CN102675604B - Preparation method for ferrocenyl-containing condensed polynuclear aromatic resin - Google Patents
Preparation method for ferrocenyl-containing condensed polynuclear aromatic resin Download PDFInfo
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 14
- 229920005989 resin Polymers 0.000 title abstract description 32
- 239000011347 resin Substances 0.000 title abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005120 petroleum cracking Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000009833 condensation Methods 0.000 claims description 36
- 230000005494 condensation Effects 0.000 claims description 36
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 33
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 31
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 29
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000012264 purified product Substances 0.000 claims description 2
- 238000004809 thin layer chromatography Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 8
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- AQUSAQRCJHSYBO-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylmethanol;iron(2+) Chemical compound [Fe+2].OCC1=CC=C[CH-]1.OCC1=CC=C[CH-]1 AQUSAQRCJHSYBO-UHFFFAOYSA-N 0.000 abstract 1
- 230000005389 magnetism Effects 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 6
- 125000003367 polycyclic group Chemical group 0.000 description 6
- 238000009998 heat setting Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- -1 phenyl aldehyde Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a novel method for preparing a ferrocenyl-containing condensed polynuclear aromatic resin from a raw material aromatics-rich residual oil produced by a petroleum cracking atmospheric and vacuum distillation unit. The method comprises the following steps of: performing synthetic reaction by taking the aromatics-rich residual oil as the raw material and taking 1,1'-ferrocenedimethanol as an acidic catalyst to generate a prepolymer of the condensed polynuclear aromatic resin; and performing thermosetting reaction on the prepolymer to obtain the condensed polynuclear aromatic resin. The condensed polynuclear aromatic resin prepared by the method has high heat resistance and a high carbon yield ratio, and can be used for a precursor of a carbon material and the like. Due to the use of a byproduct residual oil of petroleum cracking, utilization channels of the residual oil are added, problems about the residual oil treatment after the petroleum cracking are reduced, and the aims of saving energy and reducing emissions are fulfilled. A crosslinking agent has high reactivity, and ferrocene radicals are introduced into the resin, so that the resin is endowed with special magnetism and oxidation-reduction quality.
Description
Technical field
The present invention relates to a kind ofly take rich aromatic hydrocarbons residual oil as raw material prepares the method for ferrocenyl condensation polycyclic polynuclear aromatic resins, belong to the deep processing of petroleum products, technical field prepared by high-performance polymer.
Background technology
Condensation multinuclear polyaromatic hydrocarbon resin is the thermosetting resin of a kind of tridimensional network of the invention eighties in 20th century, it synthetic method mainly adopt the linking agent of difunctionality by condensation reaction, aromatic proton to be coupled together, by Japanese large space between muscles China fir youth (Otani S the earliest, RaskovicV, Oya A, et al.Journal of Material Science, 1986, (21): 2027~2034) invention.These resinoid maximum characteristics be have excellent resistance to elevated temperatures, self lubricity and with fabulous affinity of carbon material etc.Synthetic this resinoid aroamtic hydrocarbon raw material used mostly is condensed-nuclei aromatics, linking agent includes terephthalyl alcohol (PXG) (S OTANI, et al.Some properties of a condensed polynuclear aromatic resin (COPNA) as a binder for carbon fibre composites[J] .Journal of Materials Science, 1986 (21): 2027~2032.), phenyl aldehyde (BA) (Kondo H.Ishimaru M.USP, 5605401 (1997)), trioxymethylene (Yin Jie, Xu Yin. the synthetic and performance study [J] of the copna resin that three oxygen six rings of take are linking agent. polymer material science and engineering, 1996, 23~28.) and their derivative etc. 112 (3):.
Heavy aromatics residual oil is the byproduct produced in Crude Oil Processing.Present stage heavy oil residue utilize method limited, on the primary level such as practical application also only rests on and builds the road, roof Material, water-proof material or final have burnt.Research is found, has a large amount of condensed-nuclei aromatics components in petroleum residual oil, and wherein the aromatic hydrocarbons of 2~4 rings occupies significant proportion.There is certain reactive behavior in these aromatic hydrocarbon molecules, therefore can prepare multiple organic intermediate and resin material by chemical reaction, heavy aromatics residual oil is developed to high value added product.
