CN106317350B - A kind of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer and its preparation method and application - Google Patents
A kind of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer and its preparation method and application Download PDFInfo
- Publication number
- CN106317350B CN106317350B CN201510395038.8A CN201510395038A CN106317350B CN 106317350 B CN106317350 B CN 106317350B CN 201510395038 A CN201510395038 A CN 201510395038A CN 106317350 B CN106317350 B CN 106317350B
- Authority
- CN
- China
- Prior art keywords
- conjugated diene
- random
- styrol copolymer
- styrene
- copolymerizations
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of part hydrogenated polystyrene b random copolymerizations conjugated diene/styrol copolymers and its preparation method and application, the copolymer is made of the random copolymerization block of styrene block and styrene, conjugated diene and divinylbenzene, and the conjugated diene unit in copolymer is partially hydrogenated；Preparation method is styrene monomer first to be carried out homopolymerization, then carry out random copolymerization with styrene, conjugated diene and divinylbenzene mix monomer, copolymerization product carry out hydrogenation reaction to get.The preparation method is simple, technical maturity, and raw material sources are wide, can meet industrialization production requirements.Part hydrogenated polystyrene b random copolymerizations conjugated diene made from this method/styrol copolymer intensity is high, and there is preferable heat resistance and processing performance, use it for modified pitch, it is excellent that cold-resistant, heat-resisting, weather-proof, resistance to ozone, anti-ultraviolet property can be prepared, and with the modified pitch of higher elasticity and intensity, the adhesive force and bonding force of pitch and concrete stone road surface can be improved.
Description
Technical field
The present invention relates to a kind of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer and its systems
Preparation Method and application belong to modified asphalt technology field.
Background technology
Styrene can be directed to polymerize under the initiation of butyl lithium in a solvent with conjugated diene synthesizes random or block copolymerization
Object, this material is especially suitable for modified pitch.Usual block type thermoplastic elastomer SBS, SIS, SEBS, SEPS etc. use sulphur
The vulcanization of sulphur-accelerator system, processing performance is bad, and vulcanizate intensity is low, and stress at definite elongation is low, ultraviolet light and ageing-resistant performance
Difference such as makees outdoor road modified asphalt, and weather resistance is not poor, is easily influenced by hot and cold alternation, and road is also easy to produce cracking, and modified
Material is also poor with foundation stone material adhesion strength.The solution polymerized butadiene styrene rubber Sloprene 1205 of conventional commercial, ESBR1500 etc. butadiene-styrene rubber are
Random non-hydrogen fluidized polymer, this kind of polymer appearance are bulk, are not easy and pitch hybrid process.
Outside it, Wang Nini etc., the synthesis [J] of tin coupling type styrene-isoprene-butadiene terpolymer, synthesis
Rubber industry describes the side that styrene-isoprene-butadiene copolymer is coupled using butter of tin in 2010,33 (6)
Method, this to contain intermingle with SIBR not through over hydrogenation, polymer monomer unit is random distribution, and raw rubber is without intensity, cold flow is big, cannot
Be made it is granular, raw rubber be bulk, be mainly used for tire.
The hydrogenation of block type styrene-conjugated diene lithium series of polymer adds usually using cyclopentadienyl-titanium system catalysis and the catalysis of nickel system
Hydrogen, wherein cyclopentadienyl-titanium catalyst system can all hydrogenate polybutadiene section in SBS, and the polymer after hydrogenation is double without crosslinked vulcanization
Key.But cyclopentadienyl-titanium catalyst cannot hydrogenate polyisoprene section in styrene-isoprene lithium series of polymer.Such as
ZL97108078.4, USP4,980,421 (1990), EP0,471,415 (1991) etc. provide a kind of hydrogen to styrene-butadiene polymer
Change method, for degree of hydrogenation up to 99.5%, this method of hydrotreating cannot effectively control the double bond for vulcanization needed in polymer.
USP5,132,372 (1992), USP5,206,307 (1993) etc. provide a kind of nickel system catalytic hydrogenation styrene-conjugated diene
The method of polymer, especially polyisoprene section can be hydrogenated all in polymer.Above-mentioned block type polymers embody thermoplastic
Property elastomer behavior, can only be injection moulded, sulfur cross-linking, the crosslinking method of product cannot be used to belong to physical crosslinking, product is strong
Spend relatively low, UV resistant performance is bad, and it is bad to be used for a long time resistance to ag(e)ing under outdoor high temperature, strong sunlight, weather-proof at low temperature
Property is also bad.
Invention content
For SB rubber in the prior art or hydrogenation SB rubber in defect present on modified pitch, the purpose of the present invention
It is that be to provide a kind of stress at definite elongation high, there is anti-tack, and heat resistance and the good part hydrogenated polystyrene-b- of processability
Random copolymerization conjugated diene/styrol copolymer.
