CN106554470A - A kind of method for preparing the SBS latex for modified emulsifying asphalt or modified pitch - Google Patents
A kind of method for preparing the SBS latex for modified emulsifying asphalt or modified pitch Download PDFInfo
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- CN106554470A CN106554470A CN201510642070.1A CN201510642070A CN106554470A CN 106554470 A CN106554470 A CN 106554470A CN 201510642070 A CN201510642070 A CN 201510642070A CN 106554470 A CN106554470 A CN 106554470A
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- sbs
- modified
- latex
- asphalt
- emulsifying asphalt
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Abstract
The invention discloses a kind of method for preparing the SBS latex for modified emulsifying asphalt or modified pitch, the method is that SBS hexamethylene glues are added to containing initiator and in the aqueous solution of the hydrophilic monomer with thiazolinyl after emulsification pretreatment, stirring reaction 2～3 hours at a temperature of 45～65 DEG C, extract partial solvent, obtain final product SBS latex, the method has low cost, process is simple, and product stability is good, solid content is high, the characteristics of highly versatile, the SBS latex of preparation is can be applicable to cationic, anionic and the modified production modified emulsifying asphalt of nonionic emulsified asphalt, finished solid SBS can be also replaced to produce SBS modified pitch to asphalt modification.
Description
Technical field
The present invention relates to a kind of preparation method of the SBS latex for modified emulsifying asphalt or modified pitch,
Belong to Polymer Synthesizing field.
Background technology
Emulsified SBS modified asphalt is a kind of Cost of New Type Asphalt Pavement binder, is had relative to SBS modified pitch
Energy-saving and environmental protection, it is easy to use the advantages of.Thus production high-performance, high-quality emulsion SBS modified pitch pair
Highway construction has very great meaning.
At present, solid SBS is prepared after mix first makes SBS modified pitch again at high temperature by (1) with pitch
Into the technique of emulsified modified asphalt, equipment for production of emulsified bitumen is had high demands, complex process, and SBS is in pitch
Middle content is low, and the performance of emulsified SBS modified asphalt can not meet high-grade highway use requirement.Such as adopting will
Matrix pitch first emulsifies, is mixed with SBS latex again the technique of emulsified modified asphalt, then to emulsified asphalt
Equipment requirement is low, process is simple, can improve SBS contents in pitch, and the property of emulsified SBS modified asphalt
Can meet high-grade highway use requirement；(2) preparation method of existing SBS modified pitch is to use solid
SBS grinds and stirs development by colloid mill in adding heated bitumen, modified asphalt device investment greatly, complex process,
High energy consumption, such as prepares SBS modified pitch using liquid SBS latex, it is possible to decrease modified asphalt device investment,
Process is simple, energy consumption are low.Thus the SBS latex technologies of preparing of exploitation function admirable are significant.
The technology of preparing of existing SBS latex be by solid SBS finished products be dissolved in organic solvent again plus emulsifying agent,
Water, and some auxiliary agents carry out emulsification and are prepared from.Publication No. CN102936345A patent discloses one
The preparation method of SBS latex is planted, emulsifying agent, solvent is mixed with SBS, water is slowly added to into mixture
In, after placing 30min, add stabilizer and flocculant, then vacuum distillation to obtain SBS latex.This
Method prepares the technique of SBS latex, there is high product cost, performance difference and not there is versatility etc. to lack
Point.Crosslinked at low temperature emulsified SBS modified asphalt additive disclosed in Publication No. CN103965492A patent
Preparation method, Publication No. CN1580119A patent disclose a kind of preparation method of latex composition, open
Number a kind of preparation method of thermoplastic elastomer (TPE) aqueous emulsifying dispersion solution is disclosed for CN1443783A patents,
Publication No. CN102089376A patent discloses a kind of preparation method of artificial latex, in these patents
The shortcomings of all there is high complex process, product cost and performance difference in method.Existing patent is using by solid
SBS products are dissolved in corresponding organic solvent and prepared latex later, therefore there is the high cost of product, usability
Can be poor the shortcomings of, the performance indications of prepared modified emulsifying asphalt can not meet high-grade highway use requirement.
The content of the invention
For the existing defect for preparing SBS latex preparation technology presence, the purpose of the present invention is to be
A kind of low cost of offer, operating procedure are simple, performance is good, are applicable to modified emulsifying asphalt or modified drip
The method of blue or green SBS latex.
