CN114106255A - Preparation method of novel nickel-based butadiene rubber - Google Patents
Preparation method of novel nickel-based butadiene rubber Download PDFInfo
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- CN114106255A CN114106255A CN202010900401.8A CN202010900401A CN114106255A CN 114106255 A CN114106255 A CN 114106255A CN 202010900401 A CN202010900401 A CN 202010900401A CN 114106255 A CN114106255 A CN 114106255A
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- butadiene rubber
- hydroxyl
- rubber
- polybutadiene
- novel nickel
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- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 101
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 82
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- 239000012966 redox initiator Substances 0.000 claims abstract description 26
- 150000003254 radicals Chemical class 0.000 claims abstract description 22
- 238000007348 radical reaction Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 22
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 21
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 16
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 14
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 14
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- -1 thiol compounds Chemical class 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012933 diacyl peroxide Substances 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 33
- 239000005060 rubber Substances 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 27
- 238000006116 polymerization reaction Methods 0.000 abstract description 23
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 229920001195 polyisoprene Polymers 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 239000005063 High cis polybutadiene Substances 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 229910018507 Al—Ni Inorganic materials 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000002715 modification method Methods 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 240000005020 Acaciella glauca Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 235000003499 redwood Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7095—Cobalt, nickel or compounds thereof
- C08F4/7098—Nickel or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of novel nickel-based butadiene rubber, belonging to the technical field of modification of butadiene rubber. The preparation method of the novel nickel-based butadiene rubber comprises the step of adding an oligomer containing hydroxyl and a side group unsaturated bond and a redox initiator into polybutadiene rubber solution prepared by catalyzing butadiene polymerization by using a nickel-based catalyst to perform free radical reaction. The preparation method of the novel nickel-based butadiene rubber has the advantages of simple process, low cost, energy conservation and environmental protection, reduces the viscosity of butadiene rubber liquid, improves the cold flow property and the processability of raw rubber, and obviously improves the mechanical property of the butadiene rubber.
Description
Technical Field
The invention relates to a preparation method of novel nickel-based butadiene rubber, belonging to the technical field of modification of butadiene rubber.
Background
Butadiene rubber (BR for short) is the second most common synthetic rubber in the world next to styrene butadiene rubber, has the advantages of good elasticity, strong wear resistance, good low temperature resistance, low heat generation, good dynamic performance and the like, can be used together with natural rubber, chloroprene rubber, nitrile rubber and the like, and has very wide application in rubber products such as tires, adhesive tapes, rubber tubes, rubber shoes and the like. However, the improvement of the cold flow property and the processability of the crude rubber is a research direction in the field because the double bond cis structure has higher content, good flexibility, easy cold flow and difficult storage and transportation of the crude rubber. Wherein the proper branching modification is an effective method for improving the performance. The rubber containing the branched structure can reduce the viscosity of a polymerization reaction glue solution, reduce the wall hanging phenomenon in a kettle and improve the cold flow property of the butadiene rubber, and the vulcanized rubber containing the rubber with the branched structure has better mechanical property.
In recent years, numerous researchers have conducted a great deal of research work on branched rubbers:
the method for synthesizing the high-branching-degree polybutadiene (HVPB) by anion polymerization by the methods of active anion polymerization and click chemistry is adopted by Gaiwei et al (Gaiwei, Redwood, Hannaiong, and the like.) and the structure of the high-branching-degree polybutadiene (HVPB) is synthesized by the methods of anion polymerization by the academic society of Chinese chemical society, 2014.) and then the 'click chemistry' reaction of the HVPB and dodecyl mercaptan is realized by taking BPO as an initiator, so that the high-branching-degree polybutadiene is synthesized, and the synthesized branched polymer becomes a structure similar to a molecular brush.
Wuyi et al (Wuyi Jiang, high dawn, Zhu Han, et al. A method [ P ] for preparing a long-chain branched high cis-polybutadiene [ CN, CN 104231119B, 2016.) use a radical-initiated reaction of double bonds and mercapto groups to prepare branched structures, and the prepared long-chain branched polymers have improved thermal stability, cold flow resistance, and mixing uniformity of the product with fillers, but the polymers prepared by this method are susceptible to cross-linking reactions, thereby producing a large amount of gels.
