CN101158060A - Binary acrylonitrile copolymer spinning fluid and preparation method thereof - Google Patents
Binary acrylonitrile copolymer spinning fluid and preparation method thereof Download PDFInfo
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- CN101158060A CN101158060A CNA200710056329XA CN200710056329A CN101158060A CN 101158060 A CN101158060 A CN 101158060A CN A200710056329X A CNA200710056329X A CN A200710056329XA CN 200710056329 A CN200710056329 A CN 200710056329A CN 101158060 A CN101158060 A CN 101158060A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 45
- 238000009987 spinning Methods 0.000 title claims abstract description 33
- 239000012530 fluid Substances 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 128
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 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 claims abstract description 30
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 25
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 238000010907 mechanical stirring Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- -1 n-pro-pyl Chemical group 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 9
- 239000004917 carbon fiber Substances 0.000 abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 229920006350 polyacrylonitrile resin Polymers 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000012660 binary copolymerization Methods 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to binary acrylonitrile copolymer spinning solution and a corresponding production method. The spinning solution comprises main monomer acrylonitrile and dimethyl sulfoxide solution with copolymer of itaconic acid Beta- monoester; the weight of the main monomer accounts for 90% to 99.5% of that of monomer, while the weight of the comonomer accounts for 0.5% to 10% thereof. The monomer is composed of the main monomer and the comonomer and the weight percentage concentration of the monomer is from15% to 25%. The dimethyl sulfoxide solution, the main monomer acrylonitrile, the comonomer, free radical initiator of azobisisobutyronitrile are added to a reactor by proportion and then mixed at room temperature and reacted for six to thirty six hours at a constant temperature of 50 DEG C to 70 DEG C to remove bubble of residual monomer and obtain the solution with protection from nitrogen which has bubbled for twenty minutes. The solution has a uniform chain structure and itaconic acid Beta-monoester contains two functional groups of carboxy and ester, thus being able to improve spinnability of polyacrylonitrile resin as well as regulate an oxidation-carbonization process of carbon fiber precursor. Due to introduction of a bifunctional group of monomer itaconic acid Beta-monoester, the amount of acrylonitrile comonomer is greatly reduced to improve performance of carbon fiber.
Description
Technical field
The present invention relates to a kind of binary acrylonitrile copolymer spinning fluid and preparation method, be specifically related to spinning solution of a kind of polyacrylonitrile-based carbon fibre that contains the itaconic acid Beta-monoester construction unit and preparation method thereof.
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.Someone thinks, the high-quality polyacrylonitrile fibril is one of key of preparation high-performance polyacrylonitrile-based carbon fiber, 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.
The acrylonitrile homopolymer dissolubility is bad, and spinnability is relatively poor, and plays the peak temperature height during pre-oxidation, and heat release is concentrated.The acrylonitrile homopolymer cyclization process is a free radical mechanism, causes cyclisation too fast like this, causes defective to carbon fiber.In order to improve spinnability and to reduce the cyclisation temperature, add unsaturated carboxylic acid, carboxylic acid ester and amide-type comonomers such as methyl methacrylate, methyl acrylate, acrylamide, itaconic acid and acrylic acid usually.Be the reactivity ratio of monomer commonly used and acrylonitrile below.Acrylonitrile (AN)/methacrylic acid (MAA): r (AN)=0.25, r (MAA)=0.75; Acrylonitrile/acrylic acid (AA): r (AN)=1.71, r (AA)=0.54; Acrylonitrile/itaconic acid (IA): r (AN)=0.865, r (IA)=0.568; Acrylonitrile/methyl methacrylate (MMA): r (AN)=0.41, r (MMA)=1.30; Acrylonitrile/ethyl methacrylate (EMA): r (AN)=0.35, r (EMA)=1.35; Acrylonitrile/methyl acrylate (MA): r (AN)=0.76, r (MA)=1.33; Acrylonitrile/butyl acrylate (BA): r (AN)=0.71, r (BA)=1.17; Acrylonitrile/acrylamide (AM): r (AN)=1.90, r (AM)=0.21.These data declarations during polyacrylonitrile-based carbon fiber spinning solution in the comonomer commonly used, have only the reactivity ratio of itaconic acid and acrylonitrile close in preparation, and that the reactivity ratio of esters monomer or acrylamide and acrylonitrile all differs is bigger.Bigger copolymerization activity difference has caused the inhomogeneities of comonomer construction unit in the acrylonitrile copolymer strand to distribute, and this may be the one of the main reasons that is difficult for preparing the high-performance carbon fibre spinning solution.
