CN107236102B - Powdery polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber and preparation method and application thereof - Google Patents
Powdery polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber and preparation method and application thereof Download PDFInfo
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- CN107236102B CN107236102B CN201610187653.4A CN201610187653A CN107236102B CN 107236102 B CN107236102 B CN 107236102B CN 201610187653 A CN201610187653 A CN 201610187653A CN 107236102 B CN107236102 B CN 107236102B
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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 powdery polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber and a preparation method and application thereof; the rubber consists of a styrene homopolymerization block, a conjugated diene and divinylbenzene random copolymerization block; the synthesis method comprises the following steps: firstly, adding a styrene monomer into an anionic polymer system containing anisole to carry out homopolymerization; after homopolymerization is finished, adding a conjugated diene and divinylbenzene mixed monomer for random copolymerization to obtain rubber liquid; removing the solvent from the glue solution through condensation to obtain the glue solution; the preparation method is simple and low in cost, and the prepared rubber can be used for preparing self-adhesive modified asphalt waterproof coiled materials with excellent performance and the like, and has the characteristics of low temperature resistance, high ductility, high peel strength and heat resistance.
Description
Technical Field
The invention relates to a preparation method and application of polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber, belonging to the technical field of modified asphalt.
Background
Powdered styrene-butadiene rubber (PSBR) is a physical variation of conventional block rubber, and generally refers to unvulcanized raw rubber with a particle size of less than 2 mm. Compared with the traditional styrene butadiene rubber, the PSBR omits a rubber cutting process during processing, shortens the mixing period, obviously reduces the energy consumption of the processing process, and has good mixing effect because all components in the formula can be uniformly dispersed. PSBR can be directly blended with plastics, asphalt and other materials by adopting machines such as a screw extruder, a colloid mill and the like, and becomes a new application field at present. Powdering of natural rubber was first achieved in 1930 in the laboratory by mechanical grinding and addition of bone meal from Dunlop, uk. The commercial success of PSBR was marked by the production of PSBR by the Goodrich company, B.F., the U.S. Pat. No. 1950, by the conventional physical mechanical grinding of bulk rubber with the addition of a release agent. The PSBR produced by the mechanical crushing technology has the defects of high energy consumption, high cost, large product particle size and the like.
The physical crushing method is that the block rubber is crushed to proper grain size by a crushing machine with a fixed cutter or a fly cutter, and then the crushed block rubber is sieved by a sieve plate, and the grains with unqualified grain size are returned to the crusher for crushing. The separant is added once in each cycle, and the qualified granules enter a fine powder machine provided with an impeller and a radiation type blade. Adding a separant for further crushing, and passing the particles meeting the particle size requirement through a screen to finally form a product.
The PSBR with small particle size can be prepared by slicing the block rubber, freezing the rubber below the glass transition temperature and then crushing. This production technique, although saving energy in the pulverizing stage, requires a large amount of energy to cool the sheet rubber below the glass transition temperature.
In 1986, Toyo Sodo mfg. company developed a chemical pulverizing method for pulverizing bulk styrene butadiene rubber into ultrafine particles, which is totally different from physical pulverizing technology in that the effect of pulverizing bulk rubber is achieved by adding chemicals and specific chemical process. The company performed various pulverization tests on the established test apparatus. The results show that the block rubber after being crushed by the technology can be easily mixed with various fillers and additives, and the dispersibility of the fillers and the additives is powerfully improved. However, the mechanical crushing method not only consumes high kinetic energy cost, but also needs to add a blocking agent to ensure that the crushed adhesive scraps are not bonded.
At present, the PSBR is prepared by emulsion polymerization, a latex coagulation method is adopted for PSBR preparation, proper coating agents, anti-aging agents, fillers and the like are added into E-SBR latex for coagulation, and the E-SBR latex is processed by the procedures of filtering, washing, drying and the like, wherein the coating agents adopt water-insoluble substances as coating agents, and can form a layer of colloid protective film on the surfaces of latex particles, so that the rubber particles are isolated into powder. A large amount of dust is generated when PSBR is produced by traditional inorganic powder isolation rubber particles, so that environmental pollution and human health are harmed.