Another object of the present invention is to be to provide a kind of simple, low cost to prepare the part hydrogenated polystyrene-
The method of b- random copolymerizations conjugated diene/styrol copolymer, this method process conditions are ripe, and raw material sources are wide, meet industry
Metaplasia is produced.
A further object of the invention be to provide the part hydrogenated polystyrene-b- random copolymerizations conjugated diene/
Application of the styrol copolymer in preparing modified pitch can be used for preparing cold-resistant, heat-resisting, weather-proof, resistance to ozone, uvioresistant
It has excellent performance, and with the modified pitch of higher elasticity and intensity, pitch and the adhesive force on concrete stone road surface and bonding can be improved
Power.
In order to achieve the above technical purposes, the present invention provides a kind of part hydrogenated polystyrene-b- random copolymerizations conjugation
Diene/styrol copolymer is hydrogenated to obtain by the block copolymer part with 1 chemical expression of formula：
S1-B/S/I/D
Formula 1
Wherein,
S1The equal poly block being made of styrene units for being number-average molecular weight in 14000~20000 ranges；
B/S/I/D be number-average molecular weight in 180000~220000 ranges by styrene units, conjugated diene unit
The random copolymerization block constituted with divinylbenzene units；
The hydrogenation degree of conjugated diene unit is 75~85% in B/S/I/D random copolymerization blocks；
S1In-B/S/I/D block copolymers the ratio between styrene units gross mass and conjugated diene unit gross mass be 25~
35:75~65.
Conjugated diene unit in preferred part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer
It is made of butadiene unit and isoprene unit.
In preferred part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, divinylbenzene list
The quality of member is S10.05 ‰~the 0.1 ‰ of-B/S/I/D block copolymerization amount of substance.By introducing a small amount of divinylbenzene list
Member is by S1- B/S/I/D block copolymers carry out cladodification.
In preferred part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, isoprene unit
Quality be less than or equal to S1The 5% of-B/S/I/D block copolymerization amount of substance.
In preferred part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, S1In equal poly block
The quality of styrene units is S160% or more of styrene units gross mass in-B/S/I/D block copolymers.Styrene is in S1-
Distribution in B/S/I/D block copolymers can be all distributed in homopolystyrene block, can also partly be distributed in B/S/
In I/D random copolymerization blocks.Styrene units are in S1Distribution form in-B/S/I/D block copolymers, imparts S1-B/S/I/
The better heat resistance of D block copolymers and anti-tack can reduce cold flow in favor of extruding pelletization.
In preferred part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, butadiene unit
The quality of 1,2- structures and the 3,4- structures of isoprene unit accounts for 30wt%~40wt% of conjugated diene unit gross mass.It is suitable
The butadiene of the 1,2- structures of amount and the isoprene unit of 3,4- structures can improve S1The processing of-B/S/I/D block copolymers
Performance.
In preferred part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, part hydrogenates polyphenyl
300% stress at definite elongation >=1.2MPa of ethylene-b- random copolymerizations conjugated diene/styrol copolymer.
Part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer of the present invention contains the non-hydrogen in part
Change double bond, embody thermoplastic elastomer (TPE) and can sulfidation, can be crosslinked with sulphur.
The present invention also provides the part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene for preparing described is total
The method of polymers, this method first by styrene monomer by anionic polymerisation system carry out homopolymerization, after the completion of homopolymerization, then the moon from
Styrene is added in subparadigm system, conjugated diene and Ethenylbenzene mix monomer carry out random copolymerization, obtain polystyrene-b- without
Rule copolymerization conjugated diene/styrol copolymer, polystyrene-b- random copolymerizations conjugated diene/styrol copolymer carries out plus hydrogen
Reaction to get.
In preferred preparation method, homopolymerization temperature is 50 DEG C~60 DEG C, and the homopolymerization time is 20min~25min.
In preferred preparation method, random copolymerization temperature is 50 DEG C~80 DEG C, and polymerization time is 20min~25min.It is preferred that
Preparation method in, lewis base is added during random copolymerization as structure regulator adjusting polystyrene-b- random copolymerizations
The butadiene unit of 1,2- structures and 3,4- structures in B/S/I/D random copolymerizations block in conjugated diene/styrol copolymer
The quality of isoprene unit accounts for 30wt%~40wt% of total conjugated diene unit gross mass.
More preferably in preparation method, at least one in structure regulator THF, tetrahydrofurfuryl alcohol ether, tertiary amine compounds
Kind.Preferred active regulator is more advantageous to the 1,2- structural contents of butadiene unit or the 3,4- structural contents of isoprene
It is accurate to adjust.