Chinese patent (application number is respectively 02130021.6,02130023.2 and 02130024.0) shows, can first synthesis of acrylonitrile homopolymers, in reactant liquor, feed ammonia then, reacted 2 hours down at 80-100 ℃, make part functional group be converted into carboxyl and amide groups, indirectly the synthesis of ternary copolymer.Yet the reaction of ammonia and polyacrylonitrile viscous fluid is the heterogeneous reaction of a complexity, and the mass transfer difficulty reacts wayward, and reappearance is relatively poor.
The carbon current fiber industry generally adopts is that the method for acrylonitrile/unsaturated carboxylic acid/esters of unsaturated carboxylic acids ternary polymerization prepares spinning solution, wherein the main effect of unsaturated carboxylic acid is to reduce the cyclisation temperature, widen exothermic peak, relax the rate of heat release of precursor in the pre-oxidation cyclization process, and the main effect of esters of unsaturated carboxylic acids is a spinnability of improving copolymer, makes carefully dawnization of precursor.But ternary is free-radical polymerized is a very complicated process, and especially controllability is poorer under reactivity ratio between monomer differs than the situation of big and high conversion.With a kind of reactivity ratio and acrylonitrile near and the bi-functional monomer that has unsaturated carboxylic acid and two kinds of comonomer functions of esters of unsaturated carboxylic acids concurrently to carry out binary copolymerization and prepare carbon fiber spinning solution with acrylonitrile, do not see bibliographical information as yet.
Summary of the invention
The purpose of this invention is to provide a kind of binary acrylonitrile copolymer spinning fluid and preparation method.
A kind of binary acrylonitrile copolymer spinning fluid provided by the invention is the dimethyl sulphoxide solution of main monomer and comonomer copolymer, and main monomer and comonomer are monomer; Its composition constitutes and proportioning is:
Described main monomer is an acrylonitrile; Comonomer is an itaconic acid Beta-monoester; Main monomer is 90～99.5% of a monomer weight, and comonomer weight is 0.5～10% of monomer weight, and weight percent monomer concentration is 15～25%.
The structure of described comonomer is as follows:
Wherein, R is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group.
6 kinds of itaconic acid Beta-monoester that are preferably as follows:
R is the β-MMI of methyl; R is the β-MEI of ethyl; R is the β-MPI of n-pro-pyl; R is the β-MiPI of isopropyl; R is the β-MBI of normal-butyl; R is the β-MiBI of isobutyl group.
Preparation method's step and the condition that the invention provides a kind of binary acrylonitrile copolymer spinning fluid is as follows:
Press proportioning with the solvent dimethyl sulfoxide (DMSO); the main monomer acrylonitrile; the comonomer itaconic acid Beta-monoester, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device; at room temperature mix; behind the nitrogen bubble 20 minutes, under nitrogen protection, in 50-70 ℃ of isothermal reaction 6～36 hours; remove residual monomer and bubble then, obtain a kind of binary acrylonitrile copolymer spinning fluid.
Advantage of the present invention:
1, the inventor has synthesized highly purified bi-functional monomer itaconic acid Beta-monoester, and has studied the copolymerization feature of they and acrylonitrile.The result shows that the copolymerization of itaconic acid Beta-monoester is active all very close with acrylonitrile; Acrylonitrile/itaconic acid Beta-monoester is carried out binary copolymerization can obtain the uniform acrylonitrile copolymer of chain structure.
