CN107236102A - A kind of powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber and its preparation method and application - Google Patents
A kind of powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber and its preparation method and application Download PDFInfo
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- CN107236102A CN107236102A CN201610187653.4A CN201610187653A CN107236102A CN 107236102 A CN107236102 A CN 107236102A CN 201610187653 A CN201610187653 A CN 201610187653A CN 107236102 A CN107236102 A CN 107236102A
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/048—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers, conjugated dienes and polar monomers
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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
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of powdered polystyrene b random copolymerizations conjugated diene/divinylbenzene rubber and its preparation method and application；By the equal poly block of styrene, yoke diene and divinylbenzene random copolymerization block are constituted the rubber together；Its synthetic method is：In the anionic polymer system containing methyl phenyl ethers anisole, first add styrene monomer and carry out homopolymerization；After the completion of homopolymerization, add conjugated diene and carry out random copolymerization with divinylbenzene mix monomer, produce the glue of rubber；The glue is produced by condensing desolvation；The preparation method is simple, cost is low, and the rubber of system can be used for excellent self-adhering-type modified asphalt waterproof coiled material of processability etc., show low temperature resistant, higher ductility, higher peel strength and heat resistance the characteristics of.
Description
Technical field
The present invention relates to a kind of preparation method of polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber and should
With belonging to modified asphalt technology field.
Background technology
Powder styrene butadiene rubber (abbreviation PSBR) is a kind of physics variation of Traditional bulk rubber, refers generally to particle diameter at 2 millimeters
Within uncured raw rubber.PSBR is eliminated when being processed compared with traditional butadiene-styrene rubber and is cut glue process, is shortened mixed
In the refining cycle, significantly reduce process energy consumption, and each component can be dispersed in formula, and melting effect is good.PSBR can
To be blended using the mechanically direct material such as with plastics, pitch of screw extruder, colloid mill etc., as current emerging application
Field.Nineteen thirty Britain Dunlop company E.A.Murphy is by mechanical lapping and adds bone meal and is realized first in laboratory
The powdered of natural rubber.Nineteen fifty is for B.F.Goodrich companies of the U.S. are using the mechanical lapping of Traditional bulk rubber physical and add
Plus interleaving agent technology, PSBR is produced, indicates that PSBR is industrialized successfully.Mechanical comminution techniques produce PSBR, exist high energy consumption,
The shortcomings of cost is high, product cut size is big.
Physical crushing method is that, first by the size reduction machinery with fixed cutting tool or fly cutter, it is suitable to be crushed to by niggerhead
Particle diameter, then sieved by sieve tray, the underproof particle of particle diameter returns to pulverizer and crushed again.Added per circulation primary
Interleaving agent, qualified particle enters the fine powder machine equipped with impeller and radial vane.Add interleaving agent further to crush, accord with
The particle of Particle size requirements is closed by screen cloth, product is ultimately formed.
Niggerhead is cut into sheet, rubber is refrigerated to below glass transition temperature, then is crushed, can be made particle diameter compared with
Small PSBR.The production technology although having saved energy in shredding stage, but by sheet rubber be cooled to glass transition temperature with
Down, it is necessary to consume big energy.
A kind of crush block butadiene-styrene rubber of Japan's Toyo Sodo mfg. Developeies in 1986 is ultra micro
The chemical pulverization method of grain, it is entirely different with physical crushing technology to be reached by adding chemicals and specified chemical process
Crush the effect of niggerhead.The said firm has carried out a variety of crush and tested on the experimental rig of foundation.As a result table
Bright, can be mixed easily with various fillers and additive after niggerhead is crushed using the technology, and strong improves
Their dispersiveness.But the kinetic energy expense of great number will not only be consumed using mechanical crushing method, while must also add blocking agent
It just can guarantee that the buffings after crushing no longer glues connection.
At present, PSBR synthetic technology mainly uses emulsion polymerization technology, and PSBR preparation uses Latex agglutination in E-
Appropriate covering, age resistor, filler etc. are added in SBR latex and carries out co-agglomeration, is added by the process such as filtering, washing, dry
Work is formed, and covering makees covering from non-water soluble substance, and it can form one layer of colloid diaphragm on latex particle surface, from
And rubber particles are isolated into powder.Traditional inorganic powder isolation rubber particles can produce substantial amounts of dust when producing PSBR,
It is directed at environmental pollution, is detrimental to health.
