CN109134788A - A kind of carboxyl end group SBS, preparation and its application in asphalt modification - Google Patents

A kind of carboxyl end group SBS, preparation and its application in asphalt modification Download PDF

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Publication number
CN109134788A
CN109134788A CN201710513192.XA CN201710513192A CN109134788A CN 109134788 A CN109134788 A CN 109134788A CN 201710513192 A CN201710513192 A CN 201710513192A CN 109134788 A CN109134788 A CN 109134788A
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sbs
end group
carboxyl end
preparation
reaction
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CN109134788B (en
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宋丽莉
梁红文
严绍敏
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China Petroleum and Chemical Corp
Sinopec Baling Co
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China Petroleum and Chemical Corp
Sinopec Baling Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention discloses a kind of carboxyl end group SBS, have the structures such as epoxy addition flexible bond, ester bond and carboxyl end group.The invention also discloses the preparation methods of the carboxyl end group SBS, and active anion SBS block polymer is made using anionic polymerisation process；Anion SBS block polymer and epoxy hydrocarbon compound are subjected to ring-opening reaction, obtain active oxygen anion SBS block polymer；Active oxygen anion SBS block polymer and anhydride compound carry out end capping reaction；End capping reaction is terminated after terminating, is post-processed, and the carboxyl end group SBS is obtained.In addition, the application in terms of being applied to asphalt modification the invention also discloses the carboxyl end group SBS.Carboxyl end group SBS of the present invention can obviously improve the comprehensive performance of pitch, reduce isolation value, to improve the transport storage stability of modified pitch.In addition, carboxyl end group SBS preparation method of the present invention is simple, is easy industrializing implementation.

Description

A kind of carboxyl end group SBS, preparation and its application in asphalt modification
Technical field:
The invention belongs to polymer modified asphalt technical fields, and it is embedding to be related to a kind of carboxyl end group functionalized styrene/butadiene Section polymer preparation method and its for modified pitch improve storage stability.
Technical background:
S-B-S block polymer (SBS) is a kind of thermoplastic elastomer (TPE), have it is good elasticity, Self-reparability and crack self-healing are deformed, to the cold plasticity of pitch, high-temperature stability, ageing-resistant, adhesiveness, wearability and is made It is all improved significantly with the service life, has become road asphalt modifier most commonly used in the world at present.But SBS and drip Green composition, structural difference are larger, are difficult to form stable system when being blended, easily occur during thermmal storage polymer and Pitch phenomenon of phase separation is brought so the most important disadvantage of SBS modified pitch is exactly that hot storage stability is poor to production and use Larger inconvenience.
The characteristics of solving the problems, such as SBS and bitumen compatibility at present, mainly contain unsaturated double-bond using it carries out A variety of modifications are concentrated mainly on two aspect of epoxidation and grafted maleic anhydride of SBS.The China of Publication No. CN1365986A is specially Sharp document discloses a kind of raising SBS stable method compatible with pitch, and segment polarity is formed on SBS using chemical graft process Group reaches SBS and matrix pitch compatible stability, and the compound for being used to be grafted is mainly anhydride chemical combination containing double bonds Object.The Chinese patent literature of Publication No. CN102964850A discloses a kind of Epoxidized SBS modified asphalt and its production technology, Using toluene as solvent, epoxidized SBS in situ is carried out to SBS with formic acid and hydrogen peroxide and is modified, the epoxidized SBS of preparation increases The polarity of SBS improves the compatibility and storage stability of SBS and matrix pitch with its modified pitch produced.However it is such Method will be by macromolecular secondary response, at high cost, complex process, destroys the complete of original molecule chain after big molecular modification Property, self performance is affected.
And the method for using functionalized initiators or end technology in-situ polymerization, the synthetic molecules end of the chain have polarity or can be anti- Answer the SBS of functional group.It neither will increase cost, and the integrality of SBS original molecule chain will not be destroyed.Draw on SBS molecular chain-end Enter polar group, the compatibility of SBS and pitch can be improved, fundamentally solves the problems, such as that SBS modified pitch storage stability is poor, Improve the compatibility of SBS and pitch simultaneously.For example, the Chinese patent literature of Publication No. CN101041708A discloses a kind of conjunction At the method for terminal amido SBS and its application in modified pitch, a kind of aminated styrene/fourth of end group is specifically disclosed Diene/polystyrene ternary segmented copolymer preparation method, and it is used for modified pitch, it can obviously improve modified pitch Can, isolation degree be reduced, to improve storage stability.
