CN102747452A - Preparation method of acrylonitrile copolymer spinning solution - Google Patents
Preparation method of acrylonitrile copolymer spinning solution Download PDFInfo
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- CN102747452A CN102747452A CN2011100989477A CN201110098947A CN102747452A CN 102747452 A CN102747452 A CN 102747452A CN 2011100989477 A CN2011100989477 A CN 2011100989477A CN 201110098947 A CN201110098947 A CN 201110098947A CN 102747452 A CN102747452 A CN 102747452A
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Abstract
The invention relates to a preparation method of an acrylonitrile copolymer spinning solution to mainly solve a problem of easy gel generation of solutions in the prior art. The preparation method comprises the following steps: 1, adding a solvent, acrylonitrile, itaconic acid and an initiator azo-bis-iso-heptonitrile to a reactor, and reacting at 30-45DEG C for 24-50h under the protection of a gas inert to the reacting substances to obtain an acrylonitrile copolymer spinning solution I; and 2, carrying out pressure reduction on the spinning solution I to remove residual monomers and bubbles to obtain the novel acrylonitrile copolymer spinning solution. The method well solves the problem through above technical scheme, and can be applied to the industrial production of carbon fiber precursors.
Description
Technical field
The present invention relates to a kind of acrylonitrile copolymer preparation method of spinning dope.
Background technology
The prerequisite of producing high-performance carbon fibre is to use the polyacrylonitrile fibril of high-quality, and prepares the prerequisite that high performance spinning solution is the high-quality polyacrylonitrile fibril.As high performance spinning solution, except requiring modest viscosity, regular, the no branching of polyacrylonitrile molecular chain structure and crosslinked, and outside the characteristics such as comonomer being evenly distributed on main chain, spinning solution also must have high solid content and narrow molecular weight distribution.
Under the prerequisite that guarantees spinnability, spinning solution will have high solid content.The polyacrylonitrile fibril of high solids content spinning solution spinning after pre-oxidation and carbonization, is easy to form large-area graphite flake layer structure.Can reduce the grid defective in the turbostratic graphite form like this, make the structure of carbon fiber be tending towards perfect, finally improve the intensity of carbon fiber.Spinning solution has narrow molecular weight distribution.Promptly reduce the generation of oligomer and supra polymer product.The polyacrylonitrile oligomer is not only " the weak connection " in the precursor aggregated structure, and in the oxidation carbonisation, also can discharge a large amount of micromolecule product and tarry matters, makes final carbon fiber structural produce defective.The spinning solution that contains too many supra polymer is easy to produce gel structure, is unfavorable for continuous spinning.The polyacrylonitrile spinning solution of high solids content, suitable molecular weight distribution is that new approach has been opened up in the preparation of high-strength carbon fibre.
It is to be solvent with the dimethyl sulfoxide (DMSO) that present domestic carbon fiber enterprise prepares the method that spinning solution generally adopts, the copolymerization of acrylonitrile reaction that azodiisobutyronitrile causes.ABVN is a kind of good low temperature initiators; Cause the Raolical polymerizable of acrylonitrile with ABVN low temperature; Not only can effectively avoid the generation of side reactions such as oxidation, branching and bad structure such as crosslinked, and the molecular weight of polyacrylonitrile is higher, molecular weight distribution is narrower.Chinese patent 200710056083.6 has been introduced in dimethyl sulfoxide solvent with ABVN and has been caused the method for preparation molecular weight at 10～900,000 polyacrylonitrile spinning solution.Though this method can be synthesized the very polyacrylonitrile of macromolecule, because dimethyl sulfoxide (DMSO) is limited to its solvability,, be easy to generate many shortcomings such as gel and obstruction spinnerets so spinning solution viscosity is bigger than normal, be unfavorable for continuous spinning.N, dinethylformamide are a kind of solvents stronger than the solvability of dimethyl sulfoxide (DMSO), but because its chain transfer constant is big, so synthetic therein polyacrylonitrile molecular weight is not high generally below 50,000.
Summary of the invention
Technical problem to be solved by this invention is that the polyacrylonitrile molecular weight that one-step method makes in the technology in the past is lower, adopts two-step method to be prone to produce the problem of gel, and a kind of new acrylonitrile copolymer preparation method of spinning dope is provided.The molecular weight that this preparation method adopts one-step method to have and makes is higher, the less advantage of gel content in the spinning solution.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of acrylonitrile copolymer preparation method of spinning dope may further comprise the steps:
(a) with solvent N; Dinethylformamide, the first monomer acrylonitrile, the second monomer itaconic acid and initator ABVN are by the quality proportioning: ABVN: first and second monomer sum is 0.0020～0.0100: 1; First and second monomer sum: N, dinethylformamide are 0.20～0.40: 1; Acrylonitrile: itaconic acid is to join in the reactor in 95: 5～99: 1, is being the inert gasses protection down with reactive material, 30～45 ℃ react 24～50 hours down after, obtain acrylonitrile copolymer I;
(b) spinning solution I obtains novel polyacrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble.