PSBR is largely used to road modified asphalt and waterproof roll.The poly- PSBR newborn poly- PSBR compared with solution polymerized butadiene styrene rubber of breast
It is high and containing a small amount of gel, tack be big and cold flow, cohesion with molecular weight larger (Mn=20-26 ten thousand), wider distribution, the degree of branching
The features such as power is higher.But the degree of branching and cohesive force is high, a small amount of gel PSBR is detrimental to melt processing in modified pitch.
The conjugation not more than 25wt% of styrene in the poly- PSBR of breast, styrene is presented complete random distribution, polymerize in the molecule
A small amount of gel in thing can not be avoided completely.And commercially available anionic polymerisation butadiene-styrene rubber such as Solprene-1205 and phase
The similar products SSBR-1205 of pass styrene (S)/butadiene (B)=25/75, wherein first paragraph polystyrene content does not surpass
The 17wt% of total styrene amount is crossed, molecule is linear structure, and molecular weight Mn=14 ten thousand, this butadiene-styrene rubber prepares tack with pitch
Although melting performance is good at 180 DEG C during waterproof roll, initial cohesiveness is good, and its branchign of molecule degree is low, and intermolecular entanglement degree is low,
Polymer cohesive force is low, causes peel strength low, holds the weak points such as the viscous time is short.
In tack asphalt water-proof coiled material industry, Xu Maozhen, etc.：High heat resistance self-adhesive polymer modified asphalt waterproof roll is ground
Make [J], New Building Materials and Wang Shuan, polymer modified asphalt adhesive waterproof coil stripping performance research [J], investigation of materials and
A kind of high heat resistance self-adhesive rubber asphalt waterproofing coiled materials of Li Weiguo, Duan Wenfeng, Tian Fenglan：200710120808.3 [P] of China
Described in 2007-08-27. grades text and self-adhesive modified asphalt waterproof rolling material is prepared using materials such as SBS, PSBR, rubber oils,
Breast poly powder PSBR with pitch when mixing in above-mentioned technology, even in 180 DEG C of high-speed stirreds, SBR surfaces are molten to rise, particle
Between can local bonding, slowed down newborn poly- PSBR fusing speed, usual PSBR is molten to rise for up to 2.5h, this needs to consume a large amount of
Heat energy and process time；In addition, the gel that newborn poly- PSBR contains can cause rubber to be layered with pitch because not being fused in pitch,
Modified effect is bad, and local because without rubber plasticizing, causing the pitch lower temperature resistance of script not good, glass transition temperature is high, and low temperature is soft
Property is poor.It is to improve the softening point of modified pitch material, prolong from SBS purposes it is worth emphasizing that self-adhesive modified asphalt waterproof rolling material
Degree, intensity and flexibility etc., SBS under softening oil effect in itself without tack, it is necessary to just embody viscosity.In addition it is commercially available from
In viscous bitumen waterproof roll, some brands are only with SBS as modifying agent, and without adding random styrene-butadiene rubber, this kind of product is low
Tenderness is poor, ＞ -6 DEG C of brittleness temperature, the shortcomings of peel strength is relatively low.
The content of the invention
It is of the invention for existing powder styrene butadiene rubber PSBR in preparation method and in defect present on modified pitch
Purpose is to be to provide a kind of with special styrene block and conjugated diene and divinylbenzene random copolymerization block structure, and
Powdered polystyrene-b- random copolymerizations conjugated diene/divinyl with preferable tack, low temperature flexibility and peel strength
Base benzene rubber.
Second object of the present invention is to be that providing a kind of simple, low cost prepares the amount of powder shape polyphenyl second
The method of alkene-polymerized conjugated diene rubber, this method can save machine crush and without using interleaving agent under the conditions of directly obtain powder
Last shape polystyrene-poly conjugated diene rubber, process conditions are ripe, and environmental protection, raw material sources are wide, meet industrialized production.
