CN105542047A - Method for preparing polyacrylonitrile macromolecules - Google Patents
Method for preparing polyacrylonitrile macromolecules Download PDFInfo
- Publication number
- CN105542047A CN105542047A CN201510971041.XA CN201510971041A CN105542047A CN 105542047 A CN105542047 A CN 105542047A CN 201510971041 A CN201510971041 A CN 201510971041A CN 105542047 A CN105542047 A CN 105542047A
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile
- prepare polyacrylic
- polyacrylic method
- polymerization
- initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 20
- 229920002521 macromolecule Polymers 0.000 title abstract description 3
- -1 tetrafluoroborate Chemical compound 0.000 claims abstract description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000012954 diazonium Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract 2
- 239000011941 photocatalyst Substances 0.000 abstract 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012688 inverse emulsion polymerization Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/42—Nitriles
- C08F120/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing polyacrylonitrile macromolecules. According to the method, polyacrylonitrile is polymerized from acrylonitrile monomers at normal temperature in an organic solvent in a manner of taking aryl diazo tetrafluoroborate as an initiator under the conditions of organic photocatalyst presence and blue LED lamp irradiation. In a reaction process, an organic photocatalyst is firstly activated under the promotion of a blue LED lamp, then, aryl diazo tetrafluoroborate is catalyzed to generate aryl free radicals, nitrogen gas and tetrafluoroborate anions, and then, the polymerization of the acrylonitrile monomers is initiated by the aryl free radicals, so as to prepare polyacrylonitrile. The polymerization of the acrylonitrile monomers is promoted by using the blue LED lamp for the first time, so that the method has the advantages that the operation is simple, heating or other special equipment is not required, the catalyst is simple and readily available, the obtained polyacrylonitrile is high in yield, the molecular weight is high, the molecular distribution is narrow, and the like.
Description
Technical field
The present invention relates to the high molecular synthetic method of polyacrylonitrile in field of macromolecule polymerization
Background technology
Polyacrylonitrile a kind ofly has excellent chemistry and the macromolecular material of physicals, chemical stability is good, not facile hydrolysis, and resistance of oxidation is strong, solvent resistant, effectively can stop the infiltration of gas, good springiness, tensile strength are high, soft, are mainly used as fiber, be commonly called as acrylic fibers, be one of three large synthon, also can be used as the precursor of carbon fiber for the field such as aerospace and military project, purposes widely.
The method that current synthesis polyacrylonitrile is conventional has aqueous suspension polymerization, inverse emulsion polymerization, anionoid polymerization and radical polymerization etc.Although aqueous suspension polymerization and inverse emulsion polymerization can synthesize the polyacrylonitrile of high molecular, molecular weight of product wider distribution; Anionoid polymerization side reaction is many, and catalyst system is complicated, and severe reaction conditions, therefore applies less; The polyacrylonitrile molecular weight that traditional radical polymerization generates is lower, and molecular weight distribution is wider, and polyacrylonitrile insufficient strength is high, and wear resistance and fatigue resistance are also poor, has a strong impact on its performance.In recent years, controllable free-radical polymerisation obtains and develops fast.This type of polymerization is simple to operate, is applicable to the polymerization of most of monomer, and trace impurity can be allowed to exist, and product degree of isotacticity is good, the dispersed advantage such as low and be widely used in the synthesis of polyacrylonitrile.But classical controlled radical polymerization needs higher kick off temperature, or use the specific installations such as ultraviolet lamp.In addition, classical controlled radical polymerization adopts metallic copper, silver etc. as catalyzer mostly, and its shortcoming is that aftertreatment is inconvenient, and has certain pollution to environment.
Summary of the invention
The invention provides a kind of reaction conditions gentle, simple to operate, without the need to metal catalyst and molecular weight of product is high, narrow molecular weight distribution, the polyacrylonitrile synthetic method that yield is high.
Polyacrylonitrile synthetic method provided by the present invention, under normal temperature, take vinyl cyanide as monomer, with Tetrafluoroboric acid aryl diazonium salts for initiator, red Y (EosinY) is affixed one's name to for catalyzer with organic dye, take DMF as solvent, under 5 light blue look LED are irradiated, polymerization reaction take place generates polyacrylonitrile.
