CN113563549A - Asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer and preparation method thereof - Google Patents
Asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer and preparation method thereof Download PDFInfo
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- CN113563549A CN113563549A CN202010356516.5A CN202010356516A CN113563549A CN 113563549 A CN113563549 A CN 113563549A CN 202010356516 A CN202010356516 A CN 202010356516A CN 113563549 A CN113563549 A CN 113563549A
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- block copolymer
- isoprene
- polyethylene
- butylene
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 21
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 77
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 63
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 60
- 238000005984 hydrogenation reaction Methods 0.000 claims description 54
- 238000006116 polymerization reaction Methods 0.000 claims description 51
- 239000002674 ointment Substances 0.000 claims description 25
- 239000013307 optical fiber Substances 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 230000003287 optical effect Effects 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000004793 Polystyrene Substances 0.000 claims description 16
- 229920002223 polystyrene Polymers 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 14
- 229920005604 random copolymer Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000011049 filling Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 238000011925 1,2-addition Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 72
- 239000003921 oil Substances 0.000 description 29
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003349 gelling agent Substances 0.000 description 5
- 150000004678 hydrides Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000009974 thixotropic effect Effects 0.000 description 4
- 229920000428 triblock copolymer Polymers 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920000359 diblock copolymer Polymers 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 229920006030 multiblock copolymer Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000006223 plastic coating Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4479—Manufacturing methods of optical cables
- G02B6/4483—Injection or filling devices
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer, a preparation method and application thereof. The asymmetric branched polystyrene-B-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer (S-B-E/B/P/D) is obtained by hydrogenating an asymmetric branched polystyrene-B-isoprene-butadiene random copolymerization block copolymer (S-B-I/B/D), and the S-B-E/B/P/D polymer has the characteristics of asymmetric long-chain branching, high side chain group, high intermolecular entanglement degree and the like.
Description
Technical Field
The invention relates to a hydrogenated styrene-b-conjugated diene random copolymerization block copolymer, a preparation method and application thereof, in particular to an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer and a preparation method thereof, and also relates to an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer which is used as a thickening agent or a gelling agent and applied to optical fibers or optical cable filling factice, belonging to the technical field of special rubber synthesis in the optical fiber communication signal industry.
Background
The optical cable is composed of optical fibre, protective sleeve and plastic sheath, and is used as communication line for transmitting communication signals. The optical cable ointment is a filler in an optical cable sheath, plays roles of insulation, water prevention and moisture prevention, prevents water vapor (rainwater, river seawater and the like) outside the optical cable sheath from entering the optical cable by utilizing the property of incompatibility of water and oil, plays a role of liner protection on the optical fiber, and can buffer the optical fiber from being damaged due to the influence of mechanical vibration, impact, bending and the like.
Traditional mineral white oil has insulating nature good, the non-corrosive effect, but the white oil that flows easily has the sagging nature big as the filler of optical cable under normal atmospheric temperature, and when the optical cable was laid in slope or U type ground, the white oil in the sheath can sink to the lower extreme, and the sheath upper end can form hollowly, does not play the guard action. It is therefore a viable approach if a thickening polymer or gelling agent is added to the white oil to increase the state of the oil which is rendered non-flowable under static or mechanical shear. However, the white oil thickened polymer must have elements, one of which has good insulation properties; the second one has good compatibility with white oil; and thirdly, after being mutually dissolved with white oil, the polymer has low enough kinematic viscosity under the action of shearing, high enough stiffness under static state and no vertical flow (or cold flow), namely, the polymer has excellent thixotropy. Meanwhile, the ointment has moderate dropping point and viscosity, and good cone penetration and steel mesh oil separation performance. In addition, the thixotropy of the optical fiber ointment has great significance for the secondary plastic coating process and the mechanical protection of the optical fiber when the optical cable is laid, for example, in the secondary plastic coating process, the optical fiber ointment is pumped into the head of an extruder by a mechanical pump and then is injected into an optical fiber loose tube. The ointment rapidly decreases in viscosity under the shearing action of the mechanical pump to become fluid, and can be uniformly filled into the loose tube. After the loose tube is formed, the external force acting on the ointment is eliminated, and the ointment slowly recovers to a viscous state and does not flow, so that a stable buffer layer is formed. During the cable laying process, the optical fiber is subjected to external forces such as bending, vibration, impact and the like, which can cause the optical fiber to vibrate near the equilibrium position. The shaking with a small period influences the optical fiber ointment to reduce the viscosity of the optical fiber ointment, so that the optical fiber is buffered and protected, and the microbending loss caused by the rigid reaction force of the optical fiber is avoided.
