CN1401829A - Process for preparing polyacrylonitrile spinning solution - Google Patents
Process for preparing polyacrylonitrile spinning solution Download PDFInfo
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- CN1401829A CN1401829A CN 02130022 CN02130022A CN1401829A CN 1401829 A CN1401829 A CN 1401829A CN 02130022 CN02130022 CN 02130022 CN 02130022 A CN02130022 A CN 02130022A CN 1401829 A CN1401829 A CN 1401829A
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- acrylonitrile
- dimethyl sulfoxide
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Abstract
A process for preparing spinning dope of polyacrylonitrile includes homopolymerization of acrylonitrile, dimethyl sulfoxide, distilled water, azodiisobutyronitrile and chain transferring agent, introducing ammonia gas to stop reaction, and regulating pH value with ammonia gas. Its advantages are uniform distribution of functional groups in macromolecular chain, and controllable terminal group of polymer.
Description
Affiliated field:
The invention belongs to a kind of method for preparing polyacryl-nitrile spinning fluid, relate in particular to a kind of method for preparing high-performance polyacrylonitrile (PAN) based carbon fibre spinning solution.
Background technology:
Because the PAN homopolymers is the high crystalline polymer, cohesive energy is big, poorly soluble, difficulty in spinning, and its precursor is radical reaction in preoxidation process, plays the peak temperature height, heat release is concentrated, process is wayward, hot-spot occurs easily and produces fusion fracture of wire phenomenon, can't obtain high performance charcoal fiber.At present, the charcoal fiber all adopts and adds suitable comonomer and acrylonitrile carries out binary or ternary polymerization solves this problem.Usually the comonomer of introducing has: acrylic acid, methacrylic acid, itaconic acid, methyl methacrylate, acrylamide etc.Adopt solution polymerization process synthesis of acrylonitrile/itaconic acid/acrylamide ternary polymerization to obtain charcoal fiber PAN resin as viscose company of Mitsubishi.Dong Li company carries out binary copolymerization with dimethyl sulphoxide solution polymerization synthesis of acrylonitrile/itaconic acid, obtains the high-performance carbon fibre resin.Domestic scientific research and production unit use acrylonitrile/methyl acrylate/itaconic acid ternary polymerization mostly or use acrylonitrile/itaconic acid to carry out binary copolymerization.Thereby obtain the charcoal fibre resin.And when adopting free radical copolymerization method, owing to monomer reactivity ratio difference, monomer concentration than continuous reason such as variations in polymerization process, cause copolymerization construction unit skewness in the chain between macromolecular chain, the generation molecular defect finally influences the performance of charcoal fiber.
In addition, each polymer macromolecule all has two end groups, and end group also is the important chemical composition factor that influences the spinning solution quality.The end group of macromolecular chain depends on initiation and the termination in the polymerization process, end group may derive from monomer, initator, solvent, molecular weight regulator or other impurity, therefore the chemical property of end group is often different with main chain, and its behavior also is different from the PAN construction unit in pre-oxidation and carbonisation, thereby influence the performance of charcoal fiber, therefore control the chemical constitution of the big exposed terminated groups of polyacrylonitrile, make its pre-oxidation carbonization process that helps the charcoal fiber, the performance that improves the charcoal fiber is very important.And yet there are no report about this respect document.
Summary of the invention:
The purpose of this invention is to provide a kind of copolymerization units and on macromolecular chain, be evenly distributed, the preparation method of the controllable polyacrylonitrile based carbon fibre spinning solution of end group
The present invention adopts dimethyl sulfoxide (DMSO), water chain-transferring agent, acrylonitrile to carry out the solution homopolymerization, acrylonitrile homopolymer solution being carried out ammonification handles again, by the hydrolysis degree of control acrylonitrile homopolymer in the presence of ammonia, thereby obtain to contain the random PAN copolymer that is evenly distributed in the ternary interchain chain of the acrylic acid of different proportion and acrylamide construction unit, thereby obtain carboxyl and amide groups is evenly distributed, can make carboxyl occupy the PAN based carbon fiber presoma spinning solution of the position of quite a few end group.
The concrete preparation method of the present invention comprises the steps: that (1) with acrylonitrile, dimethyl sulfoxide (DMSO), distilled water, azodiisobutyronitrile and chain-transferring agent by weight: dimethyl sulfoxide (DMSO) is (10-1000) with the water ratio: 1, acrylonitrile is (100-200) with the azodiisobutyronitrile ratio: 1, dimethyl sulfoxide (DMSO) is 10 with the ratio of acrylonitrile: (1-10), dimethyl sulfoxide (DMSO) is (50-500) with the chain-transferring agent ratio: 1,50-70 ℃ of reaction 1-15 hour; (2) amine or formamide.Feeding ammonia in system, to make PH be 8-9, stops polymerisation; (3) continue to regulate PH to 9-14 with ammonia, temperature 80-100 ℃, hydrolysis was taken off list to 2 hours in 5 minutes, and deaeration makes spinning solution.
Aforesaid chain-transferring agent is acetate, formic acid, acetamide or formamide.
