CN104098743B - A kind of random butylbenzene copolymer of multi-arm star of wide distribution polyisocyanates coupling and preparation method thereof - Google Patents
A kind of random butylbenzene copolymer of multi-arm star of wide distribution polyisocyanates coupling and preparation method thereof Download PDFInfo
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- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 46
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 45
- 238000010168 coupling process Methods 0.000 title claims abstract description 15
- 230000008878 coupling Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000009826 distribution Methods 0.000 title abstract description 21
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 title abstract description 17
- 229920001577 copolymer Polymers 0.000 title abstract description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005859 coupling reaction Methods 0.000 claims abstract description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims abstract description 21
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 229920005604 random copolymer Polymers 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 10
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002174 Styrene-butadiene Substances 0.000 claims description 5
- 239000011115 styrene butadiene Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 abstract description 12
- 238000005096 rolling process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229920006978 SSBR Polymers 0.000 description 23
- 229920001971 elastomer Polymers 0.000 description 22
- 239000005060 rubber Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000002156 mixing Methods 0.000 description 15
- 239000005062 Polybutadiene Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 8
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- -1 amide compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- HASGOCLZFTZSTN-UHFFFAOYSA-N cyclohexane;hexane Chemical compound CCCCCC.C1CCCCC1 HASGOCLZFTZSTN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003446 memory effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical class NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- IUMRWGYGZHKZKF-UHFFFAOYSA-N 2-aminoprop-2-enamide Chemical compound NC(=C)C(N)=O IUMRWGYGZHKZKF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920005683 SIBR Polymers 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- OPSGNPOONBMGBQ-UHFFFAOYSA-N chlorobenzene;piperidine Chemical compound C1CCNCC1.ClC1=CC=CC=C1 OPSGNPOONBMGBQ-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of random butylbenzene copolymer of multi-arm star of wide distribution polyisocyanates coupling and preparation method thereof, preparation method is butadiene and/or isoprene mixed with styrene after be added continuously in 40~60min in solvent in tetrahydrofurfuryl alcohol C2~6In the presence of alkyl ether and butyl lithium, generation polymerization obtains active atactic butadiene styrene copolymer at 45~75 DEG C, and obtained active atactic butadiene styrene copolymer and polyisocyanates performed polymer coupling agent are coupled at 50~75 DEG C, after the completion of coupling, is terminated, produced with water；It is high compared with brachyplast chain content on multiple polar group, main chain that there is the random butylbenzene copolymer high molecular weight distribution, middle-end to have, the random butylbenzene copolymer line coordinates with the high rare earth BR of property degree and White Carbon black to be kneaded, there is good compatibility to white carbon, the mechanical property of sizing material, wet-sliding resistant performance are improved, dynamic heat build up and rolling resistance are greatly lowered, and are more satisfactory high-performance tire tread mixs；Random butylbenzene copolymer is simple, quick preparation method, can industrialized production.
Description
Technical Field
The invention relates to a multi-arm star-shaped random styrene-butadiene copolymer coupled by wide-distribution polyisocyanate and a preparation method thereof, belonging to the field of synthesis of modified styrene-butadiene rubber.
Background
Styrene and conjugated diene can be directionally polymerized in a solvent under the initiation of butyl lithium to synthesize a random copolymer, and the material is particularly suitable for manufacturing tires. As a formulation for ultra high performance tires, high vinyl content SSBR, high cis-butadiene rubber and white carbon black are the major components. However, due to the low weissenbergy effect and elastic memory effect of the universal SSBR, in the process of mixing the high cis rare earth polybutadiene rubber with high molecular chain regularity and large cold flow property with white carbon black in an internal mixer, the rubber material has insufficient shearing force and low frictional heat generation in the mixing process, the rotor of the internal mixer is idle, the white carbon black cannot be effectively melted in the rubber material, and the rubber material cannot be cured and molded.
The head end of the molecular chain of the linear styrene and conjugated diene polymer which is initiated to polymerize by commonly used butyl lithium is nonpolar butyl, and the tail end of the molecular chain also has no other polar groups.
