CN109504018B - Polymer composition of two-arm styrene-conjugated diene, preparation and application in asphalt modification - Google Patents
Polymer composition of two-arm styrene-conjugated diene, preparation and application in asphalt modification Download PDFInfo
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- CN109504018B CN109504018B CN201710831518.3A CN201710831518A CN109504018B CN 109504018 B CN109504018 B CN 109504018B CN 201710831518 A CN201710831518 A CN 201710831518A CN 109504018 B CN109504018 B CN 109504018B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 207
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 150000001993 dienes Chemical class 0.000 title claims abstract description 37
- 239000010426 asphalt Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000012986 modification Methods 0.000 title description 6
- 230000004048 modification Effects 0.000 title description 6
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000005859 coupling reaction Methods 0.000 claims description 31
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- -1 alkyl lithium Chemical compound 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- NUNQKTCKURIZQX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-2-methylpropane Chemical compound CCOCCOC(C)(C)C NUNQKTCKURIZQX-UHFFFAOYSA-N 0.000 claims description 3
- FQQBAHSCHMASLR-UHFFFAOYSA-N 2-(2-methoxyethoxy)-2-methylpropane Chemical compound COCCOC(C)(C)C FQQBAHSCHMASLR-UHFFFAOYSA-N 0.000 claims description 3
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 claims description 3
- VURQSZFNTIBNIQ-UHFFFAOYSA-N 2-methyl-2-(2-propoxyethoxy)propane Chemical compound CCCOCCOC(C)(C)C VURQSZFNTIBNIQ-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- QEHKWLKYFXJVLL-UHFFFAOYSA-N dichloro(dimethoxy)silane Chemical compound CO[Si](Cl)(Cl)OC QEHKWLKYFXJVLL-UHFFFAOYSA-N 0.000 claims description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 claims description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 2
- 229960001826 dimethylphthalate Drugs 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 6
- 229920001195 polyisoprene Polymers 0.000 abstract description 4
- 239000005062 Polybutadiene Substances 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 229920002857 polybutadiene Polymers 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000004575 stone Substances 0.000 abstract description 2
- 229920001059 synthetic polymer Polymers 0.000 abstract description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 19
- 230000008878 coupling Effects 0.000 description 16
- 238000010168 coupling process Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polymer composition of two-arm styrene-conjugated diene, which comprises (SB)2X two-arm polymer and (SB) X (is) asymmetric two-arm polymer; SB is a styrene-butadiene block polymer arm; IS a styrene-isoprene block polymer arm; and X is a coupling agent residue. The invention also comprises a preparation method and application of the polymer composition. Polyisoprene is regularly introduced into a traditional SBS structure, so that the material has better toughness, the elongation of the synthetic polymer is improved, the modified asphalt has better toughness, and the polyisoprene has stronger viscosity than polybutadiene and has better viscosity with paving base materials such as stone, mineral powder and the like, so that the rutting resistance of the pavement is further improved. In addition, the introduction of isoprene improves the fluidity of the polymer and shows better processing performance in the processing process of the modified asphalt.
Description
Technical Field
The invention relates to the field of asphalt modification, in particular to an asphalt modified polymer with two arms and containing an asymmetric radial copolymer.
Technical Field
The modified asphalt can be used for various purposes such as paving, waterproofing rolls, partition sheets, roofing materials, etc. With the development of society, the demand for the performance of modified asphalt is higher and higher, and researchers improve the performance of asphalt by adding various polymers, such as ethylene-vinyl acetate copolymer, latex, ethylene-ethyl acrylate copolymer, copolymer containing conjugated diene and vinyl aromatic hydrocarbon, and the like. However, ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer have poor low temperature properties, poor toughness, and exhibit poor aggregate bonding properties when paving. The latex modified asphalt has better low-temperature performance, but insufficient high-temperature performance and some problems in processing.
The copolymer of conjugated diene and vinyl aromatic hydrocarbon can better solve some defects of the materials. Patent publication No. CN1190459C discloses a block copolymer composition for modifying asphalt. Which contains two block polymers: a block polymer comprising at least two polymer blocks of a monoalkenyl aromatic compound and at least one copolymer block comprising a conjugated diene compound; the other block polymer contains at least one polymer block of a monoalkenyl aromatic compound and mainly comprises a conjugated diene polymer. The polymer modified asphalt is used for improving drainage performance and reducing environmental noise, and has higher softening point and mechanical strength but insufficient toughness.