Zhang Qingxu (Zhang Q, Xu H, Song Y, et al. underfluence of hydroxyl-terminated polybutadiene liquid on rhology of fused silica filled cis-polybutadiene rubber [ J ]. Polymer,2019,180:121709.) the hydroxyl-terminated polybutadiene (HTPB) oligomer was added into polybutadiene rubber for mixing, the compatibility of the obtained blend matrix and white carbon black was obviously improved, the dispersibility of white carbon black was improved, and a new thought was provided for researching the compatibility rule of the rubber matrix and the filler.
The above technique is a hot spot of current chemical modification, but the process is relatively complicated, and the processability of butadiene rubber is still unsatisfactory.
Disclosure of Invention
The invention aims to provide a preparation method of novel nickel-based butadiene rubber, which has the advantages of simple process, low cost, energy conservation and environmental protection, reduces the viscosity of butadiene rubber liquid, improves the cold flow property and the processability of raw rubber, and obviously improves the mechanical property of the butadiene rubber.
The preparation method of the novel nickel-based butadiene rubber comprises the step of adding an oligomer containing hydroxyl and a side group unsaturated bond and a redox initiator into a polybutadiene rubber solution prepared by catalyzing butadiene polymerization by using a nickel-based catalyst to perform free radical reaction.
Preferably, the oligomer containing hydroxyl and pendant unsaturation is one or more of hydroxyl terminated polybutadiene, hydroxyl terminated styrene-butadiene polymer, or hydroxyl terminated isoprene.
Preferably, the oxidizing agent in the redox initiator is one or more of tert-butyl hydroperoxide, dialkyl peroxide, diacyl peroxide, benzoyl peroxide, dibenzoyl peroxide, benzoyl peroxide tert-butyl peroxide or lauroyl peroxide.
Further preferably, the oxidizing agent in the redox initiator is dibenzoyl peroxide or lauroyl peroxide.
Preferably, the reducing agent in the redox initiator is one or more of N, N-dimethylaniline, N-dimethyltoluidine, a thiol compound, triisobutylaluminum, triethylaluminum, triethylboron or a naphthenate salt.
Further preferably, the reducing agent in the redox initiator is N, N-dimethylaniline, N-dimethyltoluidine or cuprous naphthoate.
Preferably, the mass ratio of the oligomer containing hydroxyl groups and pendant unsaturated bonds to polybutadiene is 0.1 to 10, more preferably 0.1 to 3.
Preferably, the mass ratio of redox initiator to oligomer containing hydroxyl groups and pendant unsaturated bonds is from 0.1 to 1. Further preferably 0.1 to 0.5.
Preferably, the molar ratio of the oxidizing agent to the reducing agent in the redox initiator is from 1:0.3 to 1: 0.9. Further preferably 1:0.6 to 1: 0.8.
Preferably, the temperature at the time of radical reaction is 10 to 40 ℃, and more preferably 15 to 30 ℃; the reaction time is 0.5 to 5 hours, and more preferably 0.5 to 1 hour.
Compared with the technical scheme in the literature published by Gao Wei and others (Gao Wei, Lujian Min, Han Paoyong, and the like) in 2014, the hydroxyl oligomer disclosed by the invention has the advantages that the compatibility with white carbon black is effectively increased, and the use and the recovery (treatment of unreacted mercaptan) of mercaptan with large taste and no environmental protection are avoided; compared with the technical scheme in the literature published by Wu Yigan et al (Wu Yigan, high dawn full, Zhu Han, etc.. A method for preparing long-chain branched high cis-polybutylene [ P ]: CN, CN 104231119B, 2016.), the method has more benefits of reducing the viscosity of the glue solution; the invention relates to a method for grafting a hydroxyl oligomer into a rubber matrix to generate a branched structure, wherein the hydroxyl oligomer and matrix rubber are simply and physically blended, and the compatibilization effect of the whole rubber matrix and white carbon black is better.