The invention has the advantages that:
1. the functional group of homogeneous hydrolysis generation is evenly distributed on macromolecular chain, does not have functional group
In chain, the inhomogeneities of interchain distribution.
2. technology is simple, easy control of reaction conditions.
3. the water in the mixed solvent influences the active force between resin and solvent molecule, reduces polymer solution viscosity, perhaps can obtain the more spinning solution of high solids content under identical viscosity.
4. polymer terminal group is controlled, and making polypropylene segment nitrile end group is carboxyl.
5. can impel azodiisobutyronitrile residual in the polymerization system to decompose, reduce residual initiators content in the polymer, improve PAN purity.
Specific implementation method:
Embodiment 1:(1) take by weighing the purified acrylonitrile of 150 grams, 1500 restrain dimethyl sulfoxide (DMSO)s, 150 gram water, and acetate 3 grams add 1 gram azodiisobutyronitrile, react 1 hour in 70 ℃ under nitrogen protection.(2) feed ammonia in the system and make pH value to 9, stop polymerisation.(3) regulate PH to 14, system temperature is risen to 80 ℃, list is taken off in hydrolysis 2 hours, and deaeration makes spinning solution.
Embodiment 2:(1) take by weighing the purified acrylonitrile of 1200 grams, 4000 restrain dimethyl sulfoxide (DMSO)s, 4 gram water, and acetate 80 grams, the azodiisobutyronitrile of adding 12 grams reacted 15 hours in 50 ℃ under nitrogen protection.(2) feed ammonia in the system and make pH value to 8.5, stop polymerisation.(3) regulating pH value with ammonia is 12, and system temperature is risen to 100 ℃, and list is taken off in hydrolysis 5 minutes, and deaeration makes spinning solution.
Embodiment 3:(1) take by weighing the purified acrylonitrile of 1000 grams, 3600 restrain dimethyl sulfoxide (DMSO)s, 80 gram water, and acetamide 36 grams, the azodiisobutyronitrile of adding 5 grams reacted 4 hours in 65 ℃ under nitrogen protection.(2) feed ammonia in the system and make pH value to 9, polymerisation stops.(3) keeping PH is 9, and system temperature is risen to 95 ℃, and list is taken off in hydrolysis 1.5 hours, and deaeration makes spinning solution.
Embodiment 4:(1) take by weighing the purified acrylonitrile of 1000 grams, 4400 restrain dimethyl sulfoxide (DMSO)s, 30 gram water, and formamide 10 grams, the azodiisobutyronitrile of adding 8 grams reacted 8 hours in 60 ℃ under nitrogen protection.(2) feed ammonia in the system and make pH value to 8.5, polymerisation stops.(3) regulate PH to 1.5, system temperature is risen to 90 ℃, list is taken off in hydrolysis 10 minutes, and deaeration makes spinning solution.
Embodiment 5:(1) take by weighing the purified acrylonitrile of 1000 grams, 4000 restrain dimethyl sulfoxide (DMSO)s, 40 gram water, and formic acid 10 grams, the azodiisobutyronitrile of adding 8 grams reacted 7 hours in 62 ℃ under nitrogen protection.(2) live to feed ammonia in the system and make pH value to 9, polymerisation stops.(3) regulate PH to 11, system temperature is risen to 90 ℃, list is taken off in hydrolysis 20 minutes, and deaeration makes spinning solution.
Embodiment 6:(1) take by weighing the purified acrylonitrile of 1000 grams, 1000 restrain dimethyl sulfoxide (DMSO)s, 90 gram water, and acetate 5 grams, the azodiisobutyronitrile of adding 6 grams reacted 8 hours in 59 ℃ under nitrogen protection.(2) feed ammonia in the system and make pH value to 8.5, polymerisation stops.(3) regulate PH to 11.2, system temperature is risen to 92 ℃, list is taken off in hydrolysis 30 minutes, and deaeration makes spinning solution.
Embodiment 7:(1) get the purified acrylonitrile of 1000 grams, 2000 restrain dimethyl sulfoxide (DMSO)s, 100 gram water, and acetamide 5 grams, the azodiisobutyronitrile of adding 7 grams reacted 7 hours in 61 ℃ under nitrogen protection.(2) feed ammonia in the system and make pH value to 8.6, polymerisation stops.(3) joint PH to 10.5 rises to 95 ℃ with system temperature, and list is taken off in hydrolysis 40 minutes, and deaeration makes spinning solution.
Embodiment 8:(4) take by weighing the purified acrylonitrile of 1000 grams, 5000 restrain dimethyl sulfoxide (DMSO)s, 200 gram water, and acetate 10 grams, the azodiisobutyronitrile of adding 5 grams reacted 10 hours in 55 ℃ under nitrogen protection.(5) feed ammonia in the system and make pH value to 9, polymerisation stops.(6) regulate PH to 13, system temperature is risen to 90 ℃, list is taken off in hydrolysis 20 minutes, and deaeration makes spinning solution.