Third object of the present invention is to be to provide the amount of powder shape polystyrene-poly conjugated diene rubber in system
Application in standby modified pitch, it can be used for the excellent self-adhering-type modified asphalt waterproof coiled material of processability, hot melt to be modified drip
Blue or green waterproof roll or low-temperature resistance road modified asphalt etc., show low temperature resistant, higher ductility, higher peel strength and heat-resisting
The characteristics of property.
In order to realize above-mentioned technical purpose, the invention provides a kind of powdered polystyrene-b- random copolymerizations conjugation two
Alkene/divinylbenzene rubber, by the equal poly block of styrene, yoke diene and divinylbenzene random copolymerization block are constituted together；
The number-average molecular weight of the equal poly block of styrene is 20000~30000；
The conjugated diene and the number-average molecular weight of divinylbenzene random copolymerization block are 220000~250000；
Styrene units quality and conjugation in the polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber
Diene units mass ratio is 20~30:80~70；
Divinylbenzene units quality hundred in the polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber
Ratio is divided to account for 0.05 ‰~0.15 ‰.
Polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber of the present invention has the structure of formula 1,
S-B/I/D
Formula 1
Wherein, S is the equal poly block of styrene, and B/I/D is butadiene and/or isoprene and divinylbenzene random copolymerization
It is embedding；The S block of appropriate molecular weight is introduced in rubber, strong using the intermolecular force of S block, crystal property is good, is conducive to
Powdered；But if S block is long, the Tg rises of rubber, resistance to low temperature is poor；Styrene block is too short, Tg reductions, but poly-
Compound cohesive force declines, and is unfavorable for polymer powder chemical conversion type.And B/I/D blocks are distributed or lightly crosslinked in side chain, impart
Elastomeric material has excellent tack, low temperature flexibility and peel strength.A small amount of divinylbenzene list is also introduced in rubber
Member, B/I/D block copolymers carry out cladodification, the purpose is to increase elasticity flowing and the cohesive force of polymer, also help simultaneously
Polymer after powdered, which does not glue voluntarily, is coupled group.
It is preferred that scheme, Isosorbide-5-Nitrae-structure conjugated diene unit in the conjugated diene and divinylbenzene random copolymerization block
Quality accounts for more than the 85% of conjugated diene unit gross mass.If the butadiene unit of 1,2- structures and the isoamyl two of 3,4- structures
Alkene unit too high levels, can improve the glass transition temperature of rubber, cause the brittleness temperature of modified asphalt material to rise, lower temperature resistance
Can not be good.
It is preferred that scheme, conjugated diene be butadiene and/or isoprene.Both molar ratios are 0~100%:0~
100%.Isoprene unit is introduced in rubber, can suitably increase the VISCOUS FLOW of S-B/I/D rubber, the first of modified pitch is improved
Viscous force and peel strength.
It is preferred that scheme, powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber size ＜ 2mm.
It is preferred that scheme, powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber 300% stretches surely
Stress is 0.6~1.2MPa.
Present invention also offers polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber described in preparation
Method, in the anionic polymer system containing methyl phenyl ethers anisole, first adds styrene monomer and carries out homopolymerization；After the completion of homopolymerization, then add
Enter butadiene and/or isoprene and carry out random copolymerization with divinylbenzene mix monomer, produce polystyrene-b- random copolymerizations and be total to
The glue of yoke diene/divinylbenzene rubber；The glue is produced by condensing desolvation.
It is preferred that scheme, concentration of the methyl phenyl ethers anisole in anionic polymerisation system be 25~50mg/kg.Select regulating power phase
To weaker methyl phenyl ethers anisole as structure regulator and activator, the content of conjugated diene unit Isosorbide-5-Nitrae-addition product can be effectively improved.
And be not suitable for using the strong lewis base of regulation energy, such as tetrahydrofuran, ethers or tertiary amine compounds.
It is preferred that scheme, homopolymerization condition is：20min~25min is reacted at 50 DEG C~60 DEG C.
It is preferred that scheme, random copolymerization reaction condition is：20min~25min is reacted at 60 DEG C~80 DEG C.
The glue of obtained method polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber of the present invention is first put
In boiling water, desolvation thiacyclohexane is condensed under agitation, and coacervation process is analogous to conventional SBS coacervation processes, is not required to
Extra interleaving agent or covering using powdery, the sizing material after cohesion disperses, without tack naturally, can be filtered, dries, shape
Into bulk sprills, particle diameter ＜ 2mm.