By metallic element and non-metallic element by chemical bonding in the organic polymer chain, formed polymkeric substance had often both retained organic macromolecule kindliness and workability, there is again some metal and nonmetallic performance, simultaneously also the feature that some are new may be occurred, thereby simple metal can be obtained, nonmetal or organic polymer is not available, containing metal new polymers with new characteristic.Ferrocene-based polymer is important a kind of in this class containing metal new polymers, and ferrocene is incorporated in polymer backbone and will gives the special electricity of material, magnetic, catalysis and redox property.
Heavy aromatics residual oil is prepared into to the existing patent of condensation multinuclear polyaromatic hydrocarbon resin and reported in literature, (the Yin Jie such as Yin Jie, Zhang Bin, open refined. the synthetic and performance study [J] of the Condensed Polynuclear Aromatic Hydrocarbon Resin that the pitch of take is monomer. polymer material science and engineering, 1999,115 (3): 27~29.) take pitch as monomer, trioxymethylene and phenyl aldehyde (BA) are linking agent, under the sulphuric acid catalysis effect, have synthesized Condensed Polynuclear Aromatic Hydrocarbon Resin, and after solidifying, the thermostability of resin is poor.The woods waviness, Li Tiehu etc. (woods waviness, Li Tiehu. the synthetic and performance [J] of terephthalaldehyde-coal-tar pitch copna resin. polymer material science and engineering, 2007,23 (2): 62~64.) take coal-tar pitch as monomer, terephthalaldehyde be linking agent, synthetic condensation agent polynuclear aromatic hydrocarbons resin under the katalysis of tosic acid, but there is long reaction time, the problem that temperature of reaction is high.
Summary of the invention
The purpose of this invention is to provide a kind of rich aromatic hydrocarbons residual oil of take low value-added petroleum cracking and be prepared into the method containing the condensation multinuclear polyaromatic hydrocarbon resin of ferrocenyl as raw material.The rich aromatic hydrocarbons residual oil of raw material of the present invention belongs to the waste residue part of petroleum cracking, cheap and easy to get and can effectively reduce the solid waste that petroleum cracking produces.The linking agent adopted is to have the methylol ferrocene of higher reactive behavior and the methylol ferrocene of replacement thereof.Building-up reactions following (convenient for meaning, as in reaction equation, with pyrene, to mean the polycyclic aromatic hydrocarbons in rich aromatic hydrocarbons residual oil):
Curing mechanism is as follows:
The invention provides a kind of preparation method of the condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl, it is characterized in that take that rich aromatic hydrocarbons residual oil is raw material, the ferrocene of methylol ferrocene and replacement thereof of take is linking agent, by following operation, realizes in two steps:
Described each component proportion of raw material containing the ferrocenyl resin, press mass fraction, comprising:
Residual oil: 90-100 part
Methylol ferrocene: 10-90 part
An acidic catalyst: 1-5 part;
The first step takes raw material according to above-mentioned feed ratio, by rich aromatic hydrocarbons residual oil heat fused, at N
2add linking agent under the gas protection; mix; after adding an acidic catalyst in batches; be warming up to 80-120 ℃; react and occur to twining excellent phenomenon in about 1-3 hour; obtain the thick product of performed polymer of solid condensation multinuclear polyaromatic hydrocarbon resin after the stopped reaction cooling, through the alcohol reflux washing, remove unreacting material, detect in purified product residual without the methylol ferrocene by thin-layer chromatography.
Second step at 200 ℃-350 ℃ heating 2-5 hour, obtains the condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl by the performed polymer of condensation multinuclear polyaromatic hydrocarbon resin.
The performed polymer rich aromatic hydrocarbons residual oil used of preparation condensation multinuclear polyaromatic hydrocarbon resin refers to normal pressure or the reliever bottom heavy constituent out of petroleum cracking, its aromaticity content 60-100%, optimum aromaticity content 80-95%.Aromatic component comprises mononuclear aromatics and comprises the polycyclic aromatic hydrocarbons of 2-15 ring, the List of Condensed Polycyclic Aromatic Hydrocarbons that optimum aromatic component is the 2-4 ring.
The present invention is the methylol ferrocene of methylol ferrocene and replacement thereof for the preparation of the linking agent of the condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl, and wherein methylol can be in the number with ring or different ring and methylol >=2.
