine are added in sequence to a 250 ml round-bottomed flask and stirred uniformly, followed by 55 ml of methacrylic anhydride, the solution is heated to 40℃and stirred at constant temperature for 24 hours. Methacrylic acid in the organic phase was extracted twice with saturated sodium bicarbonate solution, three times with 0.5 mol per liter of sodium hydroxide solution, and once with saturated sodium bicarbonate solution. Removing water in an organic phase by using anhydrous magnesium sulfate, removing a 2-methyltetrahydrofuran solvent by filtering and rotary evaporation, removing impurities by using petroleum ether/ethyl acetate (volume ratio of 95:5) as a mobile phase through column chromatography, and evaporating the petroleum ether/ethyl acetate solvent to remove the impurities to obtain clear yellow liquid, namely the p-methyl phenyl methacrylate.
Step 2) copolymerizing p-methyl methacrylate and acrylonitrile to prepare an acrylonitrile copolymer:
20 mg of tetrabutylammonium bromide and 20 mg of ferric bromide are sequentially added into a 100 ml round bottom flask containing 10 g of tetraethyleneglycol dimethyl ether, 0.2 g of p-methyl methacrylate, 10 g of acrylonitrile and 60 microliter of methyl bromophenylacetate are added, the air above the flask is replaced by high-purity argon for 15 minutes, the flask is sealed and placed in a box containing an LED lamp with the wavelength of 460-470nm, the power is 48 watts, the stirring speed in the flask is 90 revolutions per minute, and after 20 hours of polymerization time, the polymerization reaction is finished to obtain the acrylonitrile copolymer.
Example 6
This example prepared an acrylonitrile copolymer as follows:
step 1) preparation of o-methoxyphenyl methacrylate:
38 g of o-methoxyphenol, 100 ml of 2-methyltetrahydrofuran and 47 ml of triethylamine are added to a 250 ml round-bottomed flask in sequence and stirred uniformly, followed by 50 ml of methacrylic anhydride, the solution is heated to 40℃and stirred at constant temperature for 24 hours. Methacrylic acid in the organic phase was extracted twice with saturated sodium bicarbonate solution, three times with 0.5 mol per liter of sodium hydroxide solution, and once with saturated sodium bicarbonate solution. Removing water in an organic phase by using anhydrous magnesium sulfate, removing a 2-methyltetrahydrofuran solvent by filtering and rotary evaporation, removing impurities by using petroleum ether/ethyl acetate (volume ratio is 85:15) as a mobile phase by using column chromatography, and evaporating the petroleum ether/ethyl acetate solvent to remove the impurities to obtain clear yellow liquid, namely the o-methoxyphenylmethacrylate.
Step 2) copolymerizing o-methoxy phenyl methacrylate and acrylonitrile to prepare an acrylonitrile copolymer: the procedure was carried out in the same manner as in example 5 except that the p-methylphenyl methacrylate in example 5 was replaced with an o-methoxyphenyl methacrylate monomer.
Example 7
This example prepared an acrylonitrile copolymer as follows:
step 1) preparation of (2-methyl-5-isopropyl) phenyl methacrylate:
30 g of 2-methyl-5-isopropylphenol, 86 ml of 2-methyltetrahydrofuran and 31 ml of triethylamine are added in sequence to a 250 ml round-bottomed flask and stirred uniformly, followed by 33 ml of methacrylic anhydride, the solution is heated to 40℃and stirred at constant temperature for 24 hours. The triethylammonium salt was removed by filtration and washed with diethyl ether. The methacrylic acid in the organic phase was extracted three times with saturated sodium bicarbonate solution. Removing water in an organic phase by using anhydrous magnesium sulfate, removing a 2-methyltetrahydrofuran solvent by filtering and reduced pressure rotary evaporation, removing impurities by using petroleum ether/ethyl acetate (volume ratio is 96:4) as a mobile phase by using column chromatography, and evaporating the petroleum ether/ethyl acetate solvent to remove the impurities to obtain clear liquid, namely (2-methyl-5-isopropyl) phenyl methacrylate.
Step 2) copolymerizing (2-methyl-5-isopropyl) phenyl methacrylate with acrylonitrile to prepare an acrylonitrile copolymer:
the procedure was carried out in the same manner as in example 5 except that the p-methylphenyl methacrylate in example 5 was replaced with a (2-methyl-5-isopropyl) phenyl methacrylate monomer.