The preparation principle and the process of the star-shaped SSBR copolymer are similar to those of the linear SBS and the SIS prepared by a coupling method, and the main difference is that the coupling agent is different.
JP61-231013 provides a method for preparing solution polymerized styrene-butadiene rubber by random copolymerization of styrene and butadiene, wherein the coupling agent used in the method is stannic chloride, and the styrene-butadiene rubber synthesized by coupling has improved tensile strength and reduced rolling resistance compared with the linear solution polymerized styrene-butadiene rubber without stannic coupling. The preparation of solution polymerized styrene-butadiene rubber by using butyl lithium to initiate styrene and butadiene, and final end-capping reaction with KH-550 to prepare styrene-butadiene rubber with siloxane group at the molecular chain end, wherein the polymer with siloxane group at the molecular chain end is coagulated in hot water and hydrolyzed into hydroxyl group and decomposed into ethanol, is reported by Zhang XingYing et al, Beijing chemical university. USP4555547, USP4555548 and GB2117778A introduce that aminobenzophenone compounds carry out end capping modification on SSBR active chain ends, and the SSBR containing amino at the chain ends has the characteristics that the rebound resilience is 8-10% higher than that of a general SSBR, the wet skid resistance is not affected, and the high-temperature stability is good. The chain end contains amino SSBR and butadiene rubber are used together, and the blending rubber has excellent comprehensive performance. USP5001196 discloses that the end-capped SSBR is modified by amide compounds, so that the rebound resilience, low-temperature grip property and stable storage property of the SSBR can be improved. Amides in which the hydrocarbon group is directly bonded to the nitrogen atom are more suitable, and N-methylpyrrolidone, N-dimethylnicotinamide, aminoacrylamide and the like are generally used. But they all have their polar groups at the polymer ends. The technology only introduces the nitrogenous tertiary amine compound into the tail end of a linear solution-polymerized styrene-butadiene rubber molecular chain, the number of introduced polar groups is limited, certain limitation exists, the molecular weight distribution of a polymer cannot be changed, namely the molecular weight distribution of the polymer is narrow, the elastic memory of raw rubber is not high, Weissenbergy effect is also low, the mixing effect with white carbon black is not good, and the raw rubber cannot be matched with high-cis rare earth BR with high linearity, and the tread rubber material of the high-performance tire is prepared by mixing, and belongs to the first-generation solution-polymerized styrene-butadiene rubber.
Disclosure of Invention
The invention aims at the defects that the solution polymerized styrene-butadiene rubber in the prior art has narrow molecular weight distribution, low elastic memory of raw rubber, low Weissenbergy effect, low frictional heat generation with high molecular chain regularity and large cold flow property cis-rare earth polybutadiene rubber and white carbon black in the mixing process in an internal mixer, the white carbon black can not be effectively melted in rubber materials, the rubber materials can not be cured and formed, and the like; the multi-arm star-shaped random styrene-butadiene copolymer is characterized in that the multi-arm star-shaped random styrene-butadiene copolymer is high in molecular weight distribution, more polar groups are arranged at the middle end, and the content of short chains on a main chain is high.
The invention also provides a simple and rapid preparation method of the random styrene-butadiene copolymer, and the random styrene-butadiene copolymer can be industrially produced.
The invention provides a multi-arm star-shaped random styrene-butadiene copolymer coupled by wide-distribution polyisocyanate, which has a structure shown in a formula 1;
wherein,represents a repeating unit structure:unit structureThe number of (2) is not less than 0;
m, n and o represent the number of arms, m, n and o are non-negative integers, and m + n + o is 2-8;
a is as follows:
one or more of the above;
b is as follows:
wherein R is1Is C1～4One or more of alkyl or alkoxy;
SBS is styrene-butadiene random copolymer, including butadiene-styrene random copolymer and/or isoprene-styrene random copolymer;
the number average molecular weight of the butylbenzene random copolymer is 38-46 × 104；
The molecular weight distribution index of the butylbenzene random copolymer is 2.2-2.53;
the mass ratio of the styrene chain segment to the butadiene chain segment and/or the isoprene chain segment in the styrene-butadiene random copolymer is 25-40: 60-75;
the 1,2 structure content in the butadiene chain segment is 50-75 wt%; the 3,4 structure content in the isoprene chain segment is 50-80 wt%.