The present invention is for the preparation of the linking agent methylol ferrocene containing the condensation multinuclear polyaromatic hydrocarbon resin of ferrocenyl and the methylol ferrocene of replacement, and formula I is a kind of structure wherein:
The general formula II is a kind of structure wherein:
R in formula
1-R
8be selected from-H-,-R '-, phenyl, halogen ,-OH ,-OR ', by the R ' of N, O, R ' that the S heteroatoms replaces, halo ,-RCOO-or-RCONHR-, R is C
1-12alkyl or alkylidene group, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8.
An acidic catalyst used is Lewis acid or protonic acid, and wherein optimum an acidic catalyst is organic sulfonic acid.The ratio (weight ratio) of rich aromatic hydrocarbons residual oil and linking agent is 1:0.1-0.9, than the ratio of greater inequality example, is 1:0.5-0.7.
Heat curing temperature is 200-400 ℃, and wherein more excellent heat curing temperature is 250-350 ℃.
Testing method of the present invention is as follows:
Softening temperature test (bigness scale method): in this experiment, adopt manual needling method.Determination step: the sample of getting 1 about gram is put in hot platform central authorities, puts into a thermocouple measuring temperature, slowly heating, and per minute raises 5 ℃.Constantly try to insert resin with steel wire simultaneously, feel the fusing situation of resin with steel wire.Along with the rising of temperature, resin is softening gradually, when resin is all softening, observes the temperature indication window and writes down this temperature, is the softening temperature of institute's assize fat.
Thermogravimetric analysis: adopt PERKIN-ELMER type thermal analyzer, at N
2speed with 10 ℃/min in atmosphere heats up, N
2flow is 140mL/min.
Beneficial effect of the present invention is as follows:
(1) the present invention be take heavy aromatics residual oil and is prepared thermotolerance condensation polycyclic polynuclear aromatic resins as raw material.Raw materials used being easy to get, selected cross linker active is higher, and preparation time is short, and condition is comparatively gentle.
(2) in the prepared condensation multinuclear of the present invention polyaromatic hydrocarbon resin structure with ferrocene group, will give the special magnetic of this resin and oxidation-reducibility.
(3) the resulting condensation polycyclic polynuclear aromatic resins of the present invention has advantages of high carbon residue, and the presoma that can be used as carbon materials is used, for the high value added utilization of petroleum residual oil has been opened up new approach.
The accompanying drawing explanation:
Fig. 1 is the prepared thermogravimetric curve that solidifies rear resin of embodiment 1.
Fig. 2 is the prepared thermogravimetric curve that solidifies rear resin of embodiment 2.
Fig. 3 is the prepared thermogravimetric curve that solidifies rear resin of Comparative Examples 1.
Further narrate the preparation method of condensation polycyclic polynuclear aromatic resins provided by the present invention below in conjunction with embodiment.
Embodiment 1:
Rich aromatic hydrocarbons residual oil (the Wuhan Jin Huan petrochemical corporation (complex) that reaction is used, aromaticity content=80%), with 1, (the laboratory self-control of 1 '-ferrocene dimethanol, fusing point=106-108 ℃) as linking agent, for catalyzer carries out building-up reactions, reaction conditions is respectively tosic acid (chemical pure, China Medicine (Group) Shanghai Chemical Reagent Co., produces): rich aromatic hydrocarbons residual oil: linking agent (weight ratio)=1:0.3; Temperature of reaction 1.5 hours; In above-mentioned reaction, use tosic acid as catalyzer, the 5%(weight ratio that its content is gross weight).
Rich aromatic hydrocarbons residual oil 20g is heated to 80-90 ℃, makes its fusing, at N
2under the gas protection, add linking agent to 1; 1 '-ferrocene dimethanol 6g; mix; after adding an acidic catalyst toluenesulphonic acids 1g, be warming up to 120 ℃ in batches, be reacted to and twine excellent phenomenon generation; obtain the thick product of performed polymer of solid condensation multinuclear polyaromatic hydrocarbon resin after the stopped reaction cooling; take out thick product cooling after, remove unreacting material through alcohol reflux washing, obtain 23.5g condensation multinuclear polyaromatic hydrocarbon resin performed polymer.
