CN1043506A - Laser enhanced catalyst prepares the method for polymkeric substance - Google Patents
Laser enhanced catalyst prepares the method for polymkeric substance Download PDFInfo
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- CN1043506A CN1043506A CN 88108240 CN88108240A CN1043506A CN 1043506 A CN1043506 A CN 1043506A CN 88108240 CN88108240 CN 88108240 CN 88108240 A CN88108240 A CN 88108240A CN 1043506 A CN1043506 A CN 1043506A
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Abstract
The present invention relates to the application of a kind of laser in chemical polymerization, particularly utilize some transition metal carbonyl compound of laser radiation, the intermediate complex that forms unsaturated ligand strengthens the polymerization rate of organic monomer as active catalyst.This invention provide a kind of under normal temperature, normal pressure the quick method of synthesising macromolecule copolymer, the monomer whose transformation efficiency is more than 90%, method is easy.
Description
The present invention relates to the application of a kind of laser in chemical polymerization, particularly utilize some transition metal carbonyl compound of laser radiation, the intermediate complex that forms unsaturated ligand impels the method for polymer monomer rapid polymerization as active catalyst.
The monomer polymerization that will contain unsaturated double-bond usually becomes the method for polymkeric substance to have some kinds, for example thermochemical method, photochemical method, r-x ray irradiation x method, electron beam and Plasma Polymerization and laser chemistry method etc.The synthetic of human photochemical method research polymkeric substance just arranged a long time ago, particularly be some scholars of representative with Britain C.H.Bamford, they have just systematically studied the application of transition metal carbonyl compound in light-initiated Raolical polymerizable since the sixties.Their method characteristics are to make irradiating source with high voltage mercury lamp and so on ordinary light source, in reaction system except that adding transistion metal compound, also add Organohalogen compounds simultaneously, these two kinds of compounds produce halogen-containing free radical under the irradiation of light, thus the trigger monomer polymerization.Its directivity of ordinary light source that they use, monochromaticity, coherency and brightness can not show a candle to laser, the present invention adopts pulse laser to make light source, not only accelerated the speed of polyreaction, and produce some new nonlinear chemical effects, be general conventional photochemical method can't be obtained, about people's such as C.H.Bamford the work document C.H.Bamford that sees reference, In " Reactivity Mechanism and Structure in Polymer Chemistry " (EdA.D Jendins and A.Ledwity), Wiley, N.Y.1974, Chap3.
I.I.Bukin in 1967 etc. once used ruby laser (wavelength 6943
) shine the acrylamide monomer that contains the blue dyestuff of methyl, make its polymerization reaction take place, monomer conversion is about 15%[and sees document I.I.Bukin, V.I.Kosyakov, Vysokomal Ser.B9(9) 714(1967) (C.A.67:117483)].
Two frequency doubled lights (the wavelength 3472 of ruby laser such as nineteen sixty-eight Raymond H.Hoskin
) giant pulse (peak power 10
6Watt) the irradiation isopropyl cyanide, produce a large amount of free radicals at short notice and cause the vinyl acetate between to for plastic polymerization, but do not see detailed report.[see document Raymond H.Hoskins, San Pedro:U.S.Patent 3,405,045(1968)].
Leo P.Part in 1969 etc. once used continuous argon ion (wavelength 4880
) shine and contain eosin or 4,5 '-the acrylamide monomer solution of photosensitizer such as dibromofluorescein and organic amine co-catalyst, synthesize polyacrylamide and [seen document Leo P Parts, Dayton and Willian R, Feair heller, Jr.Kettering Ohio, U.S.Petent 3,477,932(1969).
Above-mentioned these photochemistry and laser chemistry prepare the method for polymkeric substance, all are the process of optical free radical initiated polymerization basically.We need certain hour to circulate at the photoactivation method.Therefore than with continuous wave laser efficient height, and continuous laser can not make full use of photon, and quantum yield is not high.