Patent publication CN101300306 discloses a polymer composition comprising a linear styrene-butadiene-styrene coupled block copolymer together with a plurality of diblock copolymers. The polymer has good processability, but the dynamic viscosity of the product is insufficient, and the high-temperature performance is also required to be improved.
The asymmetric radial block copolymer with four arms in the publication No. CN1138055A contains two copolymerization arms of conjugated diene and vinyl aromatic hydrocarbon and two homopolymer or copolymer arms of conjugated diene, and is block copolymerized or homopolymerized star polymer, which has relatively high molecular weight, is not easy to disperse in asphalt, has poor processability when used for modifying asphalt, and can not meet the processing requirement when used for porous pavement.
There are also a number of technical problems in the art and there is a need in the art for an asphalt-modified polymer having high performance.
Disclosure of Invention
The purpose of the present invention is to provide a polymer composition of a two-arm styrene-conjugated diene.
A second object of the present invention is to provide a method for producing a two-arm styrene-conjugated diene polymer composition.
The third purpose of the invention is to provide the application of the polymer composition in the aspect of asphalt modification.
Polymerization of two-arm styrene-conjugated dieneA composition of matter comprising (SB)2X two-arm polymer and (SB) X (is) asymmetric two-arm polymer; SB is a styrene-butadiene block polymer arm; IS a styrene-isoprene block polymer arm; and X is a coupling agent residue.
The present inventors have found, through extensive studies, (SB)2The X double-arm polymer and the (SB) X (IS) asymmetric double-arm polymer have good synergistic effect, and the (SB) X (IS) has better adhesive property and toughness, increases the compatibility with other materials, and contributes to synergistically improving the viscosity, dynamic viscosity, high-temperature performance and the like of the asphalt.
The inventors have found that, among the polymer compositions described, the ones (SB) are suitable2The content of the X two-arm polymer and the (SB) X (IS) asymmetric two-arm polymer can further improve the synergistic effect of the two.
Preferably, in the polymer composition, (SB)2The mass percentage of the X two-arm polymer is more than or equal to 50 percent; the mass percentage of the (SB) X (IS) asymmetric two-arm polymer is less than or equal to 50%.
Further preferably, in the polymer composition, (SB)2The mass percentage of the X two-arm polymer is 50-80%. (SB) X (IS) asymmetric two-arm polymer accounts for 5-20% by mass.
Preferably, the weight of bound styrene in the polymer composition is 10 to 50 Wt%; the butadiene block (B block) and the isoprene block (I block) have a 1, 2-structure content of 5 to 40 Wt%.
Preferably, the polymer further comprises a diblock polymer, the diblock polymer comprising at least one of a SB block polymer and a SI block polymer.
Preferably, in the polymer composition, the two-block polymer accounts for 5 to 40 percent by mass; preferably 5 to 20%.
More preferably, the SB block polymer accounts for 5 to 20 mass% (more preferably 5 to 8 mass%) of the polymer composition; the mass percentage of the SI block polymer is 5 to 20% (more preferably 5 to 13%).
Preferably, the polymer composition of the two-arm styrene-conjugated diene comprises the following components in percentage by weight:
(SB)250-80% of X double-arm polymer;
(SB) X (IS) 5-20% of asymmetric two-arm polymer;
5-20% of SB block polymer;
SI block polymer 5-20%.
Further preferably, in the polymer composition, the weight percentages of the components are as follows:
(SB)265-72% of X double-arm polymer;
(SB) X (IS) 10-20% of asymmetric two-arm polymer;
5-8% of SB block polymer;
SI block polymer 5-13%.
In the present invention, the molecular weight of the styrene-butadiene block polymer arm and the molecular weight of the styrene-isoprene block polymer arm are each 30000 to 100000.
The SB block polymer has an S/B ratio of 10 to 50.
In the SI block polymer, the S/I ratio is 10 to 30.
