CN101845313B - Boron and silicon-containing asphalt and preparation method thereof - Google Patents
Boron and silicon-containing asphalt and preparation method thereof Download PDFInfo
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- CN101845313B CN101845313B CN201010175573XA CN201010175573A CN101845313B CN 101845313 B CN101845313 B CN 101845313B CN 201010175573X A CN201010175573X A CN 201010175573XA CN 201010175573 A CN201010175573 A CN 201010175573A CN 101845313 B CN101845313 B CN 101845313B
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Abstract
The invention relates to boron and silicon-containing asphalt and a preparation method thereof. The invention adopts a technical scheme that: the preparation method comprises the followings steps of: dissolving asphalt in toluene, keeping the temperature of between 40 and 90 DEG C for 4 to 10 hours, centrifuging and filtering to remove undissolved substances, distilling the solution at the temperature of between 110 and 150 DEG C to remove the toluene, and drying the residue to prepare an asphalt and toluene soluble substance; mixing 1 to 10 weight percent of organic boron, 30 to 60 weight percent of organic silicon and 30 to 69 weight percent of asphalt and toluene soluble substance, adding a solvent accounting for 50 to 80 weight percent of the mixture, and uniformly stirring; keeping the temperature of between 100 and 300 DEG C for 2 to 10 hours, and distilling at the temperature of between 80 and 120 DEG C to remove the solvent to obtain the synthesized product; and keeping the temperature of the synthesized product at the temperature of between 130 and 180 DEG C for 24 hours to obtain the boron and silicon-containing asphalt. The boron and silicon-containing asphalt has the characteristics of readily available raw materials, low reaction temperature and simple operation, and can be used as a binding agent and an impregnant; and carbonized products after high temperature treatment have good oxidation resistance at a high temperature.
Description
Technical field
The invention belongs to field of bitumen technology, be specifically related to a kind of boron and silicon-containing asphalt and preparation method thereof.
Background technology
At normal temperatures, pitch is black solid, and no fixed fusing point is glassy phase, and the post softening of being heated is melted then.Because pitch can be used as the sticker and the soaker of carbon/carbon composite and other matrix material, its goods are widely used in fields such as metallurgy, chemical industry, aerospace and electronics day by day.But in air or well-oxygenated environment, the very easily oxidation of pitch and asphalt base charcoal materials is so its use temperature often is lower than 400 ℃.Along with the raising that the material environment for use is required, exploitation can be satisfied the raw material of wood-charcoal material that uses under high temperature and the hyperthermal environments, and making modifying asphalt after pyroprocessing, have oxidation-resistance becomes one of focus.
At present, existing both at home and abroad many reports about asphalt modification.As homemade high softening point bitumen and pyridine borine are mixed by a certain percentage in the autoclave of packing into (Zhang Lifang, Song Jinren is in will standing; Deng. boron replaces the preparation [J] of polyaromatic intermediate phase. novel charcoal material, 1999,14 (4): 45-48.); Under nitrogen protection, heat up; Start behind the asphalt melting and stir,, go out still and promptly get boron replacement polyaromatic mesophase pitch at 360～440 ℃ of postcooling that stay for some time.This modifying asphalt is along with the increase of its boron content, and the content of its softening temperature, carbon residue and tetrahydrofuran insoluble all has corresponding raising.But this pitch is volatile by the formed boron oxide of norbide oxidation in high-temperature oxidation environment, causes its antioxidant property very limited.Britain scholar A.V.K.Westwood at first utilizes petroleum pitch and polydimethyl silane to be raw material (A.V.K.Westwood, B.Rand, S.Lu.Oxidation resistantcarbon materials derived from boronated carbon-silicon alloys [J] .Carbon; 2004,42:3071-3080.), temperature of reaction is 390～450 ℃ in liquid phase; Temperature of reaction is 650 ℃ in gas phase, makes carbon silicon pitch after reaction for some time, utilizes toluene to be solvent again; Carbon silicon pitch is mixed with the pyridine borine according to a certain percentage, and temperature is raised to 110～130 ℃, after reaction for some time; Toluene is removed in distillation; Be heated to 440 ℃ then, can obtain not fused solid borosilicate alloy (C-B-Si alloy), this kind C-B-Si alloy has improved oxidation resistance temperature to a certain extent.Because product borosilicate ceramal no longer melts after heating, therefore can not be used as wedding agent and soaker, make its range of application receive bigger restriction.