PSBR is used in great amount in road modified asphalt and waterproof roll. Compared with solution polymerized styrene butadiene rubber, emulsion polymerized PSBR has the characteristics of large molecular weight (Mn is 20-26 ten thousand), wide distribution, high branching degree, small amount of gel, large self-adhesiveness, cold flow, high cohesive force and the like. However, the PSBR with high branching degree and cohesion and small amount of gel is not favorable for melting processing in the modified asphalt. The emulsion PSBR has styrene content not higher than 25 wt%, and has styrene in the molecule distributed randomly and small amount of gel in the polymer cannot be avoided. And the commercial anionic polymerization styrene-butadiene rubber such as Solprene-1205 and related similar products SSBR-1205 has styrene (S)/butadiene (B) of 25/75, wherein the content of the first-stage polystyrene is not more than 17 wt% of the total styrene content, the molecules are linear structures, and the molecular weight Mn is 14 ten thousand.
In the self-adhesive asphalt waterproof roll industry, the creep and shake, etc.: development of high heat-resistant self-adhesive polymer modified asphalt waterproof coiled material [ J ], novel building material and Wangshi, research on stripping performance of polymer modified asphalt self-adhesive waterproof coiled material [ J ], material research and Liweiguo, Staufeng, Paeonia ostii, a high heat-resistant self-adhesive rubber asphalt waterproof coiled material: 200710120808.3[ P ] 2007-08-27, et al describe that materials such as SBS, PSBR, rubber oil and the like are used for preparing self-adhesive modified asphalt waterproof coiled materials, in the technology, when emulsion powder PSBR is mixed with asphalt, even if the mixture is stirred at a high speed of 180 ℃, the surface of SBR is swelled, particles are locally bonded, the melting speed of emulsion powder PSBR is reduced, the PSBR swelling time is as long as 2.5h, and a large amount of heat energy and processing time are consumed; in addition, the latex PSBR has gel which is not melted in the asphalt, so that the rubber and the asphalt are layered, the modification effect is poor, and the original asphalt has poor low-temperature resistance, high glass transition temperature and poor low-temperature flexibility due to no rubber plasticization at part of the asphalt. The SBS has no self-adhesion property and needs to show the viscosity under the action of softening oil. In addition, some brands only use SBS as modifier and do not add random styrene-butadiene rubber in the self-adhesive asphalt waterproof coiled material sold in the market, and the products have the defects of poor low-temperature flexibility, brittleness temperature of more than-6 ℃, lower peel strength and the like.
Disclosure of Invention
Aiming at the defects of the existing powder styrene-butadiene rubber PSBR in the preparation method and the modified asphalt, the invention aims to provide the powder polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber which has a special styrene block and a random copolymerization block structure of conjugated diene and divinylbenzene and has better initial viscosity, low-temperature flexibility and peeling strength.
The second purpose of the invention is to provide a simple and low-cost method for preparing the partially powdered polystyrene-poly-conjugated diene rubber, which can directly obtain the powdered polystyrene-poly-conjugated diene rubber without machine crushing and using a release agent, has mature process conditions, is environment-friendly, has wide raw material sources, and meets the requirement of industrial production.
The third purpose of the invention is to provide the application of the partially powdered polystyrene-poly conjugated diene rubber in the preparation of modified asphalt, which can be used for preparing self-adhesive modified asphalt waterproof coiled materials, hot-melt modified asphalt waterproof coiled materials or low-temperature-resistant road modified asphalt and the like with excellent performance, and has the characteristics of low temperature resistance, higher ductility, higher peel strength and heat resistance.