Example 8
This example prepared an acrylonitrile copolymer as follows:
step 1) preparation of (2-methoxy-4-formyl) phenyl methacrylate (i.e., o-methoxy-p-formylphenyl methacrylate):
35 g of 2-methoxy-4-formylphenol, 100 ml of 2-methyltetrahydrofuran and 35 ml of triethylamine are added in sequence to a 250 ml round-bottomed flask and stirred uniformly, then 38 ml of methacrylic anhydride are added, the solution is heated to 40℃and stirred at constant temperature for 24 hours. The organic phase was washed with pure water once, twice with saturated sodium bicarbonate solution, twice with 0.5 mol of sodium hydroxide solution per liter, and once with saturated sodium chloride and pure water, respectively, to remove methacrylic acid. Removing water in the organic phase by anhydrous magnesium sulfate, removing 2-methyltetrahydrofuran solvent by filtration and rotary evaporation, and vacuum drying the rest substances to obtain white crystals, namely (2-methoxy-4-formyl) phenyl methacrylate.
Step 2) copolymerizing (2-methoxy-4-formyl) phenyl methacrylate and acrylonitrile to prepare an acrylonitrile copolymer:
the procedure was carried out in the same manner as in example 5 except that the p-methylphenyl methacrylate in example 5 was replaced with a (2-methoxy-4-formyl) phenyl methacrylate monomer.
Example 9
This example prepared an acrylonitrile copolymer as follows:
step 1) preparation of (2, 6-dimethoxy) phenyl methacrylate (i.e., o-dimethoxy phenyl methacrylate):
37 g of 2, 6-dimethoxyphenol, 106 ml of 2-methyltetrahydrofuran and 37 ml of triethylamine are added in sequence to a 250 ml round-bottomed flask and stirred uniformly, followed by 40 ml of methacrylic anhydride, the solution is heated to 40℃and stirred at constant temperature for 24 hours. The organic phase is washed three times with saturated sodium bicarbonate solution and three times with 0.5 mol per liter of sodium hydroxide solution in order to remove methacrylic acid and unreacted starting materials. Removing water in the organic phase by anhydrous magnesium sulfate, removing 2-methyltetrahydrofuran solvent by filtration and rotary evaporation, and vacuum drying the rest substances to obtain white crystals, namely (2, 6-dimethoxy) phenyl methacrylate.
Step 2) copolymerizing (2, 6-dimethoxy) phenyl methacrylate and acrylonitrile to prepare an acrylonitrile copolymer:
the procedure was carried out in the same manner as in example 5 except that the p-methylphenyl methacrylate in example 5 was replaced with a (2, 6-dimethoxy) phenyl methacrylate monomer.
Example 4 to example 9 the different monomer copolymerization conversions and molecular weight distribution differences are shown in table 3, with the same other experimental conditions.
Table 3 shows the copolymerization conversion and the molecular weight distribution of different monomers
Note that: the feed ratio in Table 3 is the mass percentage of phenyl methacrylate, acrylonitrile, methyl bromophenylacetate, anhydrous ferric bromide, tetrabutylammonium bromide in the solution in order.
Example 10
The acrylonitrile polymers obtained in examples 1 to 9 above were used as precursor polymers for polyacrylonitrile fibers, and were subjected to dissolution, filtration, dry-jet wet spinning as known to those skilled in the art to obtain as-spun polyacrylonitrile fibers, followed by washing with water, hot water drawing, dry heat treatment and steam drawing to obtain polyacrylonitrile fibers.
Wherein, when the acrylonitrile copolymer is dissolved, a polyacrylonitrile solution with a solid content (the mass fraction of the polyacrylonitrile to the polyacrylonitrile solution) of 20% is obtained. During filtration, the polyacrylonitrile solution was filtered with a filter having a filtration accuracy of 6 μm to obtain a spinning solution. The spinning solution was passed through a spinneret orifice having a pore diameter of 0.12 mm, and was subjected to dry-jet wet spinning with a draft ratio (ratio of the take-up roll linear velocity to the spinneret orifice outlet linear velocity) of 12 to obtain a nascent polyacrylonitrile fiber. And (3) carrying out hot water drafting on the nascent polyacrylonitrile fiber at the temperature of 70 ℃ through water washing and hot water, regulating and controlling the drafting ratio to 2, keeping the drying heat treatment temperature to 180 ℃, and carrying out steam drafting ratio to 1.5, wherein the vapor pressure of pressurized water vapor is 0.5MPa, so as to obtain the polyacrylonitrile fiber. The tensile strength of the polyacrylonitrile fiber is carried out according to the tensile property test method of high-strength fiber filaments of GB/T19975-2005. The tensile strength of the polyacrylonitrile fiber obtained by using the acrylonitrile copolymer of the present invention is shown in Table 4 as compared with that of the conventional polyacrylonitrile fiber.