In the prior art, chinese patent (CN107793542A) describes a method for synthesizing a hydrogenated styrene/isoprene block copolymer, which is to synthesize a diblock copolymer or a multiblock copolymer comprising a styrene block and an isoprene block in an anionic polymerization system using nonpolar alkane and toluene as polymerization solvents, and hydrogenate the diblock copolymer or the multiblock copolymer to obtain a hydrogenated styrene/isoprene block copolymer; the method adopts a mixed solvent of nonpolar alkane and toluene, so that the reaction probability of the active PS-Li end group and isoprene can be effectively increased, the content of micromolecule polystyrene in the hydrogenated styrene/isoprene block copolymer is reduced or eliminated, and the dropping point of the two-block or multi-block hydrogenated styrene/isoprene block copolymer when applied to optical fibers and optical cable filling factice is improved. The polymer of the present invention is only used for reducing or eliminating the content of micromolecule polystyrene in a hydrogenated styrene/isoprene block copolymer, but the polymer is a linear polymer, has low entanglement density among molecular chains, does not have the thixotropy, has small viscosity difference in static state or under the stirring and shearing action after the polymer and white oil are mutually dissolved, and has a protective effect of being used as an optical cable filling ointment which is congealing.
In Chinese patent "Lubricating oil viscosity index improver and preparation method thereofThe viscosity index improver is prepared with polyisoprene-b-polybutadiene-b-polystyrene triblock copolymer and through hydrogenating modification,the preparation method comprises the steps of adding a regulator into a polymerization reaction kettle at the temperature of 60-70 ℃ and the pressure of 0.1-0.5 MPa, and then sequentially adding an isoprene monomer, a butadiene monomer and a styrene monomer for polymerization reaction; and after the polymerization reaction is finished, obtaining a polyisoprene-b-polybutadiene-b-polystyrene triblock copolymer, and carrying out hydrogenation reaction on the obtained triblock copolymer to obtain the polyisoprene-b-polybutadiene-b-polystyrene triblock copolymer. The polymer molecular chain is long-chain linear molecules, the entanglement degree among the molecules is low, the thixotropic behavior is not ideal, but the polymer has a thickening effect when being added into mineral oil, and the polymer is not applied to optical cable factice.
Chinese patent (CN102731739A) describes a star polymer of lubricating oil viscosity index improver, its preparation method and application, the star polymer has asymmetric arms, which are composed of two different types of polymer arms, the first type of arm is hydrogenated polyisoprene homopolymer, the second type of arm is copolymer of hydrogenated polyisoprene-hydrogenated polybutadiene-polystyrene block structure, in the copolymer arm, the polystyrene block is close to the core of the star polymer, the hydrogenated polybutadiene block is in the middle of the arm, and the hydrogenated isoprene block is outside the arm. The star polymer structure contains 2-15% of polybutadiene blocks, and the polyisoprene blocks and the polybutadiene blocks in the star polymer structure are at least partially hydrogenated. The star polymer of the invention not only shows excellent tackifying effect and shear stability, but also has lower pumping viscosity and low-temperature starting viscosity in the preparation of thickened engine oil, and does not form crystals or gel in the engine oil. Research on hydrogenated SIBR used for viscosity index improvers, namely, research on a series of SIBR with controllable molecular weight and narrow molecular weight distribution in a cyclohexane solvent by using n-butyllithium as an initiator, tetrahydrofuran as a structure regulator, styrene, isoprene and butadiene as monomers and adopting a molecular design method and an anionic polymerization technology, is carried out in university of continents, and a high molecular material 2009; a tetrahydrofuran unitary regulating system is adopted to regulate and control the 1,2 structure of a polybutadiene chain segment and the 3,4 structure content of a polyisoprene chain segment in the SIBR. The nickel naphthenate/triisobutyl aluminum is used as a homogeneous catalysis system for involutionThe resultant SIBR sample was subjected to hydrogenation studies. The influence rule of the hydrogenation process conditions on the hydrogenation degree of the SIBR is researched, and the influence of temperature, pressure, time, catalyst dosage, Al/Ni, monomer content and the like on the hydrogenation degree of the SIBR is specifically considered. Research results show that the nickel naphthenate/triisobutylaluminum catalytic system has high catalytic activity and selectivity, the hydrogenation degree of the SIBR reaches 98 percent when the reaction temperature is 60 ℃, the hydrogen pressure is 4MPa, the dosage of the catalyst is 2mg/g dry glue, the Al/Ni is 7, the reaction time is 3h, and the hydrogenation reaction rate of each microstructure in the SIBR is from large to small, namely B1,2 is more than B1,4 is more than I3 and 4. The hydrogenated SIBR can be used as a viscosity index improver, and the main properties of the viscosity index improver comprise thickening capacity, shear stability, high-temperature high-shear property, low-temperature property and the like. (preparation and characterization of star hydrogenated random copolymer HSSIBR, chemical industry and engineering, 04 year 2012) discloses that a star styrene-isoprene-butadiene ternary random copolymer (SIBR) is prepared by anionic polymerization by using divinyl benzene (DVB) as a coupling agent and cyclohexane as a solvent, nickel naphthenate and triisobutylaluminum as catalysts and reacted for 4h at 60 ℃ and 4.0MPa hydrogen pressure to prepare the