Therefore, the invention adopts a simpler method to prepare the nickel-based butadiene rubber, the method carries out reaction on the basis of not changing the original nickel-based butadiene rubber device, and the reaction operation is simple because the butadiene rubber is modified by adopting the free radical reaction. Free radical reactions readily produce cross-linking reactions that produce a certain amount of gel, the presence of which affects the properties of the polymer. Therefore, the selection of proper hydroxyl-terminated oligomer and initiator to form the redox initiator is the key for regulating and controlling the crosslinking reaction in the reaction process. Through reasonable regulation and control, not only can the crosslinking reaction be avoided, but also the viscosity of the glue solution is reduced, the cold flow property and the processability of the rubber are improved, and the mechanical property of the butadiene rubber is obviously improved.
Compared with the patent (a method [ P ] for preparing long-chain branched high cis-polybutadiene, CN 104231119B, 2016), the method directly uses free radicals to initiate the reaction of double bonds and sulfydryl to prepare a branched structure, the method avoids the use and recovery of mercaptan with big taste and no environmental protection (the treatment of unreacted mercaptan), and in effect, the branched chain with terminal hydroxyl increases the compatibility of rubber and white carbon black, and the solubilizing effect is good; compared with the second document (of fluorine-based terminated polybutadiene liquid on biology of fused silica filled cis-polybutadiene rubber [ J ]. Polymer,2019,180:121709.), the present patent makes the grafting into the rubber matrix to generate a branched structure and make the compatibilization effect of the whole rubber matrix and the white carbon black better. Meanwhile, the existence of the branched chain improves the cold flow property and the processability of the raw rubber.
In a word, the ingenious conception that the redox initiation system is formed by the low polymer of hydroxyl and the oxidized compound reduces the generation of gel, the side chain with the terminal hydroxyl is grafted on the main chain of the rubber, the cold flow property of the crude rubber and the compatibility of vulcanized rubber and white carbon black are improved, the method is simple, and the effect is superior to that of the prior art.
In the presence of a free radical initiator, linear or short-chain branch butadiene rubber and a low polymer containing hydroxyl and side group unsaturated bonds are subjected to a grafting reaction to prepare high cis-polybutadiene containing a branch chain structure, namely, hydroxyl groups are introduced while the butadiene rubber is subjected to branching modification, wherein the branch structure can reduce viscosity, improve cold flow resistance and processability and improve processability; meanwhile, the existence of hydroxyl is beneficial to the dispersion of white carbon black and the improvement of the interaction between the filler and the rubber matrix, and the physical mechanical property and the dynamic mechanical property of vulcanized rubber are improved; the redox initiation system selected in the modification process initiates free radical reaction at low temperature, so that the crosslinking reaction of the butadiene rubber caused by the free radical reaction can be effectively avoided, and no gel is generated; residual low-valence Al and Ni in the polymerization reaction glue solution can be used as reducing agents of redox initiators; the modification reaction is carried out in the last step of the polymerization process, no additional solvent sol is needed, the cost is low, the environment is protected, and the method is simple and easy to implement.
Compared with the prior art, the invention has the following beneficial effects:
(1) the product prepared by the invention contains hydroxyl groups and branched chain structures, the viscosity of the glue solution of the polymer is reduced by 24 percent at most;
(2) the invention has low stirring current, shortens the period of stopping production and cleaning the kettle and the pipeline, and reduces the cost of transportation and storage;
(3) the introduced hydroxyl improves the dispersion of white carbon black in a rubber matrix and the interaction between the filler and the rubber matrix, the mechanical property of the modified rubber is obviously improved, the tensile strength of the modified rubber is improved by 28 percent at most, and the tear strength of the modified rubber is improved by 13 percent;
(4) the modification reaction of the invention occurs in the last step of the polymerization process, no additional solvent sol is needed, the cost is low, the invention is environment-friendly and simple and easy to implement.