In order to achieve the above technical objects, the present invention provides a powdery polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber consisting of a styrene homo-block, a conjugated diene and a divinylbenzene random copolymerized block;
the number average molecular weight of the styrene homopolymerization block is 20000-30000;
the number average molecular weight of the conjugated diene and divinylbenzene random copolymer block is 220000-250000;
the mass ratio of the styrene unit to the conjugated diene unit in the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber is 20-30: 80-70;
the mass percentage of the divinylbenzene unit in the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber is 0.05-0.15 per mill.
The polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber of the present invention has the structure of formula 1,
S-B/I/D
formula 1
Wherein S is a styrene homopolymerized block, and B/I/D is a random copolymerization block of butadiene and/or isoprene and divinylbenzene; the S block with proper molecular weight is introduced into the rubber, and the S block has strong intermolecular force and good crystallization property, thereby being beneficial to powdering; however, if the S block is too long, the Tg of the rubber increases and the low temperature resistance is poor; if the styrene block is too short, Tg is lowered, but the cohesive force of the polymer is lowered, which is not favorable for powdering and molding of the polymer. And the B/I/D block is distributed in a branched chain or is slightly crosslinked, so that the rubber material has excellent initial viscosity, low-temperature flexibility and peeling strength. A small amount of divinyl benzene units are introduced into the rubber, and the B/I/D block copolymer is branched, so that the elastic flow and the cohesive force of the polymer are increased, and the powdered polymer is prevented from self-bonding.
Preferably, the mass of the 1, 4-structure conjugated diene unit in the random copolymer block of the conjugated diene and divinylbenzene is 85% or more of the total mass of the conjugated diene units. If the contents of the 1, 2-structure butadiene unit and the 3, 4-structure isoprene unit are too high, the glass transition temperature of the rubber can be increased, resulting in an increase in the brittleness temperature of the modified asphalt material and poor low temperature resistance.
In a preferred embodiment, the conjugated diene is butadiene and/or isoprene. The molar ratio of the two is 0-100% to 0-100%. The introduction of isoprene unit into the rubber can properly increase the viscous flow of the S-B/I/D rubber and improve the initial adhesion and peel strength of the modified asphalt.
In a preferred embodiment, the particle size of the powdery polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber is < 2 mm.
In a preferred embodiment, the powdery polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber has a 300% stress at elongation at break of 0.6 to 1.2 MPa.
The invention also provides a method for preparing the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber, wherein in an anionic polymer system containing anisole, a styrene monomer is firstly added for homopolymerization; after homopolymerization is finished, adding butadiene and/or isoprene and divinylbenzene mixed monomer for random copolymerization to obtain a glue solution of polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber; and removing the solvent from the glue solution through condensation to obtain the glue solution.
In a preferable scheme, the concentration of the anisole in an anionic polymerization system is 25-50 mg/kg. Anisole with relatively weak regulating capacity is selected as a structure regulator and an activator, so that the content of the 1, 4-addition product of the conjugated diene unit can be effectively increased. It is not suitable to use a Lewis base having a strong energy-adjusting ability, such as tetrahydrofuran, ethers or tertiary amines.
In a preferred embodiment, the homopolymerization conditions are as follows: reacting at 50-60 deg.c for 20-25 min.
In a preferred embodiment, the random copolymerization reaction conditions are: reacting at 60-80 ℃ for 20-25 min.
The glue solution of the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber is firstly put into boiling water, and is coagulated to remove the solvent cyclohexane under stirring, the coagulation process is similar to the conventional SBS coagulation process, no powdery separant or coating agent is needed to be additionally used, the coagulated glue material is naturally dispersed and has no self-adhesion, and bulk powder with the particle size less than 2mm can be formed by filtering and drying.
The invention also provides application of the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber, and the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber is used as an asphalt modifier to be applied to self-adhesive modified asphalt waterproof coiled materials, hot-melt modified asphalt waterproof coiled materials or low-temperature-resistant road modified asphalt.
