CN109504018A - A kind of polymer composition of two arms styrene-conjugated diene and preparation and the application in asphalt modification - Google Patents
A kind of polymer composition of two arms styrene-conjugated diene and preparation and the application in asphalt modification Download PDFInfo
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- CN109504018A CN109504018A CN201710831518.3A CN201710831518A CN109504018A CN 109504018 A CN109504018 A CN 109504018A CN 201710831518 A CN201710831518 A CN 201710831518A CN 109504018 A CN109504018 A CN 109504018A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of polymer compositions of two arm styrene-conjugated dienes, include (SB)2Bis- arm polymer of X and the asymmetric two arm polymer of (SB) X (IS)；SB is Styrene-Butadiene block polymeric arms；IS is styrene-isoprene block polymer arm；X is coupling agent residue.The invention also includes the preparation method of the polymer composition and applications.Polyisoprene is regularly introduced in traditional SBS structure, the better toughness of material is invested, the elongation of synthetic polymer improves, better toughness is presented as after modified pitch, again since the viscosity of polyisoprene is stronger compared with polybutadiene, there is better viscosity with the sill such as building stones, miberal powder etc. paved the way, further improves the anti-rut behavior on road surface.In addition, the introducing of isoprene, improves the mobility of polymer, better processing performance is presented as in Modified Bitumen Manufacturing.
Description
Technical field
The present invention relates to field of asphalt modification, and in particular to it is a kind of with two arms and include asymmetric radiation copolymer drip
It is green polymer-modified.
Technical background
Modified pitch can be used for various uses what follows, such as pave the way, waterproof roll, compartment piece, roofing etc..With
The development of society, people are higher and higher to the performance requirement of modified pitch, and researchers are changed by adding various polymer
The performance of kind pitch, if ethene-vinyl acetate is copolymerized, latex, ethylene-ethyl acrylate copolymer includes conjugated diene and second
The copolymer etc. of alkenyl aroma hydrocarbon.However, ethene-vinyl acetate copolymerization and ethylene-ethyl acrylate copolymer poor performance at low temperatures,
Toughness is also poor, and poor aggregation binding performance is shown when paving the way.Latex modified asphalt has preferable cryogenic property, but high temperature
Performance is insufficient, and there is also some problems for processing aspect.
The copolymer of conjugated diene and vinylaromatic hydrocarbon can preferably solve some shortcomings existing for above-mentioned material.It is open
It number discloses for the patent document of CN1190459C and discloses a kind of block copolymer composition for being modified to pitch.
Wherein containing there are two types of block polymers: a kind of block polymer contains at least two polymer blocks of mono alkenyl aromatic compound
With at least one copolymer block containing conjugated diene compound；Another block polymer contains mono alkenyl aromatic compound
At least one polymer blocks is with main comprising conjugated diolefin polymer.This kind of polymer modified asphalt is for improving drainage performance
And environmental noise is reduced, softening point with higher and mechanical strength, but its glutinous toughness is insufficient.
The patent document of Publication No. CN101300306 discloses a kind of polymer composition, and it includes a linear benzene second
Alkene-butadiene-styrene coupling block copolymer is together with a large amount of diblock copolymers.This kind of Polymer Processing performance is good, but produces
The dynamic viscosity of product is insufficient, and high-temperature behavior is also to be improved.
The asymmetric radiation shape block copolymer of four arms in Publication No. CN1138055A, containing there are two conjugated diene and
The copolymerization arm of vinyl-arene and two conjugated diene homopolymers or copolymer arm are the star polymerization of block copolymerization or homopolymerization
Object, this general molecular weight of polymer is larger, is not easy to disperse in pitch, is used for asphalt modification poor processability, for porous
Road surface is not able to satisfy the requirement of processing.
In the prior art, there is also many technical problems, this field needs a kind of asphalt modification polymerization with high performance
Object.
Summary of the invention
The purpose of the present invention is to provide a kind of polymer compositions of two arm styrene-conjugated dienes.
It is a second object of the invention to provide a kind of preparation of the polymer composition of two arm styrene-conjugated dienes
Method.