Drawings
FIG. 1 is a graph of the change in solution viscosity of different oligomer-modified butadiene rubbers containing hydroxyl and pendant unsaturation;
FIG. 2 is a scanning electron micrograph of different oligomer-modified butadiene rubbers containing hydroxyl groups and pendant unsaturation;
FIG. 3 is a graph of strain versus G' for various oligomer-modified butadiene rubbers containing hydroxyl and pendant unsaturation.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Comparative example 1
In a polymerization kettle protected by nitrogen, n-hexane and butadiene are mixed evenly in turn in the polymerization kettle, and [ M ]]Adding Al-Ni aged solution and diluted boron solution (Ni/Bd is 1 × 10)-4，Al/Ni＝12,Al/B＝0.8，n-C8H17Polymerizing OH/B ═ 1 in a constant-temperature water bath at 60 ℃ for 4 h; after the polymerization, 1.5mL of 2, 6-di-tert-butyl-hydroquinone ethanol solution with the mass concentration of 3 wt% is added to terminate the reaction, and polymer glue solution is obtained. The properties of the obtained nickel-based butadiene rubber are shown in Table 1.
Example 1
In a 30mL polymerization tube protected by nitrogen, n-hexane and butadiene were mixed in sequence and uniformly in the polymerization tube, [ M ]]Adding 0.14g/mL of triisobutyl aluminum-nickel naphthenate aging solution, boron trifluoride diethyl etherate and n-octanol, wherein Ni/Bd is 1 × 10-4，Al/Ni＝12,Al/B＝0.8，n-C8H17OH/B1, thermostatic water at 60 deg.CPolymerizing for 4h in the bath; adding hydroxyl-terminated polybutadiene No. 1 (molecular weight 2000 and vinyl content 65%) into a nickel-based butadiene rubber glue solution, and then adding a redox initiator dibenzoyl peroxide/N, N-dimethylaniline into the glue solution, wherein the molar ratio of the dibenzoyl peroxide/N, N-dimethylaniline is 1:0.7, and the mass ratio of the hydroxyl-terminated polybutadiene to the polybutadiene rubber is 1%; the mass ratio of free radical initiator to oligomer containing hydroxyl and pendant unsaturated bond was 0.2 and the reaction was carried out at 30 ℃ for 0.8 h. After the reaction is finished, polymer is precipitated by excessive ethanol, washed by ethanol and dried in a vacuum oven at 60 ℃ to constant weight. The properties of the obtained nickel-based butadiene rubber are shown in Table 1.
Example 2
The preparation method, modification method and treatment method of the high cis-polybutadiene/n-hexane solution are the same as those of example 1. Except that the mass ratio of hydroxyl-terminated polybutadiene to polybutadiene rubber was 3%, and the reaction was carried out at 30 ℃ for 0.8 h. The properties of the obtained nickel-based butadiene rubber are shown in Table 1.
Example 3
The preparation method, modification method and treatment method of the high cis-polybutadiene/n-hexane solution are the same as those of example 1. Except that the mass ratio of hydroxyl-terminated polybutadiene to polybutadiene rubber was 5%, and the reaction was carried out at 20 ℃ for 1.5 hours. The properties of the obtained nickel-based butadiene rubber are shown in Table 1.
Example 4
In a 30mL polymerization tube protected by nitrogen, n-hexane and butadiene were mixed uniformly in sequence in the polymerization tube, [ M ]]Adding Al-Ni aged solution and diluted boron solution (Ni/Bd is 1 × 10)-4，Al/Ni＝12,Al/B＝0.8， n-C8H17Polymerizing OH/B ═ 1 in a constant-temperature water bath at 60 ℃ for 4 h; adding hydroxyl-terminated polyisoprene oligomer 2# (with the molecular weight of 4000 and the vinyl content of 85%) and a redox initiator dibenzoyl peroxide/N, N-dimethylaniline, wherein the molar ratio of the dibenzoyl peroxide/N, N-dimethylaniline is 1:0.8, and the mass ratio of the hydroxyl-terminated polybutadiene 2# to the polybutadiene rubber is 3%; the amount ratio of the radical initiator to the oligomer containing hydroxyl groups and pendant unsaturated bonds was 0.3 and the reaction was carried out at 30 ℃ for 0.8 h.After the reaction, the polymer is precipitated by using excessive ethanol, washed by the ethanol and dried in a vacuum oven at 60 ℃ to constant weight. The properties of the obtained nickel-based butadiene rubber are shown in Table 1.