In addition, improving SBS modified pitch storage stability also frequently with asphalt stabilizer, but it not can solve compatibility and asks Topic.For example, the Chinese patent literature of Publication No. CN1923901A discloses the synthesis of copolymer of terminal carboxyl styrene/butadiene And its method that stable modified pitch is stored in preparation, it uses carbon dioxide for the terminator of anionic polymerisation, is prepared for end carboxylic Base SBS.It is mixed, can effectively reduce the isolation degree of SBS modified pitch and significantly improved with pitch using prepared carboxyl end group SBS Storage stability.It is this directly to react to obtain carboxyl end group compound, this side with high-purity carbon dioxide with active polymer ends Method side reaction is more, generates a large amount of diploid ketone form structure and triploid alcohol structure at room temperature, holds carboxylic in order to obtain Based products often add a large amount of polar additives and react at -78 DEG C, at high cost, cumbersome to be unfavorable for industrial production.
Summary of the invention:
The purpose of the present invention is to provide a kind of carboxyl end group SBS.
The second object of the present invention is the provision of the preparation method of the carboxyl end group SBS, using anionic polymerisation skill The SBS of carboxyl is contained in art, preparation end, it is intended to simplify preparation process, reduce preparation cost, make it suitable for industrial production.
It is a third object of the invention to provide application of the carboxyl end group SBS in field of asphalt modification, passes through the end The addition of carboxyl SBS, it is intended to which the compatibility for improving SBS and pitch improves the comprehensive performance and storage stability of modified pitch.
A kind of carboxyl end group SBS, the structure with formula 1 or formula 2:
In formula 1, n1For 0~2 integer；R1、R2It is alone the alkyl of H, C1~4；X is that carbon number is 6 and alkyl below；
In formula 2, n2For 0~4 integer；Y is that carbon number is 6 and alkyl below.
The compound of structure of the present invention has unexpected excellent properties in terms of asphalt modification；The structure In introduce epoxy addition soft segment, the ester bond adjacent with carboxylic acid and the carboxylic acid structure；Pass through the flexible chain The interaction of section, ester bond and carboxylic acid ester bond, can promote the comprehensive performance of pitch, hence it is evident that improve the stability of modified pitch.
Preferably, the carboxyl end group SBS, in formula 1, n1For 0, an integer of 1 or 2；Preferably 0 or 1；Further preferably It is 0.
In formula 1, R1、R2It is alone the alkyl that H, carbon number are 1~4, the alkyl is, for example, alkyl (linear chain or branched chain Alkyl)；Olefin alkylation, alkyl alkylene, alkynes alkyl, alkyl alkynes base etc.；The preferably alkyl of H, C1~4；Into one Step is preferably H, methyl, ethyl.
Still more preferably, R1For H；R2For H, methyl or ethyl.
X is that carbon number is 6 and alkyl below；The alkyl is, for example, alkyl, alkylene, alkynes base, phenyl etc..
Preferably, X is the alkylene or phenyl of the alkyl of C2~4, C2~4.
Still more preferably, the X is ethylidene (- CH2-CH2-)；The ethylidene that methyl or ethyl replace；Alkylene (- CH=CH-)；The alkylene that methyl or ethyl replace；Or
Still more preferably, the X is ethylidene (- CH2-CH2-)；(-CH(CH3)-CH2-)；Alkylene (- CH= CH-)；Methyl alkylene (- C (CH3)=CH-)；Or
Y is that carbon number is 6 and alkyl below；The alkyl is, for example, alkyl, alkylene, alkynes base, phenyl etc..
Preferably, Y is the alkylene or phenyl of the alkyl of C2~4, C2~4.