hydrogenated star styrene-isoprene-butadiene ternary random copolymer (HSIBR) with the hydrogenation degree of 100%. The effect of DVB/Li usage, relative molecular mass of the single arm on polymer Coupling Efficiency (CE) and hydrogenation reactions was examined. And the performance of the lubricating oil is tested by using the self-made HSIBR as the viscosity index improver of the lubricating oil. The result shows that the coupling efficiency of the SIBR obtained by using DVB as a coupling agent reaches 86.8% at most, and the synthesized HSIBR is used as a lubricating oil viscosity index improver. Also in the text of the "molecular structure of viscosity index improver HSD", polymer science and engineering, 11.2012), FT-IR, 1H-NMR and DSC tests on a hydrogenated styrene/conjugated diene (butadiene, isoprene) copolymer (HSD) as a viscosity index improver have shown that HSD is a highly hydrogenated styrene-butadiene block copolymer with a high butadiene content, with a mass fraction of styrene of 18.50%, a mass fraction of butadiene of 81.50% and a butadiene hydrogenation degree of 98.20%. HSD12F number average molecular weight was 4.59X 105g/mol and the one-armed number average molecular weight was 6.47X 104g/mol as determined by gel chromatography GPC, indicating that HSD12F wasA star-shaped styrene-butadiene block copolymer with an arm number of 7.10 and a coupling efficiency of 86.44%. That is, the polymer was a linear living polymer before coupling and then coupled with DVB, but in such a coupling method, DVB was added to the living lithium polymer, and due to the higher activity of divinylbenzene, DVB combined with the living lithium chain soon copolymerized with DVB monomer to produce a large amount of gel, while other living molecular chains were not coupled, i.e. the coupling efficiency described herein was 86.44%, and 13.56% of the polymer was still linear. That is, the use of a polymer containing a gel or a linear polymer as a viscosity index improver for lubricating oils is not scientific and is insufficient in that the fluid has a gel which is liable to be clogged. ("Branching based on anionic polymerization Synthesis of copolymer and study of assembling behavior thereof”，HuanhuanghuaThe university of Compound denier, 2013(08)) teaches that branched block copolymers are a class of multiblock hyperbranched structures linked by polymer chains between branching points. Wherein the multi-component block leads the performance of the whole polymer to be diversified, so the macromolecule has wide application prospect in various aspects such as biology, medicine, materials and the like. Anionic polymerization, as a living polymerization in the true sense, has unique advantages in the synthesis of block copolymers with well-defined components and polymers with precisely controllable structures. Therefore, synthetic means based on anionic techniques are undoubtedly an efficient method for preparing branched block copolymers. A method for continuously synthesizing a ternary branched block copolymer by anionic polymerization is provided, and the self-assembly behavior of the obtained copolymer is studied. A method of direct conversion from anionic polymerization to reversible addition-fragmentation chain transfer polymerization is employed. However, there is no specific report on the use of the tri-branched block copolymer in optical cable factice.
At present, the existing polymer for the optical cable ointment is mainly SEP G1701 and G1702 produced by KRATON company, which are diblock polymers and have unknown molecular configurations; in addition, similar polymers appear in the market in the Chenghu chemical industry company of Zhejiang province in China, but all the produced polymers are linear polymers, and when the polymers are used as optical cable ointment, the defects of poor oil gripping performance, low stiffness, large vertical flow, high dropping point, easy separation of steel mesh oil and the like are shown, and the polymers are not suitable for a gelling thickener for the optical cable ointment.
Disclosure of Invention
Aiming at the defects that hydrogenated polystyrene-isoprene diblock polymers (SEP) in the prior art are linear molecules, the entanglement density between molecular chains is low, the thixotropic property is poor, the viscosity difference of factice formed by mutually dissolving the polymers and white oil is not large under the static state or under the stirring and shearing action, and the optical cable filling factice prepared by matching with the white oil has low oil-holding property (oil condensation is not easy to be aggregated), low stiffness, large vertical flow, high dropping point, easy separation of steel mesh oil and the like. The first purpose of the invention is to provide an asymmetric branched polystyrene-B-polyethylene-butylene-isopropylene-propylene multi-micro block copolymer (S-B-E/B/P/D), which embodies thermoplastic behavior, is stable under the conditions of light, heat and the like, does not generate qualitative change in behavior, has unexpected shear thixotropy, is particularly suitable for gelling and thickening agents in optical fiber and optical cable filling factice, and has the characteristics of small addition amount, high dissolution rate, good shear thixotropy, strong condensation capacity, low dropping point and the like when being filled into white oil.
The second purpose of the invention is to provide a method for preparing the asymmetric branched polystyrene-B-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer (S-B-E/B/P/D) with simple operation and low cost.
The third purpose of the invention is to provide an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer as a gelling agent or thickening agent in optical fiber or optical cable filling ointment, which has the characteristics of small addition amount, high dissolution rate, good shearing thixotropy, strong condensation capability, low dropping point and the like.