2, itaconic acid Beta-monoester contains carboxyl and two kinds of functional groups of ester group simultaneously, and the spinnability that both can improve polyacrylonitrile resin also can be regulated and control the oxidation-carbonisation of carbon fibre precursor; Because the introducing of bifunctional monomer's itaconic acid Beta-monoester, the consumption of comonomer finally causes the raising of carbon fiber performance in the time of can reducing with acrylonitrile greatly.
3, be a very complicated process owing to ternary is free-radical polymerized, especially controllability is poorer under reactivity ratio between monomer differs than the situation of big and high conversion.In view of having concurrently, itaconic acid Beta-monoester improves spinnability and pre-oxidation double action, itaconic acid Beta-monoester is incorporated into traditional acrylonitrile/itaconic acid (or acrylic or methacrylic acid)/(methyl) acrylic ester ternary polymerization system, itaconic acid (or acrylic or methacrylic acid) and (methyl) acrylate two class comonomers are replaced with this kind bi-functional monomer, and the binary copolymerization that carries out acrylonitrile/itaconic acid Beta-monoester prepares the novel spinning liquid of polyacrylonitrile-based carbon fibre.
The specific embodiment
Embodiment 1
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MMI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 98% of a total monomer weight, comonomer β-MMI is 2% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.5% of a total monomer weight, and total monomer (percentage by weight) is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 26.3 ten thousand, and molecular weight distributing index is 2.38.
Embodiment 2
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MEI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 90% of a total monomer weight, comonomer β-MEI is 10% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.5% of a total monomer weight, and total monomer (percentage by weight) is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 9.2 ten thousand, and molecular weight distributing index is 2.42.
Embodiment 3
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MPI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 97% of a total monomer weight, comonomer β-MPI is 3% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.5% of a total monomer weight, and total monomer (percentage by weight) is 25%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 65 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 29.8 ten thousand, and molecular weight distributing index is 2.32.
Embodiment 4
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MiPI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 98% of a total monomer weight, comonomer β-MiPI is 2% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.75% of a total monomer weight, and total monomer (percentage by weight) is 25%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 65 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 28.1 ten thousand, and molecular weight distributing index is 2.39.
Embodiment 5
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MBI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 99% of a total monomer weight, comonomer β-MBI is 1.0% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.25% of a total monomer weight, and total monomer (percentage by weight) is 23.5%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 50 ℃ of isothermal reactions 36 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 68.9 ten thousand, and molecular weight distributing index is 2.62.
Embodiment 6
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MiBI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 99.5% of a total monomer weight, comonomer β-MiBI is 0.5% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.25% of a total monomer weight, and total monomer (percentage by weight) is 23.5%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 70 ℃ of isothermal reactions 6 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 27.4 ten thousand, and molecular weight distributing index is 2.48.
Embodiment 7
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MPI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 96% of a total monomer weight, comonomer β-MPI is 4.0% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.35% of a total monomer weight, and total monomer (percentage by weight) is 15%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 70 ℃ of isothermal reactions 6 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 12.4 ten thousand, and molecular weight distributing index is 2.32.
Embodiment 8
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MEI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 97% of a total monomer weight, comonomer β-MEI is 3.0% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.75% of a total monomer weight, and total monomer (percentage by weight) is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of spinning solution of polyacrylonitrile-based carbon fibre.The copolymer weight average molecular weight is 20.4 ten thousand, and molecular weight distributing index is 2.36.
Embodiment 9
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MiBI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 97% of a total monomer weight, comonomer β-MiBI is 3.0% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.75% of a total monomer weight, and total monomer (percentage by weight) is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 18.6 ten thousand, and molecular weight distributing index is 2.45.
Embodiment 10
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MMI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 95% of a total monomer weight, comonomer β-MMI is 5.0% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.75% of a total monomer weight, and total monomer (percentage by weight) is 22%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 20.7 ten thousand, and molecular weight distributing index is 2.51.