Still more preferably, the Y is ethylidene (- CH2-CH2-)；The ethylidene that methyl or ethyl replace；Alkylene (- CH=CH-)；The alkylene that methyl or ethyl replace；Or
Still more preferably, the Y is ethylidene (- CH2-CH2-)；(-CH(CH3)-CH2-)；Alkylene (- CH= CH-)；Methyl alkylene (- C (CH3)=CH-)；Or
Preferably, in formula 2, n2It is 3 or 4.
Preferably, the mass ratio of styrene block and butadiene block is 20: 80~50 in the carboxyl end group SBS: 50。
The present invention also provides the preparation methods of the carboxyl end group SBS described in one kind, are made and are lived using anionic polymerisation process Property anion SBS block polymer；Anion SBS block polymer and the epoxy hydrocarbon compound of formula 3 are subjected to ring-opening reaction, Obtain the active oxygen anion SBS block polymer of formula 4；The anhydride chemical combination of active oxygen anion SBS block polymer and formula 5 Object carries out end capping reaction；End capping reaction is terminated after terminating, is post-processed, and the carboxyl end group SBS is obtained；
In formula 3, n1For 0~2 integer；R1、R2It is alone the alkyl of H, C1~4；n2For 0~4 integer；
In formula 5, X is that carbon number is 6 and alkyl below；Y is that carbon number is 6 and alkyl below.
Synthetic method of the present invention, first introduce negative oxygen ion reduce anion end active, then with anhydride reaction.It should Method reaction condition is mild, and side reaction is few, and functionalization is high-efficient, and production cost is low, is suitble to industrial mass production.What is used should Method can reduce the cost of SBS, to help to reduce the cost using the carboxyl end group SBS modified pitch.
The method that the present invention uses is uses anhydride substance polarity to block again by epoxy hydrocarbon compound, the end carboxylic of preparation Base SBS side reaction is few, and operating procedure is simple, at low cost.Method compared to logical high-purity carbon dioxide is more easily implemented industrial life It produces.
Preferably, by comprising non-polar hydrocarbon solvent, styrene, polar modifier, organic lithium initiator solution into The reaction of row one-step polymerization；Butadiene is added in the reaction solution reacted to one-step polymerization, carries out two sections of polymerization reactions；It is poly- to two sections again It closes and adds styrene in the reaction solution of reaction, carry out three stage polymerization reaction, obtain the active anion SBS block polymerization Object.
Preferably, the organic lithium initiator includes n-BuLi, s-butyl lithium, methyl butyl lithium, phenyl butyl At least one of lithium, naphthalene lithium, cyclohexyl lithium, dodecyl lithium.
Further preferably, the organic lithium initiator is n-BuLi.
The additional amount of the organolithium is determined by the polymer molecular weight designed.
Preferably, the polar modifier includes tetrahydrofuran (THF), ether, ethyl methyl ether, methyl phenyl ethers anisole, hexichol Ether, glycol dimethyl ether (DME), diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ethylether, triethylamine, 6-methyl phosphonic triamide, tetramethyl At least one of base ethylenediamine.
Further preferably, the polar modifier is tetrahydrofuran.The study found that using the effect of tetrahydrofuran used Fruit is best.
Preferably, the content of the polar modifier in the starting soln of one-step polymerization reaction is 50~500ppm；Into one Step is preferably 100~300ppm.
Preferably, the non-polar hydrocarbon solvent includes pentane, hexane, octane, heptane, at least one in hexamethylene Kind；Further preferably hexamethylene.
Preferably, the reaction temperature of one-step polymerization reaction, the reaction of two sections of polymerization reactions, three stage polymerization is 50-70 DEG C； Wherein, the time that one-step polymerization reaction, three stage polymerization react is 20~40min；The time of two sections of polymerization reactions is 30-50min.
In the epoxy hydrocarbon compound of formula 3, R1、R2、n1、n2Selection range and formula 1 or formula 2 in it is identical.
Preferably, the epoxy hydrocarbon compound includes ethylene oxide, and 1,2- propylene oxide, 2,3- epoxy butanes, At least one of oxetanes, 7-oxa-bicyclo[4.1.0；Further preferably 7-oxa-bicyclo[4.1.0.
Preferably, epoxy hydrocarbon compound and organic lithium initiator molar ratio are 0.6: 1~1.5: 1.