In the preferable scheme, the usage amount of the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber in the self-adhesive modified asphalt waterproof coiled material, the hot-melt modified asphalt waterproof coiled material or the low-temperature-resistant road modified asphalt is 3.7 to 5 weight percent.
In a preferred scheme, the self-adhesive modified asphalt waterproof coiled material comprises the following components in parts by mass: 30-50 parts of asphalt base material, 4-8 parts of polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber powder, 4-8 parts of SBS, 6-15 parts of rubber oil and 15-25 parts of powder.
In a further preferred embodiment, the asphalt base stock is 10# asphalt, 70# asphalt or 90# asphalt.
In a further preferred embodiment, SBS is YH-791 and/or YH-792.
Further preferred is a rubber oil CA-12 and/or CA-18; the powder material is talcum powder and/or calcium powder.
The self-adhesive modified asphalt waterproof coiled material has excellent comprehensive properties: the tearing strength is more than or equal to 28N, and the peeling strength is more than or equal to 1.3N/mm; heat resistance, no displacement at 75 ℃ for 2h, low-temperature flexibility and no crack at-25 ℃.
The method for preparing the self-adhesive modified asphalt waterproof coiled material by using the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber powder comprises the following steps:
firstly, putting a certain amount of asphalt base stock into a reaction kettle, heating the mixture on an electric furnace to 180-210 ℃, adding 3.7-5 wt% of polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber powder, SBS, rubber oil, powder and a small amount of antioxidant 1076 into the mixture, stirring the mixture for 90min under the stirring of 80-150 r/min, and then using PET non-woven fabric as an inner lining to coat and scrape modified asphalt material and related samples and detection.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the polystyrene-b-random copolymerization conjugated diene/divinyl benzene rubber simultaneously has a styrene block and a random conjugated diene block with branched chain distribution or slight crosslinking, and the special molecular structure endows the rubber with easy crushing, good initial viscosity, low-temperature flexibility, peeling strength and other properties.
(2) The preparation method of the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber is simple, can be synthesized by utilizing the existing mature process, has wide raw material sources, and meets the requirements of industrial production.
(3) The polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber powder can be used for modified asphalt, is particularly suitable for modification of materials such as self-adhesive modified asphalt waterproof coiled materials, hot-melt modified asphalt waterproof coiled materials or low-temperature-resistant road modified asphalt, does not need additional granulation or machine powdering, has no dust pollution, and effectively improves the low temperature resistance, higher ductility, higher peel strength, heat resistance and the like of the modified asphalt.
Detailed Description
The following examples are intended to illustrate the present invention, and the scope of the claims of the present invention is not limited by the examples.
In the following examples:
the number average molecular weight of the polymer was measured by Gel Permeation Chromatography (GPC).
The microstructure of the polymer was determined using a NEXUS-870 Fourier transform infrared spectrometer.
The softening point of the modified asphalt is measured by an HD L R-IV type asphalt high-temperature softening point tester.
The initial viscosity performance of the modified asphalt is measured by adopting an L T-3000 annular initial viscosity tester.
The peel strength of the modified asphalt was measured by using B L D-200S type electron peel tester.
Tensile properties of the polymer were measured using a CMT4104 model Universal tensile machine.
Example 1
Adding 10 percent by mass n-hexane solution 3500m L into a 5 liter polymerization kettle under the protection of nitrogen, then adding 0.09m L anisole, heating the solvent in the polymerization kettle to 50-60 ℃ by using hot water, then adding 100g of styrene into the polymerization kettle, stirring, then injecting 0.5 mol/L n-butyllithium 11m L into the polymerization kettle by using a syringe, reacting for 20-25 min, then adding 334.7g of butadiene and 0.05m L of a mixed monomer of divinylbenzene, reacting for 25min at 50-90 ℃, and then obtaining the polymer (S-B/D) with the number average molecular weight Mn (S) of 250000, wherein the number average molecular weight Mn (S) of the block polystyrene is 20400, and the butadiene segment 1, 4-addition content is 93.8%.