Preferred random styrene-butadiene copolymers are those in which A isOne or more of them.
More preferred random styrene-butadiene copolymers are those wherein A isOne or more of R1Is ethyl.
The Mooney viscosity of the random styrene-butadiene copolymer is 50-71.
The invention also provides a preparation method of the polymer, which is characterized in that butadiene and/or isoprene are mixed with styrene and then are continuously added into the solvent within 40-60 min, and then the mixture is added into tetrahydrofurfuryl alcohol C2～6Polymerizing at 45-75 ℃ under the action of alkyl ether and butyl lithium to obtain an active butylbenzene random copolymerCoupling the obtained active styrene-butadiene random copolymer and a polyisocyanate prepolymer coupling agent at 50-75 ℃, and terminating with water after coupling is finished to obtain the product;
the polyisocyanate prepolymer coupling agent comprises the following components in parts by mass:
1-2 parts of diisocyanate;
5-15 parts of polyisocyanate prepolymer with average functionality of 3;
15-25 parts of polyisocyanate prepolymer with average functionality of 4;
25-35 parts of polyisocyanate prepolymer with the average functionality of 5;
15-25 parts of polyisocyanate prepolymer with average functionality of 6;
5-18 parts of polyisocyanate prepolymer with the average functionality of 7;
3-10 parts of polyisocyanate prepolymer with the average functionality of 8;
the polyisocyanate prepolymer has a structure of formula 2:
wherein,represents a repeating unit structure:unit structureThe number of the polyisocyanate is not less than 0, and when the number of the polyisocyanate is 0, the polyisocyanate prepolymer is diisocyanate;
m, n and o represent the number of isocyanate groups, m, n and o are non-negative integers, and m + n + o is 2-8;
a is as follows:
one or more of the above;
b is as follows:
wherein R is1Is C1～4One or more of alkyl or alkoxy;
the diisocyanate is one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate or 4, 4' -diphenylmethane diisocyanate.
Preferably, the polyisocyanate-based prepolymer is prepared by reacting a polyisocyanate with a polyisocyanateOne or more of them.
A polyisocyanate based prepolymer is preferred, A isOne or more of R1Is ethyl.
The preferred diisocyanate is one or more of 2, 4-toluene diisocyanate or 2, 6-toluene diisocyanate.
The tetrahydrofurfuryl alcohol C2～6The concentration of the alkyl ether in the polymerization reaction system is 80-250 ppm.
The tetrahydrofurfuryl alcohol C2～6The alkyl ether is one or more of tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol butyl ether, tetrahydrofurfuryl alcohol amyl ether or tetrahydrofurfuryl alcohol.
In the method, the polymerization time is 65-95 min; the coupling time is 20-25 min; the polymerization time including the feeding time is 65-95 min.
The molar weight of the added butyl lithium in the method is 1/1.0-1.5 × 10 of the molar weight of the polymerized monomer3。
The ratio of the molar number of the isocyanic acid radical in the polyisocyanate prepolymer coupling agent to the active butylbenzene random copolymer is 1: 1.
The butyl lithium is n-butyl lithium or isobutyl lithium.
The solvent is a mixed solvent of hexane and cyclohexane.
The preparation method of the polyisocyanate prepolymer coupling agent comprises the following steps: mixing trimethyl alcohol with a structure shown in a formula 3 and diisocyanate according to a molar ratio of 1: 2.98-3.02, and reacting at 75-80 ℃ to obtain a polyisocyanate prepolymer with an average functionality of 3; respectively converting the molar ratio of trimethyl alcohol to diisocyanate into 1: 2.48-2.52, 1: 2.31-2.35 and 1: 2.23-2.27; 1: 2.18-2.22; 1: 2.15-2.19 repeating the steps to respectively prepare polyisocyanate prepolymers with average functionality of 4, 5, 6, 7 and 8; mixing the prepared polyisocyanate prepolymers with average functionality of 3,4, 5, 6, 7 and 8 and diisocyanate according to the mass part ratio to obtain the composite material;
wherein R is1Is C1～4One or more of alkyl or alkoxy;
the diisocyanate is one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate or 4, 4' -diphenylmethane diisocyanate.