Further preferably, epoxy hydrocarbon compound and organic lithium initiator molar ratio are 1~1.25: 1.
The temperature of ring-opening reaction is 50~70 DEG C；Reaction time 10-30min.
It is identical in the selection range and formula 1 or formula 2 of X, Y in the anhydride compound of formula 5.
Preferably, the anhydride compound includes adipic anhydride, succinic anhydride, maleic anhydride, methylene At least one of succinic anhydride (dimethyl succinic acid acid anhydride), dimethyl succinic acid acid anhydride, phthalic anhydride；Further preferably along fourth Enedioic acid acid anhydride.
Preferably, anhydride compound and organic lithium initiator molar ratio are 0.5: 1~2: 1.
Further preferably, anhydride compound and organic lithium initiator molar ratio are 0.5~1.5: 1.
The temperature of end capping reaction process is 50~70 DEG C；Reaction time 20-50min.
Described one section, two sections, three stage polymerization reaction, ring-opening reaction, end capping reaction is in anaerobic, anhydrous, inert nitrogen gas It is carried out under environment.
A kind of preparation method of preferred carboxyl end group SBS of the present invention, comprising the following steps:
Step (1): non-polar hydrocarbon solvent, styrene, polar modifier are added in polymeric kettle, stirred evenly, is heated up To 50-70 DEG C, organic lithium initiator is added, carries out one-step polymerization reaction, reaction time 20-40min；
Step (2): according to the design of S/B, two sections of butadiene progress for calculating quality is added into the reaction solution of step (1) Polymerization reaction, reaction temperature are 50-70 DEG C, time 30-50min；
Step (3): the styrene with one section of phase homogenous quantities is added into the reaction system of step (2), it is poly- to carry out third section It closes, temperature is 50-70 DEG C, time 20-40min；Obtain the solution comprising active anion SBS block polymer；
Step (4): being added epoxy hydrocarbon compound (solution) into the solution of step (3), carries out ring-opening reaction, adds Epoxy hydrocarbon compound and organic lithium initiator molar ratio are 0.6: 1~1.5: 1, and reaction temperature is 50~70 DEG C；Reaction time 10-30min；
Step (5): anhydride compound (solution) is added into the reaction solution of step (4) and carries out end capping reaction, adds Anhydride compound and organic lithium initiator molar ratio are 0.5: 1~2: 1, and reaction temperature is 50~70 DEG C；Reaction time 20- 50min；
Step (6): step (5) after reaction, is added ethyl alcohol and terminates reaction, and from polymeric kettle plastic emitting, antioxidant is added 1076 and 168, elutriation cohesion removing solvent is dry, obtains carboxyl end group SBS.
Preferably, the quality that the sum of styrene monomer that one-step polymerization and two sections of polymerizations add is added with divinylic monomer Than being 20: 80~50: 50.
The present invention also provides the application of the carboxyl end group SBS described in one kind, the modified additive as pitch.
In the present invention, the carboxyl end group SBS of the structure is added, light component in pitch can be improved to the swelling effect of SBS, Increase the compatibility with heavy constituent polar substances in pitch simultaneously.In the premise for not adding existing usual sulfur stabilizer Under, it still can obviously improve the compatibility of SBS and pitch, improve the performance and storage stability of modified pitch.
Preferably, the application, additive amount of the carboxyl end group SBS in pitch is 3~6wt%.
The present invention also provides a kind of modified pitch, including pitch to be processed and the carboxyl end group SBS.
The isolation value of the modified pitch is less than 5 DEG C.
Modified pitch is tested ductility and is executed by T 0605-2011 bitumen ductility test method, and test separation value presses T 0606- 2011 isolation experiments execute.
Modified pitch of the present invention can show good storage under the premise of adding sulfur stabilizer Deposit stability.
Innovative point of the invention and the utility model has the advantages that
This patent is related to a kind of synthesis that carboxyl end group is functionalized SBS and its application in modified pitch.In active benzene second First introduced after alkene-butadiene block copolymer macromolecular chain epoxy compounds end group carbanion be converted to end group oxygen bear from Son, then polymerize with anhydride compound, it protects the carboxyl in anhydride compound not to be substituted, forms the carboxylic function of end group SBS.This polar compound by the functionalized SBS modified pitch of carboxyl end group and pitch has good compatibility, improves The hot storage stability of modified pitch, makes it have preferably comprehensive performance.Synthetic method of the present invention is simple, reaction condition temperature With, be functionalized it is high-efficient, be conducive to industrialized production.
Studies have shown that it is not necessary that in the case where adding sulfur stabilizer, the carboxyl end group by the structure is functionalized The isolation value of pitch can be declined 90% or more, improve the storage stability of modified pitch, and improve SBS and pitch by effect Compatibility.
In addition, treatment process of the invention is simple, at low cost, process stabilizing in field of asphalt modification, it is easy to industrial metaplasia It produces, is more suitable for industrialization promotion application.
Specific embodiment
The following examples are further illustrations of the invention, rather than limitation is of the invention.
In the present invention, can molecular weight by GPC chromatographic determination polymer and its distribution, use tetrahydrofuran GPC chromatography Figure does calibration curve, by Q/SHBL.01.04.T.082-2013 standard test；
Modified pitch is tested ductility and is executed by T 0605-2011 bitumen ductility test method, and test softening point, separation value are pressed T 0606-2011 isolation experiment executes.
Embodiment 1
By 2800mL hexamethylene N2It is pressed into the stainless steel polymeric kettle of 5L, 50mL styrene is added, is preheating to 60-65 DEG C, with the n-BuLi initiation reaction 30min of 9.1mL (0.3mol/L), N is used after the completion of one section of reaction is basic2It is pressed into the fourth of 339mL Diene carries out second-stage reaction, 30min is stopped after high temperature, three sections of reactions of 50mL styrene progress are added, be added 1.7mL (2mol/L) 7-oxa-bicyclo[4.1.0 (additional amount with the molar ratio of active lithium be 1.2: 1) react 30min, it is suitable to add 5.4mL (2.5g/50mL) Anhydride maleique (additional amount and the molar ratio of active lithium be 1: 1) carries out end capping reaction, reacts and is basically completed after 30min, uses second Alcohol terminates.Polymerization glue is released from kettle, gpc analysis molecular chain conformation is done in sampling.It is added 0.25% and (accounts for dry glue quality point Number) antioxidant 1076 and 168, carry out elutriation cohesion after mixing evenly, it is dry.SBS blob of viscose is made and does asphalt modification application survey Examination.GPC test gained SBS number-average molecular weight is 11.0 × 104G/mol, molecular weight distribution 1.04.
Embodiment 2
With example 1, after difference is three sections of reactions, be added 1.4mL (2mol/L) 7-oxa-bicyclo[4.1.0 (additional amount and active lithium Molar ratio is 1: 1) reacting 30min, add 5.4mL (2.5g/50mL) maleic anhydride (mole of additional amount and active lithium Than being 1: 1) carrying out end capping reaction, react and be basically completed after 30min, terminated with ethyl alcohol.Polymerization glue is released from kettle, is sampled Do gpc analysis molecular chain conformation.The antioxidant 1076 and 168 of 0.25% (accounting for dry glue quality score) is added, after mixing evenly Elutriation cohesion is carried out, it is dry.SBS blob of viscose is made and does asphalt modification application test.GPC tests gained SBS number-average molecular weight 11.0×104G/mol, molecular weight distribution 1.04.
Comparative example 1
With example 1, difference be three sections reaction after, directly plus ethyl alcohol terminated.Polymerization glue is released from kettle, sampling is done Gpc analysis molecular chain conformation.The antioxidant 1076 and 168 of 0.25% (accounting for dry glue quality score) is added, stirs evenly laggard The cohesion of row elutriation, it is dry.SBS blob of viscose is made and does asphalt modification application test.GPC test gained SBS number-average molecular weight is 11.0 ×104G/mol, molecular weight distribution 1.02.