The invention also provides a preparation method of the two-arm styrene-conjugated diene polymer for asphalt modification, which comprises the following steps:
step (1): respectively preparing a living SB block polymer and a living SI block polymer through anionic polymerization;
step (2): firstly, mixing an active SB block polymer with a coupling agent, and carrying out a coupling reaction to obtain a coupling reaction solution;
and (3): adding an active SI block polymer into the coupling reaction liquid in the step (2) to carry out a second-stage coupling reaction;
and (4): and (3) after the reaction in the step (3) is finished, terminating and post-treating to obtain the polymer composition.
In the preparation method of the invention, the active SB block polymer is preferably reacted with a site of the coupling agent to form a segment of coupling agentProduct (labeled SBX-); the other coupling site of one-stage coupling product is partially reacted with the remaining living SB block polymer to form (SB)2X; the other part is reacted with the living SI block polymer to form the (SB) X (IS) asymmetric two-arm polymer.
The living polymer of the present invention is a polymer containing at least one active group (e.g., a carbanion) which is easily obtained by anionic polymerization.
In the present invention, the preparation process of the living SB block polymer is: polymerizing a solution containing styrene, a polarity modifier A, an alkyl lithium A, and a hydrocarbon solvent A; then adding butadiene for continuous polymerization to obtain the active SB block polymer;
in the invention, the preparation process of the active SI block polymer comprises the following steps: polymerizing a solution containing styrene, a polarity regulator B, an alkyl lithium B and a hydrocarbon solvent B; and then adding pentadiene for continuous polymerization to obtain the active SI block polymer.
Preferably, the alkyl lithium A and the alkyl lithium B are independently selected from butyl lithium and/or sec-butyl lithium.
The addition amount of the alkyl lithium A and the alkyl lithium B is determined according to the designed molecular weight of the SB block arm and the SI block arm, and the molecular weight is controlled to be 30000-100000.
Preferably, the polarity regulator A and the polarity regulator B are independently selected from at least one of diglyme 2G, triglyme 3G, dipiperidine ethane DPE, ethylene glycol ethyl tert-butyl ether BEE, ethylene glycol propyl tert-butyl ether BPE, ethylene glycol methyl tert-butyl ether MEB, tetramethyl ethylene diamine TMEDA, tetrahydrofuran THF, ditetraoxyethane DME, ethyl tetrahydrofurfuryl ether TEFE and N, N-dimethyltetrahydrofurfuryl amine.
Preferably, the amount of the polarity modifier A and the polarity modifier B is 10mg/Kg to 200mg/Kg (Kg is the weight of the reaction solvent).
Preferably, the hydrocarbon solvent A and the hydrocarbon solvent B are independently selected from at least one of cyclohexane, pentane, hexane, heptane and benzene.
Preferably, the polymerization temperature in the preparation process of the active SB block polymer and the active SI block polymer is 20-100 ℃, and preferably 30-80 ℃.
Under the temperature, the temperature of the styrene block polymerization process is 20-100 ℃, and the polymerization time is 20-40 min; then keeping the temperature, and continuing to polymerize with butadiene or pentadiene for 20-40 min; respectively obtain the active SB block polymer or the active SI block polymer.
In the invention, the coupling agent is a compound with two coupling reaction sites; also known as a two-arm coupling agent.
Preferably, the coupling agent comprises: at least one of dichlorodimethylsilyl, dichlorodimethyltin, dichlorodimethoxysilane, dimethyl phthalate, epoxidized soybean oil and maleic anhydride.
Preferably, the molar ratio of the coupling agent to the living diblock polymer is (1: 2) to (1: 25). It is also contemplated that the molar ratio of coupling agent to active single arm is from 1:2 to 1: 25. That is, the molar ratio of coupling agent to (the sum of living SB block polymer and living SI block polymer) is from 1:2 to 1: 25.
The temperature of the coupling reaction is 30-80 ℃.
The present invention also includes a method for preparing a two-armed styrene-conjugated diene polymer composition, comprising the steps of:
(a) respectively and fully mixing styrene with butadiene or isoprene monomer, continuously and uniformly adding the mixture and an alkyl lithium initiator into a reaction kettle, carrying out anionic polymerization in a hydrocarbon solvent under the presence of a polarity regulator, and reacting for 25-60 min to obtain a group of active styrene-butadiene or active styrene-isoprene random copolymer arms;
(b) coupling the living polymer arms of the styrene-butadiene random copolymerization obtained in step (a) with a two-arm coupling agent,
(c) completing the coupling reaction while leaving at most one unreacted coupling site on the coupling agent,
(d) adding another group of styrene-isoprene active random copolymer arms into the reaction system to carry out coupling reaction,
(e) after the reaction is finished, isopropanol is used for stopping the reaction, water vapor is condensed, and the two-arm asymmetric radiation copolymer is obtained after drying.