It is a third object of the invention to provide application of the polymer composition in terms of asphalt modification.
A kind of polymer composition of two arms styrene-conjugated diene, comprising (SB)2Bis- arm polymer of X and (SB) X
(IS) asymmetric two arm polymer；SB is Styrene-Butadiene block polymeric arms；IS is poly- for styrene-isoprene block
Close object arm；X is coupling agent residue.
The present inventor passes through numerous studies discovery, (SB)2Bis- arm polymer of X and the asymmetric two arm polymer of (SB) X (IS)
With good synergy, (SB) X (IS) has better adhesive property and toughness, increases the intermiscibility with other materials, has
Helping collaboration improves glutinous toughness, dynamic viscosity and the high-temperature behavior etc. of pitch.
The inventors discovered that in the polymer composition, suitable (SB)2Bis- arm polymer of X and (SB) X (IS)
Asymmetric two arm polymer contents facilitate the synergy for further promoting the two.
Preferably, in polymer composition, (SB)2Mass percent shared by bis- arm polymer of X be more than or equal to
50%；(SB) mass percent shared by the asymmetric two arm polymer of X (IS) is less than or equal to 50%.
Further preferably, in polymer composition, (SB)2Mass percent shared by bis- arm polymer of X is 50-80%.
(SB) mass percent 5~20% shared by the asymmetric two arm polymer of X (IS).
Preferably, the styrene weight of bonding is 10~50Wt% in polymer composition；(B is embedding for butadiene block
Section) and isoprene block (I block) in, 1,2- structural content be 5-40Wt%.
Preferably, the polymer also includes bi-block copolymer, the bi-block copolymer includes SB block
At least one of polymer, SI block polymer.
Preferably, mass percent shared by the bi-block copolymer is 5%-40% in polymer composition；
Preferably 5~20%.
Further preferably, in polymer composition, mass percent shared by SB block polymer is 5~20% (into one
Step preferably 5~8%)；Mass percent shared by SI block polymer is 5~20% (further preferably 5~13%).
Preferably, the polymer composition of the two arm styrene-conjugated dienes, includes following weight percent
Component:
(SB)2Bis- arm polymer 50-80% of X；
(SB) two arm polymer 5-20% of X (IS) asymmetry；
SB block polymer 5-20%；
SI block polymer 5-20%.
Further preferably, in the polymer composition, the weight percent of each component are as follows:
(SB)2Bis- arm polymer 65-72% of X；
(SB) two arm polymer 10-20% of X (IS) asymmetry；
SB block polymer 5-8%；
SI block polymer 5-13%.
In the present invention, the molecule of Styrene-Butadiene block polymeric arms, styrene-isoprene block polymer arm
Amount is 30000~100000 alone.
In SB block polymer, the ratio of S/B is 10~50.
In SI block polymer, the ratio of S/I is 10~30.
The present invention also provides the systems of the polymer of the two arm styrene-conjugated dienes for asphalt modification described in one kind
Preparation Method, comprising the following steps:
Step (1): activity SB block polymer and activity SI block polymer are made by anionic polymerisation respectively；
Step (2): active SB block polymer is mixed with coupling agent first, carries out one section of coupling reaction, obtains coupling reaction
Liquid；
Step (3): adding active SI block polymer into the coupling reaction liquid of step (2), carries out two sections of coupling reactions；
Step (4): step (3) after reaction, then is terminated, post-processes to obtain the polymer composition.
In preparation method of the present invention, active SB block polymer is preferably reacted with a site of coupling agent, raw
At one section of coupled product (being labeled as SBX-)；Another coupling site a part of one section of coupled product continues and remaining activity SB
Block polymer reaction generates (SB)2X；Another part is reacted with active SI block polymer again, and it is asymmetric to generate (SB) X (IS)
Two arm polymer.
Living polymer of the present invention, for it is being easy to get by anionic polymerisation, containing at least one work
The polymer of property group (such as carbanion).