Embodiment 3
Amplification verifying
Polymeric kettle is added in preheated hexamethylene 1600L, temperature controls at 60-70 DEG C, 18Kg styrene is being added, is stirring It after mixing uniformly, is first broken with the butyl lithium of 0.6L (0.3mol/L) butyl lithium miscellaneous, then adds 2.18L (0.3mol/L) butyl lithium Cause one section of reaction, after one section of reaction 30min, 84Kg butadiene is added and carries out second-stage reaction, stops 30min after high temperature and is added 18Kg styrene carries out three sections of reactions, and the 7-oxa-bicyclo[4.1.0 (additional amount and the molar ratio of active lithium be 1: 1) that 110.7mL is added is anti- 30min is answered, 107g maleic anhydride (additional amount and the molar ratio of active lithium be 1: 1) is added and carries out end capping reaction, 30min Reaction is basically completed afterwards, is terminated with water.Gpc analysis molecular chain conformation is done in sampling.Indentation glue tank is added 0.25% and (accounts for dry glue Mass fraction) antioxidant 1076 and 168 stir evenly, then be pressed into condensing field, agglomerate, post-process drying, be packaged.SBS is made Glue sample does asphalt modification application test.GPC test gained SBS number-average molecular weight is 11.2 × 104G/mol, molecular weight distribution are 1.03。
Embodiment 4
Weigh 300g SK 70#Pitch is warming up to 160-170 DEG C in 500mL beaker in heating mantle, and 14g is added SBS glue sample (blob of viscose made from Examples 1 to 3 or comparative example 1), stirring premix 10min, then the shear rate in 4200r/min Lower stirring 20min is poured into mold and is surveyed SBS performance of modified bitumen such as following table 1. according to standard
The performance of 1 SBS modified pitch of table
SBS glue sample Needle penetration/mm Softening point/DEG C Ductility/5 DEG C, cm Isolation value/DEG C
Embodiment 1 47.6 77 20.5 2
Embodiment 2 46.8 75 20.8 2
Embodiment 3 46.5 78 21.2 4
Comparative example 1 45.5 74 18.2 23
As can be known from Table 1, using terminal group functional SBS modified pitch than SBS modified pitch ductility in comparative example 1 Height illustrates to improve by the compatibility of the functionalized SBS of carboxyl end group and pitch, improves the ductility of pitch.Modified pitch from Analysis value is to measure the important indicator of pitch hot storage stability, as seen from the table using terminal group functional SBS modified pitch from Analysis value is significantly reduced than the isolation value of non-terminal group functional SBS modified pitch, is illustrated that carboxyl end group functionalization SBS is significantly improved and is changed The hot storage stability of property pitch.It is found that performance is stablized after scale-up from the result of embodiment 3.

Claims (21)

1. a kind of carboxyl end group SBS, which is characterized in that the structure with formula 1 or formula 2:
In formula 1, n1For 0~2 integer；R1、R2It is alone the alkyl of H, C1~4；X is that carbon number is 6 and alkyl below；
In formula 2, n2For 0~4 integer；Y is that carbon number is 6 and alkyl below.
2. carboxyl end group SBS as described in claim 1, which is characterized in that in formula 1 or formula 2, X, Y are the alkane of C2~4 alone Base, C2~4 alkylene or phenyl.
3. carboxyl end group SBS as claimed in claim 1 or 2, which is characterized in that in formula 1, R1、R2It is alone H, methyl or ethyl； n1It is 0 or 1.
4. carboxyl end group SBS as claimed in claim 1 or 2, which is characterized in that in formula 2, n2It is 3 or 4.
5. such as the described in any item carboxyl end group SBS of Claims 1 to 4, which is characterized in that styrene block and butadiene block Mass ratio is 20: 80~50: 50.
6. a kind of preparation method of the described in any item carboxyl end group SBS of Claims 1 to 5, which is characterized in that poly- using anion Active anion SBS block polymer is made in conjunction method；By the epoxy hydrocarbon compound of anion SBS block polymer and formula 3 Ring-opening reaction is carried out, the active oxygen anion SBS block polymer of formula 4 is obtained；Active oxygen anion SBS block polymer and formula 5 anhydride compound carries out end capping reaction；End capping reaction is terminated after terminating, is post-processed, and the carboxyl end group SBS is obtained；
In formula 3, n1For 0~2 integer；R1、R2It is alone the alkyl of H, C1~4；n2For 0~4 integer；
In formula 5, X is that carbon number is 6 and alkyl below；Y is that carbon number is 6 and alkyl below.