And then discharging the polymer, adding 1.05g of antioxidant 1076 into the glue solution, stirring the glue solution, adding the glue solution into boiling water, stirring for 40min, filtering out water after the solvent is completely evaporated, and drying at the temperature of 80 ℃ for 2h to obtain the polystyrene-b-atactic polybutadiene/divinylbenzene powder rubber, wherein the rubber particle diameter is less than or equal to 2mm, and the 300% stress at definite elongation is 0.74 MPa.
Example 2
Under otherwise unchanged conditions in example 1 above, the amount of butadiene was selected to be 257.2g, divinylbenzene 0.06m L and anisole 0.18m L, and as a result, the number average molecular weight Mn of the synthesized polymer (S-B/D) was 266000, wherein the number average molecular weight Mn of the block polystyrene (S) was 20200, the polybutadiene block 1, 4-addition content was 90.3%, the particle size of the dried polystyrene-B-random copolymerized polybutadiene/divinylbenzene rubber was 1.9mm or less, and the 300% stress at constant elongation was 0.98 MPa.
Example 3
Under otherwise unchanged conditions in example 1 above, the polymer synthesized (S-B/D) had a number average molecular weight Mn of 265000, where the number average molecular weight Mn of the block polystyrene (S) was 20600 and the polybutadiene block 1, 4-addition content was 91.5%, and the particle size of the dried polystyrene-B-random copolymerized polybutadiene/divinylbenzene rubber was not more than 1.8mm and the 300% stress at constant elongation was 0.86MPa, except that the amount of butadiene used was 400g, the amount of divinylbenzene used was 0.05m L and the amount of anisole used was 0.15m L.
Example 4
In the case where other conditions were not changed in the above example 1, only butadiene was selected as isoprene and the amount of isoprene used was 233.5g, resulting in the synthesis of a polymer (S-I/D) having a number average molecular weight Mn of 270000, a number average molecular weight Mn of block polystyrene (S) 19700 and a polyisoprene block 1, 4-addition content of 87.9%. The particle diameter of the dried polystyrene-b-random copolymerization isoprene/divinylbenzene rubber is less than or equal to 2mm, and the 300 percent stress at definite elongation is 0.62 MPa.
Example 5
Under otherwise unchanged conditions in example 4 above, the amount of isoprene was 300g, the amount of divinylbenzene was 0.04m L, and the amount of anisole was 0.17m L. As a result, the number average molecular weight Mn of the synthesized polymer (S-I/D) was 246000, wherein the number average molecular weight Mn of the block polystyrene (S) was 19300, the polyisoprene block 1, 4-addition content was 85.6%, the particle diameter of the polystyrene-b-random copolymerized isoprene/divinylbenzene rubber after drying was 1.9mm or less, and the 300% stress at constant elongation was 0.69 MPa.
Example 6
Respectively and uniformly dividing 1000g of No. 70 asphalt into 5 parts, placing the 5 parts in 500m L beakers, then respectively adding 14g of polystyrene-b-random copolymerization conjugated diene/divinylbenzene powder rubber sample, 8g of SBS (YH-791), 30g of rubber oil (CA-12), 30g of talcum powder and calcium powder and 10760.7g of antioxidant in the above examples 1-5, placing the beakers on an electric furnace, heating the beakers to 180 degrees centigrade and 210 degrees centigrade, stirring the beakers for 90min at a stirring speed of 80-150 r/min, then uniformly coating the modified asphalt material on PET non-woven fabric, and cooling the PET non-woven fabric to room temperature to form the modified asphalt material.