In order to realize the technical purpose of the present invention, the invention provides one kind is prepared for modified emulsifying asphalt or is changed
The method of the SBS latex of property pitch, the method is that SBS hexamethylene glues are added to containing initiator
After emulsification pretreatment in the aqueous solution of the hydrophilic monomer with thiazolinyl, the stirring reaction 2～3 at a temperature of 45～65 DEG C
Hour, partial solvent is extracted, SBS latex is obtained final product.
In technical scheme first using SBS hexamethylenes glue as raw material by connecing in its double bond
Branch hydrophilic radical obtains modified poly SBS latex by emulsion dispersion simultaneously.The method of the present invention is with industry
Intermediate products SBS hexamethylenes glue in finished product SBS production processes is raw material, produces SBS latex
Cost is substantially reduced, and the SBS latex for preparing can be applicable to cationic, anionic and nonionic
Being modified for type emulsified asphalt, can also replace finished solid SBS modified to heated bitumen.
SBS hexamethylene glues in technical solution of the present invention are to be prepared by a conventional method to obtain：It is with fourth two
Alkene, styrene are monomer, and hexamethylene is solvent, and butyl lithium is initiator, and tetrahydrofuran (THF) is structure
Conditioning agent, silicon tetrachloride etc. be coupling agent, Jing anionic polymerisations synthesis line style (typical structure S-B-S) or
Multi-arm star-shaped (typical structure (SB)4SI SBS hexamethylene glues), are referred to as SBS by custom；Or again
It is the chosen property of catalyst system and catalyzing to butadiene segment in SBS molecules (including 1,2- structures and 1,4- structures) using cyclopentadienyl
Double bond carries out selection hydrogenation, and retains a part of double bond, obtains SBS hexamethylene glue (SBS solid contents
15～25%).SBS hexamethylenes glue with the difference of industry SBS asphalt modifiers is, by SBS hexamethylene glue
Liquid is further obtained industry SBS asphalt modifiers by steps such as cohesion, dehydration, expanded granulation, drying.
The preparation of the present invention also includes for the method for modified emulsifying asphalt or the SBS latex of modified pitch
Following preferred version：
In preferred scheme, SBS hexamethylene glues are the intermediate products in industrial SBS modifier production process.
In preferred scheme, SBS hexamethylene glues solid content is 15%～25%.
In preferred scheme, in SBS hexamethylene glues, SBS is the benzene synthesized by living anion polymerization method
Ethene and butadiene block copolymer, S are styrene block, and B is butadiene block, styrene list in SBS
Unit is 1 with the molar ratio of butadiene unit:1.5～1:4.
More preferably in scheme, in SBS, the degree of hydrogenation of butadiene unit is 60～98%.
More preferably in scheme, the hydrophilic monomer quality with thiazolinyl is SBS mass in SBS hexamethylene glues
0.1～5%.
In preferred scheme, containing initiator and the aqueous solution of the hydrophilic monomer with thiazolinyl includes following mass parts
Component：40～55 parts of water, 4～9 parts of emulsifying agent, 1～1.5 part of the hydrophilic monomer with thiazolinyl, defoamer 1～2
Part, 0.5～1 part of initiator.
More preferably in scheme, emulsifying agent is by split in emulsified asphalt or split emulsifying agent, polyethers slowly for producing
Emulsifying agent and inorganic salts compounding composition, wherein, split in emulsified asphalt or split emulsifying agent quality hundred slowly for producing
It is 45～58% to divide than content, and polyethers emulsifying agent mass percentage content is 37～50%, inorganic salts quality hundred
It is 1～5% to divide than content.
More preferably in scheme, polyethers emulsifying agent is that OP series and/or MOA are serial.
More preferably in scheme, inorganic salts are KCl, NaCl, K2SO4And Na2SO4In at least one.
In preferred scheme, defoamer is the organic defoamer of siliceous class.Most preferably dimethyl silicone polymer and/
Or silicone emulsion.
In preferred scheme, initiator is azo-initiator.Most preferably AIBN.
In preferred scheme, SBS hexamethylenes glue is not less than 12 with the mass ratio of water in the aqueous solution:7.
More preferably in scheme, the hydrophilic monomer with thiazolinyl is the monomer while containing sulfonic group and vinyl.