7. the preparation method of carboxyl end group SBS as claimed in claim 6, which is characterized in that will include non-polar hydrocarbon solvent, benzene The solution progress one-step polymerization reaction of ethylene, polar modifier, organic lithium initiator；It is thrown in the reaction solution reacted to one-step polymerization Add butadiene, carries out two sections of polymerization reactions；Styrene is added into the reaction solution of two sections of polymerization reactions again, it is anti-to carry out three stage polymerization It answers, obtains the active anion SBS block polymer.
8. the preparation method of carboxyl end group SBS as claimed in claim 7, which is characterized in that the organic lithium initiator includes At least one of n-BuLi, s-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium, dodecyl lithium.
9. the preparation method of carboxyl end group SBS as claimed in claim 7, which is characterized in that the polar modifier includes four Hydrogen furans, ether, ethyl methyl ether, methyl phenyl ethers anisole, diphenyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ethyl At least one of ether, triethylamine, 6-methyl phosphonic triamide, tetramethylethylenediamine.
10. the preparation method of carboxyl end group SBS as claimed in claim 9, it is characterised in that；One-step polymerization reacts in starting soln Polar modifier content be 50~500ppm.
11. the preparation method of carboxyl end group SBS as claimed in claim 7, it is characterised in that；The non-polar hydrocarbon solvent packet Include at least one of pentane, hexane, octane, heptane, hexamethylene.
12. the preparation method of carboxyl end group SBS as claimed in claim 7, it is characterised in that；One-step polymerization reaction, two sections of polymerizations The reaction temperature that reaction, three stage polymerization react is 50-70 DEG C；Wherein, one-step polymerization reaction, the time of three stage polymerization reaction are equal For 20~40min；The time of two sections of polymerization reactions is 30-50min.
13. such as the preparation method of the described in any item carboxyl end group SBS of claim 6~12, it is characterised in that；The epoxy hydrocarbon Class compound include ethylene oxide, 1,2- propylene oxide, 2,3- epoxy butane, oxetanes, in 7-oxa-bicyclo[4.1.0 at least It is a kind of.
14. the preparation method of carboxyl end group SBS as claimed in claim 13, it is characterised in that；Epoxy hydrocarbon compound with it is organic Lithium initiator molar ratio is 0.6: 1~1.5: 1.
15. the preparation method of carboxyl end group SBS as claimed in claim 13, it is characterised in that；The temperature of ring-opening reaction be 50~ 70℃；Reaction time 10-30min.
16. such as the preparation method of the described in any item carboxyl end group SBS of claim 6~12, it is characterised in that；The anhydride Compound includes adipic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, dimethyl succinic acid acid anhydride, O-phthalic At least one of acid anhydrides.
17. the preparation method of carboxyl end group SBS as claimed in claim 16, it is characterised in that；Compound anhydride draws with organolithium Sending out agent molar ratio is 0.5: 1~2: 1.
18. the preparation method of carboxyl end group SBS as claimed in claim 16, it is characterised in that；The temperature of end capping reaction process is 50~70 DEG C；Reaction time 20-50min.
19. any one of carboxyl end group SBS described in a kind of Claims 1 to 5 or claim 6~18 preparation method are made Carboxyl end group SBS application, it is characterised in that；Modified additive as pitch.
20. application as claimed in claim 19, it is characterised in that；Additive amount of the carboxyl end group SBS in pitch be 3~ 6wt%.
21. a kind of modified pitch, it is characterised in that；Including the described in any item end carboxylics of pitch and Claims 1 to 5 to be modified Base SBS；The modified pitch isolation value is less than 5 DEG C.
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CN112646546A (en) * 2020-12-22 2021-04-13 张学明 Bridge deck waterproof material and preparation method thereof

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CN105237695A (en) * 2015-10-14 2016-01-13 中国石油化工股份有限公司 Preparation method of epoxy group-terminated styrene-butadiene-styrene (SBS) ternary block copolymer
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