Synthetic method comprises following operation: by Tetrafluoroboric acid aryl diazonium salts under anhydrous and oxygen-free condition, and organic dye is affixed one's name to red Y and added in reaction tubes, is filled with nitrogen, add acrylonitrile monemer again, DMF, stirs and terminates reaction in 10 hours under 5 light blue look LED are irradiated.Add methyl alcohol in mixed solution, separate out to solid, filter, 60 degrees Celsius of oven dry.
In technique scheme, described catalyzer affixes one's name to red Y and initiator Tetrafluoroboric acid aryl diazonium salts as being 0.01 ~ 0.05 to fluorine Tetrafluoroboric acid Arenediazonium salts, to the mol ratio of chlorine Tetrafluoroboric acid Arenediazonium salts, is optimized for 0.025.
In technique scheme, described acrylonitrile monemer and initiator Tetrafluoroboric acid aryl diazonium salts, as being 50 ~ 200 to fluorine Tetrafluoroboric acid Arenediazonium salts, to the mol ratio of chlorine Tetrafluoroboric acid Arenediazonium salts, are optimized for 100.
In technique scheme, the concentration of acrylonitrile monemer is 5 ~ 20mol/L, is optimized for 10mol/L.
In technique scheme, R group is halogen, and as fluorine, chlorine, bromine, different halogenic substituent has no significant effect reaction.
In technique scheme, the wavelength of blue led lamp is 450 nanometers, and power is 5 watts.
The above technical scheme of the present invention proposes a kind of novel method of synthesizing polyacrylonitrile, the reaction mechanism of polymerization is: visible ray is activated catalyst first, rear catalyst and Tetrafluoroboric acid aryldiazonium reactant salt, generate aryl radical, nitrogen and Tetrafluoroboric acid negatively charged ion, then aryl radical causes vinyl cyanide and carries out radical polymerization.The present invention uses the polyreaction that light can be promoted vinyl cyanide first, and achieves successfully, has following beneficial effect:
Reaction conditions is gentle, equipment is simple, productive rate is high, molecular weight is high, molecular distribution is narrow
Specific implementation method
Example 1
Under anhydrous and oxygen-free environment, successively 3.6mg (0.005mmol) is affixed one's name to red Y, 45.2mg (0.2mmol) to chlorine Tetrafluoroboric acid Arenediazonium salts, 1.06g (20mmol) acrylonitrile monemer, 1.7mlN, dinethylformamide, join in 25mL reaction tubes, be filled with nitrogen.Under room temperature condition with power be 5 watts, wavelength is the blue led light irradiation 10 hours of 450 nanometers.Reaction mixture pours beaker into, adds 50mL methyl alcohol, separates out solid, uses 20mL methanol wash, filters, dries at 60 c.Obtain white solid polyacrylonitrile 0.92g, transformation efficiency 87%, molecular weight 210,000, molecular weight distribution 1.33.
Claims (10)
1. the high molecular preparation method of polyacrylonitrile, its feature comprises the following steps: under anhydrous and oxygen-free condition, in nitrogen atmosphere, take DMF as solvent, take vinyl cyanide as polymerization single polymerization monomer, take diazonium tetrafluoroborate as initiator, to affix one's name to red Y (eosinY) for catalyzer, under 5 light blue look LED are irradiated, under room temperature condition, polymerization reaction take place obtains polyacrylonitrile polymer.
2. according to right 1, prepare polyacrylic method, it is characterized in that: take diazonium tetrafluoroborate as initiator.
3. according to right 1, prepare polyacrylic method, it is characterized in that: to affix one's name to red Y (eosinY) for catalyzer.
4. according to right 1, prepare polyacrylic method, it is characterized in that: under 5 light blue look LED are irradiated.
5. according to right 1, prepare polyacrylic method, it is characterized in that: monomer concentration is 10mol/L.
6. according to right 1, prepare polyacrylic method, it is characterized in that: in molar ratio, catalyzer: initiator: acrylonitrile monemer=(0.01 ~ 0.05): 1:(50:200).
7. according to right 6, prepare polyacrylic method, it is characterized in that: in molar ratio, catalyzer: initiator: acrylonitrile monemer=0.025:1:100.
8. according to right 1, prepare polyacrylic method, it is characterized in that: described polyreaction is carried out at ambient temperature.
9. according to right 1, prepare polyacrylic method, it is characterized in that: R group is halogen.
