CN104558397A - Preparation method of ammoniation-degree-controllable high-hydrophily acrylonitrile copolymer spinning solution - Google Patents
Preparation method of ammoniation-degree-controllable high-hydrophily acrylonitrile copolymer spinning solution Download PDFInfo
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Abstract
The invention relates to a preparation method of an ammoniation-degree-controllable high-hydrophily acrylonitrile copolymer spinning solution, which mainly solves the technical problem that in the prior art, an ammoniation process in which ammonia gas is fed into a spinning solution is difficult to control because the viscosity of the spinning solution is high, so that the ammoniation degree of the carbon fiber spinning solution is uncontrollable, and the batch-to-batch difference of ammoniation degrees is large, and the like. According to the invention, through the adoption of a technical scheme that by taking acrylonitrile, a second monomer itaconate/ammonium itaconate aqueous solution and a third monomer as copolymerization compositions, taking an azo compound as an initiator and taking dimethyl sulfoxide as a solvent, the materials are mixed, then the obtained mixture is added into a reactor; under inert gas protection, the copolymerization compositions are reacted for 12-24 hours at a temperature of 40-75 DEG C; and then the obtained product is subjected to residual monomer and bubble removal, so that the ammoniation-degree-controllable high-hydrophily acrylonitrile copolymer spinning solution is obtained, the problem is solved well, and therefore, the preparation method can be applied to the industrial production of carbon fiber precursors.
Description
Technical field
The present invention relates to the preparation method of the controlled high-hydrophilic acrylonitrile copolymer spinning solution of a kind of ammonification degree.
Background technology
Polyacrylonitrile (PAN) base carbon fibre is the type material developed rapidly in generation nineteen sixty, because of its have that quality is light, specific tenacity 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, launch vehicle, tactical missile, spaceship, become indispensable material in aerospace industries.Excellent carbon fiber precursor should have the features such as thermotolerance is high, hole constructs less, few surface defects, compact structure, stretchiness 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, will select excellent properties spinning solution system, the wetting ability wherein improving stoste is exactly a main research direction.Improve the hydrophilicity of polyacrylonitrile matrix, be conducive to the process of setting controlling nascent strand, make precursor in drafting process, infiltrate more abundant with WATER AS FLOW MEDIUM or water vapour, water can play the effect of plasticising to polyacrylonitrile, such spun filament is more easily drafted, and precursor subsurface defect is also more easily made up, finally can obtain the good carbon fibre precursor of high strength dense.
But up to the present people never find suitable method to improve the wetting ability of polyacrylonitrile.Chinese patent CN201110005885.0,02130023.2 etc. reports the preparation first carrying out polyacrylonitrile copolymer, then in stoste, ammonia is passed into, make stoste PH in the middle of 8 ~ 10, make the part carboxyl reaction of ammonia and methylene-succinic acid generate ammonium salt, this method is also the maximum hydrophilic method of change stoste of current domestic use.But the viscosity ratio of polyacrylonitrile copolymer is comparatively large, it is a complicated heterogeneous reaction that ammonia and full-bodied stoste be made to carry out reacting, mass transfer difficulty and wayward, and the ammonification degree repeatability between batch testing is poor.The ammonification degree of system is subject to stoste viscosity, stirring velocity, passes into the pressure of ammonia, passes into the impact of the many factors such as flow and ammonification time of ammonia, cannot accurately control.