Example 5
The preparation method, modification method and treatment method of the high cis-polybutadiene/n-hexane solution are the same as example 4, except that the mass ratio of the adopted hydroxyl-terminated polybutadiene No. 2 (molecular weight 4000, vinyl content 85%) to the polybutadiene rubber is 5%, and the reaction is carried out for 1.5h at 20 ℃. . The properties of the obtained nickel-based butadiene rubber are shown in Table 1.
TABLE 1 Property parameters of modified butadiene rubber
As can be seen from Table 1, the cis structure content of the polybutadiene modified by the hydroxyl-terminated polybutadiene is basically unchanged, the cis structure is still kept high, the solution viscosity of the modified butadiene rubber is reduced, and the solution viscosity of the polymer is the lowest when the mass ratio of the hydroxyl-terminated polybutadiene with the molecular weight of 4000 to the polybutadiene rubber is 3%. The mechanical property of the butadiene rubber modified by mercaptan is improved to a certain extent. The tensile strength and the tear strength are obviously improved, the maximum tensile strength is improved by 19.0 percent, and the maximum tear strength is improved by 9 percent.
Example 6
In a 30mL polymerization tube protected by nitrogen, n-hexane and butadiene were mixed uniformly in sequence in the polymerization tube, [ M ]]Adding 0.14g/mL of triisobutyl aluminum-nickel naphthenate aging solution, boron trifluoride diethyl etherate and n-octanol, wherein Ni/Bd is 1 × 10-4，Al/Ni＝12,Al/B＝0.8，n-C8H17Polymerizing OH/B ═ 1 in a constant-temperature water bath at 60 ℃ for 4 h; then adding hydroxyl-terminated polyisoprene 1# (with molecular weight of 10000 and vinyl content of 50%) into the glue solution, then adding redox initiator tert-butyl hydroperoxide/N, N-dimethyl toluidine into the nickel-series butadiene rubber glue solution, wherein the molar ratio of tert-butyl hydroperoxide/N, N-dimethyl toluidine is 1:0.7, and the hydroxyl-terminated polyisoprene isThe mass ratio of the isoprene No. 1 to the polybutadiene rubber is 3 percent; the mass ratio of free radical initiator to oligomer containing hydroxyl and pendant unsaturated bond was 0.2 and the reaction was carried out at 30 ℃ for 0.8 h. After the reaction, polymer is precipitated by using excessive ethanol, washed by ethanol and dried in a vacuum oven at 60 ℃ to constant weight. The properties of the obtained nickel-based butadiene rubber are shown in Table 2.
Example 7
The preparation method, modification method and treatment method of the high cis-polybutadiene/n-hexane solution are the same as those of example 6, except that the mass ratio of the hydroxyl-terminated polyisoprene 1# to the polybutadiene is 5%, and the reaction is carried out at 20 ℃ for 1.5 h. . The properties of the obtained nickel-based butadiene rubber are shown in Table 2.
Example 8
The preparation method, modification method and treatment method of the high cis-polybutadiene/n-hexane solution are the same as those in example 6, except that hydroxyl polyisoprene 2# (molecular weight is 20000, vinyl content is 65%) is added into the glue solution. The properties of the obtained nickel-based butadiene rubber are shown in Table 2.
Example 9
The preparation method, modification method and treatment method of the high cis-polybutadiene/n-hexane solution are the same as those of example 8, and the mass ratio of the hydroxyl-terminated polyisoprene 2# to the polybutadiene is 5%. The properties of the obtained nickel-based butadiene rubber are shown in Table 2.