Present invention also offers the application of described polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber,
Tack modified asphalt waterproof coiled material, hot melt modified asphalt waterproof coiled material or low-temperature resistance are applied to as asphalt modifier
Road modified asphalt.
It is preferred that scheme, polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber is in tack modified pitch
Consumption in waterproof roll, hot melt modified asphalt waterproof coiled material or low-temperature resistance road modified asphalt is 3.7wt%~5wt%.
More preferably scheme, described tack modified asphalt waterproof coiled material includes following content of component：Asphalt base-material
30~50 parts, polystyrene-b- random copolymerizations conjugated diene/4~8 parts of divinylbenzene rubber powder, SBS4~8 part, rubber
6~15 parts of oil, 15~25 parts of powder.
Further preferred scheme, asphalt base-material is 10# pitches, 70# pitches or 90# pitches.
Further preferred scheme, SBS is YH-791 and/or YH-792.
Further preferred scheme, rubber oil CA-12 and/or CA-18；Described powder is talcum powder and/or calcium powder.
The tack modified asphalt waterproof coiled material of the present invention has excellent combination property：Tearing strength >=28N, is peeled off strong
Degree >=1.3N/mm；Heat resistance, the 2h non-displacements at 75 DEG C, low temperature flexibility, the flawless at -25 DEG C.
Polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber powder of the present invention is used to prepare tack
The method of modified asphalt waterproof coiled material is as follows：
First ration pitch base-material is put into reactor, carries out being heated to 180~210 DEG C on electric furnace, now, drip is added
Blue or green base-material quality 3.7wt%~5wt% polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber powder, SBS,
Rubber oil, powder and a small amount of antioxidant 1076, under 80~150r/min stirring, stir 90min, then use PET non-woven fabrics
Make liner painting and scrape modified pitch material and related sample preparation and detection.
Compared with the prior art, the beneficial effect that technical scheme is brought：
(1) polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber of the invention has styrene embedding simultaneously
Section and with side chain distribution or lightly crosslinked random conjugated diene block, special molecular structure imparts rubber and is easy to powder
It is broken, and with performances such as preferable tack, low temperature flexibility and peel strengths.
(2) preparation method of polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber of the invention it is simple,
It can be synthesized using existing maturation process, raw material sources are wide, meet demand of industrial production.
(3) polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber powder of the invention can be used for being modified
Pitch, is particularly adapted to tack modified asphalt waterproof coiled material, hot melt modified asphalt waterproof coiled material or low-temperature resistance road and is modified
The modification of the materials such as pitch, the elastomeric material is liquor-saturated without additionally granulation or machine powder, no dust pollution, and modified pitch is resistance to low
Warm, higher ductility, higher peel strength and heat resistance etc. are effectively improved.
Embodiment
Following examples are intended to illustrate present invention, and the protection domain of the claims in the present invention is not implemented
The limitation of example.
In the following example：
The number-average molecular weight of polymer is determined using gel permeation chromatograph (GPC).
The microstructure of polymer is determined using NEXUS-870 type fourier transform infrared spectroscopies instrument.
The softening point of modified pitch is determined using HDLR-IV type asphalt high-temperatures softening point apparatus.
The initial cohesiveness of modified pitch is determined using LT-3000 annular initial adhesions tester.
The peel strength of modified drip is determined using BLD-200S type electron detachments testing machine.
The tensile property of polymer is determined using CMT4104 types tensilon.
Embodiment 1
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of polymeric kettles under nitrogen protection
3500mL, then adds 0.09mL methyl phenyl ethers anisoles, the solvent in polymeric kettle is warming up to after 50~60 DEG C with hot water, by 100g benzene second
Alkene adds in polymeric kettle and opens stirring, and the n-BuLi 11mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, reacts
After 20~25min；The mix monomer of 334.7g butadiene and 0.05mL divinylbenzene is added, is reacted at 50~90 DEG C
After 25min；Polymer (S-B/D) number-average molecular weight Mn=250000, wherein the number-average molecular weight Mn (s) of block polystyrene=
20400, butadiene section Isosorbide-5-Nitrae-addition content 93.8%.