The invention adjusts the arm number of the multi-arm star-shaped random styrene-butadiene copolymer within the range of 2-8 by controlling the polyisocyanate prepolymer coupling agent to obtain the random styrene-butadiene copolymer with wider molecular weight distribution:
when the unit structure in formula 2When the number of (A) is 0, the diisocyanate is represented by a formula 4; the random butylbenzene copolymer obtained by corresponding coupling is 2-arm;
OCN-A-NCO
formula 4
When the unit structure in formula 2When the number of the isocyanate groups is 1, the polyisocyanate-based prepolymer is a prepolymer containing 3 isocyanates and has a structure of a formula 5; the random butylbenzene copolymer obtained by corresponding coupling is 3 arms;
when the unit structure of formula 2When the number of (2) is greater, the polyisocyanate-based prepolymer is a prepolymer containing 4 isocyanate groups and has a structure of formula 6; the random butylbenzene copolymer obtained by corresponding coupling is 4-arm;
by analogy, each time adding a unit structureOne isocyanate group is added; one arm is added to the random styrene-butadiene copolymer obtained by corresponding coupling.
The random styrene-butadiene copolymer is mainly used for high-performance tire tread rubber; the formula (parts by mass) is as follows; the modified styrene-butadiene rubber material comprises, by weight, 165 parts of polyisoester-coupled styrene-butadiene rubber, BR 40, 103-145 parts of white carbon black 175GR, N3307.5 parts of carbon black, Si-696, 3 parts of stearic acid, 4.5 parts of zinc oxide, 40202.5 parts of an anti-aging agent, 2.7 parts of a promoter CZ, 2.3 parts of a promoter D, 10-30 parts of TDAE oil and 2.3 parts of sulfur.
The invention has the beneficial effects that:
according to the invention, through repeated tests, the random styrene-butadiene copolymer is coupled by the polyisocyanate prepolymer coupling agent, so that the random styrene-butadiene copolymer with wider molecular weight distribution (the polymer has a one-arm structure, a two-arm structure, a three-arm structure, a four-arm structure, a five-arm structure, a six-arm structure, a seven-arm structure and an eight-arm structure with different grades of arm numbers) is obtained, the self-adhesion and the elastic memory effect of the copolymer are improved, a plurality of polar amide groups and amide ester groups are left in the middle of the random styrene-butadiene copolymer, the compatibility of the copolymer with the white carbon black in the mixing process of the rare earth butadiene rubber and the white carbon black is increased, the effective curing of the mixed rubber can be realized, and the forming time is shortened; the high-branch random styrene-butadiene copolymer chain is obtained by regulating the short-branch structure in the copolymer by the tetrahydrofurfuryl alcohol alkyl ether compound; the random styrene-butadiene copolymer which simultaneously has polar groups, has wider molecular weight distribution and high short chain branch content on the main chain has better Weissenbergy effect and high elastic memory effect, improves the dynamic mechanical property and rebound resilience of the rubber material after being mixed with rare earth butadiene rubber, white carbon black and the like, reduces dynamic heat generation, increases wet-skid resistance, particularly greatly reduces rolling resistance, and is an ideal ultrahigh-performance tire rubber material;
the random styrene-butadiene copolymer provided by the invention is used for tread rubber, so that the problem that the mixing effect of the general SSBR and the common low-and medium-Mooney viscosity rare earth butadiene rubber is poor is solved; compared with the general SSBR and BR9000 mixed rubber with the same formula, the rubber material prepared by mixing the random styrene-butadiene copolymer, the rare earth butadiene rubber, the white carbon black and the like has the advantages that the dynamic mechanical property is improved, the rebound resilience is improved by 8-10%, the dynamic heat generation is reduced by 3-5 ℃, the wet-skid resistance is increased, and particularly the rolling resistance is greatly reduced;
the random butylbenzene copolymer synthesis method and operation are simple, the reactions are homogeneous, the reactions are easy to control, and the method can be used for industrial production.