In preferred preparation method, hydrogenation reaction temperature is 70 DEG C~85 DEG C, hydrogenation reaction pressure be 1.0MPa~
1.5MPa, hydrogenation reaction time 2 h~2.5 hour.
In preferred preparation method, hydrogenation reaction is carried out under dicyclopentadiene titanium chloride catalytic condition, bicyclic penta
The dosage of diene titanium chloride is 0.11mmol~0.13mmol/100g polystyrene-b- random copolymerizations conjugated diene/styrene
Copolymer.
In preferred preparation method, after polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation
Iodine number is the 25g iodine~45g iodine/parts 100g hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer.
The specific preparation side of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer of the present invention
Method is as follows：
1, thiacyclohexane and normal hexane mixed solvent are added in polymeric kettle, adds structure regulator, it, will after stirring evenly
Styrene monomer is added in polymeric kettle futher stir uniformly after, with suitable butyl lithium initiated polymerization, 50~60
At DEG C, after reacting 20~25min；The mix monomer for adding styrene, butadiene, isoprene and divinylbenzene, 50
After reacting 20~25min at~90 DEG C, polystyrene-b- random copolymerizations conjugated diene/styrol copolymer is obtained, sampling is surveyed poly-
Close the molecular weight and contents of ethylene of object；
2, polystyrene-b- random copolymerizations conjugated diene/styrol copolymer is moved in hydriding reactor, and hydrogenation is added and urges
Agent dicyclopentadiene titanium chloride (dosage be 0.11~0.13mmol/100g copolymers), the temperature of hydrogenation reaction is 70~
80 DEG C, it is 1.0~1.5MPa that hydrogen, which is passed through pressure, and the hydrogenation time is 2~2.5 hours, after the completion of hydrogenation, discharging,
Cohesion, dry, granulation, finally survey the iodine number of hydrogenated products.
The present invention also provides the part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymers
Application, which is using part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer as asphalt modification
Agent is applied to prepare modified pitch.
In preferred application process, part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer and drip
After green base-material is kneaded, by sulfur cross-linking, modified pitch is obtained.
More preferably in application process, part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer with
Asphalt base-material is under conditions of temperature is 165 DEG C~190 DEG C, stir speed (S.S.) is 3000rpm/min~4000rpm/min, shearing
After being kneaded 25min~30min, sulphur and auxiliary agent is added, futher stirs 5min~8min, obtains modified pitch.
More preferably in application process, part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer exists
Addition in asphalt base-material is 3wt%~4wt%.
More preferably in application process, the dosage of sulphur is part hydrogenated polystyrene-b- random copolymerizations conjugated diene/benzene
2.5wt%~3.0wt% of ethylene copolymer.
In preferred application process, modified pitch, modified pitch ductility >=80cm, softness number >=90 DEG C, breaking at 5 DEG C
Intensity >=1.6MPa.
More preferably in application process, auxiliary agent includes anti-aging agent, accelerating agent etc..
Part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer of the present invention is used to prepare modification
The component formula of pitch is following (being measured with mass parts)：Asphalt base-material 100, part hydrogenated polystyrene-b- random copolymerizations conjugation
Diene/styrol copolymer 3~4, stearic acid 0.13, zinc oxide 0.2, antioxidant 4020 0.03, accelerant CZ 0.1~0.2,
Sulphur 0.1~0.12.
Part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer of the present invention is used to prepare modification
The method of pitch is as follows：
First ration pitch base-material is put into and is kneaded in bottle, carries out being heated to 165~190 DEG C on electric furnace, at this point, drip is added
Part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer of green base-material quality 3~4%, in 3000rpm/
Under the stir speed (S.S.) of min~4000rpm/min, 20~25min is stirred, sulphur and auxiliary agent is then added, is stirred for 5~8min,
Up to modified pitch.
Compared with the prior art, the beneficial effects of the invention are as follows：Obtaining one end for the first time, there is styrene block, the other end to have
Branch is distributed or part hydrogenated polystyrene-b- random copolymerizations conjugated diene/benzene second of lightly crosslinked block of random copolymer
Alkene copolymer；The special molecular structure of the polymer imparts the preferable heat resistance of block polymer, anti-tack, low cold flow,
Improve its processing performance.By part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer in asphaltic base
By being kneaded, after vulcanization crosslinking in material, modified pitch is made to have the characteristics that cold-resistant, heat-resisting, weather-proof, resistance to ozone, uvioresistant, it is special
It is not that also there is higher elasticity and intensity, effectively enhances pitch and concrete stone road adherence and bonding force.In addition, the part hydrogen
It is wide to change polystyrene-b- random copolymerizations conjugated diene/styrol copolymer mature preparation process, raw material sources, it is raw to meet industry
Production requires.