In order to achieve the above technical object, the present invention provides an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer obtained by hydrogenating an asymmetric branched polystyrene-b-isoprene-butadiene random copolymer block copolymer;
the asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer has the following expression: S-B-I/B/D;
wherein,
s is a polystyrene block;
I/B/D is a random copolymer block of isoprene, butadiene and divinylbenzene.
The hydrogenated asymmetric branched polystyrene-B-isoprene-butadiene random copolymer block copolymer provided by the invention is an asymmetric branched polystyrene-B-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer S-B-E/B/P/D, and the polymer is obtained by hydrogenating an asymmetric branched long-chain polystyrene-B-isoprene-butadiene random copolymer block copolymer S-B-I/B/D. The asymmetric branched long-chain polystyrene-b-isoprene-butadiene random copolymerization block copolymer has the following expression: S-B-I/B/D, wherein S is a styrene homopolymerized block, B is a block, which means block covalent bonds, I/B/D is an isoprene, butadiene and divinylbenzene random copolymerization block, I, B, D is an isoprene, butadiene and divinylbenzene unit respectively, and D is a random branched chain node of divinylbenzene, and the random branched chain node is randomly distributed in polymer long chain molecular chain links, and the derived branched long chain presents asymmetric distribution in a molecular main chain. S-B-I/B/D is hydrogenated to obtain an asymmetric branched polystyrene-B-polyethylene-butylene-propylene-isopropylene multi-micro block polymer, which has the following expression: S-B-E/B/P/D, wherein S is a styrene homopolymerization unit, B is a block covalent bond, E/B/P/D is a hydrogenation product of a random copolymerization block of isoprene, butadiene and divinylbenzene, and E is ethylene-CH2-CH2Chain units, mainly resulting from the hydrogenation of butadiene 1, 2-addition or 1, 4-addition, or isoprene 1, 2-addition or 3, 4-addition or 1, 4-addition units; b is a 1-ethyl unit, mainly produced by 1, 2-addition hydrogenation of butadiene; p is a propyl or isopropyl unit, which is mainly generated by hydrogenation of an isoprene 1, 2-addition or 3, 4-addition unit; d is a benzene ring in a divinyl benzene chain node, and the preferred E/B/P/D are all randomly distributed, the polymerization degree of each unit of E, B, P is not higher than 5, and the polymerization degree of D is not higher than 2.
As a preferred embodiment, the asymmetric branched polystyrene-b-isoprene-butadiene random copolymer has a degree of hydrogenation of isoprene and butadiene units of more than 95%. Preferably the degree of hydrogenation is greater than 98%. The higher the hydrogenation degree, the better the rubber aging resistance.
In a preferred embodiment, the polymerization degree of the polyethylene, polybutene, polypropylene and polyisopropylene micro-blocks contained in the asymmetric branched polystyrene-b-polyethylene-butene-propylene-isopropene multi-micro-block copolymer is not higher than 5. The presence of a homo-block having a high degree of polymerization results in disadvantages of high rigidity, high modulus and poor compatibility with white oil.
In a preferred embodiment, the asymmetric branched polystyrene-B-isoprene-butadiene random copolymer has a block mass ratio S/(I + B) ═ 25 to 40)/(75 to 60.
In a preferred embodiment, the mass ratio of isoprene to butadiene blocks in the I/B/D is (50 to 95)/(50 to 5). The block mass ratio I/B is more preferably (80-95)/(5-20).
As a preferable technical scheme, the mass percentage content of D in the I/B/D is 0.05-0.08%. Too high a level of DVB results in a polymer with too high a degree of branching and a tendency to gel, and if the level is too low, too low a level of branching is produced and it is difficult to produce sufficiently asymmetric long chains.
In a preferred embodiment, the number average molecular weight Mn of S in the asymmetric branched polystyrene-B-isoprene-butadiene random copolymer block copolymer is 20000 to 30000, and the number average molecular weight Mn of I/B/D is 70000 to 80000. The polystyrene blocks have a molecular mass large enough to ensure that the final polymer has sufficient stiffness and strength so that the polymer is readily dispersible, non-blocking, and readily soluble in white oil.
In a preferred embodiment, the total amount of the 1, 2-addition unit of butadiene and the 1, 2-addition unit and 3, 4-addition unit of isoprene in the asymmetric branched polystyrene-b-isoprene-butadiene random copolymer is 58 to 70% of the total mass of isoprene and butadiene units. The polymer contains excessive side chains, so that the entanglement degree of the polymer can be improved, and the thixotropic property of the ointment can be improved.
In a preferred embodiment, the asymmetric branched polystyrene-b-isoprene-butadiene random copolymer has a molecular mass distribution index MW/Mn of 1.15 to 1.25.
As a preferable technical scheme, the melt index of S-B-E/B/P/D provided by the invention is 8.0g/10 min-14 g/10 min.
The invention also provides a preparation method of the hydrogenated asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer, which comprises the steps of adding styrene, a solvent and an activator into a polymerization reaction kettle, heating to the initial polymerization temperature, adding an initiator into the polymerization reaction kettle for first-stage polymerization, slowly dropwise adding a mixed monomer consisting of divinylbenzene, butadiene and isoprene into the polymerization reaction kettle after the first-stage polymerization is finished, carrying out second-stage polymerization to obtain an asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer glue solution, transferring the asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer glue solution into a hydrogenation reaction kettle for hydrogenation reaction and water vapor condensation, and (5) drying to obtain the product.