Claims (2)
1. method for preparing polyacryl-nitrile spinning fluid, it is characterized in that the preparation method comprises the steps: (1) acrylonitrile, dimethyl sulfoxide (DMSO), distilled water, azodiisobutyronitrile and chain-transferring agent by weight: dimethyl sulfoxide (DMSO) is (10-1000) with the water ratio: 1, acrylonitrile is (100-200) with the azodiisobutyronitrile ratio: 1, dimethyl sulfoxide (DMSO) is 10 with the ratio of acrylonitrile: (1-10), dimethyl sulfoxide (DMSO) is (50-500) with the chain-transferring agent ratio: 1,50-70 ℃ of reaction 1-15 hour; (2) or formamide.Feeding ammonia in system, to make PH be 8-9, stops polymerisation; (3) ammonia continues to regulate PH to 9-14, and temperature 80-100 ℃, hydrolysis was taken off list to 2 hours in 5 minutes, and deaeration makes spinning solution.
2. a kind of method for preparing polyacryl-nitrile spinning fluid as claimed in claim 1 is characterized in that described chain-transferring agent is acetate, formic acid, acetamide or formamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02130022 CN1231616C (en) | 2002-08-13 | 2002-08-13 | Process for preparing polyacrylonitrile spinning solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02130022 CN1231616C (en) | 2002-08-13 | 2002-08-13 | Process for preparing polyacrylonitrile spinning solution |
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| CN1401829A true CN1401829A (en) | 2003-03-12 |
| CN1231616C CN1231616C (en) | 2005-12-14 |
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| CN 02130022 Expired - Lifetime CN1231616C (en) | 2002-08-13 | 2002-08-13 | Process for preparing polyacrylonitrile spinning solution |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856570A (en) * | 2010-06-03 | 2010-10-13 | 西安康本材料有限公司 | Dynamic demonomerization and defoaming method and device for carbon fiber spinning solution |
| CN102277629A (en) * | 2011-06-10 | 2011-12-14 | 金发科技股份有限公司 | Dry-jet wet-spinning method for preparing polyacrylonitrile carbon fiber precursor |
| CN102732981A (en) * | 2012-06-21 | 2012-10-17 | 精源(南通)化纤制品有限公司 | Polyacrylonitrile artificial hair and preparation method thereof |
| CN104264286A (en) * | 2014-10-18 | 2015-01-07 | 中复神鹰碳纤维有限责任公司 | Method suitable for carrying out consolidation forming on polyacrylonitrile carbon fiber precursor by dry-wet method |
| US20170335491A1 (en) * | 2015-02-16 | 2017-11-23 | Kaneka Corporation | Method for producing acrylic fiber |
| CN114606579A (en) * | 2020-12-03 | 2022-06-10 | 吉林碳谷碳纤维股份有限公司 | Ammonification method and device for polyacrylonitrile spinning solution |
-
2002
- 2002-08-13 CN CN 02130022 patent/CN1231616C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856570A (en) * | 2010-06-03 | 2010-10-13 | 西安康本材料有限公司 | Dynamic demonomerization and defoaming method and device for carbon fiber spinning solution |
| CN102277629A (en) * | 2011-06-10 | 2011-12-14 | 金发科技股份有限公司 | Dry-jet wet-spinning method for preparing polyacrylonitrile carbon fiber precursor |
| CN102732981A (en) * | 2012-06-21 | 2012-10-17 | 精源(南通)化纤制品有限公司 | Polyacrylonitrile artificial hair and preparation method thereof |
| CN104264286A (en) * | 2014-10-18 | 2015-01-07 | 中复神鹰碳纤维有限责任公司 | Method suitable for carrying out consolidation forming on polyacrylonitrile carbon fiber precursor by dry-wet method |
| CN104264286B (en) * | 2014-10-18 | 2016-09-07 | 中复神鹰碳纤维有限责任公司 | A kind of method being applicable to wet-dry change polyacrylonitrile carbon fiber precursor coagulation forming |
| US20170335491A1 (en) * | 2015-02-16 | 2017-11-23 | Kaneka Corporation | Method for producing acrylic fiber |
| CN114606579A (en) * | 2020-12-03 | 2022-06-10 | 吉林碳谷碳纤维股份有限公司 | Ammonification method and device for polyacrylonitrile spinning solution |
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| Publication number | Publication date |
|---|---|
| CN1231616C (en) | 2005-12-14 |
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Owner name: ZHONGJIAN TECHNOLOGY DEVELOPMENT CO., LTD. Free format text: FORMER OWNER: SHANXI INST. OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20090828 |
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Effective date of registration: 20090828 Address after: Jiangsu Province, Changzhou City, North Industrial Park Patentee after: ZHONGJIAN SCIENCE & TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 165 mailbox, Taiyuan City, Shanxi Province Patentee before: INSTITUTE OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
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Address after: 213127 Jiangsu province Changzhou Xingfeng Road New District No. 6 Patentee after: SINOFIBERS TECHNOLOGY Co.,Ltd. Address before: 213022 Jiangsu province Changzhou City North Industrial Park Patentee before: ZHONGJIAN SCIENCE & TECHNOLOGY DEVELOPMENT Co.,Ltd. |
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