Then by polymer discharge, and add 1.05g antioxidant 1076 and enter in glue, again add glue after stirring glue
Enter in boiling water and stir after 40min, after solvent is fully steamed and finished, filter out moisture, dry 2h at a temperature of 80 DEG C, produce polyphenyl
Ethene-b- random copolymerizations butadiene/divinylbenzene powdered rubber, rubber size≤2mm, 300% stress at definite elongation is
0.74MPa。
Embodiment 2
It is merely that butadiene consumption is chosen to be 257.2g, diethyl in the case of other conditions are constant in above-described embodiment 1
The consumption of alkene benzene is 0.06mL, and methyl phenyl ethers anisole consumption is 0.18mL.As a result synthesized polymer (S-B/D) number-average molecular weight Mn=
266000, wherein number-average molecular weight Mn (s)=20200 of block polystyrene, polybutadiene section Isosorbide-5-Nitrae-addition content 90.3%.
Polystyrene-b- random copolymerizations polybutadiene/divinylbenzene rubber size≤1.9mm after drying, 300% stress at definite elongation is
0.98MPa。
Embodiment 3
It is merely that butadiene consumption is chosen to be 400g, divinyl in the case of other conditions are constant in above-described embodiment 1
The consumption of benzene is 0.05mL, and methyl phenyl ethers anisole consumption is 0.15mL.As a result synthesized polymer (S-B/D) number-average molecular weight Mn=
265000, wherein number-average molecular weight Mn (s)=20600 of block polystyrene, polybutadiene section Isosorbide-5-Nitrae-addition content 91.5%.
Polystyrene-b- random copolymerizations polybutadiene/divinylbenzene rubber size≤1.8mm after drying, 300% stress at definite elongation is
0.86MPa。
Embodiment 4
It is merely that butadiene is chosen to be isoprene in the case of other conditions are constant in above-described embodiment 1, its isoamyl
Diene amount is 233.5g, as a result synthesized polymer (S-I/D) number-average molecular weight Mn=270000, wherein block polyphenyl second
Number-average molecular weight Mn (s)=19700 of alkene, polyisoprene section Isosorbide-5-Nitrae-addition content 87.9%.Polystyrene-b- after drying
Random copolymerization isoprene/divinylbenzene rubber size≤2mm, 300% stress at definite elongation is 0.62MPa.
Embodiment 5
In the case of other conditions are constant in above-described embodiment 4, isoprene consumption is chosen to be 300g, divinylbenzene
Consumption is 0.04mL, and methyl phenyl ethers anisole consumption is 0.17mL.As a result synthesized polymer (S-I/D) number-average molecular weight Mn=
246000, wherein number-average molecular weight Mn (s)=19300 of block polystyrene, polyisoprene section Isosorbide-5-Nitrae-addition content
85.6%.Polystyrene-b- random copolymerizations isoprene/divinylbenzene rubber size≤1.9mm after drying, 300% determines
Stress is stretched for 0.69MPa.
Embodiment 6
1000g 70# pitches are uniformly divided into 5 parts respectively to be placed in 500mL beaker, above-mentioned implementation is then respectively adding
Polystyrene-b- random copolymerizations conjugated diene/divinylbenzene powdered rubber sample 14g, SBS (YH-791) 8g in example 1~5,
Rubber oil (CA-12) 30g, talcum powder and calcium powder are respectively 30g, antioxidant 1076 0.7g.Then beaker is placed on electric furnace and added
Hot 180-210 DEG C, under 80~150r/min stir speed (S.S.)s stir 90min after, then by modified pitch material uniformly apply scrape in PET without
Spin on cloth, be cooled to room temperature i.e. plastic.
The physical property of rubber modified asphalt material prepared by the embodiment 1~5 of table 1.
Embodiment 7
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of polymeric kettles under nitrogen protection
3500mL, then adds 0.1mL methyl phenyl ethers anisole, the solvent in polymeric kettle is warming up to after 50~60 DEG C with hot water, by 100g benzene
Ethene adds in polymeric kettle and opens stirring, and the n-BuLi 9mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, reacts
After 20~25min；The mix monomer of 200g butadiene and 200g isoprene and 0.05mL divinylbenzene is added, 50
Reacted at~90 DEG C after 25min；Polymer (S-B/I/D) number-average molecular weight Mn=266000, the wherein number of block polystyrene
Average molecular weight Mn (s)=22300, polymerized conjugated diene section Isosorbide-5-Nitrae-addition content 88.4%.