The objective of the invention is in order to overcome the shortcoming of above-mentioned the whole bag of tricks, make full use of the high-throughput of pulse laser, monochromaticity, characteristics and the transition metal carbonyl compound character big such as directivity to the ultraviolet photon absorption cross, make reactant molecule be energized into high excited electronic state, produce ground state molecule and be difficult to the reaction carried out, thereby provide a kind of quick, the method of easy synthetic polymer, promptly use the pulse laser transition metal carbonyl compound that dissociates, make the active body in centre that its generation contains unsaturated ligand make catalyzer, impel the laser enhanced catalyst polymerization of organic monomer rapid polymerization.
The present invention is different from other prior art, and it is to realize the laser enhanced catalyst polyreaction like this, promptly adopts pulsed laser irradiation W(CO)
6, Mn(CO) 6, Cr(CO) 6, Fe(CO) 5, Ni(CO) 4, V(CO) 6, Mn2(CO) 10, Re2(CO) 10, and Co2(CO) transistion metal compounds such as 8, selection interrupts the key of metal and carbonyl corresponding to the photon (being suitable wavelengths) of M-C0 bond energy, makes M(CO) m dissociates, generate M(CO) n+(m-n) wherein n＜m), M(CO) n is the active body in centre with unsaturated ligand to CO(, makes catalyzer with it, at normal temperature, make the organic compound monomer that contains unsaturated double-bond under the normal pressure, aggregate into high molecular weight polymers in the short period of time, the monomer that the present invention is suitable for has: divinyl, isoprene, hexene, butine, pentyne, hexin, vinylbenzene, phenylacetylene, ethene, vinyl-acetic ester, methyl acrylate, methyl methacrylate, vinyl cyanide, vinyl carbazole, phenol, diphenyl sulfide, the pyrroles, aniline, vinyl fluoride.Select different wavelength regions according to the differential responses system, laser output energy needs 1 millijoule/pulse at least, general use 1～2 millijoule/pulse, used laser apparatus can be the dye laser, nitrogen molecular laser, excimer laser of YAG laser apparatus and pumping thereof etc.
Accompanying drawing with concrete examples of implementation and preparation process describes in detail below:
Get 500 gram technical pure vinyl carbazole monomers, purify with the recrystallizing methanol method, step-down drying in vacuum drying oven, survey its fusing point and be 64.5 ℃～65 ℃ standby.Weighing 140.8mgW(CO) 6, (U.S. Afa company product), put into the 200ml lucifuge the ground triangle and, add 20ml benzene (analytical pure) and make solvent, after stirring CL, add the vinyl carbazole that 1.54g purifies again, continue to be stirred to CL, these steps all at room temperature with in the atmosphere are carried out, then the solution container for preparing is placed in the light path that mixes up, as shown in Figure 1: [1] is frequency tripled laser (wavelength the is 355nm) width of cloth product in the same old way of YAG laser apparatus (Spectra-Physics's generation), and spot diameter is 2 millijoules/pulse for the 10mm. light intensity, and pulse-repetition is 10Hz.When laser radiation sample [7], use magnetic stirrer [8] stirred sample always, shine after 30 minutes, excessive methyl alcohol is added reaction soln (effect of methyl alcohol is to make precipitation agent), just there is flocculent precipitate to separate out at once, be oyster white.With the dissolving reprecipitation method gained throw out is purified three times, dry back weighing, obtain the 1.40g polymkeric substance, the monomer whose transformation efficiency is 90.9%, and [4] are laser power meter among Fig. 1, [5] be optical multi-channel analyzer, be used for the variation of system absorption characteristic in the monitoring reaction course, [2] are dye lasers, [6] lens, [9] the high pressure tungsten lamp is made probe source.At last, the polymkeric substance that obtains is carried out infrared spectrometry with the KBr pressed disc method, the gained infrared absorption spectra is identical with the polyvinyl carbazole infrared absorption spectrum of using conventional thermopolymerization method preparation, proves and contains W(CO) 6 vinyl carbazole monomer solution changed into corresponding polymer fast under the 355nm pulsed laser irradiation.Viscosity-average molecular weight Mn through measuring is 10
5Magnitude.Polymerization process provided by the invention can also be used the method that changes optical maser wavelength, energy, pulse-repetition and irradiation time, obtains the polymkeric substance of different molecular weight.