In the technique scheme; Reactive material is inert gasses to be selected from: at least a in nitrogen, argon gas or the helium; Raw materials used quality proportion optimization scope: ABVN: first and second monomer sum is 0.0040～0.0080: 1; First and second monomer sum: N, dinethylformamide are 0.25～0.35: 1; Acrylonitrile: itaconic acid is 96～99: 4～1.
The present invention selects N for use, and dinethylformamide is that dinethylformamide is big for the solubility of polyacrylonitrile because of N as spin solvent, so can prepare the high relatively spinning solution of solid content, the spinning solution gel content for preparing simultaneously is few; It is initator that the present invention selects ABVN for use, is because the polyacrylonitrile stoste molecular weight that ABVN low temperature initiated polymerization generates is big, narrow molecular weight distribution.
Adopt scheme of the present invention, the polyacrylonitrile spinning solution that obtains, molecular weight can reach 100,000, molecular weight distribution≤3, gel content is few, can obtain better technical effect and obtain better technical effect through the filtration of 1 μ m filter membrane.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
With the N of 61.75g through acrylonitrile (AN), 0.75g itaconic acid (IA), 0.31g ABVN (ABVN) and the 187.50g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 40 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 14.3%, and it is 52700 that GPC records weight average molecular weight, and molecular weight distribution is 2.7.In the time of 48 hours, the spinning solution solid content that records is 20.0%, and it is 46200 that GPC records weight average molecular weight, and molecular weight distribution is 3.2, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 2]
With the N of 49.40g through acrylonitrile (AN), 0.60g itaconic acid (IA), 0.10g ABVN (ABVN) and the 200g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 38 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 11.0%, and it is 86800 that GPC records weight average molecular weight, and molecular weight distribution is 2.2.In the time of 48 hours, the spinning solution solid content that records is 15.0%, and it is 79400 that GPC records weight average molecular weight, and molecular weight distribution is 2.5, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 3]
With the N of 81.51g through acrylonitrile (AN), 0.99g itaconic acid (IA), 0.83g ABVN (ABVN) and the 167.50g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 33 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 19.8%, and it is 80700 that GPC records weight average molecular weight, and molecular weight distribution is 2.6.In the time of 48 hours, the spinning solution solid content that records is 23.8%, and it is 75300 that GPC records weight average molecular weight, and molecular weight distribution is 3.0, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 4]
With the N of 71.25g through acrylonitrile (AN), 3.75g itaconic acid (IA), 0.15g ABVN (ABVN) and the 175.00g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 45 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 21.0%, and it is 70500 that GPC records weight average molecular weight, and molecular weight distribution is 2.1.In the time of 48 hours, the spinning solution solid content that records is 25.5%, and it is 69200 that GPC records weight average molecular weight, and molecular weight distribution is 2.5, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 5]
With the N of 81.68g through acrylonitrile (AN), 0.83g itaconic acid (IA), 0.17g ABVN (ABVN) and the 167.50g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 30 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 18.2%, and it is 101800 that GPC records weight average molecular weight, and molecular weight distribution is 1.8.In the time of 48 hours, the spinning solution solid content that records is 24.8%, and it is 93300 that GPC records weight average molecular weight, and molecular weight distribution is 2.1, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 6]
With the N of 64.03g through acrylonitrile (AN), 0.98g itaconic acid (IA), 0.18g ABVN (ABVN) and the 190.00g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 42 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 21.6%, and it is 69800 that GPC records weight average molecular weight, and molecular weight distribution is 2.6.In the time of 48 hours, the spinning solution solid content that records is 22.9%, and it is 67500 that GPC records weight average molecular weight, and molecular weight distribution is 2.8, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 7]
With the N of 68.95g through acrylonitrile (AN), 1.05g itaconic acid (IA), 0.15g ABVN (ABVN) and the 182.00g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 40 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 24.1%, and it is 69000 that GPC records weight average molecular weight, and molecular weight distribution is 2.1.In the time of 48 hours, the spinning solution solid content that records is 25.5%, and it is 68100 that GPC records weight average molecular weight, and molecular weight distribution is 2.6, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 8]
With the N of 69.10g through acrylonitrile (AN), 0.90g itaconic acid (IA), 0.18g ABVN (ABVN) and the 177.00g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 42 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 23.5%, and it is 73200 that GPC records weight average molecular weight, and molecular weight distribution is 2.2.In the time of 48 hours, the spinning solution solid content that records is 25.8%, and it is 69700 that GPC records weight average molecular weight, and molecular weight distribution is 2.4, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[embodiment 9]
With the N of 72.75g through acrylonitrile (AN), 2.25g itaconic acid (IA), 0.38g ABVN (ABVN) and the 175.00g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 35 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 15.9%, and it is 75500 that GPC records weight average molecular weight, and molecular weight distribution is 1.8.In the time of 48 hours, the spinning solution solid content that records is 21.0%, and it is 72300 that GPC records weight average molecular weight, and molecular weight distribution is 2.2, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane.