TABLE 2 structural Properties of modified butadiene rubber
As can be seen from Table 2, the cis-structure content of the butadiene rubber added with the hydroxyl-terminated polyisoprene is not obviously changed, the molecular weight is slightly increased, the solution viscosity of the polymer is reduced, and the solution viscosity is reduced by about 25%. When hydroxyl-terminated polyisoprene 2# is added at 3% of the polybutadiene level, the solution viscosity of the polymer is reduced by about 25% the most. The mechanical property of the modified butadiene rubber of the hydroxyl-terminated polyisoprene is improved to a certain extent, the tensile strength is improved by 28 percent, the tearing strength is obviously improved by 13 percent at most.
Example 10
In a polymerization kettle protected by nitrogen, n-hexane and butadiene are mixed evenly in a polymerization tube in sequence, and [ M ]]Adding Al-Ni aged solution and diluted boron solution (Ni/Bd is 1 × 10)-4，Al/Ni＝12,Al/B＝0.8，n-C8H17Polymerizing OH/B ═ 1 in a constant-temperature water bath at 60 ℃ for 4 h; adding hydroxyl-terminated polybutadiene-styrene oligomer 1# (with molecular weight of 8000 and vinyl content of 65%) into the glue solution, adding a redox initiator dibenzoyl peroxide/cuprous naphthoate to initiate a free radical reaction, wherein the molar ratio of dibenzoyl peroxide/cuprous naphthoate is 1:0.8, and the mass ratio of the hydroxyl-terminated polybutadiene-styrene oligomer 1# to the polybutadiene rubber is 3%; the mass ratio of free radical initiator to oligomer containing hydroxyl and pendant unsaturated bond was 0.2 and the reaction was carried out at 30 ℃ for 0.8 h. After the reaction, polymer is precipitated by using excessive ethanol, washed by ethanol and dried in a vacuum oven at 60 ℃ to constant weight. The properties of the obtained nickel-based butadiene rubber are shown in Table 3.
Example 11
In a polymerization kettle protected by nitrogen, n-hexane and butadiene are mixed evenly in a polymerization tube in sequence, and [ M ]]Adding Al-Ni aged solution and diluted boron solution (Ni/Bd is 1 × 10)-4，Al/Ni＝12,Al/B＝0.8，n-C8H17Polymerizing OH/B ═ 1 in a constant-temperature water bath at 60 ℃ for 4 h; adding hydroxyl-terminated polybutadiene-styrene oligomer 1# (with molecular weight of 8000 and vinyl content of 65%) into the glue solution, adding a redox initiator dibenzoyl peroxide/cuprous naphthoate to initiate a free radical reaction, wherein the molar ratio of dibenzoyl peroxide/cuprous naphthoate is 1:0.8, and the mass ratio of the hydroxyl-terminated polybutadiene-styrene oligomer 1# to the polybutadiene rubber is 5%; the mass ratio of free radical initiator to oligomer containing hydroxyl and pendant unsaturated bond was 0.3 and the reaction was carried out at 20 ℃ for 1.5 h. After the reaction, polymer is precipitated by using excessive ethanol, washed by ethanol and dried in a vacuum oven at 60 ℃ to constant weight. The properties of the obtained nickel-based butadiene rubber are shown in Table 3.
Example 12
In a polymerization kettle protected by nitrogen, n-hexane and butadiene are mixed evenly in a polymerization tube in sequence, and [ M ]]Adding Al-Ni aged solution and diluted boron solution (Ni/Bd is 1 × 10)-4，Al/Ni＝12,Al/B＝0.8，n-C8H17Polymerizing OH/B ═ 1 in a constant-temperature water bath at 60 ℃ for 4 h; adding hydroxyl-terminated polybutadiene-styrene oligomer 2# (with the molecular weight of 6000 and the vinyl content of 77%) into the glue solution, then adding a redox initiator dibenzoyl peroxide/cuprous naphthoate to initiate a free radical reaction, wherein the molar ratio of dibenzoyl peroxide/cuprous naphthoate is 1:0.6, and the mass ratio of the hydroxyl-terminated polybutadiene-styrene oligomer 2# to the polybutadiene rubber is 3%; the mass ratio of free radical initiator to oligomer containing hydroxyl and pendant unsaturated bond was 0.2 and the reaction was carried out at 20 ℃ for 1.5 h. After the reaction, polymer is precipitated by using excessive ethanol, washed by ethanol and dried in a vacuum oven at 60 ℃ to constant weight. The properties of the obtained nickel-based butadiene rubber are shown in Table 3.