Summary of the invention
Technical problem to be solved by this invention is difficult to because dope viscosity is high control by the ammonification technique of ammonia logical in spinning solution in conventional art, and carbon fiber spinning primary fluid ammonification degree is uncontrollable, and between batch, difference is large.And the words of copolymerization are carried out again with the first ammonification of methylene-succinic acid, because methylene-succinic acid ammonium is difficult to be dissolved in dimethyl sulfoxide solution, thus make methylene-succinic acid ammonium be difficult to industrially to be applied to problem prepared by polyacrylonitrile spinning solution as methyl-sulphoxide system comonomer, provide the preparation method of the controlled high-hydrophilic acrylonitrile copolymer spinning solution of a kind of ammonification degree.The solubility property that this preparation method utilizes methylene-succinic acid/methylene-succinic acid ammonium excellent in water, methylene-succinic acid aqueous ammonium is prepared the advantage of high-hydrophilic acrylonitrile copolymer spinning solution as comonomer, the ammonification degree simultaneously by regulating the ratio of methylene-succinic acid and methylene-succinic acid ammonium in methylene-succinic acid/methylene-succinic acid aqueous ammonium accurately to control to be polymerized stoste.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the preparation method of the high-hydrophilic acrylonitrile copolymer spinning solution that a kind of ammonification degree is controlled, comprises the following steps:
(a) using vinyl cyanide, comonomer 1, comonomer 2 as copolymerization component, using azo compound as initiator, be after solvent with dimethyl sulfoxide (DMSO), join in reactor, under being the gas shield of inertia with reactive material, react 12 ~ 24 hours at 40 ~ 75 DEG C of temperature, obtain high-hydrophilic acrylonitrile copolymer spinning solution I; Wherein, comonomer 1 is methylene-succinic acid/methylene-succinic acid aqueous ammonium;
B () spinning solution I is after removing residual monomer and bubble, obtain high-hydrophilic acrylonitrile copolymer spinning solution, described spinning solution molecular weight is 8 ~ 200,000, molecular weight distribution is below 1 ~ 4, viscosity is 50 ~ 130PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 40 ° ~ 58 °.
In technique scheme, preferred technical scheme: comonomer 1 methylene-succinic acid used/methylene-succinic acid aqueous ammonium is first carried out by methylene-succinic acid after ammonification obtains methylene-succinic acid ammonium, methylene-succinic acid ammonium and methylene-succinic acid are dissolved in the water according to mol ratio 1:10 ~ 10:1, the mass ratio of methylene-succinic acid and methylene-succinic acid ammonium and water is 0.1:1 ~ 1:10; Methylene-succinic acid ammonium and methylene-succinic acid are preferably 1:4 ~ 5:1 according to mol ratio and are dissolved in the water, and the mass ratio of methylene-succinic acid and methylene-succinic acid ammonium and water is preferably 0.3:1 ~ 1:5; Comonomer 2 is at least one in vinylformic acid, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isobutyl-vinylformic acid, β-itaconic acid n-butyl, acrylamide, acryloyl amidoxime, hydroxylethyl nitrile, α chloroacrylonitrile or diacetone-acryloamide(DAA); Comonomer 2 is preferably at least one in methyl acrylate, methyl methacrylate, acrylamide, acryloyl amidoxime; It is 10 ~ 35 parts that the proportioning of polymer raw counts copolymerization component by weight, and wherein vinyl cyanide is 8 ~ 33 parts, and comonomer 1 is 1 ~ 4 part, and comonomer 2 is 1 ~ 4 part, and solvent is 65 ~ 90 parts, and initiator amount is 0.2 ~ 1% of copolymerization component gross weight; The proportioning of polymer raw is counted copolymerization component by weight and is preferably 15 ~ 25 parts, and wherein vinyl cyanide is preferably 13 ~ 23 parts, and comonomer 1 is preferably 1 ~ 4 part, and comonomer 2 is preferably 1 ~ 4 part, and solvent is preferably 75 ~ 84 parts; Reactive material is at least one that the gas of inertia is selected from nitrogen, argon gas or helium; Azo-initiator is selected from the one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile); The method removing residual monomer and bubble is decompression vacuum pumping method, and the time removing monomer is 2 ~ 40 hours, and the time removing bubble is 4 ~ 72 hours.