In the present invention, the preparation process of active SB block polymer are as follows: will include styrene, polar modifier A, alkyl
The polymerisation in solution of lithium A, hydrocarbon solvent A；Butadiene is then added again to continue to polymerize, and obtains the active SB block polymer；
In the present invention, the preparation process of active SI block polymer are as follows: will include styrene, polar modifier B, alkyl
The polymerisation in solution of lithium B, hydrocarbon solvent B；Penta different diene is then added again to continue to polymerize, and obtains the active SI block polymerization
Object.
Preferably, lithium alkylide A, lithium alkylide B are independently chosen from butyl lithium and/or s-butyl lithium.
Lithium alkylide A, the dosage of lithium alkylide B are determining according to the molecular weight of designed SB segmented arms and SI segmented arms, point
Son amount control is 30000-100000.
Preferably, polar modifier A, polar modifier B are independently chosen from diethylene glycol dimethyl ether 2G, triglyme
3G, dipiperidinoethane DPE, ethylene glycol ethyl tert-butyl ether (ETBE) BEE, ethylene glycol propyl tertbutyl ether BPE, Ethylene Glycol Methyl tert-butyl
Ether MEB, tetramethylethylenediamine TMEDA, tetrahydrofuran THF, two or four oxygroup ethane DME, ethyl tetrahydrofurfuryl ether TEFE, N, N mono-
At least one of diformazan tetrahydrofurfuryl amine.
Preferably, the dosage of polar modifier A, polar modifier B are that (Kg is that reaction is molten to 10mg/kg~200mg/kg
The weight of agent).
Preferably, hydrocarbon solvent A, hydrocarbon solvent B be independently chosen from hexamethylene, pentane, hexane, heptane, in benzene at least
It is a kind of.
Preferably, the polymerization temperature of activity SB block polymer, activity SI block polymer preparation process is 20 DEG C
~100 DEG C, preferably 30~80 DEG C.
At a temperature of described, the temperature of styrene block polymerization process is 20 DEG C~100 DEG C, polymerization time 20-
40min；It then keeps at this temperature, continuing to polymerize with butadiene or pentadiene again, the time of polymerization is 20-40min；Respectively
Obtain active SB block polymer or activity SI block polymer.
In the present invention, the coupling agent is that there are two the compounds in coupling reaction site for tool；Also referred to as two arm coupling agents.
Preferably, coupling agent includes: dichloro-dimethyl silicon, dimethyl tin dichloride, dichloro dimethoxysilane, adjacent benzene two
At least one of formic acid dimethyl ester, epoxidized soybean oil, maleic anhydride.
Preferably, the molar ratio of coupling agent and active bi-block copolymer is (1: 2)~(1: 25).It is also contemplated that
The molar ratio of coupling agent and active single armed is 1: 2-1: 25.That is to say, coupling agent with (active SB block polymer and activity SI are embedding
Section polymer sum) molar ratio be 1: 2-1: 25.
30-80 DEG C of the temperature of coupling reaction.
The invention also includes a kind of preparation method of the polymer composition of two arm styrene-conjugated dienes, preparation steps
Suddenly include:
(a) add after styrene is sufficiently mixed with butadiene or penta different diene monomers respectively with alkyl lithium initiator continuous uniform
Enter reaction kettle, under polar modifier, anionic polymerisation is carried out in hydrocarbon solvent, after reacting 25min~60min, is made one group
Active styrene-butadiene or active styrene-isoprene random copolymerization polymers arm；
(b) the living polymer arm of the styrene-butadiene random copolymerization obtained with two arm coupling agent steps (a),
(c) coupling reaction is completed, and at most leaves a unreacted coupling position on coupling agent simultaneously,
(d) another group of styrene-isoprene activity random copolymerization object arm is added in the reaction system be coupled instead
It answers,
(e) it is terminated and is reacted with isopropanol after reaction, water vapor accumulation obtains the copolymerization of two arm asymmetric radiations after dry
Object.
The present invention also provides the applications of the polymer composition of two arm styrene-conjugated dienes described in one kind, are used as
Asphalt modification additive.
Preferably, additive amount of the polymer composition in pitch is 4.5- in the application
12wt%.
The present invention also provides a kind of modified pitch, include pitch to be modified and combination of polymers of the present invention
Object.