Then by polymer discharge, and add 1.05g antioxidant 1076 and enter in glue, again add glue after stirring glue
Enter in boiling water and stir after 40min, after solvent is fully steamed and finished, filter out moisture, dry 2h at a temperature of 80 DEG C, produce polyphenyl
Ethene-b- random copolymerizations butadiene-isoprene/divinylbenzene powdered rubber, rubber size≤1.8mm, 300% stretch surely should
Power is 1.20MPa.
Embodiment 8
It is merely that methyl phenyl ethers anisole consumption is chosen to be 0.15mL, butyl in the case of other conditions are constant in above-described embodiment 7
The butadiene consumption that lithium consumption is chosen to be in 8mL, mix monomer is chosen to be 35g, and isoprene consumption is 300g, divinylbenzene
Consumption is 0.04mL.As a result synthesized polymer (S-B/I/D) number-average molecular weight Mn=268000, wherein block polystyrene
Number-average molecular weight Mn (s)=25200.Random copolymerization diene section 1,4- additions content 86.8%.Polystyrene-b- after drying
Random copolymerization butadiene-isoprene/divinylbenzene rubber size≤1.9mm, 300% stress at definite elongation is 0.94MPa.
Embodiment 9
It is merely that methyl phenyl ethers anisole consumption is chosen to be 0.17mL, butyl in the case of other conditions are constant in above-described embodiment 7
The butadiene consumption that lithium consumption is chosen to be in 7mL, mix monomer is chosen to be 100g, and isoprene consumption is 200g, divinylbenzene
Consumption be 0.04mL.As a result synthesized polymer (S-B/I/D) number-average molecular weight Mn=268000, wherein block polyphenyl second
Number-average molecular weight Mn (s)=29200 of alkene.Random copolymerization diene section Isosorbide-5-Nitrae-addition content 86.8%.Polystyrene after drying-
B- random copolymerizations butadiene-isoprene/divinylbenzene rubber size≤1.9mm, 300% stress at definite elongation is 1.16MPa.
Embodiment 10
It is merely that methyl phenyl ethers anisole consumption is chosen to be 0.08mL, butyl in the case of other conditions are constant in above-described embodiment 7
The butadiene consumption that lithium consumption is chosen to be in 7mL, mix monomer is chosen to be 200g, and isoprene consumption is 100g, divinylbenzene
Consumption be 0.02mL.As a result synthesized polymer (S-B/I/D) number-average molecular weight Mn=246000, wherein block polyphenyl second
Number-average molecular weight Mn (s)=29500 of alkene.Random copolymerization diene section Isosorbide-5-Nitrae-addition content 89.2%.Polystyrene after drying-
B- random copolymerizations butadiene-isoprene/divinylbenzene rubber size≤1.8mm, 300% stress at definite elongation is 1.12MPa.
Embodiment 11
It is merely that methyl phenyl ethers anisole consumption is chosen to be 0.10mL, butyl in the case of other conditions are constant in above-described embodiment 7
The butadiene consumption that lithium consumption is chosen to be in 8mL, mix monomer is chosen to be 340g, and isoprene consumption is 60g, divinylbenzene
Consumption is 0.07mL.As a result synthesized polymer (S-B/I/D) number-average molecular weight Mn=281000, wherein block polystyrene
Number-average molecular weight Mn (s)=25600.Random copolymerization diene section Isosorbide-5-Nitrae-addition content 89.8%.Polystyrene-b- after drying
Random copolymerization butadiene-isoprene/divinylbenzene rubber size≤1.9mm, 300% stress at definite elongation is 1.23MPa.
Embodiment 12
It is merely to select the butadiene consumption in mix monomer in the case of other conditions are constant in above-described embodiment 11
For 250g, isoprene consumption is 104.5g, and the consumption of divinylbenzene is 0.03mL.As a result synthesized polymer (S-B/I/
D) number-average molecular weight Mn=258000, wherein block polystyrene number-average molecular weight Mn (s)=25300.Random copolymerization diene
Section Isosorbide-5-Nitrae-addition content 89.2%.Polystyrene-b- random copolymerizations butadiene-isoprene/divinylbenzene rubber after drying
Micelle footpath≤1.8mm, 300% stress at definite elongation is 1.17MPa.