Drawings
FIG. 1 is a ZY-SSBR2565 gel permeation chromatogram prepared in example 4 of the present invention: ESBR1712 is emulsion polymerized styrene butadiene rubber, the molecular weight distribution index is 3.25, and the Mooney viscosity is 54; ZY-SSBR2565 is the solution polymerized styrene-butadiene rubber prepared by the invention, the molecular weight distribution is 2.53, the Mooney viscosity is 70.4; VSL5025HM was a solution-polymerized styrene-butadiene rubber available from LANXESS, with a molecular weight distribution index of 1.86 and a Mooney viscosity of 64; 37.5phr of environment-friendly rubber oil is filled in all the three styrene butadiene rubbers.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Determination of the isocyanate content in the coupling agent according to GBT12009.4-1998
The determination method comprises the following steps:
weighing 0.2-0.3 g of sample (quasi-0.0002 g) and placing the sample in a 300mL beaker, adding 10mL of trichloromethane to dissolve the sample, adding 10mL of 0.2mol/L hexahydropyridine chlorobenzene solution by a pipette, shaking up, placing for 15-20 min, adding 150mL of ethanol in the beaker, inserting a calomel electrode and a glass electrode, carrying out potentiometric titration by using a hydrochloric acid standard solution, and dropping until a mutation point occurs.
The results were calculated as follows:
-NCO wt％＝(V0-V0).C×0.04202×100/M
in the formula, V0 represents the amount of hydrochloric acid standard solution in a blank titration period, mL.
V0 amount of hydrochloric acid standard solution in mL when the sample is titrated.
C, the concentration of the hydrochloric acid standard solution, mol/L.
X 100; 0.04202: the mass of isocyanate groups in grams, corresponding to 1.00mL of hydrochloric acid standard solution.
M: mass of sample, grams.
The results of the analyses of the two parallel samples were calculated as the arithmetic mean.
And finally, the mass content is changed into molar concentration.
Example 1
(1) And adding 425mL of anhydrous toluene, 80g of TMP and 290.58g of TDI into a clean and dry 1000mL three-neck bottle under the protection of nitrogen, wherein the ratio of TMP/TDI is 1: 3.02 (mass ratio of substances), stirring for 6-8 h at the constant temperature of 75-80 ℃, and measuring the solid content to be 49.6 wt% and the concentration of the isocyanic acid radical to be 0.83 mol/L. Wherein the average functionality of the adduct molecule contains 3-NCO groups.
(2) And adding 425mL of anhydrous toluene, 80g of TMP and 239.60g of TDI into a clean and dry 1000mL three-neck bottle under the protection of nitrogen, wherein the ratio of TMP/TDI is 1: 2.52 (mass ratio of substances), keeping the temperature at 75-80 ℃, and stirring for 6-8 hours, wherein the measured solid content is 50.3 wt%, and the concentration of the isocyanic acid radical is 0.74 mol/L. Wherein the average functionality of the adduct molecule contains 4-NCO groups.
(3) And adding 425mL of anhydrous toluene, 80g of TMP and 219.87g of TDI into a clean and dry 1000mL three-neck bottle under the protection of nitrogen, wherein the ratio of TMP/TDI is 1: 2.34 (mass ratio of substances), keeping the temperature at 75-80 ℃, and stirring for 6-8 hours to obtain a solid content of 50.1 wt% and an isocyanate concentration of 0.62 mol/L. Wherein the average functionality of the adduct molecule contains 5-NCO groups.
(4) And adding 425mL of anhydrous toluene, 80g of TMP and 212.35g of TDI into a clean and dry 1000mL three-neck bottle under the protection of nitrogen, wherein the ratio of TMP/TDI is 1: 2.26 (mass ratio of substances), keeping the temperature at 75-80 ℃, and stirring for 6-8 hours to obtain a solid content of 50.7 wt% and an isocyanate concentration of 0.57 mol/L. Wherein the average functionality of the adduct molecule contains 6-NCO groups.