Description of the drawings
【Fig. 1】Polystyrene-b- random copolymerizations conjugated diene/styrol copolymer the virgin rubber and hydrogen prepared for embodiment 1
The infrared spectrogram of polymer after change；Upper curve is virgin rubber, and lower curve is after hydrogenating；
【Fig. 2】Polystyrene-b- random copolymerizations conjugated diene/styrene copolymerized after the part hydrogenation prepared for embodiment 1
Object H-NMR spectrum.
Specific implementation mode
Following embodiment is intended to illustrate the content of present invention, and the protection domain of the claims in the present invention is not implemented
The limitation of example.
The number-average molecular weight of polymer is measured in the following example with gel permeation chromatograph (GPC).
The microstructure content of quantitative determination polymer is composed using H-NMR.
Using the microstructure change before and after the hydrogenation of FTIR analyzing polymers.
The ductility of modified pitch is measured using JN1006 type pitch low temperature speed change ductility analyzers.
The needle penetration of modified pitch is measured using JNZR-97A type Asphalt Penetration analyzers.
The softening point of modified pitch is measured using HDLR-2 type computer ring and ball apparatus.
Embodiment 1
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
Then 4.8mL tetrahydrofurans are added in 3500mL, after being warming up to 50~60 DEG C with hot water, 100g styrene is added in polymeric kettle
And stirring is opened, the n-BuLi 10mL that 0.5mol/L is then injected with syringe enters in polymeric kettle, after reacting 20~25min；Again
The mix monomer of 286.5g butadiene and the divinylbenzene of 13.5g isoprene and 0.015mL is added, is reacted at 50~90 DEG C
After 25min；Measure the vinyl mass content 31.23% of butadiene segment in polymer, isopropenyl in isoprene segment
Mass content 3.34%, polymer number-average molecular weight Mn=154000, wherein the number-average molecular weight Mn=of block polystyrene
15000。
Then, after pumping the polymer into hydriding reactor, the dicyclopentadiene titanium chloride 0.13g of mass fraction 99% is added,
Hydrogen Vapor Pressure 1.2MPa is controlled, after 2 hours are stirred to react at 70~80 DEG C, glue measures raw rubber iodine number through agglomerating, drying
40.6g iodine/100g polymer.
From the infrared of the polymer after polystyrene-b- random copolymerizations conjugated diene/styrol copolymer virgin rubber and hydrogenation
It can be seen that in spectrogram (Fig. 1)：980cm-1For 3,4- structure absorption peaks, 836cm-1It is tied for cis-1,4 in isoprene unit
Structure absorption peak, 540cm-1For S block characteristic peak, 966cm-1Corresponding trans- Isosorbide-5-Nitrae-structure absorption peak, 910cm-1Corresponding 1,2- structures
Absorption peak adds the Isosorbide-5-Nitrae of the polymer after hydrogen-structure and 1,2- structure absorption peaks obviously to weaken, especially Isosorbide-5-Nitrae-structure absorption peak with
1,2- structure absorption peak becomes apparent compared to decline, illustrates that Isosorbide-5-Nitrae-structure adds hydrogen to be easier than 1,2- structures.In addition from part hydrogen
Change the nuclear-magnetism it can be seen from the figure that of polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, A (5.3-5.5) is PB sections
The integral area of middle Isosorbide-5-Nitrae-structure, A4.9 are the integral area of 1,2- structures in PB sections, and A5.25 is the product of Isosorbide-5-Nitrae-structure in PI sections
Facet is accumulated；It is the block of S, the random section for being S at chemical shift 7.4 at chemical shift 6.6.
Embodiment 2
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
Then 6mL tetrahydrofurans are added in 3500mL, after being warming up to 50~60 DEG C, stirring is added in polymeric kettle and opens by 80g styrene,
Then entered with syringe injection 0.5mol/L n-BuLis 12mL after reacting 20min in polymeric kettle；Add 285g butadiene,
The mix monomer of the divinylbenzene of 15.0g isoprene, 17g styrene and 0.03mL, after reacting 25min at 50~90 DEG C；
Measure the vinyl mass content 42.20% of butadiene segment in polymer, the isopropenyl mass content of isoprene segment
4.65%, polymer number-average molecular weight Mn=160000, wherein the number-average molecular weight Mn=14000 of block polystyrene.
After polymer moves into hydriding reactor, the dicyclopentadiene titanium chloride 0.11g of mass fraction 99% is added, controls hydrogen
Pressure 1.5MPa, after 2 hours are stirred to react at 70~80 DEG C, glue is through agglomerating, drying.Measure raw rubber iodine number 60.4g iodine/
100g polymer.