TABLE 1 physical Properties of rubber-modified asphalt materials prepared in examples 1-5
Example 7
Adding 10 percent by mass n-hexane solution 3500m L into a 5 liter polymerization kettle under the protection of nitrogen, then adding 0.1m L of anisole, heating the solvent in the polymerization kettle to 50-60 ℃ by hot water, then adding 100g of styrene into the polymerization kettle and stirring, then injecting 0.5 mol/L of n-butyl lithium 9m L into the polymerization kettle by using an injector, reacting for 20-25 min, then adding 200g of butadiene, 200g of isoprene and 0.05m L of divinylbenzene, reacting for 25min at 50-90 ℃, and then obtaining the polymer (S-B/I/D) with the number average molecular weight Mn (S) ═ 266000, wherein the number average molecular weight Mn (S) ═ 22300 of the block polystyrene and the 1, 4-addition content of the poly conjugated diene block is 88.4%.
And then discharging the polymer, adding 1.05g of antioxidant 1076 into the glue solution, stirring the glue solution, adding the glue solution into boiling water, stirring for 40min, filtering out water after the solvent is completely evaporated, and drying at the temperature of 80 ℃ for 2h to obtain the polystyrene-b-atactic polybutadiene-isoprene/divinylbenzene powder rubber, wherein the rubber particle diameter is less than or equal to 1.8mm, and the 300% stress at definite elongation is 1.20 MPa.
Example 8
Under otherwise unchanged conditions in the above example 7, only anisole was selected to be 0.15m L, butyllithium was selected to be 8m L, butadiene was selected to be 35g, isoprene was selected to be 300g, and divinylbenzene was selected to be 0.04m L, and as a result, the number average molecular weight Mn of the synthesized polymer (S-B/I/D) was 268000, where the number average molecular weight Mn of the block polystyrene (S) (S) (-25200.) the random copolymerized diene segment 1, 4-addition content was 86.8%. the polystyrene-B-random copolymerized polybutadiene-isoprene/divinylbenzene rubber after drying had a particle diameter of 1.9mm or less and a 300% proof stress of 0.94 MPa.
Example 9
In the case where other conditions were not changed in the above example 7, only anisole was selected as 0.17m L, butyllithium as 7m L, butadiene as 100g, isoprene as 200g and divinylbenzene as 0.04m L, the number average molecular weight Mn of the synthesized polymer (S-B/I/D) was 268000, wherein the number average molecular weight Mn of the block polystyrene (S) was 29200, the random copolymerized diene segment 1, 4-addition content was 86.8%, the particle diameter of the dried polystyrene-B-random copolymerized polybutadiene-isoprene/divinylbenzene rubber was 1.9mm or less, and the 300% proof stress was 1.16 MPa.
Example 10
In the case where other conditions were not changed in the above example 7, only anisole was selected as 0.08m L, butyllithium as 7m L, butadiene as 200g, isoprene as 100g and divinylbenzene as 0.02m L, the number average molecular weight Mn of the synthesized polymer (S-B/I/D) was 246000, where the number average molecular weight Mn of the block polystyrene (S) was 29500, the random copolymerized diene block 1, 4-addition content was 89.2%, the particle diameter of the dried polystyrene-B-random copolymerized polybutadiene-isoprene/divinylbenzene rubber was 1.8mm or less, and the 300% proof stress was 1.12 MPa.
Example 11
In the case where other conditions were not changed in the above example 7, only anisole was selected as 0.10m L, butyllithium as 8m L, butadiene as 340g, isoprene as 60g and divinylbenzene as 0.07m L, the number average molecular weight Mn of the synthesized polymer (S-B/I/D) was 281000, wherein the number average molecular weight Mn of the block polystyrene (S) was 25600, the random copolymerized diene segment 1, 4-addition content was 89.8%, the particle diameter of the dried polystyrene-B-random copolymerized polybutadiene-isoprene/divinylbenzene rubber was 1.9mm or less, and the 300% proof stress was 1.23 MPa.