The softening temperature of the modified pitch is greater than 90 DEG C；Isolation value is less than 5 DEG C；Ductility is greater than 25cm.
Further preferably, in the modified pitch, needle penetration >=45dmm, softening point >=90 DEG C, ductility >=34cm, glue
Toughness >=24N.m, toughness >=18N.m, 90 DEG C of rotary viscosity 330Pa.s.
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 is suitable for such as porous pavements, has high softening-point, excellent prolongs
Malleability and storage stability.
The amount of molecular weight possessed by polymer of the invention and combinated styrene content can be in a wide range of interior variation.These are two embedding
The molecular weight of section polymeric arms is generally 30000 to the range for exceeding 100000.The content range of combinated styrene content of the present invention is
10%~50%.
The arm of Radial polymers and its arm number use the test method of gel permeation chromatography (GPC) in the present invention, the
Sampling carries out gpc analysis after the completion of the coupling of one step, that is, may know that the coupling degree of first coupled arm and the content of SB, to second
A different coupled arm samples carry out gpc analysis again after the reaction was completed, can analyze the content of total coupling degree and SI, then
GPC comparative analysis after being coupled with first time, the distribution situation of you can get it two dissimilar arms.
Beneficial effect
Polyisoprene is regularly introduced in traditional SBS structure, has invested the better toughness of material, synthetic polymer
Elongation improve, better toughness is presented as after modified pitch, and since the viscosity of polyisoprene is stronger compared with polybutadiene,
There is better viscosity with the sill such as building stones, miberal powder etc. paved the way, further improves the anti-rut behavior on road surface.In addition, different
The introducing of pentadiene, improves the mobility of polymer, and better processing performance is presented as in Modified Bitumen Manufacturing.
Specific embodiment
Some embodiments of the present invention are set forth below, so as to further illustrating its feature, but should not be limited thereto.
Embodiment 1- polymer 1:
1500g hexamethylene and 0.3g tetrahydrofuran are added in first reaction kettle, 3.4ml (0.5mol/l) is being added just
Butyl lithium is warming up to 50 DEG C as initiator, and 22g styrene is added in reaction kettle, reacts 25min, adds 88g isoamyl two
Alkene, it is spare after reaction 30 minutes.1500g hexamethylene and 0.3g tetrahydrofuran are added in second reaction kettle, 7.7ml is added
(0.5mol/l) n-BuLi is warming up to 50 DEG C as initiator, and 50g styrene is added in reaction kettle, reacts 25min, so
Afterwards plus then the dichlorodimethylsilane of 7.1ml (0.31mol/l) is added in 200g butadiene, reaction 30min in the kettle,
40min is reacted at 60 DEG C, sampling uses gel permeation chromatography (GPC), measures molecular weight product and distribution.Next in this portion
The styrene-isoprene polymer solution that first reactor is added in reaction system after dividing coupling, reacts at 60 DEG C
40min, allows the remainder of the intermediate of moiety to realize coupling, and methanol is added after the reaction was completed and terminates, it is molten to obtain polymer
Liquid；Sampling measures product using gel permeation chromatography (GPC) and is essentially two arm conjugates, illustrates there is two-arm SB's substantially originally
The SI of part two-arm has been accessed on polymer again.Then water vapor accumulation is dried to obtain polymer.SB polymer molecular weight is
63,900g/mol, SI polymer molecular weight are 64,080g/mol, and two blocks (SI and SB) content is 20%.
In polymer solution, (SB)2Bis- arm polymer 65% of X；
(SB) the asymmetric two arm polymer 15% of X (IS)；
SB block polymer 8%；
SI block polymer 12%.
Embodiment 2:
In the way of polymer 1, only changes butadiene and the additional amount of styrene SB polymerization initiator n-BuLi is
The additional amount of 3.85ml (0.5mol/l), SI polymerization initiator n-BuLi is 2.75ml (0.5mol/l), SB polymer molecule
It is 80,350g/mol that amount, which is 77,690g/mol, SI polymer molecular weight, and two block concentrations are 10%.
In polymer solution, (SB)2Bis- arm polymer 71% of X；
(SB) the asymmetric two arm polymer 19% of X (IS)；
SB block polymer 5%；
SI block polymer 5%.