Embodiment 3
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
Then 1.5mL tetrahydrofurfuryl alcohol ethylethers are added in 3500mL, after being warming up to 50~60 DEG C, 90g styrene is added in polymeric kettle simultaneously
Stirring is opened, is then entered with syringe injection 0.5mol/L n-BuLis 8mL after reacting 20min in polymeric kettle；Add 285g fourths
The mix monomer of diene, 15.0g isoprene, 10g styrene and divinylbenzene 0.02mL reacts 25min at 50~90 DEG C
Afterwards, the vinyl mass content 35.9% of butadiene segment in polymer is measured, the isopropenyl quality of isoprene segment contains
Measure 4.21%, polymer number-average molecular weight Mn=176000, wherein the number-average molecular weight Mn=17000. of block polystyrene
After polymer moves into hydriding reactor, the dicyclopentadiene titanium chloride 0.13g of mass fraction 99% is added, controls hydrogen
Pressure 1.4MPa, after 2 hours are stirred to react at 70~80 DEG C, glue is through agglomerating, drying.Measure raw rubber iodine number 36g iodine/100g
Polymer.
Embodiment 4
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
Then 0.8mL tetrahydrofurfuryl alcohol ethylethers are added in 3500mL, after being warming up to 50~60 DEG C, 85g styrene is added in polymeric kettle simultaneously
Stirring is opened, is then entered with syringe injection 0.5mol/L n-BuLis 9mL after reacting 20min in polymeric kettle；Add 278.5g
Butadiene, 21.5g isoprene, 15g styrene and 0.025mL divinylbenzene mix monomer, reacted at 50~90 DEG C
After 25min；Measure the vinyl mass content 34.4% of butadiene segment in polymer, the isopropenyl matter of isoprene segment
Measure content 3.98%, polymer number-average molecular weight Mn=182000, wherein the number-average molecular weight Mn=of block polystyrene
17500。
After polymer moves into hydriding reactor, the dicyclopentadiene titanium chloride 0.14g of mass fraction 99% is added, controls hydrogen
Pressure 1.5MPa, after 2 hours are stirred to react at 70~80 DEG C, glue is through agglomerating, drying.Measure raw rubber iodine number 35.3g iodine/
100g polymer.
Embodiment 5
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
Then 3.6mL tetrahydrofurans are added in 3500mL, after being warming up to 50~60 DEG C, 83g styrene is added in polymeric kettle and is opened and is stirred
It mixes, is then entered with syringe injection 0.5mol/L n-BuLis 7mL after reacting 20min in polymeric kettle；Add 260g butadiene,
The mix monomer of the divinylbenzene of 20g isoprene, 37g styrene and 0.015mL, after reacting 25min at 50-90 DEG C.It surveys
Obtain the vinyl mass content 28.5% of butadiene segment in polymer, the isopropenyl mass content of isoprene segment
4.02%, polymer number-average molecular weight Mn=202000, wherein the number-average molecular weight Mn=18900 of block polystyrene.
After polymer moves into hydriding reactor, the dicyclopentadiene titanium chloride 0.13g of mass fraction 99% is added, controls hydrogen
Pressure 1.5MPa, after 2 hours are stirred to react at 70~80 DEG C, glue is through agglomerating, drying.Measure hydropolymer raw rubber iodine number
28.9g iodine/100g polymer.
Embodiment 6
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
Then 1.5mL N, N- dimethyl-tetrahydro chaff amine is added in 3000mL, after being warming up to 50-60 DEG C, 83g styrene is added and is polymerize
In kettle and stirring is opened, is then entered with syringe injection 0.5mol/L n-BuLis 8mL after reacting 20min in polymeric kettle；It adds
240g butadiene, 20g isoprene, 57g styrene and 0.03mL divinylbenzene mix monomer, reacted at 50-90 DEG C
After 25min；Measure the vinyl mass content 45.8% of butadiene segment in polymer, the isopropenyl matter of isoprene segment
Measure content 4.54%, polymer number-average molecular weight Mn=206000, wherein the number-average molecular weight Mn=of block polystyrene
20100。
After polymer moves into hydriding reactor, the dicyclopentadiene titanium chloride 0.12g of mass fraction 99% is added, controls hydrogen
Pressure 1.3MPa, after 2 hours are stirred to react at 70~80 DEG C, glue is through agglomerating, drying.Measure hydropolymer raw rubber iodine number
55.6g iodine/100g polymer.
Embodiment 7
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
Then 1.2mL N, N- dimethyl-tetrahydro chaff amine is added in 3000mL, after being warming up to 50~60 DEG C, 108g styrene is added poly-
It closes in kettle and opens stirring, then entered with syringe injection 0.5mol/L n-BuLis 8mL after reacting 20min in polymeric kettle；Again plus
The mix monomer for entering the divinylbenzene of 276g butadiene, 16g isoprene and 0.02mL, after reacting 25min at 50-90 DEG C.