Embodiment 13
1200g70# pitches are homogeneously disposed in six 500mL beaker respectively, i.e., are separately added into each beaker
200g70# pitches, then add polystyrene-b- random copolymerizations conjugated diene/divinylbenzene powder in above-described embodiment 7~12
Last rubber sample 14g, other component and process conditions be the same as Examples 6, the results are shown in Table 2.
The physical property of rubber modified asphalt material prepared by the embodiment 7~12 of table 2.
Claims (13)
1. a kind of powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber, it is characterised in that：By benzene second
Polyamino alkenyl block is constituted with conjugated diene and divinylbenzene random copolymerization block；
The number-average molecular weight of the equal poly block of styrene is 20000~30000；
The conjugated diene and the number-average molecular weight of divinylbenzene random copolymerization block are 220000~250000；
Styrene units quality and conjugated diene in the polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber
Element quality ratio is 20~30:80~70；
Divinylbenzene units mass percent in the polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber
Account for 0.05 ‰~0.15 ‰.
2. powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 1, its
It is characterised by：1,4- structure conjugated diene unit quality accounts for conjugation in the conjugated diene and divinylbenzene random copolymerization block
More than the 85% of diene units gross mass.
3. powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 2, its
It is characterised by：Described conjugated diene is butadiene and/or isoprene.
4. powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 1, its
It is characterised by：Particle diameter ＜ 2mm.
5. powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 1, its
It is characterised by：300% stress at definite elongation is 0.6~1.2MPa.
6. prepare polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber described in any one of Claims 1 to 5
Method, it is characterised in that：In the anionic polymer system containing methyl phenyl ethers anisole, first add styrene monomer and carry out homopolymerization；
After the completion of poly-, add conjugated diene and carry out random copolymerization with divinylbenzene mix monomer, produce polystyrene-b- random copolymerizations
The glue of conjugated diene/divinylbenzene rubber；The glue is produced by condensing desolvation.
7. the method for polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 6, its
It is characterised by：Concentration of the described methyl phenyl ethers anisole in anionic polymerisation system is 25~50mg/kg.
8. the method for polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 6, its
It is characterised by：Described homopolymerization condition is：20min~25min is reacted at 50 DEG C~60 DEG C.
9. the method for polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 6, its
It is characterised by：Described random copolymerization reaction condition is：20min~25min is reacted at 60 DEG C~80 DEG C.
10. polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber described in any one of Claims 1 to 5 should
With, it is characterised in that：Tack modified asphalt waterproof coiled material, hot melt modified asphalt waterproof are applied to as asphalt modifier to roll up
Material or low-temperature resistance road modified asphalt.
11. the application of polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 10,
It is characterized in that：Polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber is rolled up in tack modified asphalt waterproof
Consumption in material, hot melt modified asphalt waterproof coiled material or low-temperature resistance road modified asphalt is 3.7wt%~5wt%.
12. the application of polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 11,
It is characterized in that：Described tack modified asphalt waterproof coiled material includes following content of component：30~50 parts of asphalt base-material, gathers
Styrene-b- random copolymerizations conjugated diene/4~8 parts of divinylbenzene rubber powder, SBS4~8 part, 6~15 parts of rubber oil, powder
15~25 parts of material.
13. the application of polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber according to claim 12,
It is characterized in that：Described asphalt base-material is 10# pitches, 70# pitches or 90# pitches；Described SBS is YH-791 and/or YH-
792；Described rubber oil CA-12 and/or CA-18；Described powder is talcum powder and/or calcium powder.
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| CN114106274B (en) * | 2020-08-31 | 2024-04-12 | 中国石油化工股份有限公司 | Waterproof coiled material asphalt modifier and preparation and application thereof |
| CN114539491A (en) * | 2020-11-24 | 2022-05-27 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene block copolymer, preparation method thereof, oil-extended rubber and application |
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