Embodiment 3-6:
In the way of polymer 1, the line style coupled polymer of 4 kinds of different coupling agents is prepared, it is anti-that table 1 lists polymer
It answers and test result.
Table 1
The reaction for emphasizing different coupling agents, as two embedding structure distributions of other cases.
Embodiment 7:
1500g hexamethylene and 0.3g tetrahydrofuran are added in first reaction kettle, 3.4ml (0.5mol/l) is being added just
Butyl lithium is warming up to 50 DEG C as initiator, and 44 styrene are added in reaction kettle, reacts 25min, adds 66g isoamyl two
Alkene, it is spare after reaction 30 minutes.1500g hexamethylene and 0.3g tetrahydrofuran are added in second reaction kettle, 7.7ml is added
(0.5mol/l) n-BuLi is warming up to 50 DEG C as initiator, and 100g styrene is added in reaction kettle, reacts 25min,
Then plus then the dichlorodimethylsilane of 7.1ml (0.31mol/l) is added in 1500g butadiene, reaction 30min in the kettle,
40min is reacted at 60 DEG C, sampling uses gel permeation chromatography (GPC), measures molecular weight product and distribution.Next at this
The styrene-isoprene polymer solution of first reactor is added in reaction system after the coupling of part, it is anti-at 60 DEG C
40min is answered, the remainder of the intermediate of moiety is allowed to realize coupling, methanol is added after the reaction was completed and terminates, sampling uses
Gel permeation chromatography (GPC) measures product and is essentially two arm conjugates, illustrates have on the polymer of two-arm SB substantially again originally
The SI of part two-arm is accessed.Then water vapor accumulation is dried to obtain polymer.SB polymer molecular weight is 64,100g/mol,
SI polymer molecular weight is 65,030g/mol, and two blocks (SB and SI) content is 17.5%.
In polymer solution, (SB)2Bis- arm polymer 72% of X；
(SB) the asymmetric two arm polymer 10.5% of X (IS)；
SB block polymer 5.5%；
SI block polymer 12%.
Embodiment 8:
1500g hexamethylene and 0.3g tetrahydrofuran are added in first reaction kettle, 3.4ml (0.5mol/l) is being added just
Butyl lithium is warming up to 50 DEG C as initiator, and 25 styrene are added in reaction kettle, reacts 25min, adds 37.5g isoamyl
Diene, it is spare after reaction 30 minutes.1500g hexamethylene and 0.3g tetrahydrofuran are added in second reaction kettle, 7.7ml is added
(0.5mol/l) n-BuLi is warming up to 50 DEG C as initiator, and 100g styrene is added in reaction kettle, reacts 25min,
Then plus then the dichlorodimethylsilane of 6.1ml (0.31mol/l) is added in 1500g butadiene, reaction 30min in the kettle,
40min is reacted at 60 DEG C, sampling uses gel permeation chromatography (GPC), measures molecular weight product and distribution.Next at this
The styrene-isoprene polymer solution of first reactor is added in reaction system after the coupling of part, it is anti-at 60 DEG C
40min is answered, the remainder of the intermediate of moiety is allowed to realize coupling, methanol is added after the reaction was completed and terminates, sampling uses
Gel permeation chromatography (GPC) measures product and is essentially two arm conjugates, illustrates have on the polymer of two-arm SB substantially again originally
The SI of part two-arm is accessed.Then water vapor accumulation is dried to obtain polymer.SB polymer molecular weight is 65,020g/mol,
SI polymer molecular weight is 64,830g/mol, and two block concentrations are 19.5%.
In polymer solution, (SB)2Bis- arm polymer 68% of X；
(SB) the asymmetric two arm polymer 12% of X (IS)；
SB block polymer 6.5%；
SI block polymer 13%.