(5) And adding 425mL of anhydrous toluene, 80g of TMP and 207.65g of TDI into a clean and dry 1000mL three-neck bottle under the protection of nitrogen, wherein the ratio of TMP/TDI is 1: 2.21 (mass ratio of substances), keeping the temperature at 75-80 ℃, and stirring for 6-8 hours to obtain a solid content of 49.7 wt% and an isocyanate concentration of 0.53 mol/L. Wherein the average functionality of the adduct molecule contains 7-NCO groups.
(6) And adding 425mL of anhydrous toluene, 80g of TMP and 203.89g of TDI into a clean and dry 1000mL three-neck bottle under the protection of nitrogen, wherein the ratio of TMP/TDI is 1: 2.17 (mass ratio of substances), keeping the temperature at 75-80 ℃, and stirring for 6-8 hours to obtain a solid content of 49.8 wt% and an isocyanate concentration of 0.51 mol/L. The average functionality of the adduct molecule contains 8-NCO.
1mL of chemically pure TDI with the mass content of 99 percent, 10mL of prepolymer in (1), 20mL of prepolymer in (2), 35mL of prepolymer in (3), 15mL of prepolymer in (4), 12mL of prepolymer in (5) and 3mL of prepolymer in (6) are respectively taken and injected into a 100mL dried solvent flask, and then proper amount of toluene is added for even mixing to prepare the polyisocyanate coupling agent with the isocyanate group concentration of 0.68 mol/L.
Example 2
Steps (1) to (6) were the same as in example 1,
2mL of chemically pure TDI with the mass content of 99 percent, 15mL of prepolymer in (1), 20mL of prepolymer in (2), 35mL of prepolymer in (3), 15mL of prepolymer in (4), 18mL of prepolymer in (5) and 3mL of prepolymer in (6) are respectively taken and injected into a 100mL dried measuring flask, and proper amount of toluene is added for even mixing to prepare the polyisocyanate coupling agent with the isocyanate group concentration of 0.85 mol/L.
Example 3
Under the protection of nitrogen, 3.5L of hexane-cyclohexane mixed solvent and 0.98g of tetrahydrofurfuryl alcohol ether are added into a 5-liter polymerization kettle, stirring is started within 40min, 0.5mol/L n-butyl lithium 13mL, 132.5g of styrene and 397.5g of butadiene mixed monomer are respectively and continuously and uniformly added, polymerization is carried out at 50-75 ℃, the monomer is reacted for 25min after being added, 9.5mL of prepolymer with 0.68mol/L isocyanate concentration in example 1 is added for coupling reaction, the coupling reaction temperature is 60-75 ℃, the coupling reaction time is 25min, the obtained single-arm to eight-arm SSBR is filled with 198.1g of TDAE oil, and then the SSBR oil-filled crude rubber is obtained through condensation and drying, wherein the number-average molecular weight of the single-arm polymer is 8.1 × 10, and the number-average molecular weight of the single-arm polymer is 8.14Average number average molecular weight of 42 × 104Molecular weight distribution index 2.23, vinyl content 74.6%, Mooney viscosity 56.1.
Example 4
Under the protection of nitrogen, 3.5L of hexane-cyclohexane mixed solvent and 0.65g of tetrahydrofurfuryl alcohol propyl ether are added into a 5-liter polymerization kettle, stirring is started, 11mL of 0.5mol/L n-butyl lithium and 159g of mixed monomer of styrene and 371g are respectively and simultaneously and uniformly added within 60min, polymerization is carried out at 50-75 ℃, the monomer is reacted for 26min after being added, 7mL of prepolymer with 0.85mol/L isocyanate concentration in the embodiment 2 is added for coupling reaction, the coupling reaction temperature is 60-75 ℃, the coupling reaction time is 20min, the obtained single-arm to eight-arm SSBR is filled with 198.1g of TDAE oil, and then the SSBR oil-filled crude rubber is obtained through condensation and drying, wherein the number-average molecular weight of the single-arm polymer is 10.1 × 10.10, and the number-average molecular weight of the single-arm polymer is 10.1 89104Average number average molecular weight of the conjugate 46 × 104Molecular weight distribution index 2.53, vinyl content 65.3%, Mooney viscosity 70.4.