The method for preparing SBS latex of the present invention is comprised the following steps：
1) by 40～55 weight portion water, 4～9 parts by weight Emulsifier, 1～1.5 part by weight of hydrophilic monomer (as right
Vinylbenzenesulfonic acid sodium), 1～2 weight portion defoamer (such as dimethyl silicone polymer or silicone emulsion) and 0.5～1
Weight portion initiator (such as AIBN), is added in reactor, stirring be warming up to 50～80 DEG C premix be made into it is water-soluble
Liquid；
2) 250～450 weight portion SBS hexamethylene glues are added in the pre- mixed aqueous solution, and employing can
The colloid mill emulsification pretreatment of production emulsified asphalt forms latex；
3) 45～65 DEG C of stirring reactions are maintained the temperature at 2～3 hours, makes the upper hydrophily list of SBS strands grafting
Body (such as vinyl sodium benzosulfonate)；
4) vacuum pump pressure distillation is opened, hexamethylene and part water is extracted, SBS latex is obtained.
Hinge structure, the beneficial effect that technical solution of the present invention is brought：
The primary raw material that adopts of the present invention for the intermediate products SBS hexamethylene glues during industrial production SBS,
Gained SBS latex is compared needs again solubilizer dissolving using industrial SBS modifier product, then emulsify again and
The process program for extracting solvent can greatly save material and production cost；The present invention is grafted SBS strands
Hydrophilic monomer, prepared SBS latex solid content are high, and viscosity is low, and performance is good；And using this
The softening point of the modified emulsifying asphalt of the prepared SBS latex production of invention is high, and performance is excellent；Prepare SBS to be modified
Pitch, it is low that modified asphalt device invests little, process is simple, energy consumption.
As prepared latex is applicable to the emulsified asphalt of different type emulsifying agent preparation, it is a kind of function admirable
, can be applicable to cationic, anionic and nonionic emulsified asphalt it is modified, can also replace finished solid
SBS is applied to production SBS modified pitch modified to matrix pitch.
Specific embodiment
Following examples are intended to further illustrate present invention, rather than limit the claims in the present invention protection model
Enclose.
Comparative example 1
According to SBS latex of the application publication number disclosed in the Chinese invention patent of " 102936345 A of CN "
Preparation method prepares SBS latex.By SBS in SBS latex with the mass ratio of pitch in emulsified bases pitch it is
4:100, the SBS latex prepared by this comparative example is added in middle extra large 70# emulsified bases pitch, and is fully mixed
Close, make modified emulsifying asphalt.
Softening point is carried out to modified emulsifying asphalt obtained in the comparative example according to standard GB/T/T 4507-2014
Test, as a result as shown in table 1.
Comparative example 2
According to SBS latex of the application publication number disclosed in the Chinese invention patent of " 102936345 A of CN "
Preparation method prepares SBS latex.By SBS in SBS latex with the mass ratio of pitch in emulsified bases pitch it is
4:100, the SBS latex prepared by this comparative example is added in the 70# emulsified bases pitches of Shandong, and is fully mixed
Close, make modified emulsifying asphalt.
Softening point is carried out to modified emulsifying asphalt obtained in the embodiment according to standard GB/T/T 4507-2014
Test, as a result as shown in table 1.
Embodiment 1
300g DS-02 SBS emulsifying agents, 75g vinyl sodium benzosulfonates, 56g froth breakings are added in a kettle.
Agent, 23g initiators, and 3375g water, stir and are heated to 58 DEG C, add 17% content
SBS hexamethylene glue 14kg, the overground circulation of ON cycle cutting system stopped circulation, 55 DEG C of constant temperature after 10 minutes
Stirring reaction 2.5 hours, opens vacuum pumping negative pressure, is existed according to foam situation control vacuum in kettle
Between 0.03～0.06MPa, the SBS latex that 5.5kg solid contents are 40.7% is finally obtained.
It is 4 by the mass ratio of SBS in SBS latex and emulsified bases pitch studies on asphaltene:100, to middle extra large 70#
The SBS latex prepared by embodiment 1 is added in emulsified bases pitch, and is sufficiently mixed, make modified emulsifying
Pitch.Modified emulsifying asphalt obtained in the embodiment is softened according to standard GB/T/T 4507-2014
Point test, as a result as shown in table 1.