Measure the vinyl mass content 27.7% of butadiene segment in polymer, the isopropenyl mass content of isoprene segment
3.90%, polymer number-average molecular weight Mn=212000, wherein the number-average molecular weight Mn=19000 of block polystyrene.
After polymer moves into hydriding reactor, the dicyclopentadiene titanium chloride 0.11g of mass fraction 99% is added, controls hydrogen
Pressure 1.3MPa, after 2 hours are stirred to react at 70~80 DEG C, glue is through agglomerating, drying.Measure hydropolymer raw rubber iodine number
66.9g iodine/100g polymer.
Embodiment 8
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
Then 2.2mL N, N- tetramethyl-ethylenediamines are added in 2800mL, after being warming up to 50-60 DEG C, polymeric kettle is added in 108g styrene
In and open stirring, then with syringe injection 0.5mol/L n-BuLis 7mL enter in polymeric kettle react 20min after；It adds
The mix monomer of the divinylbenzene of 250g butadiene, 18g isoprene, 24g styrene and 0.015mL, reacts at 50-90 DEG C
Measures the vinyl mass content 38.6% of butadiene segment in polymer, the isopropenyl matter of isoprene segment after 25min
Measure content 2.98%, polymer number-average molecular weight Mn=230000, wherein the number-average molecular weight Mn=of block polystyrene
21000.
After polymer moves into hydriding reactor, the dicyclopentadiene titanium chloride 0.13g of mass fraction 99% is added, controls hydrogen
Pressure 1.4MPa, after 2 hours are stirred to react at 70~80 DEG C, glue measures hydropolymer raw rubber iodine number through agglomerating, drying
28.9g iodine/100g polymer
Embodiment 9
Hydrogenation raw rubber in Examples 1 to 8 is blended with pitch.
Modified pitch formula (mass parts)：Pitch 100, part hydrogenate raw rubber 3, stearic acid 0.13, and zinc oxide 0.2 is prevented old
Agent 4,020 0.03, accelerant CZ 0.2, sulphur 0.12.
Blending technology:Temperature is 165~190 DEG C when hydropolymer is kneaded with pitch, and 25~30min of mixing time is cut
It cuts 3000~4000rpm/min. of stir speed (S.S.) then, after stearic acid, zinc oxide, 4020, accelerant CZ, sulphur is added, is stirred for 5
Modified pitch material is finally poured into detection mold and carries out shaping and quantitative measurement by~8min
Hydrogenate the physical property such as table 1 of raw rubber and asphalt modification material.
The physical property of hydrogenation raw rubber and asphalt modification material in 1 Examples 1 to 8 of table
Claims (19)
1. a kind of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, which is characterized in that by having
The block copolymer part of 1 chemical expression of formula hydrogenates to obtain：
S1-B/S/I/D
Formula 1
Wherein,
S1The equal poly block being made of styrene units for being number-average molecular weight in 14000~20000 ranges；
B/S/I/D be number-average molecular weight in 180000~220000 ranges by styrene units, conjugated diene unit and two
The random copolymerization block that vinyl benzene unit is constituted；
The hydrogenation degree of conjugated diene unit is 75~85% in B/S/I/D random copolymerization blocks；
S1The ratio between styrene units gross mass and conjugated diene unit gross mass are 25~35 in-B/S/I/D block copolymers:75
~65.
2. part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer according to claim 1,
It is characterized in that, the quality of divinylbenzene units is S10.05 ‰~the 0.1 ‰ of-B/S/I/D block copolymerization amount of substance.
3. part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer according to claim 1,
It is characterized in that, the conjugated diene unit is made of butadiene unit and isoprene unit；The quality of isoprene unit
Less than or equal to S1The 5% of-B/S/I/D block copolymerization amount of substance.
4. part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer according to claim 1,
It is characterized in that, S1The quality of styrene units is S in equal poly block1Styrene units gross mass in-B/S/I/D block copolymers
60% or more.
5. part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer according to claim 3,
It is characterized in that, the quality of 1, the 2- structures of butadiene unit and 3, the 4- structures of isoprene unit accounts for the total matter of conjugated diene unit
30wt%~40wt% of amount.
6. part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer according to claim 1,
It is characterized in that, 300% stress at definite elongation of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer >=
1.2MPa。
7. preparing claim 1~6 any one of them part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene
The method of copolymer, which is characterized in that styrene monomer is first subjected to homopolymerization by anionic polymerisation system, after the completion of homopolymerization,
Styrene, conjugated diene and divinylbenzene mix monomer are added in anionic polymerisation system again and carries out random copolymerization, obtains
Polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, polystyrene-b- random copolymerizations conjugated diene/styrene are total
Polymers carry out hydrogenation reaction to get.