Summary of the invention
The object of the invention provides that a kind of raw material is easy to get, the preparation method of boron and silicon-containing asphalt simple to operate; Boron and silicon-containing asphalt with this method preparation can be used as wedding agent and soaker, and the carbonizing production of pyroprocessing has good high-temperature oxidation-resistance and shock resistance.
For realizing above-mentioned purpose; The technical scheme that the present invention adopts is: earlier pitch is dissolved in the toluene; Under 40～90 ℃ of conditions, be incubated 4～10 hours, centrifugation is filtered, and removes insolubles; Solution is distilled removal toluene under 110～150 ℃ of conditions, residuum makes pitch toluene solvend after oven dry; Again organic boron of 1～10wt%, the organosilicon of 30～60wt% and the pitch toluene solvend of 30～69wt% are mixed, add the solvent of said mixture 50～80wt%, stir.
Under 100～300 ℃ of conditions, be incubated 2～10 hours then, solvent is removed in distillation under 80～120 ℃ of conditions, obtains the synthetic product; The synthetic product is incubated 24 hours under 130～180 ℃ of conditions, promptly obtains boron and silicon-containing asphalt.
Wherein: pitch is coal-tar pitch or is petroleum pitch; Organic boron is the pyridine borine or is in the 2-picoline borine; Organosilicon is Polycarbosilane or is polydimethyl silane; Solvent is a THF or for toluene or for pyridine.
Because adopt technique scheme, raw material Polycarbosilane and pyridine borine that the present invention is used both can be made by oneself, also can on market, buy, pitch can buy in market and cost lower.Organic boron used in the present invention, organosilicon and pitch toluene solvend all are dissolved in solvent; Have wellability and dispersiveness preferably; So utilize organic boron and organosilicon and pitch in solvent, to have wellability and operability preferably; Make boron, silicon and asphaltene molecule form more stable chemical bond, under lesser temps and normal pressure, make boron and silicon-containing asphalt at molecular level.
Therefore; The present invention has the advantages that raw material is easy to get, temperature of reaction is low and simple to operate; Prepared this kind of boron and silicon-containing asphalt can be used as wedding agent and soaker, its 900 ℃ of carbonizing productions in 1100～1200 ℃ of air ambients 24 hours rate of weight loss of constant temperature less than 1.00%.
Embodiment
Below in conjunction with embodiment the present invention being further described, is not the restriction to its protection domain.
Embodiment 1
A kind of boron and silicon-containing asphalt and preparation method thereof.Earlier coal-tar pitch is dissolved in the toluene, under 40～50 ℃ of conditions, is incubated 4～6 hours, centrifugation is filtered, and removes insolubles, solution is distilled under 110～130 ℃ of conditions remove toluene, and residuum makes pitch toluene solvend after oven dry; Again the pyridine borine of 1～3wt%, the Polycarbosilane of 30～40wt% and the pitch toluene solvend of 57～69wt% are mixed, add the pyridine of said mixture 50～60wt%, stir; Under 110～120 ℃ of conditions, be incubated 2～4 hours then, pyridine is removed in distillation under 80～90 ℃ of conditions, obtains the synthetic product; At last the synthetic product is incubated 24 hours under 130～140 ℃ of conditions, promptly obtains boron and silicon-containing asphalt.
900 ℃ of carbonizing productions of the boron and silicon-containing asphalt that present embodiment 1 is prepared constant temperature 24 hours in 1100～1200 ℃ of air ambients, its rate of weight loss is 0.95～0.98%.
Embodiment 2
A kind of boron and silicon-containing asphalt and preparation method thereof.Earlier coal-tar pitch is dissolved in the toluene, under 45～70 ℃ of conditions, is incubated 5～8 hours, centrifugation is filtered, and removes insolubles, solution is distilled under 130～150 ℃ of conditions remove toluene, and residuum makes pitch toluene solvend after oven dry; Again the pyridine borine of 3～5wt%, the Polycarbosilane of 35～55wt% and the pitch toluene solvend of 40～62wt% are mixed, add the toluene of said mixture 60～80wt%, stir; Under 140～200 ℃ of conditions, be incubated 3～6 hours then, toluene is removed in distillation under 85～110 ℃ of conditions, obtains the synthetic product; At last the synthetic product is incubated 24 hours under 140～160 ℃ of conditions, promptly obtains boron and silicon-containing asphalt.
900 ℃ of carbonizing productions of the boron and silicon-containing asphalt that present embodiment 2 is prepared constant temperature 24 hours in 1100～1200 ℃ of air ambients, its rate of weight loss is 0.90～0.95%.