Embodiment 2
In a kettle. add 7kgDS-02 SBS emulsifying agents, 1.5kg sodium p styrene sulfonates, 3kg defoamers,
0.45kg initiators and 70kg water, stir and are warming up to 57 DEG C, add the SBS hexamethylenes of 17% content
Alkane glue 275kg, the overground circulation of ON cycle cutting system stop circulation, 56 DEG C of stirrings of constant temperature after 15 minutes
Reaction 2.3 hours, opens vacuum pumping negative pressure, is existed according to level of filler material control vacuum in kettle
0.03～0.06MPa.Finally obtain the SBS latex that 150kg solid contents are 32.6%.
Mass ratio by pitch in SBS in SBS latex and emulsified bases pitch is 4:100, it is newborn to Shandong 70#
The SBS latex prepared by embodiment 1 and 2 is added in changing matrix pitch, and is sufficiently mixed, make modified milk
Change pitch.Modified emulsifying asphalt obtained in embodiment 1 and 2 is entered according to standard GB/T/T 4507-2014
Row softening point is tested, as a result as shown in table 1.
The softening point contrast table of 1 comparative example of table and modified emulsifying asphalt obtained by embodiment
| Softening point | |
| Embodiment 1 | 65.3 |
| Comparative example 1 | 53.6 |
| Embodiment 2 | 67.8 |
| Comparative example 2 | 53.1 |
Can be obtained by table 1：Using process of the present invention, the latex prepared by with SBS glues as raw material
Softening point is apparently higher than common SBS latex.
Claims (15)
1. a kind of method for preparing the SBS latex for modified emulsifying asphalt or modified pitch, it is characterised in that
SBS hexamethylene glues are added to containing initiator and breast in the aqueous solution of the hydrophilic monomer with thiazolinyl, is sheared
After change, at a temperature of 45～65 DEG C, stirring reaction 2～3 hours, extract partial solvent, obtain final product SBS
Latex.
2. it is according to claim 1 to prepare SBS latex for modified emulsifying asphalt or modified pitch
Method, it is characterised in that described SBS hexamethylene glues be in industrial SBS modifier production process in
Between product.
3. the SBS glue prepared for modified emulsifying asphalt or modified pitch according to claim 1 and 2
The method of breast, it is characterised in that described SBS hexamethylene glues solid content is 15%～25%.
4. it is according to claim 3 to prepare SBS latex for modified emulsifying asphalt or modified pitch
Method, it is characterised in that SBS is the benzene synthesized by living anion polymerization method in SBS hexamethylene glues
Ethene and butadiene block copolymer, S are styrene block, and B is butadiene block, styrene list in SBS
Unit is 1 with the molar ratio of butadiene unit:1.5～1:4.
5. it is according to claim 4 to prepare SBS latex for modified emulsifying asphalt or modified pitch
Method, it is characterised in that the degree of hydrogenation of butadiene unit is 60～98% in described SBS.
6. the method for preparing the SBS latex for emulsified modified asphalt according to claim 1, which is special
Levy and be, the described hydrophilic monomer quality with thiazolinyl is SBS mass in SBS hexamethylene glues
0.1～5%.
7. it is according to claim 1 to prepare SBS latex for modified emulsifying asphalt or modified pitch
Method, it is characterised in that it is described containing initiator and the hydrophilic monomer with thiazolinyl the aqueous solution include it is following
Content of component：40～55 parts of water, 4～9 parts of emulsifying agent, 1～1.5 part of the hydrophilic monomer with thiazolinyl, froth breaking
1～2 part of agent, 0.5～1 part of initiator.
8. it is according to claim 7 to prepare SBS latex for modified emulsifying asphalt or modified pitch
Method, it is characterised in that described emulsifying agent split in emulsified asphalt or split slowly emulsifying agent, poly- by for producing
Ethers emulsifying agent and inorganic salts compounding composition, wherein, split in emulsified asphalt or split emulsifying agent matter slowly for producing
Amount degree is 45～58%, and polyethers emulsifying agent mass percentage content is 37～50%, inorganic salts matter
Amount degree is 1～5%.
9. it is according to claim 8 to prepare SBS latex for modified emulsifying asphalt or modified pitch
Method, it is characterised in that described polyethers emulsifying agent is that OP series and/or MOA are serial.
