CN103422188B - The preparation method of low viscosity, high-performance binary acrylonitrile copolymer spinning solution - Google Patents
The preparation method of low viscosity, high-performance binary acrylonitrile copolymer spinning solution Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of low viscosity, high-performance binary acrylonitrile copolymer spinning solution, mainly solve that the polyacrylonitrile spinning solution molecular weight that one-step method obtains in prior art is higher, narrow molecular weight distribution time, viscosity is excessive, the problem of spinnability difference.The present invention is by adopting a kind of preparation method of acrylonitrile copolymer spinning solution, step is by solvent dimethyl sulfoxide (DMSO), first monomers acrylonitrile, second comonomer itaconic acid and initator azodiisobutyronitrile, conditioning agent adds in reactor by quality proportioning, under being the gas shield of inertia with reactive material, react at 50 ~ 70 DEG C after 20 ~ 40 hours, after de-single deaeration, obtaining spinning solution molecular weight is 10 ~ 160,000, molecular weight distribution is below 3, viscosity is that the technical scheme of 30 ~ 100PaS polyacrylonitrile copolymer spinning solution preferably resolves this problem at 60 DEG C, in the industrial production of the carbon fibre precursor that can be used for.
Description
Technical field
The present invention relates to the preparation method of a kind of low viscosity, high-performance binary acrylonitrile copolymer spinning solution.
Background technology
Polyacrylonitrile (PAN) base carbon fibre is the new material developed rapidly in generation nineteen sixty, because of its have that quality is light, specific strength is high, specific modulus is high, high temperature resistant, corrosion-resistant, wear-resisting, antifatigue, conduction, the excellent properties such as heat conduction, be widely used in the military industries such as satellite, carrier rocket, tactical missile, spaceship, become indispensable material in aerospace industries.Excellent carbon fiber precursor should have the features such as heat resistance is high, hole constructs less, few surface defects, compact structure, draftability are good.
Initial copolymer structure and performance determine the stuctures and properties of final carbon fiber.Therefore, set about from polyacrylonitrile synthesis, determine the effect of different comonomers to polyacrylonitrile Structure and Properties, the development carrying out polyacrylonitrile fibril is necessary.In order to obtain excellent polyacrylonitrile fibril, excellent properties spinning solution system will be selected.And the acrylonitrile spinning solution of function admirable should possess following performance: moderate molecular weight, Narrow Molecular Weight Distribution, good spinnability etc.
The means of conventional industrially Molecular regulator amount have control temperature, regulate initiator content, add molecular weight regulator etc., but low-molecular-weight words fall in raised temperature, can make while Molecular regulator amount, molecular weight distribution is broadened, and polymerization process is difficult to control; Increase initiator content and fall low-molecular-weight words, while molecular weight distribution can be caused to broaden, initiator content is too many, forms the bubble being difficult to remove, be unfavorable for commercial operations in spinning solution; Use thio-alcohol based on lauryl mercaptan or isopropyl alcohol etc. as the chain-transferring agent of radical polymerization, effectively can regulate the molecular weight of acrylonitrile, but the shortcomings such as the conversion ratio of monomer can be reduced.
Preparing in high-performance polyacrylonitrile spinning solution process at present, many employings be that azo compound is as initator, azodiisobutyronitrile (ABIN) is adopted to be initator, polyacrylonitrile matrix (Carbon is prepared with DMSO one-step method, 2003, 41, 2805 ~ 2812), weight average molecular weight mostly is about 200,000, and molecular weight distribution is 3 ~ 3.5, dope viscosity is larger, course of reaction is restive, the side reactions such as easy generation small amounts, the generation of the Poor structure such as Branching and cross-linking, product also can turn to be yellow, even also microgel can be produced, unfavorable to follow-up spinning.
Conventional spinning solution uses thio-alcohol based on lauryl mercaptan or isopropyl alcohol etc. as the chain-transferring agent of radical polymerization in producing, effectively can regulate the molecular weight of acrylonitrile, but can reduce the conversion ratio of monomer.In addition, mercaptan has strong impulse smell and very strong toxicity, though and isopropyl alcohol does not have penetrating odor, but regulating power is inadequate.Use traditional chain-transferring agent while adjustment molecular weight of copolymer, can cause the decline of molecular weight, molecular weight distribution broadens, and these transfer agents are unsuitable for removal (number of patent application: 200710056083.6) in spinning solution simultaneously.