Embodiment 3
A kind of boron and silicon-containing asphalt and preparation method thereof.Earlier coal-tar pitch is dissolved in the toluene, under 60～90 ℃ of conditions, is incubated 7～10 hours, centrifugation is filtered, and removes insolubles, solution is distilled under 110～120 ℃ of conditions remove toluene, and residuum makes pitch toluene solvend after oven dry; Again the pyridine borine of 5～10wt%, the Polycarbosilane of 30～60wt% and the pitch toluene solvend of 50～60wt% are mixed, add the toluene of said mixture 70～80wt%, stir; Under 200～300 ℃ of conditions, be incubated 6～10 hours then, toluene is removed in distillation under 100～120 ℃ of conditions, obtains the synthetic product; Last synthetic product is incubated 24 hours under 150～180 ℃ of conditions, promptly obtain boron and silicon-containing asphalt.
900 ℃ of carbonizing productions of the boron and silicon-containing asphalt that present embodiment 3 is prepared constant temperature 24 hours in 1100～1200 ℃ of air ambients, its rate of weight loss is 0.85～0.92%.
Embodiment 4
A kind of boron and silicon-containing asphalt and preparation method thereof.Earlier petroleum pitch is dissolved in the toluene, under 50～80 ℃ of conditions, is incubated 5～8 hours, centrifugation is filtered, and removes insolubles, solution is distilled under 120～130 ℃ of conditions remove toluene, and residuum makes pitch toluene solvend after oven dry; Again the 2-picoline borine of 3～6wt%, the Polycarbosilane of 40～50wt% and the pitch toluene solvend of 44～57wt% are mixed, add the THF of said mixture 60～70wt%, stir; Under 180～260 ℃ of conditions, be incubated 4～7 hours then, THF is removed in distillation under 90～110 ℃ of conditions, obtains the synthetic product; The synthetic product is incubated 24 hours under 150～170 ℃ of conditions, promptly obtains boron and silicon-containing asphalt.
900 ℃ of carbonizing productions of present embodiment 4 prepared boron and silicon-containing asphalt constant temperature 24 hours in 1100～1200 ℃ of air ambients, its rate of weight loss is 0.90～0.99%.
Embodiment 5
A kind of boron and silicon-containing asphalt and preparation method thereof.Earlier coal-tar pitch is dissolved in the toluene, under 40～75 ℃ of conditions, is incubated 4～6 hours, centrifugation is filtered, and removes insolubles, solution is distilled under 130～140 ℃ of conditions remove toluene, and residuum makes pitch toluene solvend after oven dry; Again the pyridine borine of 8～10wt%, the polydimethyl silane of 45～60wt% and the pitch toluene solvend of 30～47wt% are mixed, add the pyridine of said mixture 50～60wt%, stir; Under 260～300 ℃ of conditions, be incubated 7～10 hours then, pyridine is removed in distillation under 100～120 ℃ of conditions, obtains the synthetic product; The synthetic product is incubated 24 hours under 160～180 ℃ of conditions, promptly obtains boron and silicon-containing asphalt.
900 ℃ of carbonizing productions of the boron and silicon-containing asphalt that present embodiment 5 is prepared constant temperature 24 hours in 1100～1200 ℃ of air ambients, its rate of weight loss is 0.80～0.95%.
Embodiment 6
A kind of boron and silicon-containing asphalt and preparation method thereof.Earlier petroleum pitch is dissolved in the toluene, under 70～90 ℃ of conditions, is incubated 8～10 hours, centrifugation is filtered, and removes insolubles, solution is distilled under 140～150 ℃ of conditions remove toluene, and residuum makes pitch toluene solvend after oven dry; Again the 2-picoline borine of 1～4wt%, the polydimethyl silane of 30～40wt% and the pitch toluene solvend of 56～69wt% are mixed, add the toluene of said mixture 70～80wt%, stir; Under 130～210 ℃ of conditions, be incubated 2～6 hours then, toluene is removed in distillation under 80～110 ℃ of conditions, obtains the synthetic product; The synthetic product is incubated 24 hours under 130～150 ℃ of conditions, promptly obtains boron and silicon-containing asphalt.
900 ℃ of carbonizing productions of the boron and silicon-containing asphalt that present embodiment 6 is prepared constant temperature 24 hours in 1100～1200 ℃ of air ambients, its rate of weight loss is 0.85～0.96%.
Raw material Polycarbosilane and pyridine borine that this embodiment is used both can be made by oneself, also on market, bought easily, pitch can buy in market and cost lower.The employed organic boron of this embodiment, organosilicon and pitch toluene solvend all are dissolved in solvent; Have wellability and dispersiveness preferably; So utilize organic boron and organosilicon and pitch in solvent, to have wellability and operability preferably; Make boron, silicon and asphaltene molecule form more stable chemical bond, under lesser temps and normal pressure, make boron and silicon-containing asphalt at molecular level.
Therefore; This embodiment has the advantages that raw material is easy to get, temperature of reaction is low and simple to operate; Prepared this kind of boron and silicon-containing asphalt can be used as wedding agent and soaker, its 900 ℃ of carbonizing productions in 1100～1200 ℃ of air ambients 24 hours rate of weight loss of constant temperature less than 1.00%.
Claims (4)
1. the preparation method of a boron and silicon-containing asphalt is characterized in that earlier pitch being dissolved in the toluene, under 40～90 ℃ of conditions, is incubated 4～10 hours; Centrifugation is filtered; Remove insolubles, solution is distilled under 110～150 ℃ of conditions remove toluene, residuum makes pitch toluene solvend after oven dry; Again organic boron of 1～10wt%, the organosilicon of 30～60wt% and the pitch toluene solvend of 30～69wt% are mixed, add the solvent of said mixture 50～80wt%, stir;
Under 100～300 ℃ of conditions, be incubated 2～10 hours then, solvent is removed in distillation under 80～120 ℃ of conditions, obtains the synthetic product; The synthetic product is incubated 24 hours under 130～180 ℃ of conditions, promptly obtains boron and silicon-containing asphalt;
Described organic boron is the pyridine borine or is 2-picoline borine;
Described organosilicon is Polycarbosilane or is polydimethyl silane.
2. the preparation method of boron and silicon-containing asphalt according to claim 1 is characterized in that described pitch is coal-tar pitch or is petroleum pitch.
3. the preparation method of boron and silicon-containing asphalt according to claim 1 is characterized in that described solvent is a THF or for toluene or be pyridine.
4. according to the prepared boron and silicon-containing asphalt of preparation method of each described boron and silicon-containing asphalt in the claim 1～3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010175573XA CN101845313B (en) | 2010-05-11 | 2010-05-11 | Boron and silicon-containing asphalt and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010175573XA CN101845313B (en) | 2010-05-11 | 2010-05-11 | Boron and silicon-containing asphalt and preparation method thereof |
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| CN101845313A CN101845313A (en) | 2010-09-29 |
| CN101845313B true CN101845313B (en) | 2012-11-28 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382480B (en) * | 2011-12-15 | 2013-03-20 | 周其强 | Application of organosilicon residues in preparation of synthetic rubber asphalt |
| CN104230367B (en) * | 2014-09-10 | 2015-12-02 | 武汉科技大学 | A kind of SiC-ZrC-ZrB 2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof |
| CN108315837B (en) * | 2018-03-19 | 2020-07-10 | 武汉科技大学 | Boron-doped silicon carbide fiber and preparation method thereof |
| CN108559296B (en) * | 2018-05-15 | 2021-03-19 | 苏州太星新材料科技有限公司 | Si (B) C fiber high-viscosity high-elasticity asphalt modifier and preparation and application thereof |
| CN109762351B (en) * | 2018-12-24 | 2021-05-14 | 湖南鑫长胜材料科技有限公司 | Modified asphalt and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392822A2 (en) * | 1989-04-14 | 1990-10-17 | Ethyl Corporation | Preceramic compositions and ceramic products |
| CN1354221A (en) * | 2001-12-12 | 2002-06-19 | 太原理工大学 | Preparation method of asphalt modifying agent |
| CN1388209A (en) * | 2001-05-29 | 2003-01-01 | 中国科学院山西煤炭化学研究所 | Prepn of boron substituted carbon material |
| CN101423766A (en) * | 2008-12-15 | 2009-05-06 | 中国海洋石油总公司 | Durable asphalt and preparation method thereof |
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2010
- 2010-05-11 CN CN201010175573XA patent/CN101845313B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392822A2 (en) * | 1989-04-14 | 1990-10-17 | Ethyl Corporation | Preceramic compositions and ceramic products |
| CN1388209A (en) * | 2001-05-29 | 2003-01-01 | 中国科学院山西煤炭化学研究所 | Prepn of boron substituted carbon material |
| CN1354221A (en) * | 2001-12-12 | 2002-06-19 | 太原理工大学 | Preparation method of asphalt modifying agent |
| CN101423766A (en) * | 2008-12-15 | 2009-05-06 | 中国海洋石油总公司 | Durable asphalt and preparation method thereof |
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Granted publication date: 20121128 Termination date: 20130511 |