Embodiment 11
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MBI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 98% of a total monomer weight, comonomer β-MBI is 2.0% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.50% of a total monomer weight, and total monomer (percentage by weight) is 18.5%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 60 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 14.8 ten thousand, and molecular weight distributing index is 2.19.
Embodiment 12
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MiPI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 94% of a total monomer weight, comonomer β-MiPI is 6.0% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.60% of a total monomer weight, and total monomer (percentage by weight) is 20%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 65 ℃ of isothermal reactions 24 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 13.2 ten thousand, and molecular weight distributing index is 2.43.
Embodiment 13
With the solvent dimethyl sulfoxide (DMSO), the main monomer acrylonitrile, comonomer β-MEI, the radical initiator azodiisobutyronitrile joins in the reactor that has condenser pipe and mechanical stirring device.Add raw-material percentage by weight proportioning and be: the main monomer acrylonitrile is 97.5% of a total monomer weight, comonomer β-MEI is 2.5% of a total monomer weight, the consumption of azodiisobutyronitrile is 0.50% of a total monomer weight, and total monomer (percentage by weight) is 18%.Mixture at room temperature mixes, and nitrogen bubble under nitrogen protection, in 65 ℃ of isothermal reactions 18 hours, removes residual monomer and bubble after 20 minutes then, obtains a kind of binary acrylonitrile copolymer spinning fluid.The copolymer weight average molecular weight is 16.2 ten thousand, and molecular weight distributing index is 2.35.
Claims (3)
1. binary acrylonitrile copolymer spinning fluid and preparation method, it is the dimethyl sulphoxide solution of main monomer and comonomer copolymer, main monomer and comonomer are monomer; It is characterized in that composition constitutes and proportioning is: main monomer is an acrylonitrile; Comonomer is an itaconic acid Beta-monoester; Main monomer is 90～99.5% of a monomer weight, and comonomer weight is 0.5～10% of monomer weight, and weight percent monomer concentration is 15～25%;
The structure of described comonomer is as follows:
Wherein, R is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl group.
2. a kind of binary acrylonitrile copolymer spinning fluid as claimed in claim 1 is characterized in that, described itaconic acid Beta-monoester is: R is the β-MMI of methyl; R is the β-MEI of ethyl; R is the β-MPI of n-pro-pyl; R is the β-MiPI of isopropyl; R is the β-MBI of normal-butyl; R is the β-MiBI of isobutyl group.
3. the preparation method of a kind of binary acrylonitrile copolymer spinning fluid as claimed in claim 1; it is characterized in that step and condition are as follows: press proportioning with the solvent dimethyl sulfoxide (DMSO); the main monomer acrylonitrile; the comonomer itaconic acid Beta-monoester; the radical initiator azodiisobutyronitrile; join in the reactor that has condenser pipe and mechanical stirring device; at room temperature mix; behind the nitrogen bubble 20 minutes; under nitrogen protection; in 50-70 ℃ of isothermal reaction 6～36 hours, remove residual monomer and bubble then, obtain a kind of binary acrylonitrile copolymer spinning fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710056329XA CN100545327C (en) | 2007-11-20 | 2007-11-20 | The uniform carbon fiber of a kind of chain structure is with binary acrylonitrile copolymer spinning fluid and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710056329XA CN100545327C (en) | 2007-11-20 | 2007-11-20 | The uniform carbon fiber of a kind of chain structure is with binary acrylonitrile copolymer spinning fluid and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN101158060A true CN101158060A (en) | 2008-04-09 |
| CN100545327C CN100545327C (en) | 2009-09-30 |
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| US2583325A (en) * | 1949-01-06 | 1952-01-22 | Koppers Co Inc | Acrylonitrile itaconic monoester copolymers |
| US3484487A (en) * | 1965-12-27 | 1969-12-16 | Phillips Petroleum Co | Amination of aryl halides |
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