Summary of the invention
Technical problem to be solved by this invention is polyacrylonitrile spinning solution that in conventional art, one-step method is obtained when not usage chain transfer agent, and viscosity is excessive, spinnability is poor, after employing the Molecular regulator amount means such as chain-transferring agent, while polyacrylonitrile spinning solution molecular weight and molecular weight, the problem that broadens of molecular weight distribution, provide the preparation method of a kind of new low viscosity, high-performance binary acrylonitrile copolymer spinning solution.This preparation method has makes spinning solution molecular weight controlled, and viscosity declines, and while spinnability is improved, keeps the advantage that molecular weight distribution is almost constant.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of acrylonitrile copolymer spinning solution, comprises the following steps: (a) by solvent dimethyl sulfoxide (DMSO), the first monomers acrylonitrile, second comonomer itaconic acid and initator azodiisobutyronitrile, conditioning agent by quality proportioning: azodiisobutyronitrile: first and second monomer sum is 0.0020 ~ 0.0100:1; First and second monomer sum: gross mass is 0.10 ~ 0.40:1; Acrylonitrile: itaconic acid is 95:5 ~ 99.9:0.1; Conditioning agent: dimethyl sulfoxide (DMSO) is that 0.010 ~ 0.30:1 joins in reactor, under being the gas shield of inertia with reactive material, reacting after 20 ~ 40 hours, obtains acrylonitrile copolymer I at 50 ~ 70 DEG C; B () spinning solution I is after removed under reduced pressure residual monomer and bubble, obtain low viscosity, high-performance binary polyacrylonitrile copolymer spinning solution, spinning solution molecular weight is 10 ~ 160,000, and molecular weight distribution is below 3, and viscosity is 30 ~ 100PaS at 60 DEG C; Wherein conditioning agent is selected from: at least one in DMF, DMA.
In technique scheme: the reactive material gas preferred version that is inertia is selected at least one in nitrogen, argon gas or helium; Raw materials used quality proportion optimization scheme is azodiisobutyronitrile: first and second monomer sum is 0.0040 ~ 0.0080:1; First and second monomer sum: gross mass is 0.20 ~ 0.30:1; Acrylonitrile: itaconic acid is 96 ~ 99.9:0.1; Conditioning agent: dimethyl sulfoxide (DMSO) is 0.010 ~ 0.10:1.
The present invention selects at least one in DMF, DMA to be because their chain transfer constant is larger than the chain transfer constant of methyl-sulfoxide as conditioning agent; They are large for the solubility of polyacrylonitrile simultaneously, so make dope viscosity decline while spinning solution molecular weight can being made by adjustment in use agent adjustment, spinnability is improved, and keeps molecular weight distribution almost constant simultaneously, system also can not be allowed to introduce unnecessary impurity.
Adopt the solution of the present invention, the polyacrylonitrile spinning solution obtained, weight molecule amount is 10 ~ 160,000, and molecular weight distribution is less than 3, and viscosity is 30 ~ 100PaS at 60 DEG C, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
By the acrylonitrile (AN) of 97g through distilling, 3g itaconic acid (IA), 0.6g azodiisobutyronitrile (AIBN), 380g dimethyl sulfoxide (DMSO) (DMSO) and 20gN, dinethylformamide (DMF) joins in reactor, magneton stirs and makes to mix, sealed reactor.With under nitrogen protection, react 20 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 100560, and molecular weight distribution is 2.74, and viscosity is 36PaS at 60 DEG C.
[embodiment 2]
By the acrylonitrile (AN) of 121g through distilling, 3.75g itaconic acid (IA), 0.75g azodiisobutyronitrile (AIBN), 357g dimethyl sulfoxide (DMSO) (DMSO) and 19g N, dinethylformamide (DMF) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under helium protection, react 24 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 145067, and molecular weight distribution is 2.61, and viscosity is 76PaS at 60 DEG C.
[embodiment 3]
By the acrylonitrile (AN) of 146g through distilling, 5g itaconic acid (IA), 0.9g azodiisobutyronitrile (AIBN), 332g dimethyl sulfoxide (DMSO) (DMSO) and 18g N, dinethylformamide (DMF) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under argon shield, react 26 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 152560, and molecular weight distribution is 2.91, and viscosity is 87PaS at 60 DEG C.