Advantage of the present invention is that whole reaction is carried out under normal temperature, normal pressure, and experiment is convenient, conserve energy; It is relevant with laser energy, pulse frequency, wavelength, irradiation time that next is the polymer that generates in same system, therefore, can at random control the polymer that experiment condition obtains different molecular weight, this is that other methods that prepare polymer are difficult to accomplish at present, in addition, method monomer conversion height provided by the invention.
Claims (4)
1, a kind of laser enhanced catalyst polymerization process for preparing polymkeric substance, this method comprises with laser makes light source, it is characterized in that: use pulse laser wavelength from 266nm to the 700nm scope, irradiation contains the monomer solution of W (CO) 6 or Mo (CO) 6 transition metal carbonyl compounds under normal temperature, normal pressure, irradiation time is 20 to 40 minutes, and the concentration of contained transition metal carbonyl compound is 10
-2M～10
-4M, monomeric benzole soln concentration is 2M～3M.
2, a kind of laser enhanced catalyst polymerization process by the described preparation polymkeric substance of claim 1, it is characterized in that: transition metal carbonyl compound is W(CO)
6, Cr(CO)
6, Fe(CO)
5, Ni(CO) 4, V(CO) 6, Mn2(CO) 10, Re2(CO)
10, Co2(CO)
8
3, a kind of laser enhanced catalyst polymerization process by the described preparation polymkeric substance of claim 1, it is characterized in that: used laser is two frequencys multiplication of YAG laser, frequency tripling, the laser of quadruple, the laser and the excimer laser of frequency multiplication and mixing again behind two frequencys multiplication of YAG laser or the frequency tripled laser pumping dye laser.
4, a kind of laser enhanced catalyst polymerization process by the described preparation polymkeric substance of claim 1, it is characterized in that: polymerisable monomer is a divinyl, isoprene, hexene, butine, pentyne, hexin, vinylbenzene, phenylacetylene, ethene, vinyl-acetic ester, methyl acrylate, methyl methacrylate, vinyl cyanide, vinyl carbazole, aniline, pyrroles, phenol, thiophene phenol, diphenyl sulfide, tetrafluoroethylene.
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|---|---|---|---|
| CN 88108240 CN1043506A (en) | 1988-12-02 | 1988-12-02 | Laser enhanced catalyst prepares the method for polymkeric substance |
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| CN 88108240 CN1043506A (en) | 1988-12-02 | 1988-12-02 | Laser enhanced catalyst prepares the method for polymkeric substance |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7335081B2 (en) | 2000-09-01 | 2008-02-26 | Canon Kabushiki Kaisha | Method for manufacturing image-forming apparatus involving changing a polymer film into an electroconductive film |
| CN106084092A (en) * | 2016-07-28 | 2016-11-09 | 江南大学 | A kind of carbazyl two-photon initiator and preparation method thereof |
| CN109912740A (en) * | 2018-06-29 | 2019-06-21 | 郑州轻工业学院 | A kind of preparation method of polyphenylacetylene |
-
1988
- 1988-12-02 CN CN 88108240 patent/CN1043506A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7335081B2 (en) | 2000-09-01 | 2008-02-26 | Canon Kabushiki Kaisha | Method for manufacturing image-forming apparatus involving changing a polymer film into an electroconductive film |
| CN106084092A (en) * | 2016-07-28 | 2016-11-09 | 江南大学 | A kind of carbazyl two-photon initiator and preparation method thereof |
| CN109912740A (en) * | 2018-06-29 | 2019-06-21 | 郑州轻工业学院 | A kind of preparation method of polyphenylacetylene |
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