Comparative example:
1500g hexamethylene and 0.3g tetrahydrofuran are added in a kettle, 7.5ml (0.5mol/l) n-BuLi is added and makees
For initiator, 50 DEG C are warming up to, 50g styrene is added in reaction kettle, 25min is reacted, then plus 200g butadiene, reaction
Then the dichlorodimethylsilane of 5.1ml (0.31mol/l) is added in the kettle, 40min is reacted at 60 DEG C by 30min, sample
Using gel permeation chromatography (GPC), molecular weight product and distribution are measured.SB polymer molecular weight is 65,900g/mol, and two is embedding
The content of section SB is 19.3%.
In polymer solution, (SB)2Bis- arm polymer 80.7% of X；
SB block polymer 19.3%；
Sample Performance Properties Evaluation result:
1, matrix pitch 660g is accurately weighed, when being warming up to 180 DEG C；
2, polymer 54g and the 36g thermoplastic resin (rosin) in each embodiment are granulated mixing, are then added, 5min
Inside add.
3, temperature control is at 180~190 DEG C, then shears 30min, revolving speed 3500rpm；
4, it after shearing 30min, takes out after baking oven stands 1-2min and removes bubble removing；
5, performance of modified bitumen index is tested after pouring sample cooling.
The different sample modification asphalt performance results of table 1
* " standard specification for construction and acceptance of highway asphalt pavement (JTG F40-2004) ".
Claims (28)
1. a kind of polymer composition of two arm styrene-conjugated dienes, which is characterized in that include (SB)2Bis- arm polymer of X and
(SB) the asymmetric two arm polymer of X (IS)；SB is Styrene-Butadiene block polymeric arms；IS is that styrene-isoprene is embedding
Section polymeric arms；X is coupling agent residue.
2. the polymer composition of two arms styrene-conjugated diene as described in claim 1, which is characterized in that polymer group
It closes in object, (SB)2Mass percent shared by bis- arm polymer of X is greater than or equal to 50%；(SB) the asymmetric two arms polymerization of X (IS)
Mass percent shared by object is less than or equal to 50%.
3. the polymer composition of two arms styrene-conjugated diene as claimed in claim 2 or claim 3, which is characterized in that polymer
In composition, (SB)2Mass percent shared by bis- arm polymer of X is 50-80%.
4. the polymer composition of two arms styrene-conjugated diene as claimed in claim 3, which is characterized in that SB) X (IS)
Mass percent 5~20% shared by asymmetric two arm polymer.
5. the polymer composition of two arms styrene-conjugated diene as described in claim 1, which is characterized in that polymer group
It closes in object, the styrene weight of bonding is 10~50Wt%；In butadiene block (B block) and isoprene block (I block),
1,2- structural content is 5~40Wt%.
6. the polymer composition of two arms styrene-conjugated diene as claimed in any one of claims 1 to 5, which is characterized in that
The polymer also includes bi-block copolymer, and the bi-block copolymer includes SB block polymer, SI block polymerization
At least one of object.
7. the polymer composition of two arms styrene-conjugated diene as claimed in claim 6, which is characterized in that polymer group
It closes in object, mass percent shared by SB block polymer is 2~20%；Mass percent shared by SI block polymer is 2
~20%.
8. the polymer composition of two arms styrene-conjugated diene as claimed in claim 7, which is characterized in that polymer group
It closes in object, mass percent shared by the bi-block copolymer is 5%-40%.
9. the polymer composition of two arms styrene-conjugated diene as claimed in claim 7, which is characterized in that polymer group
It closes in object, mass percent shared by the bi-block copolymer is 5~20%.
10. the polymer composition of two arms styrene-conjugated diene as claimed in claim 6, which is characterized in that styrene-
Butadiene block polymeric arms, styrene-isoprene block polymer arm molecular weight be alone 30000~100000.
11. the polymer composition of two arms styrene-conjugated diene as described in claim 1, which is characterized in that SB block is poly-
It closes in object, the ratio of S/B is 10~50.
12. the polymer composition of two arms styrene-conjugated diene as described in claim 1, which is characterized in that SI block is poly-
It closes in object, the ratio of S/I is 10~30.