10. the SBS latex prepared for modified emulsifying asphalt or modified pitch according to claim 8
Method, it is characterised in that described inorganic salts be KCl, NaCl, K2SO4And Na2SO4In at least
It is a kind of.
The 11. SBS latex prepared for modified emulsifying asphalt or modified pitch according to claim 7
Method, it is characterised in that described defoamer be the organic defoamer of siliceous class.
The 12. SBS latex prepared for modified emulsifying asphalt or modified pitch according to claim 11
Method, it is characterised in that described defoamer is dimethyl silicone polymer and/or silicone emulsion.
The 13. SBS latex prepared for modified emulsifying asphalt or modified pitch according to claim 7
Method, it is characterised in that described initiator be azo-initiator.
The 14. SBS latex prepared for modified emulsifying asphalt or modified pitch according to claim 1
Method, it is characterised in that described SBS hexamethylenes glue is not low with the mass ratio of water in the aqueous solution
In 12:7.
15. preparations according to claim 1,6 or 7 are for modified emulsifying asphalt or the SBS of modified pitch
The method of latex, it is characterised in that the described hydrophilic monomer with thiazolinyl is for simultaneously containing sulfonic group and ethene
The monomer of base.
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| CN201510642070.1A CN106554470B (en) | 2015-09-30 | 2015-09-30 | A method of preparing the Aggregate SBS latex for modified emulsifying asphalt or modified pitch |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804316A (en) * | 2019-11-14 | 2020-02-18 | 湖北大学 | Cationic system high-solid-content SBS (styrene butadiene styrene) modified emulsified asphalt |
| CN111164106A (en) * | 2017-10-11 | 2020-05-15 | 日本瑞翁株式会社 | Method for producing polymer latex |
| CN111205660A (en) * | 2020-01-19 | 2020-05-29 | 山东大山路桥工程有限公司 | Process method for preparing foam SBS modified asphalt and mixture from SBS latex |
| CN111218008A (en) * | 2019-11-14 | 2020-06-02 | 湖北大学 | High-stability SBS emulsion for emulsified asphalt |
| CN113683898A (en) * | 2021-09-02 | 2021-11-23 | 曾亮亮 | Asphalt modifier, modified asphalt and preparation method |
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| CN1554700A (en) * | 2003-12-25 | 2004-12-15 | 中国石化集团巴陵石油化工有限责任公 | Process for preparing SBS water emulsion |
| CN101407563A (en) * | 2007-10-09 | 2009-04-15 | 中国石油化工集团公司 | Method for polarizing polymer |
| JP4784081B2 (en) * | 2004-12-01 | 2011-09-28 | 株式会社ブリヂストン | Tread rubber composition for tire and pneumatic tire |
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| CN1365986A (en) * | 2001-01-19 | 2002-08-28 | 巴陵石化岳阳石油化工总厂 | Process for improving compatible stability between SBS and asphalt |
| CN1554700A (en) * | 2003-12-25 | 2004-12-15 | 中国石化集团巴陵石油化工有限责任公 | Process for preparing SBS water emulsion |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111164106A (en) * | 2017-10-11 | 2020-05-15 | 日本瑞翁株式会社 | Method for producing polymer latex |
| CN111164106B (en) * | 2017-10-11 | 2022-03-01 | 日本瑞翁株式会社 | Method for producing polymer latex |
| CN110804316A (en) * | 2019-11-14 | 2020-02-18 | 湖北大学 | Cationic system high-solid-content SBS (styrene butadiene styrene) modified emulsified asphalt |
| CN111218008A (en) * | 2019-11-14 | 2020-06-02 | 湖北大学 | High-stability SBS emulsion for emulsified asphalt |
| CN111205660A (en) * | 2020-01-19 | 2020-05-29 | 山东大山路桥工程有限公司 | Process method for preparing foam SBS modified asphalt and mixture from SBS latex |
| CN111205660B (en) * | 2020-01-19 | 2021-10-29 | 山东大山路桥工程有限公司 | Process method for preparing foam SBS modified asphalt and mixture from SBS latex |
| CN113683898A (en) * | 2021-09-02 | 2021-11-23 | 曾亮亮 | Asphalt modifier, modified asphalt and preparation method |
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| CN106554470B (en) | 2018-12-25 |
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