Although the present invention selects methylene-succinic acid/methylene-succinic acid aqueous ammonium to be because methylene-succinic acid is comonomer the most frequently used at present as comonomer, but its wetting ability is bad, follow-up words of carrying out ammonification, operation inconvenience, technique is difficult to control, between batch, difference is large, ammonification degree is owing to being subject to the impact of the many factors such as system viscosity and uncontrollable, so the comonomer methylene-succinic acid ammonium with hydrophilic radical will be introduced, but methylene-succinic acid ammonium is insoluble in methyl-sulphoxide, when 60 DEG C, solubleness is only 0.2wt%, dissolution rate also slowly, limit methylene-succinic acid ammonium as the use of comonomer in methyl-sulphoxide system, so be mainly used in aqueous deposited polymerization at present, the wetting ability that the present invention utilizes methylene-succinic acid/methylene-succinic acid ammonium excellent in water, first methylene-succinic acid and methylene-succinic acid ammonium are dissolved in water, again methylene-succinic acid aqueous ammonium is added in polymeric kettle as Third monomer, namely in system, hydrophilic radical is introduced, solve again the problem that methylene-succinic acid ammonium is insoluble in methyl-sulphoxide, simultaneously because the solvability of methylene-succinic acid ammonium in water is very excellent, so the water introduced in system is less than 1000ppm, for copolyreaction without any impact, the ammonification degree of whole system then accurately can control by regulating the ratio of methylene-succinic acid and methylene-succinic acid ammonium.
Adopt the solution of the present invention, the polyacrylonitrile spinning solution obtained, spinning solution molecular weight is 8 ~ 200,000, molecular weight distribution is below 1 ~ 4, viscosity is 50 ~ 130PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 40 ° ~ 58 °, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The vinyl cyanide (AN) of 97g through distilling, 4g methylene-succinic acid/methylene-succinic acid aqueous ammonium (methylene-succinic acid ammonium 1g, methylene-succinic acid 1g being dissolved in 2g water), 1g methyl acrylate, 0.6g Diisopropyl azodicarboxylate (AIBN), 400g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; with under nitrogen protection; react 20 hours under the steady temperature of 60 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 114567, and molecular weight distribution is 3.24, and viscosity is 69PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 46.5 °.
[embodiment 2]
The vinyl cyanide (AN) of 97g through distilling, 4g methylene-succinic acid/methylene-succinic acid aqueous ammonium (methylene-succinic acid ammonium 1.5g, methylene-succinic acid 0.5g being dissolved in 2g water), 1g β-itaconic acid n-butyl, 0.75g Diisopropyl azodicarboxylate (AIBN), 400g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under helium protection; react 24 hours under the steady temperature of 60 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 131067, and molecular weight distribution is 2.91, and viscosity is 87PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 42.5 °.
[embodiment 3]
The vinyl cyanide (AN) of 97g through distilling, 4g methylene-succinic acid/methylene-succinic acid aqueous ammonium (methylene-succinic acid ammonium 0.5g, methylene-succinic acid 1.5g being dissolved in 2g water), 1g acrylamide, 0.75g Diisopropyl azodicarboxylate (AIBN), 400g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under helium protection; react 24 hours under the steady temperature of 60 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 131067, and molecular weight distribution is 2.91, and viscosity is 87PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 49.5 °.
[embodiment 4]
The vinyl cyanide (AN) of 146g through distilling, 4g methylene-succinic acid/methylene-succinic acid aqueous ammonium (methylene-succinic acid 0.2g, methylene-succinic acid ammonium 1.8g being dissolved in 2g water), 2g methyl methacrylate, 0.9g Diisopropyl azodicarboxylate (AIBN) and 350g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under argon shield; react 26 hours under the steady temperature of 60 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 152560, and molecular weight distribution is 3.78, and viscosity is 92PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 42.6 °.
[embodiment 5]
The vinyl cyanide (AN) of 120g through distilling, 4g methylene-succinic acid/methylene-succinic acid aqueous ammonium (methylene-succinic acid 1.7g, methylene-succinic acid ammonium 0.3g being dissolved in 4g water), 0.5g acryloyl amidoxime, 0.5g Diisopropyl azodicarboxylate (AIBN) and 375g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 28 hours under the steady temperature of 50 DEG C; 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, and the contact angle of the co-polymer membrane that this stoste is made and water is 54.1 °.
[embodiment 5]
The vinyl cyanide (AN) of 120g through distilling, 4g methylene-succinic acid/methylene-succinic acid aqueous ammonium (methylene-succinic acid 1.6g, methylene-succinic acid ammonium 0.4g being dissolved in 4g water), 3g vinylformic acid, 0.5g Diisopropyl azodicarboxylate (AIBN), 375g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 32 hours under the steady temperature of 60 DEG C; 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 62PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 52.6 °.