8. the method according to the description of claim 7 is characterized in that homopolymerization temperature is 50 DEG C~60 DEG C, the homopolymerization time is 20min
~25min.
9. the method according to the description of claim 7 is characterized in that random copolymerization temperature is 50 DEG C~80 DEG C, polymerization time is
20min~25min.
10. the method according to the description of claim 7 is characterized in that lewis base is added during random copolymerization as structure
1,2- in B/S/I/D random copolymerization blocks in conditioning agent adjusting polystyrene-b- random copolymerizations conjugated diene/styrol copolymer
The quality of the butadiene unit of structure and the isoprene unit of 3,4- structures accounts for the 30wt% of total conjugated diene unit gross mass
~40wt%.
11. according to the method described in claim 10, it is characterized in that, the structure regulator be THF, tetrahydrofurfuryl alcohol ether,
At least one of tertiary amine compounds.
12. the method according to the description of claim 7 is characterized in that hydrogenation reaction temperature be 70 DEG C~85 DEG C, hydrogenation reaction pressure
Power is 1.0MPa~1.5MPa, hydrogenation reaction time 2 h~2.5 hour.
13. the method according to the description of claim 7 is characterized in that hydrogenation reaction is catalyzed in dicyclopentadiene titanium chloride
Under the conditions of carry out, the dosage of dicyclopentadiene titanium chloride be 0.11mmol~0.13mmol/100g polystyrene-b- randomly altogether
Polymerized conjugated diene/styrol copolymer.
14. the method according to the description of claim 7 is characterized in that polystyrene-b- random copolymerizations conjugated diene/styrene
Iodine number after copolymer hydrogenation be the 25g iodine~45g iodine/parts 100g hydrogenated polystyrene-b- random copolymerizations conjugated diene/
Styrol copolymer.
15. claim 1~6 any one of them part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene copolymerized
The application of object, which is characterized in that be applied to prepare modified pitch as asphalt modifier.
16. application according to claim 15, which is characterized in that part hydrogenated polystyrene-b- random copolymerizations conjugation two
After alkene/styrol copolymer is kneaded with asphalt base-material, by sulfur cross-linking, modified pitch is obtained.
17. application according to claim 16, which is characterized in that part hydrogenated polystyrene-b- random copolymerizations conjugation two
Alkene/styrol copolymer is with asphalt base-material in the item that temperature is 165 DEG C~190 DEG C, stir speed (S.S.) is 3000rpm~4000rpm
Under part, after shearing is kneaded 25min~30min, sulphur and auxiliary agent is added, futher stirs 5min~8min, obtains modified pitch.
18. application according to claim 16, which is characterized in that part hydrogenated polystyrene-b- random copolymerizations conjugation two
Addition of the alkene/styrol copolymer in asphalt base-material is 3wt%~4wt%, and the dosage of sulphur is part hydrogenation polyphenyl second
2.5wt%~3.0wt% of alkene-b- random copolymerizations conjugated diene/styrol copolymer.
19. application according to claim 15, which is characterized in that modified pitch, modified pitch ductility >=80cm, softness number
Stretch breaking strength >=1.6MPa at >=90 DEG C, 5 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510395038.8A CN106317350B (en) | 2015-07-07 | 2015-07-07 | A kind of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510395038.8A CN106317350B (en) | 2015-07-07 | 2015-07-07 | A kind of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106317350A CN106317350A (en) | 2017-01-11 |
| CN106317350B true CN106317350B (en) | 2018-07-31 |
Family
ID=57724862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510395038.8A Active CN106317350B (en) | 2015-07-07 | 2015-07-07 | A kind of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106317350B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA035569B1 (en) * | 2015-07-16 | 2020-07-08 | Асахи Касеи Кабусики Кайся | Partially hydrogenated block copolymer, adhesive composition, adhesive tape, label, modified asphalt composition, modified asphalt mixture, and paving binder composition |
| CN111718454B (en) * | 2019-03-20 | 2024-07-05 | 中国石油化工股份有限公司 | Partially hydrogenated styrene-b-conjugated diene/divinylbenzene random copolymer, preparation and application thereof |
| CN111718555B (en) * | 2019-03-20 | 2024-03-12 | 中国石油化工股份有限公司 | Sealing strip material based on partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer and preparation thereof |
| CN111718453B (en) * | 2019-03-20 | 2024-03-08 | 中国石油化工股份有限公司 | Partially hydrogenated styrene-b-butadiene-divinylbenzene/isoprene random copolymer, and preparation and application thereof |
