CN101144203A - Method for preparing high molecular weight acrylonitrile copolymer with narrow molecular weight distribution - Google Patents
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Abstract
The present invention initiates the copolymerization reaction of acrylonitrile and a comonomer with azo-bis-iso-heptonitrile in the dimethyl sulphoxide solution, and can adjust the molecular weight of an acrylonitrile copolymer with a bit of acrylonitrile, under the condition of 30 to 45 DEG C, the acrylonitrile copolymer having high molecular weight and narrow molecular weight. The present invention is characterized in that by adopting a traditional free radical polymerization method, the azo-bis-iso-heptonitrile is initiating agent, the molecular weight of a copolymer is adjusted with propenol, the synthetic molecular weight can be adjusted and controlled in 100 thousands to 900 thousands, the molecular weight distributes an acrylonitrile copolymer with an index smaller than 2.3, and the acrylonitrile copolymer solution can be used for preparing the spinning liquid of high performance carbon fiber.
Description
Affiliated field
The present invention relates to a kind of method for preparing the acrylonitrile copolymer of high molecular, Narrow Molecular Weight Distribution.
Background technology
Carbon fiber has characteristics such as high specific strength, high ratio modulus, heat-resisting, corrosion-resistant, endurance, creep resistant, is a kind of high performance fibre material, has been widely used in industries such as Aero-Space, national defense construction, Leisure Sport articles for use, medicine equipment and building.Polyacrylonitrile-based carbon fibre has outstanding mechanical property, is the focus of carbon fiber research in recent years.The key of restriction polyacrylonitrile-based carbon fibre development is the quality of polyacrylonitrile fibril, must set about from synthetic high-quality acrylonitrile copolymer and optimization spinning technique two aspects and will obtain the high-quality polyacrylonitrile fibril, have only the acrylonitrile copolymer of excellent performance just can spin out the high-quality polyacrylonitrile fibril, thereby prepare high performance polyacrylonitrile-based carbon fibre.Theory analysis and experimental study show, desirable acrylonitrile copolymer should have suitable high molecular and Narrow Molecular Weight Distribution, moderate apparent viscosity, no branching and bad structure such as crosslinked.
People are initator usually with the azodiisobutyronitrile, under 60～70 ℃ condition, method with the dimethyl sulphoxide solution radical copolymerization prepares the used for high-performance carbon fibre acrylonitrile copolymer, the molecular weight of gained acrylonitrile copolymer is not high, how about 200,000, and the molecular weight distribution broad, molecular weight distributing index is 3.0～3.5 (Carbon, 2003,41,2805～2812).If reaction condition control is improper, because the generation of side reactions such as small amounts, branching and bad structure such as crosslinked, product also can turn to be yellow, even also can produce microgel, and is unfavorable to follow-up spinning.
Cause the Raolical polymerizable of acrylonitrile with 2,2'-Azobis(2,4-dimethylvaleronitrile), can effectively avoid the generation of side reaction such as oxidation, branching and bad structure such as crosslinked.There are some researches show (EuropeanPolymerJournal, 1999,35,647～653): by adopting 2,2'-Azobis(2,4-dimethylvaleronitrile) is initator, under 30 ℃ condition, with the method for dimethyl sulphoxide solution radical polymerization, synthetic weight average molecular weight is greater than 850,000, and molecular weight distributing index is 1.89 acrylonitrile homopolymer.But because the molecular weight of synthetic acrylonitrile homopolymer is too big, and monomer conversion is low, can not be used as the spinning solution of polyacrylonitrile-based carbon fibre.In order to lauryl mercaptan is the chain-transferring agent as radical polymerization such as main thio-alcohol or isopropyl alcohol, can effectively regulate the molecular weight of acrylonitrile copolymer, but can reduce the conversion ratio of monomer.In addition, mercaptan strong impulse smell and very strong toxicity all are the industrial unfavorable factors of restriction, though and isopropyl alcohol not have the smell that is pungent, toxicity is less, its regulating power is not high.Chinese patent 94194602.9 and 01140852.9 report, the molecular weight of the adjustable Raolical polymerizable of allyl compound, reduction polymer, but this class allyl compound complex structure, synthetic difficulty are not suitable as the molecular weight regulator of acrylonitrile-based carbon fiber spinning solution.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the acrylonitrile copolymer of high molecular, Narrow Molecular Weight Distribution.
The preparation method's of the acrylonitrile copolymer of this kind high molecular, Narrow Molecular Weight Distribution step and condition are as follows:
Press proportioning with solvent dimethyl sulfoxide (DMSO), main monomer, comonomer 1, comonomer 2, radical initiator and chain-transferring agent, join in the reactor that has condenser pipe and mechanical stirring device, mixture is under nitrogen protection, in 30～45 ℃ of isothermal reactions 6～48 hours, remove residual monomer and bubble then, obtain the acrylonitrile copolymer of high molecular, Narrow Molecular Weight Distribution;
Described monomer is divided into main monomer and comonomer, and wherein main monomer is an acrylonitrile; Comonomer has 2 two kinds of comonomer 1 and comonomers, and comonomer 1 is an acrylate, and comonomer 2 is itaconic acid, acrylic acid, methacrylic acid or their mixture;
Described acrylate is: methyl acrylate, ethyl acrylate, acrylic acid n-propyl, n-butyl acrylate or isobutyl acrylate;
Described radical initiator is: 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described chain-transferring agent is: propenyl;
Described raw materials quality percentage proportioning is: main monomer is 90～99.5% of a monomer gross mass, the comonomer gross mass is 0.5～10% of a monomer gross mass, wherein comonomer 1 is 10～90% of a comonomer gross mass, comonomer 2 is 90～10% of a comonomer gross mass, radical initiator is 0.2～1.0% of a monomer gross mass, chain-transferring agent is 0～3.0% of a monomer gross mass, and total monomer is 15～25%.
Advantage of the present invention:
1. because traditional acrylonitrile radical polymerization adopts azodiisobutyronitrile as initator more, synthetic acrylonitrile polymer weight average molecular weight is about 200,000, and molecular weight distribution is generally more than 3.0, wider distribution.The present invention adopts the initator of 2,2'-Azobis(2,4-dimethylvaleronitrile) as copolymerization of acrylonitrile, propenyl is the chain-transferring agent of radical polymerization, synthetic acrylonitrile copolymer molecular weight is controlled between 10-90 ten thousand, molecular weight distributing index is less than 2.3, I reaches 1.85, and the polymer fluid color is water white transparency.
2. in the general acrylonitrile radical polymerization adopt mercaptan based on lauryl mercaptan as chain-transferring agent, its toxicity is big more, and smell is pungent all to be the industrial unfavorable factor of restriction, the employing isopropyl alcohol is also arranged as chain-transferring agent, but its regulating power is not high.The present invention takes propenyl to solve the problems referred to above well, and its free from extraneous odour, the characteristics that toxicity is little, regulating power is strong make it be expected to become the first-selected chain-transferring agent of acrylonitrile radical polymerization.
3. for the initator azodiisobutyronitrile, the 2,2'-Azobis(2,4-dimethylvaleronitrile) of the present invention half-life is wanted much shorter under uniform temp, thereby polymerization finishes the residual 2,2'-Azobis(2,4-dimethylvaleronitrile) in back and is easy to thoroughly decompose at short notice behind elevated temperature, makes to take off list and deaeration is easier carries out.
Specific implementation method
Embodiment 1
Take by weighing 19.62 gram acrylonitrile; 0.20 gram itaconic acid; 0.20 gram methyl acrylate; 80 gram dimethyl sulfoxide (DMSO)s; 0.1001 the gram 2,2'-Azobis(2,4-dimethylvaleronitrile) added the raw material that weigh up in the polyplant under nitrogen protection, 35 ℃ of polymerisations 24 hours; remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 99.8%, and the weight average molecular weight of copolymer is 58.0 ten thousand, and molecular weight distribution is 2.04.
The comparative example 1
Take by weighing 19.62 gram acrylonitrile; 0.20 gram itaconic acid; 0.20 gram ethyl acrylate; 80 gram dimethyl sulfoxide (DMSO)s; 0.1001 the gram azodiisobutyronitrile added the raw material that weigh up in the polyplant under nitrogen protection, 60 ℃ of polymerisations 24 hours; remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 99.7%, and the weight average molecular weight of copolymer is 24.3 ten thousand, and molecular weight distribution is 3.38.
By embodiment 1 and comparative example 1 as can be seen: after adopting 2,2'-Azobis(2,4-dimethylvaleronitrile) to replace the traditional initator of azodiisobutyronitrile as this system, the molecular weight distribution of resulting acrylonitrile copolymer obviously narrows down, and becomes 2.04 by 3.38.
Embodiment 2
Take by weighing 19.61 gram acrylonitrile; 0.20 gram acrylic acid; 0.20 gram ethyl acrylate; 0.3 the gram propenyl, 80 gram dimethyl sulfoxide (DMSO)s, 0.1002 gram 2,2'-Azobis(2,4-dimethylvaleronitrile); under nitrogen protection, the raw material that weigh up are added in the polyplant; 35 ℃ of polymerisations 24 hours, remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 96.4%, and the weight average molecular weight of copolymer is 17.1 ten thousand, and molecular weight distribution is 2.06.
The comparative example 2
Take by weighing 19.61 gram acrylonitrile; 0.20 gram itaconic acid; 0.20 gram methyl acrylate; 80 gram dimethyl sulfoxide (DMSO)s, 0.04 gram n-dodecyl mercaptan, 0.1002 gram 2,2'-Azobis(2,4-dimethylvaleronitrile); under nitrogen protection, the raw material that weigh up are added in the polyplant; 35 ℃ of polymerisations 24 hours, remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 91.2%, and the weight average molecular weight of copolymer is 16.7 ten thousand, and molecular weight distribution is 2.26.
The comparative example 3
Take by weighing 19.61 gram acrylonitrile; 0.20 gram itaconic acid; 0.20 gram methyl acrylate; 1.60 the gram isopropyl alcohol, 78.4 gram dimethyl sulfoxide (DMSO)s, 0.1002 gram 2,2'-Azobis(2,4-dimethylvaleronitrile); under nitrogen protection, the raw material that weigh up are added in the polyplant; 35 ℃ of polymerisations 24 hours, remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 63.5%, and the weight average molecular weight of copolymer is 15.7 ten thousand, and molecular weight distribution is 2.11.
By embodiment 2, comparative example 2 and comparative example 3 as can be seen: the chain-transferring agent propenyl that is adopted among the present invention, the combination property that the molecular weight of this invention system is regulated and control is better than traditional chain-transferring agent n-dodecyl mercaptan and isopropyl alcohol.
Embodiment 3
Take by weighing 19.90 gram acrylonitrile; 0.05 gram itaconic acid; 0.05 gram isobutyl acrylate; 80 gram dimethyl sulfoxide (DMSO)s; 0.1605 the gram 2,2'-Azobis(2,4-dimethylvaleronitrile) added the raw material that weigh up in the polyplant under nitrogen protection, 35 ℃ of polymerisations 6 hours; remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 47.9%, and the weight average molecular weight of copolymer is 51.5 ten thousand, and molecular weight distribution is 2.13.
Embodiment 4
Take by weighing 18.0 gram acrylonitrile; 1.0 gram itaconic acid; 1.0 gram methyl acrylate; 80 gram dimethyl sulfoxide (DMSO)s; 0.1597 the gram 2,2'-Azobis(2,4-dimethylvaleronitrile) added the raw material that weigh up in the polyplant under nitrogen protection, 35 ℃ of polymerisations 48 hours; remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 95.6%, and the weight average molecular weight of copolymer is 32.1 ten thousand, and molecular weight distribution is 1.98.
Embodiment 5
Take by weighing 19.0 gram acrylonitrile; 0.25 gram acrylic acid; 0.25 gram methacrylic acid; 0.5 the gram n-butyl acrylate, 80 gram dimethyl sulfoxide (DMSO)s, 0.1602 gram 2,2'-Azobis(2,4-dimethylvaleronitrile); under nitrogen protection, the raw material that weigh up are added in the polyplant; 35 ℃ of polymerisations 9 hours, remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 65.4%, and the weight average molecular weight of the copolymer of acquisition is 38.0 ten thousand, and molecular weight distribution is 2.04.
Embodiment 6
Take by weighing 19.62 gram acrylonitrile; 0.20 gram acrylic acid; 0.21 gram ethyl acrylate; 80 gram dimethyl sulfoxide (DMSO)s; 0.1596 the gram 2,2'-Azobis(2,4-dimethylvaleronitrile) added the raw material that weigh up in the polyplant under nitrogen protection, 45 ℃ of polymerisations 12 hours; remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 99.4%, and the weight average molecular weight of copolymer is 28.2 ten thousand, and molecular weight distribution is 2.28.
Embodiment 7
Take by weighing 19.6 gram acrylonitrile; 0.2 gram itaconic acid; 0.2 gram methyl acrylate; 80 gram dimethyl sulfoxide (DMSO)s; 0.1601 the gram 2,2'-Azobis(2,4-dimethylvaleronitrile) added the raw material that weigh up in the polyplant under nitrogen protection, 30 ℃ of polymerisations 36 hours; remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 86.5%, and the weight average molecular weight of copolymer is 58.0 ten thousand, and molecular weight distribution is 2.04.
Embodiment 8
Take by weighing 19.40 gram acrylonitrile; 0.21 gram methacrylic acid; 0.60 gram acrylic acid n-propyl; 80 gram dimethyl sulfoxide (DMSO)s; 0.1602 the gram 2,2'-Azobis(2,4-dimethylvaleronitrile) added the raw material that weigh up in the polyplant under nitrogen protection, 35 ℃ of polymerisations 16 hours; remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 84.1%, and the weight average molecular weight of copolymer is 42.1 ten thousand, and molecular weight distribution is 2.25.
Embodiment 9
Take by weighing 19.61 gram acrylonitrile; 0.21 gram itaconic acid; 0.19 gram methyl acrylate; 0.1 the gram propenyl, 80 gram dimethyl sulfoxide (DMSO)s, 0.1602 gram 2,2'-Azobis(2,4-dimethylvaleronitrile); under nitrogen protection, the raw material that weigh up are added in the polyplant; 35 ℃ of polymerisations 24 hours, remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 96.7%, and the weight average molecular weight of copolymer is 32.3 ten thousand, and molecular weight distribution is 2.02.
Embodiment 10
Take by weighing 19.61 gram acrylonitrile; 0.20 gram itaconic acid; 0.21 gram methyl acrylate; 80 gram dimethyl sulfoxide (DMSO)s; 0.0603 the gram 2,2'-Azobis(2,4-dimethylvaleronitrile) added the raw material that weigh up in the polyplant under nitrogen protection, 35 ℃ of polymerisations 23 hours; remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 78.6%, and the weight average molecular weight of copolymer is 89.5 ten thousand, and molecular weight distribution is 1.95.
Embodiment 11
Take by weighing 19.60 gram acrylonitrile; 0.20 gram itaconic acid; 0.21 gram methyl acrylate; 0.6 the gram propenyl, 80 gram dimethyl sulfoxide (DMSO)s, 0.1001 gram 2,2'-Azobis(2,4-dimethylvaleronitrile); under nitrogen protection, the raw material that weigh up are added in the polyplant; 35 ℃ of polymerisations 25 hours, remove residual monomer and bubble then, obtain a kind of acrylonitrile copolymer.Monomer conversion is 73.1%, and the weight average molecular weight of copolymer is 9.7 ten thousand, and molecular weight distribution is 2.10.
Claims (3)
1. the method for the acrylonitrile copolymer of a synthetic high polymer amount, Narrow Molecular Weight Distribution; it is characterized in that; step and condition are as follows: with solvent dimethyl sulfoxide (DMSO), main monomer, comonomer 1, comonomer 2, radical initiator, chain-transferring agent; join in the reactor that has condenser pipe and mechanical stirring device; mixture is under nitrogen protection; in 30～45 ℃ of isothermal reactions 6～48 hours; remove residual monomer and bubble then, obtain the acrylonitrile copolymer of high molecular, Narrow Molecular Weight Distribution.
2. as the method for the acrylonitrile copolymer of right 1 described a kind of synthetic high polymer amount, Narrow Molecular Weight Distribution, it is characterized in that, described radical initiator is a 2,2'-Azobis(2,4-dimethylvaleronitrile), described chain-transferring agent is a propenyl, described monomer is divided into main monomer and comonomer, and wherein main monomer is an acrylonitrile; Comonomer comprises 2 two kinds of comonomer 1 and comonomers, and comonomer 1 is an acrylate, and comonomer 2 is itaconic acid, acrylic acid, methacrylic acid or their mixture; Described acrylate is: methyl acrylate, ethyl acrylate, acrylic acid n-propyl, n-butyl acrylate or isobutyl acrylate.
3. as the method for the acrylonitrile copolymer of right 1 described a kind of synthetic high polymer amount, Narrow Molecular Weight Distribution, it is characterized in that, described raw materials quality percentage proportioning is: main monomer accounts for 90～99.5% of monomer gross mass, the comonomer gross mass accounts for 0.5～10% of monomer gross mass, wherein comonomer 1 accounts for 10～90% of comonomer gross mass, radical initiator is 0.2～1.0% of a monomer gross mass, chain-transferring agent is 0～3.0% of a monomer gross mass, and total monomer is 15～25%.
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| DE1069818B (en) * | 1958-10-29 | 1959-11-26 | The Dow Chemical Company, Midland, Mich. (V. St. A.) | Process for the production of deformable solutions from polyacrylonitrile |
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