[embodiment 6]
The vinyl cyanide (AN) of 120g through distilling, 4g methylene-succinic acid (IA)/methylene-succinic acid aqueous ammonium (methylene-succinic acid 1.6g, methylene-succinic acid ammonium 0.4g being dissolved in 6g water), 3g vinylformic acid, 0.5g Diisopropyl azodicarboxylate (AIBN), 375g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 40 hours under the steady temperature of 70 DEG C; 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 55PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 52.6 °.
[embodiment 7]
The vinyl cyanide (AN) of 120g through distilling, 4g methylene-succinic acid (IA)/methylene-succinic acid aqueous ammonium (methylene-succinic acid 1.6g, methylene-succinic acid ammonium 0.4g being dissolved in 6g water), 3g vinylformic acid, 0.5g 2,2'-Azobis(2,4-dimethylvaleronitrile) (AMBN), 375g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 40 hours under the steady temperature of 50 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 156871, and molecular weight distribution is 2.51, and viscosity is 80PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 52.5 °.
[embodiment 8]
The vinyl cyanide (AN) of 120g through distilling, 4g methylene-succinic acid (IA)/methylene-succinic acid aqueous ammonium (methylene-succinic acid 1.6g, methylene-succinic acid ammonium 0.4g being dissolved in 6g water), 3g vinylformic acid, 0.5g 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN), 375g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 24 hours under the steady temperature of 40 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 198567, and molecular weight distribution is 2.11, and viscosity is 200PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 52.6 °.
[comparative example 1]
The vinyl cyanide (AN) of 97g through distilling, 3g vinylformic acid, 0.6g Diisopropyl azodicarboxylate (AIBN), 380g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 20 hours under the steady temperature of 60 DEG C; 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 3.78, and viscosity is 110PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 58.1 °.
[comparative example 2]
The vinyl cyanide (AN) of 97g through distilling, 3g vinylformic acid, 8g water, 0.6g Diisopropyl azodicarboxylate (AIBN), 380g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 20 hours under the steady temperature of 60 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 112651, and molecular weight distribution is 3.71, and viscosity is 113PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 58.2 °.
[comparative example 3]
The vinyl cyanide (AN) of 97g through distilling, 3g acrylamide, 0.6g 2,2'-Azobis(2,4-dimethylvaleronitrile) (AMBN), 380g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 20 hours under the steady temperature of 50 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 139870, and molecular weight distribution is 2.50, and viscosity is 178PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 58.0 °.
[comparative example 4]
The vinyl cyanide (AN) of 97g through distilling, 3g acrylamide, 8g water, 0.6g 2,2'-Azobis(2,4-dimethylvaleronitrile) (AMBN), 380g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 20 hours under the steady temperature of 60 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 14087, and molecular weight distribution is 2.51, and viscosity is 178PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 58.2 °.
[comparative example 5]
The vinyl cyanide (AN) of 97g through distilling, 3g methyl methacrylate, 0.6g 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN), 380g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 20 hours under the steady temperature of 40 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 160950, and molecular weight distribution is 2.20, and viscosity is 210PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 58.1 °.
[comparative example 6]
The vinyl cyanide (AN) of 97g through distilling, 3g methyl methacrylate, 8g water, 0.6g 2,2'-Azobis(2,4-dimethylvaleronitrile) (AVBN), 380g dimethyl sulfoxide (DMSO) (DMSO) are joined in reactor; under nitrogen protection; react 20 hours under the steady temperature of 60 DEG C; then spinning solution is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution.After tested, molecular weight is 159883, and molecular weight distribution is 2.21, and viscosity is 212PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 58.2 °.
Claims (10)
1. a preparation method for the high-hydrophilic acrylonitrile copolymer spinning solution that ammonification degree is controlled, comprises the following steps:
(a) using vinyl cyanide, comonomer 1, comonomer 2 as copolymerization component, using azo compound as initiator, be after solvent with dimethyl sulfoxide (DMSO), join in reactor, under being the gas shield of inertia with reactive material, react 12 ~ 24 hours at 40 ~ 75 DEG C of temperature, obtain high-hydrophilic acrylonitrile copolymer spinning solution I; Wherein, comonomer 1 is methylene-succinic acid/methylene-succinic acid aqueous ammonium;
B () spinning solution I is after removing residual monomer and bubble, obtain high-hydrophilic acrylonitrile copolymer spinning solution, described spinning solution molecular weight is 8 ~ 200,000, molecular weight distribution is below 1 ~ 4, viscosity is 50 ~ 130PaS at 60 DEG C, and the contact angle of the co-polymer membrane that this stoste is made and water is 40 ° ~ 58 °.