Example 5
Under the protection of nitrogen, 3.5L of hexane-cyclohexane mixed solvent and 0.55g of tetrahydrofurfuryl alcohol n-hexyl ether are added into a 5-liter polymerization kettle, stirring is started, 10.6mL of 0.5mol/L n-butyl lithium and 212g of mixed monomer of styrene and 318g of butadiene are respectively and simultaneously and uniformly added within 50min, polymerization is carried out at 50-75 ℃, the monomer is reacted for 20min after being added, 6.3mL of prepolymer with 0.85mol/L of isocyanate in example 2 is added for coupling reaction, the coupling reaction temperature is 60-75 ℃, the coupling reaction time is 20min, the obtained single-arm to eight-arm SSBR is filled with 198.1g of TDAE oil, and the SSBR oil-filled crude rubber is obtained through condensation and drying, wherein the number-average molecular weight of the single-arm polymer is 10.0 × 10 10.04Average number average molecular weight of the conjugate 43.7 × 104Molecular weight distribution index 2.41, vinyl content 63.1%, Mooney viscosity 65.4.
Example 6
Under the protection of nitrogen, 3.5L of hexane-cyclohexane mixed solvent and 0.45g of bistetrahydrofurfuryl propane are added into a 5-liter polymerization kettle, stirring is started within 45min, 0.5mol/L n-butyl lithium 13mL, 132.5g of styrene, 297.5g of butadiene and 100g of isoprene mixed monomer are continuously and uniformly added respectively, polymerization is carried out at 50-75 ℃, reaction is carried out for 25min after the monomer addition is finished, 9.5mL of prepolymer with 0.68mol/L of isocyanate in example 1 is added for coupling reaction, the coupling reaction temperature is 60-75 ℃, the coupling reaction time is 20min, the obtained single-arm to eight-arm SIBR is filled with 198.1g of TDAE oil, and the SSBR oil-filled crude rubber is obtained through condensation and drying, wherein the number-average molecular weight of the single-arm polymer is 8.1 × 10, and the number-average molecular weight of the single-arm polymer is 8.1 89104Average number average molecular weight of the conjugate 38.6 × 104The molecular weight distribution index was 2.33, the total content of 3.4-structures and 1.2-structures was 57.6%, and the Mooney viscosity was 50.7.
Example 7
The SSBR prepared in example 3, VSL-5025HM sold on the market and rare earth BR (Buna CB-24) are respectively mixed in an internal mixer according to the following formula, and the results are shown in Table 1 after vulcanization and detection;
165 parts of styrene butadiene rubber (variable varieties), Buna CB-2440 parts, 175GR 103 parts of white carbon black, N3307.5 parts of carbon black, Si-696 parts, 3 parts of stearic acid, 4.5 parts of zinc oxide, 40202.5 parts of an anti-aging agent, 2.7 parts of an accelerator CZ, 2.3 parts of an accelerator D, 10 parts of TDAE oil and 2.3 parts of sulfur.
TABLE 1 Polyisoate coupled styrene butadiene rubber and highly linear rare earth BR match
| The invention SSBR/Buna CB-24 | VSL-5025HM/Buna CB-24 | |
| Mixing time/second in internal mixer | 160 | 300 |
| 300% stress at definite elongation/MPa | 11.3 | 10.2 |
| Elongation at break/%) | 450 | 430 |
| Tensile strength/MPa | 18.6 | 16.7 |
| Permanent deformation/%) | 20 | 24 |
| hardness/A | 65 | 66 |
| Rebound resilience/%) | 42 | 37 |
| Compression temperature rise/. degree.C | 23 | 26 |
| 0℃@tanδ | 0.5632 | 0.5218 |
| 60℃@tanδ | 0.1451 | 0.1526 |
Note: buna CB-24 is rare earth BR produced by Langsheng company, Mooney viscosity is 44; VSL-5025HM is SSBR from Langshan and has a Mooney viscosity of 64.