Condensation multinuclear polyaromatic hydrocarbon resin is heated in curing oven, 200 ℃ of lower constant temperature 2 hours, 250 ℃ of lower constant temperature obtain condensation multinuclear polyaromatic hydrocarbon resin in 2 hours, obtain insoluble not molten condensation polycyclic polynuclear aromatic resins after thermofixation.Softening temperature is 117 ℃.The thermogravimetric curve of condensation multinuclear polyaromatic hydrocarbon resin is shown in accompanying drawing 1.Can find out that from accompanying drawing 1 it is 390 ℃ that the synthesized resin starts weightless temperature, stopping temperature all the time is 470 ℃, and total rate of weight loss is 37%.
Embodiment 2:
Raw materials used and preparation process is with embodiment 2, and institute's difference is rich aromatic hydrocarbons residual oil and 1, and the weight ratio of 1 '-ferrocene dimethanol is 1:0.7, and reaction result obtains the condensation multinuclear polyaromatic hydrocarbon resin performed polymer that softening temperature is 135 ℃.
The thermofixation condition is with embodiment 1, and the thermogravimetric curve of condensation multinuclear polyaromatic hydrocarbon resin is shown in accompanying drawing 2.Can find out that from accompanying drawing 2 it is 388 ℃ that the synthesized resin starts weightless temperature, stopping weightless temperature is 460 ℃, and total rate of weight loss is 42%.
Comparative Examples 1:
React the raw materials used middle terephthalyl alcohol of using as linking agent, other reaction raw materials and consumption, synthesis condition, thermofixation condition are all identical with embodiment 1.Reaction result obtains the condensation multinuclear polyaromatic hydrocarbon resin performed polymer that softening temperature is 113 ℃.The thermogravimetric curve of the condensation multinuclear polyaromatic hydrocarbon resin obtained after thermofixation is shown in accompanying drawing 3.Can find out that from accompanying drawing 3 it is 350 ℃ that the synthesized resin starts weightless temperature, stopping weightless temperature is 490 ℃, and total rate of weight loss is 80%.
Claims (5)
1. the preparation method containing the condensation multinuclear polyaromatic hydrocarbon resin of ferrocenyl, is characterized in that take that rich aromatic hydrocarbons residual oil is raw material, and the methylol ferrocene of methylol ferrocene and replacement thereof of take is linking agent, by following operation, realizes in two steps:
Prepare each component proportion of raw material of the described condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl, press mass fraction, comprising:
Residual oil: 90-100 part
Methylol ferrocene: 10-90 part
An acidic catalyst: 1-5 part;
The first step takes raw material according to above-mentioned feed ratio, by rich aromatic hydrocarbons residual oil heat fused, at N
2add linking agent under the gas protection, mix, after adding an acidic catalyst in batches, be warming up to 80-120 ℃, react and occur to twining excellent phenomenon in about 1-3 hour, obtain the performed polymer thick product of solid containing the condensation multinuclear polyaromatic hydrocarbon resin of ferrocenyl after the stopped reaction cooling, through the alcohol reflux washing, remove unreacting material, detect in purified product residual without the methylol ferrocene by thin-layer chromatography;
Second step will, containing the performed polymer of the condensation multinuclear polyaromatic hydrocarbon resin of ferrocenyl at 200 ℃-400 ℃ heating 2-5 hour, obtain the condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl.
2. the preparation method of a kind of condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl according to claim 1, it is characterized in that described rich aromatic hydrocarbons residual oil refers to normal pressure or the reliever bottom heavy constituent out of petroleum cracking, its aromaticity content 60-100%, aromatic component comprises mononuclear aromatics and comprises the polycyclic aromatic hydrocarbons of 2-15 ring.
3. the preparation method of a kind of condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl according to claim 1, is characterized in that in the methylol ferrocene of methylol ferrocene and replacement thereof, methylol can be in the number with ring or different ring and methylol >=2.
4. the preparation method of a kind of condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl according to claim 1 is characterized in that the constitutional features of the methylol ferrocene that replaces is a kind of structure in formula I:
R in formula
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be selected from-H, phenyl, halogen, hydroxyl.
5. the preparation method of a kind of condensation multinuclear polyaromatic hydrocarbon resin containing ferrocenyl according to claim 1 is characterized in that the constitutional features of the methylol ferrocene that replaces is a kind of structure in the general formula II:
R in formula
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8be selected from-H, phenyl, halogen, hydroxyl.
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