10. according to right 1, prepare polyacrylic method, it is characterized in that: the reaction times is 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971041.XA CN105542047A (en) | 2015-12-21 | 2015-12-21 | Method for preparing polyacrylonitrile macromolecules |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971041.XA CN105542047A (en) | 2015-12-21 | 2015-12-21 | Method for preparing polyacrylonitrile macromolecules |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105542047A true CN105542047A (en) | 2016-05-04 |
Family
ID=55821635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510971041.XA Pending CN105542047A (en) | 2015-12-21 | 2015-12-21 | Method for preparing polyacrylonitrile macromolecules |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105542047A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487844A (en) * | 1983-08-22 | 1984-12-11 | Phillips Petroleum Company | Benzenediazonium tetrafluoroborate/titanium tetrahalide-based catalysts |
-
2015
- 2015-12-21 CN CN201510971041.XA patent/CN105542047A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487844A (en) * | 1983-08-22 | 1984-12-11 | Phillips Petroleum Company | Benzenediazonium tetrafluoroborate/titanium tetrahalide-based catalysts |
Non-Patent Citations (5)
| Title |
|---|
| DURGA PRASAD HARI等: ""Metal-Free,Visible-Light-Mediated Direct C-H Arylation of Heteroarenes with Aryl Diazonium Salts"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| TENG-FEI NIU等: ""Visible-Light-Induced Meerwein Cascade Reactions for the Preparation of α-ArylEsters"", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| XU ZHANG等: ""Studies of Arenediazonium Salts as a New Class of Electropolymerization Initiator"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 邱家白等: ""用重氮盐引发N-乙烯咔唑之光聚合研究"", 《高分子学报》 * |
| 黄志桂等编: "《有机化学（下）》", 30 June 1990 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101712736B (en) | Method for preparing fast responsive temperature-sensitive hydrogel by adopting frontal polymerization technology | |
| CN110305267A (en) | A kind of high-intensitive response type hydrogel and preparation method thereof based on block copolymer | |
| CN113444229A (en) | Preparation method of fluorine-containing alternating polymer | |
| CN1119652A (en) | Process for preparing acrylic polymers | |
| Li et al. | Photoinduced organocatalyzed controlled radical polymerization feasible over a wide range of wavelengths | |
| CN105037609B (en) | A kind of preparation method of methyl methacrylate polymer | |
| CN102633700A (en) | Preparation of water-soluble RAFT (reversible addition-fragmentation) chain transfer agent and synthesis method for polyacrylic acid with low molecular weight | |
| CN108794743B (en) | Preparation method of large-aperture organic covalent framework material | |
| CN102746453A (en) | Method for preparing high-performance polyacrylonitrile solution for carbon fibers | |
| CN1331899C (en) | Method for preparing carbon nano tube/polymer nano composite material | |
| CN105542047A (en) | Method for preparing polyacrylonitrile macromolecules | |
| CN102964543A (en) | Amphiphilic fluorinated acrylate penta-block copolymer and preparation method thereof | |
| CN104031214A (en) | St/MAH-g-MMA (styrene/maleic anhydride-grafted-methyl methacrylate) graft copolymer, and preparation method and application thereof | |
| Kumru et al. | Regio‐selective peroxybromination of poly (vinyl methyl ketone) as versatile tool for generation active ATRP initiation sites on solid surfaces | |
| CN103804658A (en) | Polymerizable polyfluorene macromonomer and synthesis method thereof | |
| CN102633923A (en) | Water-soluble triple response intelligent polymer and preparation method thereof | |
| CN1230454C (en) | Process for preparing perfluorosulfonyl resin | |
| Xu et al. | Synthesis of Poly (N‐isopropylacrylamide)‐Block‐Poly (tert‐Butyl Methacrylate) Block Copolymer by Visible Light–Induced Metal‐Free Atom Transfer Polymerization | |
| CN102120786B (en) | Method for preparing highly syndiotactic polyacrylonitrile resin | |
| JP4616593B2 (en) | Stereoregular polyacrylonitrile-based polymerization composition and method for producing the same | |
| CN115947883B (en) | High-quality polyacrylonitrile and controllable synthesis method and application thereof | |
| CN101475665A (en) | Preparation of polyacrylonitrile for high performance carbon fibre | |
| KR20100042151A (en) | Manufacturing process of high molecular weight polyacrylonitrile-base precursor for carbon fiber production by drop-weight method | |
| CN101338192B (en) | Nanometer modified high molecular fluorescent material and method for preparing same | |
| CN109251259B (en) | Method for realizing controllable free radical polymerization based on catalyst and Finkelstein reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160504 |