In the first-stage polymerization process, the active lithium polystyrene has enough molecular mass to ensure that the polymer has enough stiffness and strength, so that the polymer is easy to disperse, non-adhesive and easy to dissolve in white oil; the second stage of polymerization employs continuous feeding of mixed monomers, which is aimed at the relatively uniform participation of butadiene, isoprene and Divinylbenzene (DVB) monomers in chain growth, because divinylbenzene has two forward orbitals in common with the other two diene monomers and two vinyl groups have strong "donor-acceptor" electronic effects on the large benzene ring, so that the rate of polymerization is much higher than that of butadiene and isoprene, and it is highly desirable to employ continuous feeding to maintain a relatively low concentration of DVB in the bulk, reduce the probability of molecular "collision" or formation of buttresses, and avoid homopolymerization (or polymerization of less than 2) of DVB. With the growth of the active polymer chain, the branching degree of the polymer molecular chain is also increased, and the entanglement degree of the molecular chain of the final polymer is improved. This is one of the technical cores of the present invention. In addition, the number of living polymer chains is constant, and the molecular weight of the final polymer is not excessively widened and low molecular weight fractions are not excessively generated as the molecular chain grows.
As a preferable technical scheme, the dropping time of the mixed monomer consisting of the divinyl benzene, the butadiene and the isoprene is 40-50 min. The randomness of the polymer can be effectively controlled by controlling the dropping rate of the mixed monomers.
As a preferable technical scheme, the initial polymerization temperature is 50-60 ℃, the time for polymerization is 20-25 min, and after the mixed monomers are dripped, the temperature is controlled to be 50-75 ℃ and then the polymerization reaction is carried out for 20-25 min.
As a preferable technical scheme, the hydrogenation reaction adopts a nickel-based catalytic system to carry out selective catalytic hydrogenation. The further preferable hydrogenation catalyst is hexane complex of nickel naphthenate-diisobutylaluminum hydride, the preferable nAl/nNi is 1/(3.0-3.5), and n is the number of molecules; the preferable hydrogenation temperature is 65-85 ℃, the hydrogenation time is 2.0-3.0 h, the hydrogenation hydrogen pressure is 1.2-1.6 MPa, the hydrogenation degree of the polymer is not less than 95%, and the hydrogenation degree is not less than 98% more preferably. The preferable dosage of the nickel naphthenate-diisobutylaluminum hydride complex is 0.4-0.8 mmoL/100g of polymer calculated by Ni.
As an optimal technical scheme, in the hydrogenation reaction process, the temperature is controlled to be 65-85 ℃, the time is 2.5-3.0 h, and the hydrogen pressure is 1.2-1.6 MPa.
As a preferred embodiment, cyclohexane is selected as the polymerization solvent.
As a preferred technical scheme, the activating agent is at least one of tetrahydrofurfuryl alcohol vinyl ether, tetrahydrofurfuryl amine and ditetrahydrofurfuryl propane; the dosage of the activating agent is 280-350 mg/kg of solvent.
The preparation method of the asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer comprises the following steps: in the presence of hydrocarbon as solvent, n-butyl lithium as initiator, furfuryl alcohol ether as activating structure regulator and divinyl benzene as branching agent, styrene, butadiene and isoprene are made to produce anionic copolymerization to obtain S-B-I/B/D glue solution. The specific polymerization method adopts a two-step method: firstly, adding quantitative cyclohexane, styrene and a small amount of activating agent into a closed steel container with stirring, heating the polymerization solution to 50-60 ℃ by using a hot water bath, adding butyl lithium into a polymerization kettle for initiation once again, and polymerizing for 20-25 min; and secondly, slowly and continuously adding a mixed monomer of butadiene, isoprene and divinylbenzene into the polymerization system in the first step, wherein the polymerization temperature is 50-75 ℃, the continuous feeding time of the mixed monomer is 50-60 min, and after the mixed monomer is fed, reacting for 20min, so as to completely convert the monomer.
The method for preparing the S-B-E/B/P/D by hydrogenating the asymmetric branched polystyrene-B-isoprene-butadiene random copolymerization block copolymer comprises the following steps: adding a certain amount of nickel naphthenate-diisobutyl aluminum hydride complex catalyst into a steel kettle filled with S-B-I/B/D glue solution, starting stirring, introducing hydrogen into the hydrogenation kettle to carry out hydrogenation reaction, adding an antioxidant 1076 with the mass part of total dry glue of 0.3-0.4% into the hydrogenated glue solution when the hydrogenation degree of a polymer reaches more than 95%, uniformly mixing, and finally condensing, drying and briquetting the polymer glue solution containing the antioxidant by using water vapor to obtain the S-B-E/B/P/D bulk raw glue.