[comparative example 1]
With the N of 81.68g through acrylonitrile (AN), 0.83g itaconic acid (IA), 0.17g azodiisobutyronitrile (AIBN) and the 167.50g of distillation, dinethylformamide (DMF) joins in the reactor, and magneton stirs to make and mixes sealed reactor.Be under the inert gasses protection with reactive material, reaction is 50 hours under 30 ℃ steady temperature, obtains acrylonitrile copolymer.Spinning solution obtains novel acrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble then.When reaction recorded 24 hours, the spinning solution solid content that records was 18.2%, and it is 31800 that GPC records weight average molecular weight, and molecular weight distribution is 6.2.In the time of 50 hours, the spinning solution solid content that records is 24.8%, and it is 29300 that GPC records weight average molecular weight; Molecular weight distribution is 5.4, and the spinning solution gel content is few, can be through the filtration of 1 μ m filter membrane; But the spinning solution molecular weight that makes is too small, and molecular weight distribution is wide.
[comparative example 2]
With the 30g molecular weight is that 100,000 molecular weight are distributed as 2.5 acrylonitrile itaconic acid copolymer and 70g N; Dissolved 24 hours down at 60 ℃ in dinethylformamide (DMF) the adding flask; The solution of gained produces a large amount of gels; Fail filtration through 1 μ m filter membrane, can only use 10 μ m filter membranes to filter.
Claims (3)
1. acrylonitrile copolymer preparation method of spinning dope may further comprise the steps:
(a) with solvent N; Dinethylformamide, the first monomer acrylonitrile, the second monomer itaconic acid and initator ABVN are by the quality proportioning: ABVN: first and second monomer sum is 0.0020～0.0100: 1; First and second monomer sum: N, dinethylformamide are 0.20～0.40: 1; Acrylonitrile: itaconic acid is to join in the reactor in 95: 5～99: 1, is being the inert gasses protection down with reactive material, 30～45 ℃ react 24～50 hours down after, obtain acrylonitrile copolymer I;
(b) spinning solution I obtains novel polyacrylonitrile copolymer spinning solution after decompression removes residual monomer and bubble.
2. acrylonitrile copolymer preparation method of spinning dope according to claim 1 is characterized in that reactive material is inert gasses to be selected from: at least a in nitrogen, argon gas or the helium.
3. acrylonitrile copolymer preparation method of spinning dope according to claim 1; It is characterized in that raw materials used quality proportioning: ABVN: first and second monomer sum is 0.0040～0.0080: 1; First and second monomer sum: N, dinethylformamide are 0.25～0.35: 1.
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| CN103145915A (en) * | 2013-02-27 | 2013-06-12 | 威海拓展纤维有限公司 | Method for preparing polyacrylonitrile spinning solution |
| CN104558395A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of high-hydrophilcity acrylonitrile copolymer spinning solution |
| CN104562265A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber precursor |
| CN105524213A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile spinning stock solution |
| CN105671670A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile carbon fiber precursor |
| CN106591995A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | High-quality polyacrylonitrile spinning raw solution preparation method |
| CN106589223A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrophilic acrylonitrile copolymer spinning raw liquid preparation method |
| CN110158159A (en) * | 2019-05-30 | 2019-08-23 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of spinning acrylonitrile polymer solution |
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| CN103145915A (en) * | 2013-02-27 | 2013-06-12 | 威海拓展纤维有限公司 | Method for preparing polyacrylonitrile spinning solution |
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| CN104562265A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber precursor |
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| CN106591995A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | High-quality polyacrylonitrile spinning raw solution preparation method |
| CN106589223A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrophilic acrylonitrile copolymer spinning raw liquid preparation method |
| CN106591995B (en) * | 2015-10-19 | 2019-04-12 | 中国石油化工股份有限公司 | The preparation method of high-quality polyacrylonitrile spinning solution |
| CN110158159A (en) * | 2019-05-30 | 2019-08-23 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of spinning acrylonitrile polymer solution |
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Application publication date: 20121024 |