Example 13
In a polymerization kettle protected by nitrogen, n-hexane and butadiene are mixed evenly in a polymerization tube in sequence, and [ M ]]Adding Al-Ni aged solution and diluted boron solution (Ni/Bd is 1 × 10)-4，Al/Ni＝12,Al/B＝0.8，n-C8H17Polymerizing OH/B ═ 1 in a constant-temperature water bath at 60 ℃ for 4 h; hydroxyl polybutadiene-styrene oligomer 2# (molecular weight 6000, vinyl content 77%) is added into the glue solution, then a redox initiator dibenzoyl peroxide/cuprous naphthoate is added to initiate a free radical reaction, and the molar ratio of dibenzoyl peroxide/cuprous naphthoate is 1:0.6, the mass ratio of hydroxyl-terminated polybutadiene-styrene oligomer 2# to the polybutadiene rubber is 3 percent; the mass ratio of free radical initiator to oligomer containing hydroxyl and pendant unsaturated bond was 0.35 and the reaction was carried out at 30 ℃ for 0.8 h. After the reaction, polymer is precipitated by using excessive ethanol, washed by ethanol and dried in a vacuum oven at 60 ℃ to constant weight. The properties of the obtained nickel-based butadiene rubber are shown in Table 3.
TABLE 3 structural Properties of modified butadiene rubber
As can be seen from Table 3, the solution viscosity of the butadiene rubber modified with the hydroxyl-terminated polybutadiene-styrene oligomer was reduced, and the mechanical properties of the butadiene rubber modified with the hydroxyl-terminated polybutadiene-styrene oligomer were significantly improved as compared with the unmodified butadiene rubber. The tearing strength of the vulcanized rubber of the hydroxyl-terminated polybutadiene-styrene oligomer No. 1 modified butadiene rubber is improved by 7 percent, and the tensile strength is improved by 23 percent. The tensile strength of the butadiene rubber modified by hydroxyl-terminated polybutadiene-styrene oligomer No. 2 is improved by 25.8%, and the tear strength is improved by 11.2%.
The raw rubber was cut into rectangular blocks each having a length, width and height of 5X 2cm, and after leaving for 45 days, the length, width and height were measured, and the calculated dimensional change ratio ((initial size-initial size)/initial size) was as shown in Table 4.
TABLE 4 Cold flow characterization of modified butadiene rubber
From Table 4, it can be seen that the dimensional change after the branched modification and after leaving for 45 days was greatly reduced in examples 6 and 12 compared to the non-branched modified comparative example 1, indicating that the improvement in cold flow properties of the green rubber was significant.
FIG. 1 is a graph of the solution viscosity of various oligomer-modified butadiene rubbers containing hydroxyl and pendant unsaturation, illustrating the solution viscosity of comparative example 1 and the examples.
As is evident from FIG. 1, the solution viscosity of the butadiene rubber modified with oligomers having hydroxyl and pendant unsaturation was significantly reduced, the solution viscosity of the butadiene rubber modified with hydroxyl-terminated polyisoprene oligomers was most significantly reduced, and the solution viscosity was reduced by 24.9% compared to the unmodified butadiene rubber.
FIG. 2 is a scanning electron micrograph of various oligomer-modified cis-butadiene rubbers containing hydroxyl groups and pendant unsaturation illustrating the compatibility of comparative example 1 and the examples with fillers.
As is apparent from the attached figure 2, the mixing effect of the modified butadiene rubber and the filler is obviously improved, and the agglomeration of the white carbon black is weakened. The polybutadiene rubber modified by the polybutadiene oligomer containing the terminal hydroxyl group has the best dispersion effect with the filler, and the polyisoprene containing the terminal hydroxyl group has the second best dispersion effect.
FIG. 3 is a graph of strain versus G' for various oligomer-modified cis-butadiene rubbers containing hydroxyl and pendant unsaturation, illustrating the Payne effect for comparative example 1 and examples.