In the preparation method of the asymmetric branched polystyrene-b-polyethylene-butylene-isopropylene-propylene multi-micro block copolymer, units such as polymerization, hydrogenation, drying and the like are realized according to the well-known lithium SEBS or SEPS process in the industry.
The invention also provides an application of the asymmetric branched polystyrene-b-polyethylene-butylene-isopropylene-propylene multi-micro block copolymer, which is used as a thickening agent or a gelling agent to optical fiber or optical cable filling ointment.
As a preferable scheme, the asymmetric branched polystyrene-B-polyethylene-butylene-isopropylene-propylene multi-micro block copolymer is matched with white oil for use, and the S-B-E/B/P/D and the white oil have good intersolubility.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
aiming at the defects that polymers with similar purposes in the prior art are mainly linear molecules, the entanglement density between molecular chains is low, the thixotropic property is poor, the viscosity difference of factice formed by mutually dissolving the polymers and white oil is not large under static state or shearing action, the oil-grabbing property is low, the stiffness is low, the vertical flow is large, the dropping point is high, steel mesh oil is easy to separate and the like, and the use requirement of the factice for filling optical fibers of optical cables is difficult to meet. The asymmetric branched polystyrene-B-polyethylene-butylene-propylene-isopropylene multi-tiny block copolymer S-B-E/B/P/D has proper molecular mass and molecular mass distribution index, the long chain branching degree and side branch unit content of a molecular chain are high, the entanglement degree among polymer molecular chains is high, and meanwhile, the double bond content of the polymer is extremely low, so that the gel is not easy to occur; the prepared ointment has proper viscosity, and the ointment has good shear thixotropy (namely good use performance), high static stiffness, low dropping point, difficult separation of steel mesh oil and the like when being sheared during the processing of the filled optical fiber, and is very suitable for being used as a material for filling and protecting the optical fiber of the optical cable.
The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer can be prepared by the traditional equipment and process, and has simple preparation method and low cost.
Detailed Description
The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention. The number average molecular weight and molecular weight distribution index of the polymer were measured by Gel Permeation Chromatography (GPC) in the following examples; determining the microstructure content of the polymer by H-NMR spectroscopy by using Aacend (TM) 400; the melt index MFR (g/10min, 200 ℃/5kg) of the polymer finished raw rubber is determined by adopting Zwick roll; the drop point of the ointment is tested at 200 ℃; testing the steel mesh oil separation under the condition of 70 ℃/24h, wherein the fiber paste is less than 1 percent; the penetration degree is determined by the penetration depth of the cone after the ointment is placed for 24h and the cone penetrates into the ointment for 5 seconds; other testing methods were performed as is well known in the art.
Example 1
Adding 3500mL of cyclohexane solution of 10% by mass of n-hexane into a 5-liter polymerization kettle under the protection of nitrogen, then adding 1.0mL of tetrahydrofurfuryl alcohol ethyl ether into the polymerization kettle, then heating the materials to 55-60 ℃ by using steam, then adding 80g of styrene, immediately adding 4.5mL of 1.02mol/L n-butyllithium solution into the polymerization kettle, starting initiation, after 20min of polymerization reaction, adding a mixed monomer mixed with 193mL of butadiene, 176mL of isoprene and 0.15mL of divinylbenzene into the polymerization kettle at a uniform speed within 45min, controlling the polymerization temperature to be not higher than 75 ℃, and reacting for 20min after the mixed monomer is added. As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn 82500 (wherein the polystyrene stage number average molecular weight was Mn 22300), a molecular weight distribution index of 1.18 and a content of a pendant unit (containing a vinyl group, a 3, 4-addition unit, etc.) in the molecular chain of 58.4%.
Putting the glue solution into a 5-liter hydrogenation kettle, adding 25.6mL of hexane complex of nickel naphthenate-diisobutylaluminum hydride (wherein nAl/nNi is 1/3.3, and the content of nickel is 0.50mol/L of hexane aging solution), controlling the hydrogen pressure to be 1.3-1.5 MPa, after hydrogenation is carried out for 150min at 70-85 ℃, measuring the hydrogenation degree to be 98.7%, stopping the hydrogenation reaction at the moment, adding 1.0g of 1076 antioxidant into the glue solution, uniformly mixing, condensing by water vapor, and drying to obtain the catalyst. The melt index of the hydride was measured to be 8.3g/10 min.
Example 2
The relevant polymerization conditions in example 1 were kept unchanged except for changing the amount of n-butyllithium solution to 4.0mL, the amount of tetrahydrofurfuryl alcohol ethyl ether to be used to 1.2mL, the amount of butadiene to be used to 26mL, the amount of isoprene to be used to 300mL, the amount of divinylbenzene to be used to 0.14mL, and the monomer mixture addition time to be 40 min. As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn of 78700 (wherein the polystyrene segment number average molecular weight was Mn of 24600), a molecular weight distribution index of 1.13 and a content of pendant unit (containing vinyl group and 3, 4-addition unit) of 63.4% in the molecular chain.