13. a kind of preparation side of the polymer composition of the described in any item two arms styrene-conjugated dienes of claim 1~12
Method, which comprises the following steps:
Step (1): activity SB block polymer and activity SI block polymer are made by anionic polymerisation respectively；
Step (2): active SB block polymer is mixed with coupling agent first, carries out one section of coupling reaction, obtains coupling reaction liquid；
Step (3): adding active SI block polymer into the coupling reaction liquid of step (2), carries out two sections of coupling reactions；
Step (4): step (3) after reaction, then is terminated, post-processes to obtain the polymer composition.
14. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 13, feature exist
In by the polymerisation in solution comprising styrene, polar modifier A, lithium alkylide A, hydrocarbon solvent A；Butadiene continuation is then added again
Polymerization obtains the active SB block polymer.
15. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 13, feature exist
In by the polymerisation in solution comprising styrene, polar modifier B, lithium alkylide B, hydrocarbon solvent B；Then add again penta different diene after
Continuous polymerization, obtains the active SI block polymer.
16. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 13, feature exist
In lithium alkylide A, lithium alkylide B are independently chosen from butyl lithium and/or s-butyl lithium.
17. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 13, feature exist
In polar modifier A, polar modifier B are independently chosen from diethylene glycol dimethyl ether 2G, triglyme 3G, dipiperidinoethane
DPE, ethylene glycol ethyl tert-butyl ether (ETBE) BEE, ethylene glycol propyl tertbutyl ether BPE, Ethylene Glycol Methyl tertbutyl ether MEB, tetramethyl
Ethylenediamine TMEDA, tetrahydrofuran THF, two or four oxygroup ethane DME, ethyl tetrahydrofurfuryl ether TEFE, N, in N- diformazan tetrahydrofurfuryl amine
At least one.
18. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 17, feature exist
In polar modifier A, polar modifier B are 10~200mg/kg alone.
19. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 13, feature exist
In hydrocarbon solvent A, hydrocarbon solvent B are independently chosen from least one of thiacyclohexane, pentane, hexane, heptane, benzene.
20. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 13, feature exist
In the polymerization temperature of, active SB block polymer, activity SI block polymer preparation process be 20 DEG C~100 DEG C.
21. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 20, feature exist
In the polymerization temperature of, active SB block polymer, activity SI block polymer preparation process be 30~80 DEG C.
22. the preparation side of the polymer composition such as the described in any item two arms styrene-conjugated dienes of claim 13~21
Method, which is characterized in that coupling agent includes: dichloro-dimethyl silicon, dimethyl tin dichloride, dichloro dimethoxysilane, O-phthalic
At least one of dimethyl phthalate, epoxidized soybean oil, maleic anhydride.
23. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 22, feature exist
In the molar ratio of, coupling agent and (active SB block polymer and activity SI block polymer and) be 1: 2-1: 25.
24. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 23, feature exist
In the temperature of coupling reaction is 30 DEG C -80 DEG C.
25. the preparation method of the polymer composition of two arms styrene-conjugated diene as claimed in claim 24, feature exist
It is respectively 20-40min in the coupling reaction time of, step (2), step (3).
26. a kind of application of the polymer composition of the described in any item two arms styrene-conjugated dienes of claim 1~12,
It is characterized in that, being used as the modified additive of pitch.
27. the application of the polymer composition of two arms styrene-conjugated diene as claimed in claim 26, which is characterized in that
Additive amount of the polymer composition in pitch is 4.5-12wt%.
28. a kind of modified pitch, which is characterized in that include described in any item two arms of pitch to be processed and claim 1~7
The polymer composition of styrene-conjugated diene；Needle penetration >=45dmm, softening point >=90 DEG C, ductility >=34cm, viscous toughness >=
24N.m, toughness >=18N.m, 90 DEG C of rotary viscosity 330Pa.s.
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| CN112745468A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Linear dihydroxy SBS and preparation method thereof |
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| CN107501488A (en) * | 2016-06-14 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of star-like butadiene-styrene rubber of asymmetry and preparation method thereof and the application as sole rubber material |
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| US20050101702A1 (en) * | 2003-11-12 | 2005-05-12 | Stuart Richard K.Jr. | Modified asphalt compositions |
| US20050272849A1 (en) * | 2004-06-03 | 2005-12-08 | Clair David J S | Gels from high molecular weight block copolymers |
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