Example 8
SSBR/rare earth BR (Buna CB-24) and VSL-5025HM/BR9000 prepared in example 4
The following formula is matched, mixing is carried out in an internal mixer, and the results are shown in table 2 after vulcanization and detection;
165 parts of styrene butadiene rubber (variant), 40 parts of BR (variant), 175GR 145 parts of white carbon black, N3307.5 parts of carbon black, Si-696 parts, 3 parts of stearic acid, 4.5 parts of zinc oxide, 40202.5 parts of an anti-aging agent, 2.7 parts of an accelerator CZ, 2.3 parts of an accelerator D, 40 parts of TDAE oil and 2.3 parts of sulfur.
TABLE 2 polyisocyanate type SSBR/rare earth BR and VSL-5025HM/BR9000 matching glue properties
Claims (8)
1. A preparation method of a random styrene-butadiene copolymer is characterized in that butadiene and/or isoprene and styrene are mixed and then are continuously added into a solvent within 40-60 min, and then are added into tetrahydrofurfuryl alcohol C2～6Polymerizing at 45-75 ℃ under the action of alkyl ether and butyl lithium to obtain an active styrene-butadiene random copolymer, coupling the obtained active styrene-butadiene random copolymer and a polyisocyanate prepolymer coupling agent at 50-75 ℃, and terminating with water after coupling is finished to obtain the modified styrene-butadiene random copolymer;
the polyisocyanate prepolymer coupling agent comprises the following components in parts by mass:
1-2 parts of diisocyanate;
5-15 parts of polyisocyanate prepolymer with average functionality of 3;
15-25 parts of polyisocyanate prepolymer with average functionality of 4;
25-35 parts of polyisocyanate prepolymer with the average functionality of 5;
15-25 parts of polyisocyanate prepolymer with average functionality of 6;
5-18 parts of polyisocyanate prepolymer with the average functionality of 7;
3-10 parts of polyisocyanate prepolymer with the average functionality of 8;
the polyisocyanate prepolymer has a structure of formula 2:
wherein,represents a repeating unit structure:unit structureThe number of the polyisocyanate is not less than 0, and when the number of the polyisocyanate is 0, the polyisocyanate prepolymer is diisocyanate;
m, n and o represent the number of isocyanate groups, m, n and o are non-negative integers, and m + n + o is 2-8;
a is as follows:
one or more of the above;
b is as follows:
wherein R is1Is C1～4One or more of alkyl or alkoxy;
the diisocyanate is one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate or 4, 4' -diphenylmethane diisocyanate.
2. The method of claim 1, wherein A isOne or more of them.
3. The method of claim 1, wherein R is1Is ethyl.
4. The method of claim 1, wherein the diisocyanate is one or more of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
5. The method of claim 1, wherein said tetrahydrofurfuryl alcohol C is2～6The concentration of the alkyl ether in the polymerization reaction system is 80-250 ppm.
6. The process according to claim 1 or 5, wherein the tetrahydrofurfuryl alcohol C is2～6The alkyl ether is one or more of tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol propyl ether, tetrahydrofurfuryl alcohol butyl ether, tetrahydrofurfuryl alcohol amyl ether or tetrahydrofurfuryl alcohol.
7. The method of claim 1, wherein the polymerization time is 65 to 95 min; the coupling time is 20-25 min.
8. Preparation according to claim 1The method is characterized in that the molar weight of the added butyl lithium is 1/1.0-1.5 × 10 of the molar weight of the polymerized monomer3。
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| CN102190757A (en) * | 2011-03-17 | 2011-09-21 | 北京化工大学 | Method for synthesizing end-functionalized star-shaped solution polymerized styrene-butadiene rubber |
| CN102558465A (en) * | 2010-12-29 | 2012-07-11 | 中国石油化工股份有限公司 | Synthesizing method of solution polymerized styrene butadiene rubber |
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| CN1073950A (en) * | 1991-12-31 | 1993-07-07 | 兰州化学工业公司化工研究院 | A kind of preparation method of styrene-butadiene block copolymer |
| CN102558465A (en) * | 2010-12-29 | 2012-07-11 | 中国石油化工股份有限公司 | Synthesizing method of solution polymerized styrene butadiene rubber |
| CN102190757A (en) * | 2011-03-17 | 2011-09-21 | 北京化工大学 | Method for synthesizing end-functionalized star-shaped solution polymerized styrene-butadiene rubber |
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