The same hydrogenation process as in example 1 except that 30.0mL of the catalyst aging solution was added, the hydrogenation reaction time was 120min, and the hydrogenation gel solution was condensed with water vapor and dried, to obtain 98.2% hydrogenation degree of the hydride and a melt index of 11.6g/10 min.
Example 3
The relevant polymerization conditions in example 1 were kept unchanged except that the amount of styrene used was 4.0mL of 100g of an n-butyllithium solution, the amount of tetrahydrofurfuryl alcohol ethyl ether used was 1.5mL, the amount of butadiene used was 55mL, the amount of isoprene used was 300mL, the amount of divinylbenzene used was 0.14mL, and the mixed monomer addition time was 50 min. As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn 95600 (wherein the polystyrene segment number average molecular weight was Mn 25700), a molecular weight distribution index of 1.18 and a content of a side chain unit (containing a vinyl group and a 3, 4-addition unit) of 67.3%.
The hydrogenation process of the polymerization virgin rubber is the same as that of example 1, except that 26.0mL of the added catalyst aging solution is added, after the hydrogenation reaction time is 130min, the hydrogenation rubber solution is condensed and dried by water vapor, and the hydrogenation degree of the hydride is measured to be 98.4%, and the melt index is 9.3g/10 min.
Example 4
The relevant polymerization conditions in example 3 were kept unchanged except for changing the amount of tetrahydrofurfuryl alcohol ethyl ether to 1.5mL, the amount of n-butyllithium solution to 3.0mL, the amount of butadiene to 120mL, the amount of isoprene to 130mL, the amount of divinylbenzene to 0.13mL, and the mixed monomer addition time to 50 min. As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn-102300 (wherein the polystyrene segment number average molecular weight was Mn-28600), a molecular weight distribution index of 1.16, and a content of a side chain unit (containing a vinyl group and a 3, 4-addition unit) of 68.5%.
The same hydrogenation process as in example 1 except that 22.0mL of the catalyst aging solution was added, the hydrogenation reaction time was 120min, and after the hydrogenated gum solution was condensed with water vapor and dried, the hydrogenation degree of the hydride was 98.4% and the melt index was 9.4g/10 min.
Example 5
The relevant polymerization conditions in example 3 were kept unchanged except for changing the amount of tetrahydrofurfuryl alcohol ethyl ether used to 1.2mL, the amount of butadiene used to 100mL, the amount of isoprene used to 220mL, the amount of divinylbenzene to 0.15mL, and the mixed monomer addition time to 40 min. As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn 83600 (wherein the polystyrene stage number average molecular weight was Mn 29500), a molecular weight distribution index of 1.12 and a content of a molecular chain side unit (containing a vinyl group and a 3, 4-addition unit) of 62.6%.
The same hydrogenation process as in example 1 except that 28.0mL of the catalyst aging solution was added, the hydrogenation reaction time was 140min, and after the hydrogenated gum solution was condensed with water vapor and dried, the hydrogenation degree of the hydride was 98.9% and the melt index was 10.6g/10 min.
Example 6
The asymmetric branched polystyrene-B-polyethylene-butylene-propylene-isopropenyl multi-small block copolymer S-B-E/B/P/D prepared in examples 1 to 5 and SEP (G1702) produced by kraton company of a comparison sample are respectively added into 300mL of 6 naphthenic white oil (KN4006) in 500mL beakers, then the beakers are heated to 80 ℃, the temperature is maintained and the mixture is stirred for 2 hours, at this time, S-B-EBP/D sizing material is dissolved in the white oil, and the prepared optical fiber filling ointment is analyzed and determined according to the regulations, and the results are shown in Table 1.
TABLE 1
Note ". about" assay conditions: is prepared from 15g ointment and 10 g water.
It can be easily found that the optical fiber filling ointment made of the polymer of the invention has excellent comprehensive performance and good thixotropy and processing behavior.
Claims (16)
1. An asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer, which is characterized in that: obtained by hydrogenating an asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer;
the asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer has the following expression: S-B-I/B/D;
wherein,
s is a polystyrene block;
I/B/D is a random copolymer block of isoprene, butadiene and divinylbenzene.
2. The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 1, wherein: the asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer has a hydrogenation degree of isoprene and butadiene units of more than 95%.
3. The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 1, wherein: the mass ratio S/(I + B) of the blocks in the asymmetric branched polystyrene-B-isoprene-butadiene random copolymer is (25-40)/(75-60).
4. The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 1, wherein: in the I/B/D, the mass ratio of isoprene to butadiene blocks, I/B, is (50-95)/(50-5).
5. The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 1, wherein: the mass percentage content of the divinylbenzene in the I/B/D is 0.05-0.08%.
6. The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 1, wherein: the number average molecular weight Mn of S in the asymmetric branched polystyrene-B-isoprene-butadiene random copolymerization block copolymer is 20000-30000, and the number average molecular weight Mn of I/B/D is 70000-80000.