The invention also provides application of the polymer composition of the two-arm styrene-conjugated diene as an asphalt modification additive.
Preferably, in said application, said polymer composition is added to the bitumen in an amount of from 4.5 to 12% by weight.
The invention also provides modified asphalt, which comprises the asphalt to be modified and the polymer composition.
The softening temperature of the modified asphalt is more than 90 ℃; the segregation value is less than 5 ℃; the ductility is more than 25 cm.
More preferably, in the modified asphalt, the penetration degree is more than or equal to 45dmm, the softening point is more than or equal to 90 ℃, the ductility is more than or equal to 34cm, the viscosity and toughness are more than or equal to 24N.m, the toughness is more than or equal to 18N.m, and the rotational viscosity at 90 ℃ is 330 Pa.s.
The ductility test of the modified asphalt is carried out according to a T0605-. The modified asphalt of the present invention is suitable for, for example, porous pavements, and has a high softening point, excellent ductility and storage stability.
The polymers of the invention can have a molecular weight and an amount of bound styrene that can vary over a wide range. The molecular weight of these diblock polymer arms is generally in the range of 30000 to over 100000. The content range of the combined styrene is 10-50%.
The arms and the number of the arms of the radial polymer are tested by a Gel Permeation Chromatography (GPC) method, a sample is taken after the first coupling is completed to carry out GPC analysis, so that the coupling degree and the SB content of the first coupling arm can be known, a sample is taken again after the second different coupling arm is reacted to carry out GPC analysis, so that the total coupling degree and the SI content can be analyzed, and then the total coupling degree and the SI content are compared and analyzed with the GPC after the first coupling, so that the distribution conditions of two different arms can be obtained.
Advantageous effects
Polyisoprene is regularly introduced into a traditional SBS structure, so that the material has better toughness, the elongation of the synthetic polymer is improved, the modified asphalt has better toughness, and the polyisoprene has stronger viscosity than polybutadiene and has better viscosity with paving base materials such as stone, mineral powder and the like, so that the rutting resistance of the pavement is further improved. In addition, the introduction of isoprene improves the fluidity of the polymer and shows better processing performance in the processing process of the modified asphalt.
Detailed Description
Some examples of the invention are set forth below to further illustrate the features thereof, but should not be construed as being limited thereto.
Example 1-polymer 1:
1500g of cyclohexane and 0.3g of tetrahydrofuran are added into a first reaction kettle, 3.4ml (0.5mol/l) of n-butyllithium is added as an initiator, the temperature is raised to 50 ℃, 22g of styrene is added into the reaction kettle for reaction for 25min, 88g of isoprene is added for reaction for 30min for later use. 1500g of cyclohexane and 0.3g of tetrahydrofuran were charged into a second reactor, 7.7ml (0.5mol/l) of n-butyllithium as an initiator were added, the temperature was raised to 50 ℃ and 50g of styrene were charged into the reactor to conduct a reaction for 25min, then 200g of butadiene were added to conduct a reaction for 30min, then 7.1ml (0.31mol/l) of dichlorodimethylsilane was charged into the reactor to conduct a reaction at 60 ℃ for 40min, and a sample was taken to measure the molecular weight and distribution of the product by Gel Permeation Chromatography (GPC). Then adding the styrene-isoprene polymer solution of the first reactor into the coupled reaction system, reacting for 40min at 60 ℃ to couple the rest part of the partially coupled intermediate, and adding methanol to terminate the reaction to obtain a polymer solution; the sample was taken and the product was found to be essentially a two-armed conjugate using Gel Permeation Chromatography (GPC), indicating that a portion of the SI of the two arms was incorporated into the polymer that originally had essentially two arms SB. Then the water vapor is condensed and dried to obtain the polymer. The molecular weight of the SB polymer was 63, 900g/mol, the molecular weight of the SI polymer was 64, 080g/mol, and the diblock (SI and SB) content was 20%.
In the Polymer solution, (SB)265% of an X two-arm polymer;
(SB) X (IS) 15% of an asymmetric two-arm polymer;
SB Block Polymer 8%;
SI Block Polymer 12%.
Example 2:
according to the manner of the polymer 1, the amount of n-butyllithium added was changed to 3.85ml (0.5mol/l) as a butadiene and styrene SB polymerization initiator only, to 2.75ml (0.5mol/l) as an SI polymerization initiator, to a molecular weight of 77, 690g/mol for the SB polymer, 80, 350g/mol for the SI polymer and 10% for the diblock content.
In the Polymer solution, (SB)271% of an X double-arm polymer;
(SB) X (IS) 19% of an asymmetric two-arm polymer;
5% of SB block polymer;
SI Block Polymer 5%.
Examples 3 to 6:
linear coupled polymers of 4 different coupling agents were prepared as Polymer 1, with the polymer reactions and test results listed in Table 1.
TABLE 1
The reactions of different coupling agents are emphasized, as are the two-block structure distributions of the other cases.
Example 7:
1500g of cyclohexane and 0.3g of tetrahydrofuran are added into a first reaction kettle, 3.4ml (0.5mol/l) of n-butyllithium is added as an initiator, the temperature is raised to 50 ℃, 44 styrene is added into the reaction kettle for reaction for 25min, 66g of isoprene is added for reaction for 30min for later use. 1500g of cyclohexane and 0.3g of tetrahydrofuran were charged into a second reactor, 7.7ml (0.5mol/l) of n-butyllithium as an initiator were added, the temperature was raised to 50 ℃ and 100g of styrene were charged into the reactor to conduct a reaction for 25min, then 1500g of butadiene were added to conduct a reaction for 30min, then 7.1ml (0.31mol/l) of dichlorodimethylsilane was charged into the reactor to conduct a reaction at 60 ℃ for 40min, and a sample was taken to measure the molecular weight and distribution of the product by Gel Permeation Chromatography (GPC). Then adding the styrene-isoprene polymer solution in the first reactor into the reaction system after the partial coupling, reacting for 40min at 60 ℃, enabling the rest part of the partial coupled intermediate to be coupled, adding methanol to stop after the reaction is finished, sampling and measuring the product to be basically a two-arm coupling product by using Gel Permeation Chromatography (GPC), and indicating that the original polymer basically provided with two arms SB is connected with part of the SI of the two arms. Then the water vapor is condensed and dried to obtain the polymer. The molecular weight of the SB polymer was 64, 100g/mol, the molecular weight of the SI polymer was 65, 030g/mol, and the diblock (SB and SI) content was 17.5%.
In the Polymer solution, (SB)272% of an X double-arm polymer;
(SB) X (IS) asymmetric two-arm Polymer 10.5%;
5.5% of SB block polymer;
SI Block Polymer 12%.
Example 8:
1500g of cyclohexane and 0.3g of tetrahydrofuran are added into a first reaction kettle, 3.4ml (0.5mol/l) of n-butyllithium is added as an initiator, the temperature is raised to 50 ℃, 25 g of styrene is added into the reaction kettle for reaction for 25min, 37.5g of isoprene is added for reaction for 30min for later use. 1500g of cyclohexane and 0.3g of tetrahydrofuran were charged into a second reactor, 7.7ml (0.5mol/l) of n-butyllithium as an initiator were added, the temperature was raised to 50 ℃ and 100g of styrene were charged into the reactor to conduct a reaction for 25min, then 1500g of butadiene were added to conduct a reaction for 30min, then 6.1ml (0.31mol/l) of dichlorodimethylsilane was charged into the reactor to conduct a reaction at 60 ℃ for 40min, and a sample was taken to measure the molecular weight and distribution of the product by Gel Permeation Chromatography (GPC). Then adding the styrene-isoprene polymer solution in the first reactor into the reaction system after the partial coupling, reacting for 40min at 60 ℃, enabling the rest part of the partial coupled intermediate to be coupled, adding methanol to stop after the reaction is finished, sampling and measuring the product to be basically a two-arm coupling product by using Gel Permeation Chromatography (GPC), and indicating that the original polymer basically provided with two arms SB is connected with part of the SI of the two arms. Then the water vapor is condensed and dried to obtain the polymer. The molecular weight of the SB polymer is 65, 020g/mol, the molecular weight of the SI polymer is 64, 830g/mol, and the diblock content is 19.5%.
In the Polymer solution, (SB)268% of an X double-arm polymer;
(SB) X (IS) 12% of an asymmetric two-arm polymer;
6.5% of SB block polymer;
SI Block Polymer 13%.
Comparative example:
1500g of cyclohexane and 0.3g of tetrahydrofuran were charged into a reaction vessel, 7.5ml (0.5mol/l) of n-butyllithium was added as an initiator, the temperature was raised to 50 ℃ and 50g of styrene was charged into the reaction vessel to conduct a reaction for 25min, then 200g of butadiene was added to conduct a reaction for 30min, then 5.1ml (0.31mol/l) of dichlorodimethylsilane was charged into the reaction vessel to conduct a reaction at 60 ℃ for 40min, and a sample was taken to measure the molecular weight and distribution of the product by Gel Permeation Chromatography (GPC). The molecular weight of the SB polymer was 65, 900g/mol, and the SB content of the diblock was 19.3%.
In the Polymer solution, (SB)280.7% of X double-arm polymer;
SB block polymer 19.3%;
evaluation results of sample application properties:
1. weighing 660g of matrix asphalt accurately, and heating to 180 ℃;
2. the polymer 54g and the thermoplastic resin (rosin) 36g in each example were pelletized and mixed, and then added over 5 min.
3. Controlling the temperature to be 180-190 ℃, and then shearing for 30min at the rotation speed of 3500 rpm;
4. shearing for 30min, taking out the oven, standing for 1-2min, and removing bubbles;
5. and testing the performance index of the modified asphalt after pouring and cooling.
TABLE 1 results of Properties of modified asphalt for different samples
Technical Specification for road asphalt pavement construction (JTG F40-2004).
Claims (23)
1. A two-arm styrene-conjugated diene polymer composition comprising (SB)2X two-arm polymer, (SB) X (is) asymmetric two-arm polymer, and diblock polymer; SB is a styrene-butadiene block polymer arm; IS a styrene-isoprene block polymer arm; x is a coupling agent residue;
the two-block polymer comprises an SB block polymer and an SI block polymer;
in the Polymer composition, (SB)2The mass percentage of the X two-arm polymer is more than or equal to 50 percent; (SB) X (IS) the mass percentage of the asymmetric two-arm polymer is less than or equal to 50%; the mass percentage of the SB block polymer is 2-20%; the mass percentage of the SI block polymer is 2-20%.
2. The polymer composition of a two-armed styrene-conjugated diene according to claim 1, wherein (SB) is present in the polymer composition2The mass percentage of the X two-arm polymer is 50-80%.
3. The polymer composition of a two-arm styrene-conjugated diene according to claim 1, wherein the mass percentage of the (SB) X (IS) asymmetric two-arm polymer is 5 to 20%.
4. The polymer composition of a two-armed styrene-conjugated diene as claimed in claim 1, wherein the weight of bound styrene in the polymer composition is from 10 to 50 Wt%; the 1, 2-structure content in the butadiene block and the isoprene block is 5-40 Wt%.
5. The two-armed styrene-conjugated diene polymer composition according to claim 1, wherein the diblock polymer is present in an amount of 5 to 40% by mass of the polymer composition.
6. The polymer composition of a two-arm styrene-conjugated diene according to claim 1, wherein the diblock polymer accounts for 5 to 20% by mass of the polymer composition.
7. The two-armed styrene-conjugated diene polymer composition according to claim 1, wherein the styrene-butadiene block polymer arms and the styrene-isoprene block polymer arms independently have a molecular weight of 30000 to 100000.
8. The two-armed styrene-conjugated diene polymer composition according to claim 1, wherein the SB block polymer has an S/B ratio of 10 to 50.
9. The two-armed styrene-conjugated diene polymer composition according to claim 1, wherein the SI block polymer has an S/I ratio of 10 to 30.
10. A method for preparing the polymer composition of a two-armed styrene-conjugated diene as claimed in any one of claims 1 to 9, comprising the steps of:
step (1): respectively preparing a living SB block polymer and a living SI block polymer through anionic polymerization;
step (2): firstly, mixing an active SB block polymer with a coupling agent, and carrying out a coupling reaction to obtain a coupling reaction solution;
and (3): adding an active SI block polymer into the coupling reaction liquid in the step (2) to carry out a second-stage coupling reaction;
and (4): and (3) after the reaction in the step (3) is finished, terminating and post-treating to obtain the polymer composition.
11. The method for producing a two-armed styrene-conjugated diene polymer composition according to claim 10, wherein a solution comprising styrene, a polarity modifier A, an alkyl lithium A, a hydrocarbon solvent A is polymerized; then adding butadiene for continuous polymerization to obtain the active SB block polymer;
the polarity regulator A is at least one selected from diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dipiperidine ethane, ethylene glycol ethyl tert-butyl ether, ethylene glycol propyl tert-butyl ether, ethylene glycol methyl tert-butyl ether, tetramethyl ethylenediamine, tetrahydrofuran, ethyl tetrahydrofurfuryl ether and N, N-dimethyl tetrahydrofurfuryl amine;
the alkyl lithium A is selected from butyl lithium and/or sec-butyl lithium;
the hydrocarbon solvent A is at least one selected from cyclohexane, pentane, hexane, heptane and benzene.
12. The method for preparing a two-armed styrene-conjugated diene polymer composition according to claim 11, wherein the amount of the polarity modifier A is 10 to 200 mg/kg.
13. The method for producing a two-armed styrene-conjugated diene polymer composition according to claim 10, wherein a solution comprising styrene, a polarity modifier B, an alkyl lithium B, a hydrocarbon solvent B is polymerized; then adding pentadiene for continuous polymerization to obtain the active SI block polymer;
the polarity regulator B is at least one selected from diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dipiperidine ethane, ethylene glycol ethyl tert-butyl ether, ethylene glycol propyl tert-butyl ether, ethylene glycol methyl tert-butyl ether, tetramethyl ethylenediamine, tetrahydrofuran, ethyl tetrahydrofurfuryl ether and N, N-dimethyl tetrahydrofurfuryl amine;
the alkyl lithium B is selected from butyl lithium and/or sec-butyl lithium;
the hydrocarbon solvent B is at least one selected from cyclohexane, pentane, hexane, heptane and benzene.
14. The method for preparing a two-armed styrene-conjugated diene polymer composition according to claim 13, wherein the amount of the polarity modifier B is 10 to 200 mg/kg.
15. The method for preparing a two-armed styrene-conjugated diene polymer composition according to claim 10, wherein the polymerization temperature for the preparation of the living SB block polymer and the living SI block polymer is 20 ℃ to 100 ℃.
16. The method for preparing a two-armed styrene-conjugated diene polymer composition according to claim 15, wherein the polymerization temperature in the preparation of the living SB block polymer and the living SI block polymer is 30 to 80 ℃.
17. The method for producing a two-armed styrene-conjugated diene polymer composition as claimed in any one of claims 10 to 16, wherein the coupling agent comprises: at least one of dichlorodimethylsilyl, dichlorodimethyltin, dichlorodimethoxysilane, dimethyl phthalate, epoxidized soybean oil and maleic anhydride.
18. The method of preparing a two-armed styrene-conjugated diene polymer composition according to claim 17, wherein the molar ratio of coupling agent to (sum of living SB block polymer and living SI block polymer) is from 1:2 to 1: 25.
19. The method of preparing a two-armed styrene-conjugated diene polymer composition as claimed in claim 18, wherein the temperature of the coupling reaction is from 30 ℃ to 80 ℃.
20. The method for preparing a two-armed styrene-conjugated diene polymer composition as claimed in claim 19, wherein the coupling reaction time of step (2) and step (3) is 20 to 40 min.
21. Use of a two-armed styrene-conjugated diene polymer composition according to any one of claims 1 to 9 as a modifying additive for asphalt.
22. Use of a two-armed styrene-conjugated diene polymer composition according to claim 21, wherein said polymer composition is added to the bitumen in an amount of from 4.5 to 12% by weight.
23. A modified asphalt comprising an asphalt to be treated and the polymer composition of a two-arm styrene-conjugated diene according to any one of claims 1 to 9; the penetration degree is more than or equal to 45dmm, the softening point is more than or equal to 90 ℃, the ductility is more than or equal to 34cm, the viscosity and toughness are more than or equal to 24N.m, the toughness is more than or equal to 18N.m, and the rotational viscosity at 90 ℃ is 330 Pa.s.
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