As is evident from fig. 3, G' of the mix decreases with increasing strain, showing a so-called Payne effect. The mixing effect of the modified butadiene rubber and inorganic fillers such as white carbon black is obviously improved, and the Payne effect is reduced. The Payne effect of the polybutadiene rubber modified by hydroxyl-terminated polybutadiene is obviously reduced, and the reduction degree of delta G' is reduced by 4.6 percent; the reduction degree of the Delta G' of the butadiene rubber modified by hydroxyl-terminated polyisoprene is reduced by 2.4 percent.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of novel nickel-based butadiene rubber is characterized by comprising the following steps: adding oligomer containing hydroxyl and unsaturated bonds of side groups and redox initiator into polybutadiene glue solution prepared by polymerizing butadiene under the catalysis of nickel-based catalyst to carry out free radical reaction.
2. The method for producing a novel nickel-based cis-butadiene rubber according to claim 1, characterized in that: the oligomer containing hydroxyl and pendant unsaturated bonds is one or more of hydroxyl-terminated polybutadiene, hydroxyl-terminated styrene-butadiene polymer or hydroxyl-terminated isoprene.
3. The method for producing a novel nickel-based cis-butadiene rubber according to claim 1, characterized in that: the oxidant in the redox initiator is one or more of tert-butyl hydroperoxide, dialkyl peroxide, diacyl peroxide, benzoyl peroxide, dibenzoyl peroxide, benzoyl peroxide tert-butyl ester or lauroyl peroxide.
4. The method for producing a novel nickel-based cis-butadiene rubber according to claim 3, characterized in that: the oxidant in the redox initiator is dibenzoyl peroxide or lauroyl peroxide.
5. The method for producing a novel nickel-based cis-butadiene rubber according to claim 1, characterized in that: the reducing agent in the redox initiator is one or more of N, N-dimethylaniline, N-dimethyl toluidine, thiol compounds, triisobutyl aluminum, triethyl boron or naphthenate.
6. The method for producing a novel nickel-based cis-butadiene rubber according to claim 5, characterized in that: the reducing agent in the redox initiator is N, N-dimethylaniline, N-dimethyl toluidine or cuprous naphthoate.
7. The method for producing a novel nickel-based cis-butadiene rubber according to claim 1, characterized in that: the mass ratio of the oligomer containing hydroxyl and side group unsaturated bonds to polybutadiene is 0.1-10.
8. The method for producing a novel nickel-based cis-butadiene rubber according to claim 1, characterized in that: the mass ratio of the redox initiator to the oligomer containing hydroxyl groups and pendant unsaturated bonds is from 0.1 to 1.
9. The method for producing a novel nickel-based cis-butadiene rubber according to claim 1, characterized in that: the molar ratio of the oxidizing agent to the reducing agent in the redox initiator is 1:0.3 to 1: 0.9.
10. The method for producing a novel nickel-based cis-butadiene rubber according to claim 1, characterized in that: the temperature of the free radical reaction is 10-40 ℃, and the reaction time is 0.5-5 h.
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| CN104448059A (en) * | 2014-12-03 | 2015-03-25 | 浙江大学 | High cis-1,4 content epoxy hydroxyl-terminated polybutadiene liquid rubber and preparation method thereof |
| CN105601770A (en) * | 2016-02-01 | 2016-05-25 | 浙江大学 | Polyhydroxy polybutadiene liquid rubber and controllable preparation method thereof |
| CN107793534A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of butadiene rubber |
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| CN102372831A (en) * | 2010-08-12 | 2012-03-14 | 中国石油化工股份有限公司 | Preparation method of structure-modified 1,2-polybutadiene rubber |
| CN104448059A (en) * | 2014-12-03 | 2015-03-25 | 浙江大学 | High cis-1,4 content epoxy hydroxyl-terminated polybutadiene liquid rubber and preparation method thereof |
| CN105601770A (en) * | 2016-02-01 | 2016-05-25 | 浙江大学 | Polyhydroxy polybutadiene liquid rubber and controllable preparation method thereof |
| CN107793534A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of butadiene rubber |
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