| CN112210054B (en) * | 2019-07-09 | 2024-01-30 | 中国石油化工股份有限公司 | Tire sidewall rubber material based on block distribution lithium BIR and preparation method thereof |
| CN112480341B (en) * | 2019-09-12 | 2024-05-03 | 中国石油化工股份有限公司 | Branched polystyrene-b-conjugated diene diblock copolymer, and preparation method and application thereof |
| CN113563549B (en) * | 2020-04-29 | 2024-05-03 | 中国石油化工股份有限公司 | Asymmetric branched polystyrene-b-polyethylene-butene-propylene-isopropenyl multi-micro block copolymer and preparation method thereof |
| CN117487102B (en) * | 2023-12-29 | 2024-03-19 | 新疆独山子石油化工有限公司 | SBS modifier and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473178A (en) * | 2001-08-13 | 2004-02-04 | �ձ��Ϳ��������ɷ�����˾ | Block copolymer compositions |
| WO2004048426A2 (en) * | 2002-11-26 | 2004-06-10 | Kometra Kunststoff-Modifikatoren Und -Additiv Ag | Functionalized styrol/olefin block copolymers |
| CN102101902A (en) * | 2009-12-21 | 2011-06-22 | 中国石油化工股份有限公司 | Method for preparing irregular copolymer of conjugated diene and vinyl arene |
| CN103073831A (en) * | 2010-12-30 | 2013-05-01 | 中国石油化工股份有限公司 | Block copolymer, and preparation method and application thereof |
-
2015
- 2015-07-07 CN CN201510395038.8A patent/CN106317350B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473178A (en) * | 2001-08-13 | 2004-02-04 | �ձ��Ϳ��������ɷ�����˾ | Block copolymer compositions |
| WO2004048426A2 (en) * | 2002-11-26 | 2004-06-10 | Kometra Kunststoff-Modifikatoren Und -Additiv Ag | Functionalized styrol/olefin block copolymers |
| CN102101902A (en) * | 2009-12-21 | 2011-06-22 | 中国石油化工股份有限公司 | Method for preparing irregular copolymer of conjugated diene and vinyl arene |
| CN103073831A (en) * | 2010-12-30 | 2013-05-01 | 中国石油化工股份有限公司 | Block copolymer, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106317350A (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106317350B (en) | A kind of part hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer and its preparation method and application | |
| CN100369941C (en) | Hydrogenated styrene analog thermoplastic elastomer and its preparation method | |
| CN105175659B (en) | A kind of transparent type hydrogenated polystyrene b random copolymerizations conjugated diene/styrene resin and preparation method thereof | |
| US4152370A (en) | Preparation, composition, and use of block polymers | |
| CN105658676A (en) | Modified conjugated diene-based polymer, preparation method therefor, and rubber composition comprising same | |
| EP3093302A1 (en) | Modified conjugated diene-based polymer, modified rubber composition containing same, and method for preparing modified conjugated diene-based polymer | |
| CN111718454B (en) | Partially hydrogenated styrene-b-conjugated diene/divinylbenzene random copolymer, preparation and application thereof | |
| CN104945559B (en) | A kind of hydrogenated polystyrene-b- phenylethylene/butadiene/isoprene random copolymer and its preparation method and application | |
| US5047484A (en) | Tapered block copolymers | |
| EP3143057B1 (en) | Branched broad mwd conjugated diene polymer | |
| US4891410A (en) | Butadiene/sytrene block copolymers having an asymmetric structure, their preparation and their use as molding materials | |
| CN103819635B (en) | A kind of star hydrogenated styrene-butadiene block copolymer and its preparation method and application | |
| CN103804603B (en) | The application of a kind of solution polymerized butadiene styrene rubber and synthetic method and acid anhydrides | |
| US5071920A (en) | Tapered block copolymers | |
| CN109836547A (en) | Five block styrene analog thermoplastic elastomers of a kind of hydrogenation and preparation method thereof | |
| CN114478954B (en) | Preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber | |
| CN116987236A (en) | Dendritic styrene-butadiene block copolymer and preparation method and application thereof | |
| CN111718453B (en) | Partially hydrogenated styrene-b-butadiene-divinylbenzene/isoprene random copolymer, and preparation and application thereof | |
| EP3466995B9 (en) | Conjugated diene polymer, formulation and manufacturing method thereof | |
| EP3883978B1 (en) | Method for preparing random low vinyl copolymers, copolymers prepared by this method, and rubber mixtures based on these copolymers | |
| EP2042531B1 (en) | Block copolymer, composition for resin modification, and modified resin composition | |
| CN109575189B (en) | Monovinylarene-conjugated diene polymer and preparation method and application thereof | |
| CN106977656B (en) | Dendritic polydiene rubber and preparation method thereof | |
| CN114163585B (en) | Preparation method of ultra-wide-distribution four-hetero-arm comb-shaped star-shaped branched butyl rubber | |
| CN114478956B (en) | Preparation method of high-width-distribution three-hetero-arm comb-shaped star-shaped branched butyl rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |