CN102977619A - Polymer modified asphalt stabilizer and preparation method thereof - Google Patents
Polymer modified asphalt stabilizer and preparation method thereof Download PDFInfo
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- CN102977619A CN102977619A CN2012105651616A CN201210565161A CN102977619A CN 102977619 A CN102977619 A CN 102977619A CN 2012105651616 A CN2012105651616 A CN 2012105651616A CN 201210565161 A CN201210565161 A CN 201210565161A CN 102977619 A CN102977619 A CN 102977619A
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Abstract
The invention relates to a polymer modified asphalt stabilizer and a preparation method thereof. The polymer modified asphalt stabilizer is prepared from the following substances in parts by weight: 5-40 parts of acidification accelerator M waste residue, 5-45 parts of sulfur, 5-20 parts of accelerator, 5-20 parts of resin and 5-30 parts of auxiliary additive. According to the invention, the waste residue generated in the accelerator M produced by an acid-alkali method is fully utilized and is modified through chemical reaction, so that the waste residue has certain flowability, thereby solving the problem that the waste residue scatters in asphalt. Meanwhile, through the addition of proper assistant, an SBS (styrene-butadiene-styrene) modified asphalt stabilizer can be compounded. Thus, the invention fully utilizes the effect of the accelerator M waste residue on vulcanization acceleration and solves the problem on the treatment of the waste residue, thereby reducing pollution to the environment.
Description
Technical field
The present invention relates to a kind of additive that can be used for the stable polymer modification road bitumen material of production high-temperature storage, the concrete a kind of polymer modified asphalt stablizer and preparation method thereof that relates to.
Background technology
The twenties in 20th century, Bedford C. W etc. has found that with Bruni, Romani 2-thiol benzothiazole (abbreviation captax) can be used as vulcanization accelerator, and this is a milestone of promotor development history.Captax is vulcanization accelerator important in the rubber industry, it simultaneously is again the fertile material of other times of great majority sulfamido promotor, in the output of all kinds of rubber ingredients, account for the first place, to produce the indispensable intermediate of thiazoles vulcanization accelerator, can output DM, CZ after further synthetic processing, the multiple rubber accelerators such as NS, DZ.In addition, captax also can be used as mineral flotation agent, vector resin and corrosion inhibitor, and sterling can be used as the metal special reagent.
The production method commonly used of captax is acid-base method, namely reacts under high temperature, high pressure with aniline, dithiocarbonic anhydride and sulphur, is promoted agent M through a series of separation, purification process again.But residual a large amount of waste residue (hereinafter to be referred as the captax waste residue) in the process of high-pressure process production captax, this waste residue is a kind of mixture of complexity, unreacted raw material is namely arranged, also contain intermediate product, by product and the tarry material of name structure not, total amount accounts for 10%～15% of captax output.In addition, residual waste residue can not be degraded, and the residue of bulk deposition had both taken the soil, has polluted again environment, day by day becomes the difficult problem in the environmental protection.Therefore, explore the M waste residue the processing approach, solve environmental pollution and take full advantage of resource and become very urgent problems.
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of polymer modified asphalt stablizer for above-mentioned prior art, utilizes the waste residue that produces in the captax production process as additive, promotes the effect of sulfuration, has reduced again the pollution of waste residue to environment.
Another object of the present invention provides the preparation method of polymer modified asphalt stablizer.
The present invention solves the problems of the technologies described above the technical scheme that adopts: the polymer modified asphalt stablizer, and it is mixed with by weight proportion by following each material and forms:
5 ~ 40 parts in acidifying captax waste residue
5 ~ 45 parts in sulphur
5 ~ 20 parts of promotor
5 ~ 20 parts of resins
5 ~ 30 parts of supplementary additives.
Press such scheme, described acidifying captax waste residue is obtained by laxative remedy: the waste residue heating that produces in the captax process with acid-base method production, temperature is controlled between 180 ~ 230 ℃, and adding mass ratio is 0.5 ~ 1.5 times mineral acid of waste residue, and reaction 0.5-3hr obtains acidifying captax waste residue.
Press such scheme, described mineral acid is sulfuric acid, chlorsulfonic acid, phosphoric acid, polyphosphoric acid, nitric acid or hydrochloric acid.
Press such scheme, described sulphur is elemental sulfur or insoluble sulfur.
Press such scheme, described promotor is captax, altax, promotor PZ, promotor EZ, acceterator TE TD, Vulcanization accelerator TMTD or accelerant MBT.
Press such scheme, described resin is coumarone indene resin, C5 petroleum resin, C9 petroleum resin, terpine resin or resol.
Press such scheme, described supplementary additive is Zinic stearas.
The preparation method of polymer modified asphalt stablizer, it is characterized in that including following steps: adding sulphur, promotor, resin and supplementary additive in the acidifying captax waste residue mixes, and wherein each material is by weight proportion: 5 ~ 40 parts in acidifying captax waste residue; 5 ~ 45 parts in sulphur; 5 ~ 20 parts of promotor; 5 ~ 20 parts of resins; 5 ~ 30 parts of supplementary additives add mixed material in the shredder, grind 15 ~ 30min and namely get described polymer modified asphalt stablizer.
Press such scheme, described acidifying captax waste residue is obtained by laxative remedy: wherein said acidifying captax waste residue is obtained by laxative remedy: the waste residue heating that produces in the captax process with acid-base method production, temperature is controlled between 180 ~ 230 ℃, adding mass ratio is 0.5 ~ 1.5 times mineral acid of waste residue, and reaction 0.5-3hr obtains acidifying captax waste residue.
The present invention carries out chemical liquefaction processing to the captax waste residue of acid-base method production, and purpose is to recover the crosslinked and promotion functions of captax waste residue, and the consistency of increase and pitch; The 2nd, utilize the captax waste residue after the chemical modification, add again that an amount of sulphur, secondary accelerator and resin etc. are composite to be a kind of SBS modified asphalt stabilizer.
Using method of the present invention: matrix pitch is heated to 170-200 ℃ first, add the SBS resin, add-on is 2% ~ 10% of matrix pitch, after stirring 30 minutes, carry out high speed shear 1.5 ~ 2hr, shear temperature is controlled between 175 ~ 185 ℃ again, then add the SBS modified asphalt stabilizer, its add-on is 0.1% ~ 0.5% of matrix pitch, keeps high-temperature stirring 1 ~ 2hr again, namely gets the good SBS modifying asphalt of over-all properties.
The present invention takes full advantage of the waste residue that produces in the captax of acid-base method production, carries out modification by chemical reaction, makes it possess certain flowability, has solved the scattering problem of waste residue in pitch.Simultaneously, add suitable additive compound and go out a kind of SBS modified asphalt stabilizer.The present invention had both given full play to the effect of the promotion sulfuration of captax waste residue, had solved again the processing problem of waste residue, had reduced the pollution to environment.
Embodiment
The present invention will be further described in detail below in conjunction with embodiment, but this explanation can not be construed as limiting the invention.
Embodiment 1:
In glass reactor, add the captax waste residue that the 20g acid-base method is produced, be heated to 180 ℃, add 10.8g sulfuric acid, reaction 30min, obtain acidifying captax waste residue 30.8g after the cooling, add sulphur 40g, captax 15g, coumarone indene resin 8g and Zinic stearas 5g.Material after mixing is added in the shredder, grind 15min and namely get polymer modified asphalt stablizer A.
Embodiment 2:
In glass reactor, add the captax waste residue that the 20g acid-base method is produced, be heated to 230 ℃, add the phosphoric acid of 27g 80%, reaction 60min, obtain acidifying captax waste residue 42g after the cooling, add insoluble sulfur 20g, vulkacit D 20g, C5 petroleum resin 20g and Zinic stearas 20g.Material after mixing is added in the shredder, grind 20min, namely get polymer modified asphalt stablizer B.
Embodiment 3:
In glass reactor, add the captax waste residue that the 20g acid-base method is produced, be heated to 190 ℃, add the 30g chlorsulfonic acid, reaction 90min, obtain acidifying captax waste residue 50g after the cooling, add elemental sulfur 40g, Vulcanization accelerator TMTD 15g, terpine resin 10g and Zinic stearas 28g.Material after mixing is added in the shredder, grind 30min, namely get polymer modified asphalt stablizer C.
Embodiment 4:
In glass reactor, add the captax waste residue that the 20g acid-base method is produced, be heated to 185 ℃, add the 21g chlorsulfonic acid, reaction 150min, obtain acidifying captax waste residue 40g after the cooling, add insoluble sulfur 40g, accelerant MBT 20g, resol 10g and Zinic stearas 5g.Material after mixing is added in the shredder, grind 30min, namely get polymer modified asphalt stablizer D.
Embodiment 5:
In glass reactor, add the captax waste residue that the 30g acid-base method is produced, be heated to 185 ℃, add the sulfuric acid of 36g, reaction 180min, obtain acidifying captax waste residue 66g after the cooling, add insoluble sulfur 45g, acceterator TE TD 20g, coumarone indene resin 20g and Zinic stearas 20g.Material after mixing is added in the shredder, grind 30min, namely get polymer modified asphalt stablizer E.
Application Example 1:
Take by weighing the 400gA-90 matrix pitch, be heated to about 170 ℃, add the 16gSBS resin, stirring 30min is uniformly dispersed SBS in pitch, behind 185 ℃ of left and right sides high speed shear 2hr, add and press the polymer modified asphalt stablizer A1.2g that embodiment 1 method is produced, under 185 ℃ of conditions, stir 2hr, namely get the SBS modified bitumen product, its performance index see Table 1.
Application Example 2:
Take by weighing the 400gA-90 matrix pitch, be heated to about 180 ℃, add the 18gSBS resin, stirring 30min is uniformly dispersed SBS in pitch, behind 185 ℃ of left and right sides high speed shear 2hr, add and press the polymer modified asphalt stablizer B1.4g that embodiment 2 methods are produced, under 185 ℃ of conditions, stir 2hr, namely get the SBS modified bitumen product, its performance index see Table 1.
Application Example 3:
Take by weighing the 400gSK matrix pitch, be heated to about 200 ℃, add the 16gSBS resin, stirring 30min is uniformly dispersed SBS in pitch, behind 185 ℃ of left and right sides high speed shear 2hr, add and press the polymer modified asphalt stablizer C1.6g that embodiment 3 methods are produced, under 185 ℃ of conditions, stir 1hr, namely get the SBS modified bitumen product, its performance index see Table 1.
Application Example 4:
Take by weighing the 400gSK matrix pitch, be heated to about 175 ℃, add the 18gSBS resin, stirring 30min is uniformly dispersed SBS in pitch, behind 185 ℃ of left and right sides high speed shear 2hr, add and press the polymer modified asphalt stablizer D1.8g that embodiment 4 methods are produced, under 185 ℃ of conditions, stir 1.5hr, namely get the SBS modified bitumen product, its performance index see Table 1.
Application Example 5:
Take by weighing the 400gSK matrix pitch, be heated to about 175 ℃, add the 18gSBS resin, stirring 30min is uniformly dispersed SBS in pitch, behind 185 ℃ of left and right sides high speed shear 2hr, add and press the polymer modified asphalt stablizer E2.0g that embodiment 4 methods are produced, under 180 ℃ of conditions, stir 2hr, namely get the SBS modified bitumen product, its performance index see Table 1.
The performance index of Application Example 1-5 modifying asphalt see Table 1:
Table 1 SBS performance of modified bitumen index
。
Claims (9)
1. polymer modified asphalt stablizer, it is mixed with by weight proportion by following each material and forms:
5 ~ 40 parts in acidifying captax waste residue
5 ~ 45 parts in sulphur
5 ~ 20 parts of promotor
5 ~ 20 parts of resins
5 ~ 30 parts of supplementary additives.
2. polymer modified asphalt stablizer according to claim 1, it is characterized in that, described acidifying captax waste residue is obtained by laxative remedy: the waste residue heating that produces in the captax process with acid-base method production, temperature is controlled between 180 ~ 230 ℃, adding mass ratio is 0.5 ~ 1.5 times mineral acid of waste residue, and reaction 0.5-3hr obtains acidifying captax waste residue.
3. polymer modified asphalt stablizer according to claim 2, it is characterized in that: described mineral acid is sulfuric acid, chlorsulfonic acid, phosphoric acid, polyphosphoric acid, nitric acid or hydrochloric acid.
4. according to claim 1 and 2 or 3 described polymer modified asphalt stablizers, it is characterized in that: described sulphur is elemental sulfur or insoluble sulfur.
5. according to claim 1 and 2 or 3 described polymer modified asphalt stablizers, it is characterized in that: described promotor is captax, altax, promotor PZ, promotor EZ, acceterator TE TD, Vulcanization accelerator TMTD or accelerant MBT.
6. according to claim 1 and 2 or 3 described polymer modified asphalt stablizers, it is characterized in that: described resin is coumarone indene resin, C5 petroleum resin, C9 petroleum resin, terpine resin or resol.
7. according to claim 1 and 2 or 3 described polymer modified asphalt stablizers, it is characterized in that: described supplementary additive is Zinic stearas.
8. the preparation method of polymer modified asphalt stablizer claimed in claim 1, it is characterized in that including following steps: adding sulphur, promotor, resin and supplementary additive in the acidifying captax waste residue mixes, and wherein each material is by weight proportion: 5 ~ 40 parts in acidifying captax waste residue; 5 ~ 45 parts in sulphur; 5 ~ 20 parts of promotor; 5 ~ 20 parts of resins; 5 ~ 30 parts of supplementary additives add mixed material in the shredder, grind 15 ~ 30min and namely get described polymer modified asphalt stablizer.
9. the preparation method of polymer modified asphalt stablizer according to claim 8, it is characterized in that, described acidifying captax waste residue is obtained by laxative remedy: wherein said acidifying captax waste residue is obtained by laxative remedy: the waste residue heating that produces in the captax process with acid-base method production, temperature is controlled between 180 ~ 230 ℃, adding mass ratio is 0.5 ~ 1.5 times mineral acid of waste residue, and reaction 0.5-3hr obtains acidifying captax waste residue.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479169A (en) * | 2014-11-19 | 2015-04-01 | 武汉理工大学 | Chemical reaction type SBS modified asphalt thermal storage stabilizer and preparation method thereof |
| CN106318424A (en) * | 2015-07-03 | 2017-01-11 | 上海宝钢化工有限公司 | Novel environment-friendly method for improving asphalt softening point |
| CN108793802A (en) * | 2018-06-08 | 2018-11-13 | 太原理工大学 | A kind for the treatment of process of coal chemical industry low-quality sulfur |
| CN112143039A (en) * | 2020-09-30 | 2020-12-29 | 山东理工大学 | Direct-vat M resin-based modified asphalt stabilizer, and preparation method and application thereof |
Citations (1)
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| CN102093730A (en) * | 2011-02-15 | 2011-06-15 | 青海弘川新源实业股份有限公司 | Method for preparing self-healing type procuring asphalt |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093730A (en) * | 2011-02-15 | 2011-06-15 | 青海弘川新源实业股份有限公司 | Method for preparing self-healing type procuring asphalt |
Non-Patent Citations (1)
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| 刘安华等: "促进剂M的生产及其废渣利用", 《橡胶工业》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479169A (en) * | 2014-11-19 | 2015-04-01 | 武汉理工大学 | Chemical reaction type SBS modified asphalt thermal storage stabilizer and preparation method thereof |
| CN104479169B (en) * | 2014-11-19 | 2017-03-22 | 武汉理工大学 | Chemical reaction type SBS modified asphalt thermal storage stabilizer and preparation method thereof |
| CN106318424A (en) * | 2015-07-03 | 2017-01-11 | 上海宝钢化工有限公司 | Novel environment-friendly method for improving asphalt softening point |
| CN106318424B (en) * | 2015-07-03 | 2019-04-12 | 宝武炭材料科技有限公司 | Novel environment-friendly method for improving asphalt softening point |
| CN108793802A (en) * | 2018-06-08 | 2018-11-13 | 太原理工大学 | A kind for the treatment of process of coal chemical industry low-quality sulfur |
| CN108793802B (en) * | 2018-06-08 | 2021-05-04 | 太原理工大学 | Treatment process of low-quality sulfur in coal chemical industry |
| CN112143039A (en) * | 2020-09-30 | 2020-12-29 | 山东理工大学 | Direct-vat M resin-based modified asphalt stabilizer, and preparation method and application thereof |
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Effective date of registration: 20151202 Address after: Ten mile Industrial Park, Hubei, Guangshui, China 432700 Patentee after: Hubei Yong Yang material limited company Address before: 430074 Wuhan, Hongshan Province District, hung Chu street, No. 693 Patentee before: Wuhan Institute of Technology Patentee before: Wuhan Aisifate New Material Co., Ltd. |
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