[embodiment 4]
By the acrylonitrile (AN) of 120g through distilling, 5g itaconic acid (IA), 0.5g azodiisobutyronitrile (AIBN), 360g dimethyl sulfoxide (DMSO) (DMSO) and 15g N, dinethylformamide (DMF) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 28 hours under the steady temperature of 50 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 148567, and molecular weight distribution is 2.74, and viscosity is 77PaS at 60 DEG C.
[embodiment 5]
By the acrylonitrile (AN) of 120g through distilling, 5g itaconic acid (IA), 0.5g azodiisobutyronitrile (AIBN), 360g dimethyl sulfoxide (DMSO) (DMSO) and 15g N, dinethylformamide (DMF) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 32 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 140567, and molecular weight distribution is 2.76, and viscosity is 72PaS at 60 DEG C.
[embodiment 6]
By the acrylonitrile (AN) of 120g through distilling, 5g itaconic acid (IA), 0.5g azodiisobutyronitrile (AIBN), 360g dimethyl sulfoxide (DMSO) (DMSO) and 15g N, dinethylformamide (DMF) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 40 hours under the steady temperature of 70 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 128567, and molecular weight distribution is 2.89, and viscosity is 60PaS at 60 DEG C.
[embodiment 7]
By the acrylonitrile (AN) of 113g through distilling, 2.3g itaconic acid (IA), 0.5g azodiisobutyronitrile (AIBN), 374g dimethyl sulfoxide (DMSO) (DMSO) and 11g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 36 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 168547, and molecular weight distribution is 2.34, and viscosity is 97PaS at 60 DEG C.
[embodiment 8]
By the acrylonitrile (AN) of 113g through distilling, 2.3g itaconic acid (IA), 0.8g azodiisobutyronitrile (AIBN), 374g dimethyl sulfoxide (DMSO) (DMSO) and 11g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 30 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 127851, and molecular weight distribution is 2.68, and viscosity is 46PaS at 60 DEG C.
[embodiment 9]
By the acrylonitrile (AN) of 113g through distilling, 2.3g itaconic acid (IA), 0.92g azodiisobutyronitrile (AIBN), 374g dimethyl sulfoxide (DMSO) (DMSO) and 11g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under helium protection, react 36 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 108575, and molecular weight distribution is 2.84, and viscosity is 39PaS at 60 DEG C.
[embodiment 10]
By the acrylonitrile (AN) of 99g through distilling, 1g itaconic acid (IA), 0.5g azodiisobutyronitrile (AIBN), 376g dimethyl sulfoxide (DMSO) (DMSO) and 24g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under helium protection, react 30 hours under the steady temperature of 65 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 108547, and molecular weight distribution is 2.74, and viscosity is 37PaS at 60 DEG C.
[embodiment 11]
By the acrylonitrile (AN) of 139g through distilling, 1.4g itaconic acid (IA), 0.7g azodiisobutyronitrile (AIBN), 338g dimethyl sulfoxide (DMSO) (DMSO) and 22g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under argon shield, react 30 hours under the steady temperature of 65 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 154721, and molecular weight distribution is 2.74, and viscosity is 79PaS at 60 DEG C.
[embodiment 12]
By the acrylonitrile (AN) of 148.5g through distilling, 1.5g itaconic acid (IA), 0.75g azodiisobutyronitrile (AIBN), 329g dimethyl sulfoxide (DMSO) (DMSO) and 21g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 36 hours under the steady temperature of 65 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 150240, and molecular weight distribution is 2.94, and viscosity is 80PaS at 60 DEG C.
[embodiment 13]
By acrylonitrile (AN), 2.3g itaconic acid (IA), 0.72g azodiisobutyronitrile (AIBN), 342g dimethyl sulfoxide (DMSO) (DMSO), the 11g N of 118g through distillation, dinethylformamide (DMF) and 11g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 30 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 130026, and molecular weight distribution is 2.74, and viscosity is 50PaS at 60 DEG C.
[embodiment 14]
By acrylonitrile (AN), 2.4g itaconic acid (IA), 0.72g azodiisobutyronitrile (AIBN), 361g dimethyl sulfoxide (DMSO) (DMSO), the 10g N of 118g through distillation, dinethylformamide (DMF) and 10g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 30 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 130526, and molecular weight distribution is 2.72, and viscosity is 58PaS at 60 DEG C.