7. The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 1, wherein: the total amount of 1, 2-addition units of butadiene and 1, 2-addition units and 3, 4-addition units of isoprene in the asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer accounts for 58-70% of the total mass of isoprene and butadiene units.
8. The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 1, wherein: the molecular mass distribution index of the asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer is 1.15-1.25.
9. The asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 1, wherein: the polymerization degree of the polyethylene, the polybutylene, the polypropylene and the polyisopropene micro-blocks contained in the asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropene multi-micro block copolymer is not higher than 5.
10. The method for preparing an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to any one of claims 1 to 9, wherein the method comprises the following steps: adding styrene, a solvent and an activating agent into a polymerization reaction kettle, heating to the initial polymerization temperature, adding an initiator into the polymerization reaction kettle to carry out first-stage polymerization, slowly dropwise adding a mixed monomer consisting of divinylbenzene, butadiene and isoprene into the polymerization reaction kettle after the first-stage polymerization is finished, carrying out second-stage polymerization to obtain an asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer glue solution, transferring the asymmetric branched polystyrene-b-isoprene-butadiene random copolymerization block copolymer glue solution into a hydrogenation reaction kettle, carrying out hydrogenation reaction, condensing water vapor, and drying to obtain the styrene-b-isoprene-butadiene random copolymerization block copolymer glue solution.
11. The method for preparing an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 10, wherein: the dropping time of the mixed monomer consisting of the divinylbenzene, the butadiene and the isoprene is 40-50 min.
12. The method for preparing an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 10, wherein: the initial polymerization temperature is 50-60 ℃, the time for one-stage polymerization is 20-25 min, and after the mixed monomers are dripped, the temperature is controlled to be 50-75 ℃ and then the polymerization reaction is carried out for 20-25 min.
13. The method for preparing an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 10, wherein: the hydrogenation reaction adopts a nickel-based catalytic system to carry out selective catalytic hydrogenation.
14. The method for preparing an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 10, wherein: in the hydrogenation reaction process, the temperature is controlled to be 65-85 ℃, the time is 2.5-3.0 h, and the hydrogen pressure is 1.2-1.6 MPa.
15. The method for preparing an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer according to claim 10, wherein: the activating agent is at least one of tetrahydrofurfuryl alcohol vinyl ether, tetrahydrofurfuryl amine and ditetrahydrofurfuryl propane; the dosage of the activating agent is 280-350 mg/kg of solvent.
16. The use of an asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-mini-block copolymer according to any one of claims 1 to 9, wherein: can be used as thickener or gel for filling ointment for optical fiber or optical cable.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4156673A (en) * | 1976-02-10 | 1979-05-29 | Shell Oil Company | Hydrogenated star-shaped polymer |
| US4412087A (en) * | 1981-12-16 | 1983-10-25 | Phillips Petroleum Company | Viscosity index improver with high thickening power |
| US5096973A (en) * | 1988-02-13 | 1992-03-17 | Huels Aktiengesellschaft | Abc block copolymers based on butadiene, isoprene and styrene, process for their production and their use |
| CN105175659A (en) * | 2015-07-23 | 2015-12-23 | 湖南博瑞康新材料有限公司 | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor |
| CN106317350A (en) * | 2015-07-07 | 2017-01-11 | 中国石油化工股份有限公司 | Partially hydrogenated polystyrene-b-random copolymer conjugated diene/styrene copolymer and its preparation method and use |
| CN107236102A (en) * | 2016-03-29 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber and its preparation method and application |
| CN110719924A (en) * | 2017-06-09 | 2020-01-21 | 科腾聚合物有限责任公司 | Highly asymmetric triblock polymer compositions and methods of making the same |
-
2020
- 2020-04-29 CN CN202010356516.5A patent/CN113563549B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4156673A (en) * | 1976-02-10 | 1979-05-29 | Shell Oil Company | Hydrogenated star-shaped polymer |
| US4412087A (en) * | 1981-12-16 | 1983-10-25 | Phillips Petroleum Company | Viscosity index improver with high thickening power |
| US5096973A (en) * | 1988-02-13 | 1992-03-17 | Huels Aktiengesellschaft | Abc block copolymers based on butadiene, isoprene and styrene, process for their production and their use |
| CN106317350A (en) * | 2015-07-07 | 2017-01-11 | 中国石油化工股份有限公司 | Partially hydrogenated polystyrene-b-random copolymer conjugated diene/styrene copolymer and its preparation method and use |
| CN105175659A (en) * | 2015-07-23 | 2015-12-23 | 湖南博瑞康新材料有限公司 | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor |
| CN107236102A (en) * | 2016-03-29 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber and its preparation method and application |
| CN110719924A (en) * | 2017-06-09 | 2020-01-21 | 科腾聚合物有限责任公司 | Highly asymmetric triblock polymer compositions and methods of making the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115785357A (en) * | 2022-12-06 | 2023-03-14 | 沈阳化工研究院有限公司 | Hydrogenated styrene-b-conjugated diene-isoprene triblock copolymer and preparation method and application thereof |
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