2. the preparation method of the high-hydrophilic acrylonitrile copolymer spinning solution that ammonification degree according to claim 1 is controlled, it is characterized in that comonomer 1 methylene-succinic acid used/methylene-succinic acid aqueous ammonium is first carried out by methylene-succinic acid after ammonification obtains methylene-succinic acid ammonium, methylene-succinic acid ammonium and methylene-succinic acid are dissolved in the water according to mol ratio 1:10 ~ 10:1, the mass ratio of methylene-succinic acid and methylene-succinic acid ammonium and water is 0.1:1 ~ 1:10.
3. the preparation method of the high-hydrophilic acrylonitrile copolymer spinning solution that ammonification degree according to claim 2 is controlled, it is characterized in that methylene-succinic acid ammonium and methylene-succinic acid are that 1:4 ~ 5:1 is dissolved in the water according to mol ratio, the mass ratio of methylene-succinic acid and methylene-succinic acid ammonium and water is 0.3:1 ~ 1:5.
4. the preparation method of the high-hydrophilic acrylonitrile copolymer spinning solution that ammonification degree according to claim 1 is controlled, is characterized in that comonomer 2 is at least one in vinylformic acid, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isobutyl-vinylformic acid, β-itaconic acid n-butyl, acrylamide, acryloyl amidoxime, hydroxylethyl nitrile, α chloroacrylonitrile or diacetone-acryloamide(DAA).
5. the preparation method of the high-hydrophilic acrylonitrile copolymer spinning solution that ammonification degree according to claim 1 is controlled, is characterized in that comonomer 2 is at least one in methyl acrylate, methyl methacrylate, acrylamide, acryloyl amidoxime.
6. the preparation method of the high-hydrophilic acrylonitrile copolymer spinning solution that ammonification degree according to claim 1 is controlled, it is characterized in that the proportioning of polymer raw counts copolymerization component is by weight 10 ~ 35 parts, wherein vinyl cyanide is 8 ~ 33 parts, comonomer 1 is 1 ~ 4 part, comonomer 2 is 1 ~ 4 part, solvent is 65 ~ 90 parts, and initiator amount is 0.2 ~ 1% of copolymerization component gross weight.
7. the preparation method of the high-hydrophilic acrylonitrile copolymer spinning solution that ammonification degree according to claim 6 is controlled, it is characterized in that the proportioning of polymer raw counts copolymerization component is by weight 15 ~ 25 parts, wherein vinyl cyanide is 13 ~ 23 parts, comonomer 1 is 1 ~ 4 part, comonomer 2 is 1 ~ 4 part, and solvent is 75 ~ 84 parts.
8. the preparation method of high-hydrophilic 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.
9. the preparation method of high-hydrophilic acrylonitrile copolymer spinning solution according to claim 1, is characterized in that azo-initiator used is selected from the one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile).
10. the preparation method of high-hydrophilic acrylonitrile copolymer spinning solution according to claim 1, it is characterized in that the method removing residual monomer and bubble used is decompression vacuum pumping method, the time removing monomer is 2 ~ 40 hours, and the time removing bubble is 4 ~ 72 hours.
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| CN110672781B (en) * | 2019-10-17 | 2021-11-02 | 中复神鹰碳纤维股份有限公司 | Detection method for polyacrylonitrile spinning liquid ammonia ion replacement rate |
| IT202100014159A1 (en) | 2021-05-31 | 2022-12-01 | Montefibre Mae Tech S R L | One-stage process for the production of carbon fiber precursor |
| EP4098784A1 (en) | 2021-05-31 | 2022-12-07 | Montefibre Mae Technologies S.R.L. | Single-step process for the production of a carbon fiber precursor |
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