[embodiment 15]
By acrylonitrile (AN), 2.3g itaconic acid (IA), 0.72g azodiisobutyronitrile (AIBN), 376g dimethyl sulfoxide (DMSO) (DMSO), the 2g N of 118g through distillation, dinethylformamide (DMF) and 2g N, N-dimethyl amide (DMAc) joins in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 30 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 131026, and molecular weight distribution is 2.68, and viscosity is 78PaS at 60 DEG C.
[comparative example 1]
The acrylonitrile (AN) of 97g through distilling, 3g itaconic acid (IA), 0.6g azodiisobutyronitrile (AIBN), 380g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor, magneton stirs and makes to mix, sealed reactor.Under nitrogen protection, react 20 hours under the steady temperature of 60 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 112560, and molecular weight distribution is 2.70, and viscosity is 167PaS at 60 DEG C.
Claims (3)
1. a preparation method for acrylonitrile copolymer spinning solution, comprises the following steps:
(a) by solvent dimethyl sulfoxide (DMSO), the first monomers acrylonitrile, second comonomer itaconic acid and initator azodiisobutyronitrile, conditioning agent by quality proportioning azodiisobutyronitrile: first and second monomer sum is 0.0020 ~ 0.0100:1, first and second monomer sum: gross mass is 0.10 ~ 0.40:1; Acrylonitrile: itaconic acid is 95:5 ~ 99.9:0.1; Conditioning agent: dimethyl sulfoxide (DMSO) is that 0.010 ~ 0.30:1 joins in reactor, under being the gas shield of inertia with reactive material, reacting after 20 ~ 40 hours, obtains acrylonitrile copolymer I at 50 ~ 70 DEG C;
B () spinning solution I is after removed under reduced pressure residual monomer and bubble, obtain low viscosity, high-performance binary polyacrylonitrile copolymer spinning solution, spinning solution molecular weight is 10 ~ 160,000, and molecular weight distribution is below 3, and viscosity is 30 ~ 100PaS at 60 DEG C;
Wherein conditioning agent is selected from: at least one in DMF, DMA.
2. the preparation method of acrylonitrile copolymer spinning solution according to claim 1, the gas that to it is characterized in that reactive material be inertia is selected from least one in nitrogen, argon gas or helium.
3. the preparation method of acrylonitrile copolymer spinning solution according to claim 1, is characterized in that raw materials used quality proportioning: azodiisobutyronitrile: first and second monomer sum is 0.0040 ~ 0.0080:1; First and second monomer sum: gross mass is 0.20 ~ 0.30:1; Acrylonitrile: itaconic acid is 96 ~ 99.9:0.1; Conditioning agent: dimethyl sulfoxide (DMSO) is 0.010 ~ 0.10:1.
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| CN1598090A (en) * | 2004-08-16 | 2005-03-23 | 中国科学院长春应用化学研究所 | Process for preparing spin silk liquid of carbon fibre |
| CN1657666A (en) * | 2005-02-07 | 2005-08-24 | 中国科学院长春应用化学研究所 | High-performance polyacrylonitrile base carbon fibre spinning solution and its preparation method |
| CN101280041A (en) * | 2008-05-28 | 2008-10-08 | 北京化工大学 | Acrylic nitrile-containing polymerization composition for carbon fibre and preparation thereof |
| CN102199248A (en) * | 2010-03-26 | 2011-09-28 | 中国石油化工股份有限公司 | Acrylonitrile ternary interpolymer and preparation method thereof |
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| CN1598090A (en) * | 2004-08-16 | 2005-03-23 | 中国科学院长春应用化学研究所 | Process for preparing spin silk liquid of carbon fibre |
| CN1657666A (en) * | 2005-02-07 | 2005-08-24 | 中国科学院长春应用化学研究所 | High-performance polyacrylonitrile base carbon fibre spinning solution and its preparation method |
| CN101280041A (en) * | 2008-05-28 | 2008-10-08 | 北京化工大学 | Acrylic nitrile-containing polymerization composition for carbon fibre and preparation thereof |
| CN102199248A (en) * | 2010-03-26 | 2011-09-28 | 中国石油化工股份有限公司 | Acrylonitrile ternary interpolymer and preparation method thereof |
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