Table 4 tensile strength comparisons of PAN fibers made from the polymers of the different examples
| Test number | Polymers of examples | PAN fiber tensile strength/MPa |
| 1 | Example 1 | 892 |
| 2 | Example 2 | 900 |
| 3 | Example 3 | 898 |
| 4 | Example 4 | 908 |
| 5 | Example 5 | 905 |
| 6 | Example 6 | 903 |
| 7 | Example 7 | 910 |
| 8 | Example 8 | 909 |
| 9 | Example 9 | 907 |
| 10 | Itaconic acid acrylonitrile copolymer | 820 |
| 11 | Itaconic acid acrylonitrile copolymer | 856 |
| 12 | Itaconic acid acrylonitrile copolymer | 885 |
Note that: the PAN fiber tensile strength values for numbers 10 to 12 in table 4 are from polyacrylonitrile-based carbon fiber, wang Chengguo, zhu Bo, beijing: scientific press, 2011, page 171, data of table 4.13, wherein intensity units are converted to 1 cN/dtex=118 MPa.
As can be seen from Table 4, the acrylonitrile copolymer prepared by the examples of the present invention has excellent mechanical properties as compared with the existing polyacrylonitrile fiber prepared from the itaconic acid acrylonitrile copolymer.
In summary, the embodiment of the invention provides an acrylonitrile copolymer and a preparation method thereof, in particular, a random acrylonitrile copolymer with molecular weight distribution of 1.2-1.4 is prepared by adopting phenol or terpenoid derivative monomers and acrylonitrile as raw materials through ATRP reaction, and the molecular weight distribution of the random acrylonitrile copolymer is obviously narrower than that of the existing acrylonitrile copolymer containing itaconic acid and acrylonitrile monomer units, thereby being beneficial to improving the mechanical property of polyacrylonitrile fibers. In addition, in the preparation process, low toxic substances such as cyclopentyl methyl ether, 2-methyltetrahydrofuran, tetraethyleneglycol dimethyl ether and the like are used as solvents, and the blue light irradiation iron-catalyzed ATRP polymerization reaction is carried out at room temperature, and compared with the existing 'azo initiator initiation', the acrylonitrile copolymerization reaction process has the advantages of environmental friendliness and lower energy consumption at the temperature of 60-80 ℃. In addition, the tensile strength of the polyacrylonitrile fiber prepared by the acrylonitrile copolymer can reach 910MPa, which is obviously higher than that of the prior polyacrylonitrile fiber prepared by itaconic acid and acrylonitrile copolymer.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (12)
1. A method for preparing an acrylonitrile copolymer, which is characterized by comprising the following steps:
enabling acrylonitrile and comonomer to generate atom transfer radical copolymerization reaction to obtain acrylonitrile copolymer; wherein the comonomer is methacrylic acid modified phenolic derivative monomer or methacrylic acid modified terpene derivative monomer.
2. The method for producing an acrylonitrile copolymer according to claim 1, wherein the step of causing an atom transfer radical copolymerization reaction of acrylonitrile and a comonomer comprises:
mixing a comonomer, acrylonitrile, a green solvent, an iron salt catalyst, an organic ligand and an ATRP initiator, and carrying out blue light induced iron catalyzed copolymerization reaction under the protection of inert gas to obtain the acrylonitrile copolymer.
3. The method for producing an acrylonitrile copolymer according to claim 2, wherein the comonomer is used in an amount of 0.1 to 5wt%, preferably 0.1 to 4wt%, further preferably 0.1 to 3wt% based on the mass of acrylonitrile.
4. A process for producing an acrylonitrile copolymer according to claim 2, wherein,
the green solvent is one of cyclopentyl methyl ether, 2-methyltetrahydrofuran and tetraethylene glycol dimethyl ether; and/or
The mass ratio of the green solvent to the acrylonitrile is 1:1-2:1, preferably 1:1 to 1.5:1, and more preferably 1:1 to 1.2:1.