Example 12
In the case where other conditions were not changed in the above example 11, only the amount of butadiene in the mixed monomers was selected to be 250g, the amount of isoprene was 104.5g, and the amount of divinylbenzene was 0.03m L. As a result, the number average molecular weight Mn of the synthesized polymer (S-B/I/D) was 258000, wherein the number average molecular weight Mn of the block polystyrene (S) was 25300. the random copolymerized diene block 1, 4-addition content was 89.2%, the particle diameter of the dried polystyrene-B-random copolymerized polybutadiene-isoprene/divinylbenzene rubber was 1.8mm or less, and the 300% proof stress was 1.17 MPa.
Example 13
1200g of 70# asphalt was uniformly placed in six 500m L beakers, i.e., 200g of 70# asphalt was added to each beaker, 14g of the polystyrene-b-random copolymer conjugated diene/divinylbenzene powder rubber sample of examples 7 to 12, the other components and process conditions were the same as those of example 6, and the results are shown in Table 2.
Table 2 physical Properties of rubber-modified asphalt mixtures prepared in examples 7 to 12
Claims (13)
1. A powdery polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber characterized in that: the styrene homopolymer block, the conjugated diene and the divinylbenzene random copolymer block form a copolymer;
the number average molecular weight of the styrene homopolymerization block is 20000-30000;
the number average molecular weight of the conjugated diene and divinylbenzene random copolymer block is 220000-250000;
the mass ratio of the styrene unit to the conjugated diene unit in the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber is 20-30: 80-70;
the mass percentage of the divinylbenzene unit in the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber is 0.05-0.15 per mill.
2. The powdery polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 1, wherein: the mass of the conjugated diene unit having a 1, 4-structure in the random copolymer block of a conjugated diene and divinylbenzene is 85% or more of the total mass of the conjugated diene units.
3. The powdery polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 2, wherein: the conjugated diene is butadiene and/or isoprene.
4. The powdery polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 1, wherein: the grain diameter is less than 2 mm.
5. The powdery polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 1, wherein: the 300% stress at definite elongation is 0.6-1.2 MPa.
6. A process for producing the polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to any one of claims 1 to 5, wherein: firstly, adding a styrene monomer into an anionic polymer system containing anisole to carry out homopolymerization; after homopolymerization is finished, adding a conjugated diene and divinylbenzene mixed monomer for random copolymerization to obtain a glue solution of polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber; and removing the solvent from the glue solution through condensation to obtain the glue solution.
7. The process of polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 6, wherein: the concentration of the anisole in an anionic polymerization system is 25-50 mg/kg.
8. The process of polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 6, wherein: the homopolymerization reaction conditions are as follows: reacting at 50-60 ℃ for 20-25 min.
9. The process of polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 6, wherein: the random copolymerization reaction conditions are as follows: reacting at 60-80 ℃ for 20-25 min.
10. Use of a polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber as claimed in any one of claims 1 to 5, wherein: the modified asphalt modifier is used as an asphalt modifier for self-adhesive modified asphalt waterproof coiled materials, hot-melt modified asphalt waterproof coiled materials or low-temperature-resistant road modified asphalt.
11. Use of a polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 10, wherein: the dosage of the polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber in the self-adhesive modified asphalt waterproof coiled material, the hot-melt modified asphalt waterproof coiled material or the low-temperature-resistant road modified asphalt is 3.7-5 wt%.
12. Use of a polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 11, wherein: the self-adhesive modified asphalt waterproof coiled material comprises the following components in parts by mass: 30-50 parts of asphalt base material, 4-8 parts of polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber powder, 4-8 parts of SBS, 6-15 parts of rubber oil and 15-25 parts of powder; the powder material is talcum powder and/or calcium powder.
13. Use of a polystyrene-b-random copolymerized conjugated diene/divinylbenzene rubber according to claim 12, wherein: the asphalt base material is 10# asphalt, 70# asphalt or 90# asphalt; the SBS is YH-791 and/or YH-792; the rubber oil CA-12 and/or CA-18.
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| 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 |
| CN112480341A (en) * | 2019-09-12 | 2021-03-12 | 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 |
| CN113563549A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer and preparation method 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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