5. A process for producing an acrylonitrile copolymer according to claim 2, wherein,
the ferric salt catalyst is anhydrous ferric bromide; preferably, the anhydrous ferric bromide is used in an amount of 0.1 to 0.5wt%, preferably 0.1 to 0.4wt%, further preferably 0.1 to 0.3wt% based on the mass of acrylonitrile; and/or
The organic ligand is tetrabutylammonium bromide; preferably, tetrabutylammonium bromide is used in an amount of 0.1 to 0.5wt%, preferably 0.1 to 0.4wt%, further preferably 0.1 to 0.3wt% based on the mass of acrylonitrile; and/or
The ATRP initiator is methyl bromophenylacetate; preferably, the ATRP initiator is used in an amount of 0.1 to 1wt%, preferably 0.1 to 0.8wt%, further preferably 0.2 to 0.8wt% based on the mass of acrylonitrile; and/or
The inert gas is argon; and/or
The blue light refers to light with a wavelength of 460-470 nm.
6. The method for producing an acrylonitrile copolymer according to any one of claims 1 to 5, wherein the methacrylic acid-modified phenol-derived monomer is one or more of phenyl methacrylate, p-methylphenyl methacrylate, o-methoxyphenyl methacrylate, o-methoxy-p-formylphenyl methacrylate, and o-dimethoxyphenyl methacrylate; and/or
The methacrylic acid modified terpenes derivative monomer is (2-methyl-5-isopropyl) phenyl methacrylate.
7. The method for producing an acrylonitrile copolymer according to any one of claims 1 to 5, wherein the methacrylic acid-modified phenol-derived monomer is produced by the steps of:
esterifying the phenol derivative with methacrylic anhydride to generate the methacrylic acid modified phenol derivative monomer;
preferably, the phenol-based derivative includes: one or more of phenol, p-methylphenol, 2-methoxyphenol, 2-methoxy-4-formylphenol, 2, 6-dimethoxyphenol;
the methacrylic acid modified phenolic derivative monomer is one or more of phenyl methacrylate, p-methylphenyl methacrylate, o-methoxyphenyl methacrylate, o-methoxy-p-formylphenyl methacrylate and o-dimethoxy phenyl methacrylate.
8. The method for producing an acrylonitrile copolymer according to any one of claims 1 to 5, wherein the methacrylic acid-modified terpene-derived monomer is produced by the steps of:
esterifying the terpenoid derivative with methacrylic anhydride to generate the methacrylic acid modified phenolic derivative monomer;
preferably, the terpenoid derivative is 2-methyl-5-isopropyl phenol;
the methacrylic acid modified terpenes derivative monomer is (2-methyl-5-isopropyl) phenyl methacrylate.
9. An acrylonitrile copolymer characterized in that the acrylonitrile copolymer contains disordered acrylonitrile units and copolymerized units; wherein the copolymerized units are methacrylic acid modified phenolic derivative monomer units; or the copolymerized units are methacrylic acid modified terpenoid derivative monomer units;
preferably, the acrylonitrile copolymer has a weight average molecular weight of 150000-250000 and a molecular weight distribution of 1.2-1.4;
preferably, the mass percentage of the copolymerized units in the acrylonitrile copolymer is 0.1-5wt%;
preferably, the acrylonitrile copolymer is prepared by the method for preparing an acrylonitrile copolymer according to any one of claims 1 to 8.
10. Use of the acrylonitrile copolymer according to claim 9 for the preparation of polyacrylonitrile fibers, polyacrylonitrile-based carbon fibers.
11. A polyacrylonitrile fiber, characterized in that it is prepared from the acrylonitrile copolymer according to claim 9;
preferably, the acrylonitrile copolymer is prepared into the polyacrylonitrile fiber by a wet spinning or dry-jet wet spinning process;
preferably, the tensile strength of the polyacrylonitrile fiber is 830-910MPa.
12. A polyacrylonitrile-based carbon fiber, characterized in that the polyacrylonitrile-based carbon fiber is prepared from the polyacrylonitrile fiber of claim 11;
preferably, the polyacrylonitrile-based carbon fiber is obtained after the polyacrylonitrile-based fiber is subjected to pre-oxidation and carbonization treatment;
preferably, the tensile strength of the polyacrylonitrile-based carbon fiber is greater than or equal to 4GPa.
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