CN114853948A - Branched high-cis rare earth conjugated diene rubber and preparation method and application thereof - Google Patents

Branched high-cis rare earth conjugated diene rubber and preparation method and application thereof Download PDF

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CN114853948A
CN114853948A CN202210231077.4A CN202210231077A CN114853948A CN 114853948 A CN114853948 A CN 114853948A CN 202210231077 A CN202210231077 A CN 202210231077A CN 114853948 A CN114853948 A CN 114853948A
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rare earth
cis
polyene
neodymium
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刘恒
王凤
张春雨
张学全
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Qingdao University of Science and Technology
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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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Abstract

A branched high cis-rare earth conjugated diene rubber and a preparation method and application thereof belong to the field of rare earth catalytic synthetic rubber. The preparation method is to add polyene substrate branching agent into a catalyst system or a polymerization system. PolyenesThe substrate branching agent is divided into (i) a polyfunctional conjugated polyene substrate and (ii) a polyfunctional nonconjugated polyene substrate; wherein the structural formula of (i) is as follows:
Figure DDA0003538381730000011
or

Description

Branched high-cis rare earth conjugated diene rubber and preparation method and application thereof
Technical Field
The invention relates to the field of rare earth catalytic synthetic rubber, in particular to branched high-cis rare earth conjugated diene rubber and a preparation method and application thereof.
Background
The main industrial products in the conjugated diene rubber are cis-1, 4-butadiene rubber (cis-butadiene rubber), cis-1, 4-isoprene rubber (isoprene rubber), high vinyl butadiene rubber, low-crystallinity syndiotactic high 1, 2-butadiene rubber, trans-1, 4-isoprene rubber and the like. Among the rubbers, the butadiene rubber and the isoprene rubber have excellent performances such as flexure resistance, wear resistance and low rolling resistance, are widely used in tire treads and tire sidewalls, and are essential key basic rubber species for producing high-performance green tires at present. In two rubber systems, the current performance is the best of rare earth butadiene rubber and rare earth isoprene rubber prepared by taking rare earth as a catalyst, but the two rubber chains have higher structural linearity, rubber glue solution viscosity is higher, glue solution conveying is difficult, energy consumption is high, and rubber post-processing is difficult. The introduction of a certain branched structure into a linear molecular chain can obviously reduce the hydrodynamic volume of a macromolecule in a solution, thereby reducing the viscosity of a glue solution and lowering the material conveying cost. The branched rubber also has better processing performance, easy material consumption during mixing and better dispersion of the filler in the rubber compound. In addition, the branched structure can obviously improve the cold flow property of the rare earth butadiene and isoprene rubber, enhance the storage stability and facilitate transportation and storage.
At present, the method for preparing the high cis-branched rare earth butadiene rubber and the high cis-branched rare earth isoprene rubber mainly comprises the following steps: post-functionalization modification and chain end coupling. For the post-functionalization modification, the addition of disulfur dichloride, sulfur dichloride or thionyl chloride compounds to rubber solutions is described in patents US5567784A, EP 0707017B1, DE4436059a 1; strategies for adding dithiol compounds are described in patents CN104231119A, CN 104231120B. Both strategies adopt a free radical mechanism, and generate inter-chain local crosslinking reaction through free radicals generated in situ, so as to construct a long-chain branched structure. However, the generated high-activity free radicals are easy to generate side reactions such as uneven reaction, local crosslinking and the like in high-viscosity glue solution, and the uniformity of the product performance is influenced. In addition, the unpleasant odor of sulfur-containing compounds also affects the storage and use of the rubber products at a later stage. For the chain end coupling method, a method of adding compounds such as isocyanate, halogenated metal, halogenated silane, halogenated hydrocarbon and the like is described in patents EP863165A1, EP102618A1 and US7319126B2, but due to the fact that the viscosity of glue solution is large at the later stage of polymerization, the movement of the active chain end of the polymerization is limited, the coupling efficiency is low, the branching degree is limited and the like are easily caused. And the residual compounds in the reaction also cause pollution to the polymerization solvent and the like, so that the recovery is difficult and the cost is increased.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a branched high-cis rare earth conjugated diene rubber, a preparation method and application thereof, and particularly provides a method for constructing a branched high-cis rare earth butadiene rubber and a branched high-cis rare earth isoprene rubber. By an in-situ copolymerization method, a high-activity polyene substrate component is added, a branched structure can be formed in situ, and the rare earth conjugated diene rubber with adjustable weight average molecular weight, controllable distribution, high branching efficiency, adjustable branching factor (branching coefficient) and cis-1, 4-content higher than 85 percent can be prepared. The obtained rubber has obviously lower solution viscosity, excellent processing performance and greatly improved cold flow resistance.
The invention relates to a preparation method of branched high-cis rare earth conjugated diene rubber, which adds a polyene substrate branching agent into a catalyst system or a polymerization system.
The polyene substrate branching agent is a polyfunctional polyene substrate, and is divided into (i) a polyfunctional conjugated polyene substrate and (ii) a polyfunctional nonconjugated polyene substrate according to whether or not conjugation is performed;
the structural formula of the (i) polyfunctional conjugated polyene substrate is as follows:
Figure BDA0003538381720000021
wherein X is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon or aromatic hydrocarbon of C2-C25, and most preferably ethylidene- (CH) 2 ) 2 -, butylidene- (CH) 2 ) 4 -, pentylidene- (CH) 2 ) 5 -, hexylidene- (CH) 2 ) 6 -, benzylidene- (C) 6 H 4 ) -, 1, 4-dimethylenephenyl (-CH) 2 PhCH 2 -, 1, 3-dimethylenephenyl (-CH) 2 PhCH 2 -) is selected;
the (ii) polyfunctional non-conjugated polyene substrate is selected from one or more of (a) diene compounds, (b) polyene compounds containing hetero atoms, and (c) diene and conjugated diene oligomers.
The diene compound (a) is preferably one or more of an aliphatic diene compound with a linear or branched structure of C4-C30, an aromatic diene compound with a linear or branched structure of C4-C30 and a cyclic diene compound with C4-C30;
the aliphatic diene compound with a linear or branched structure of C4-C30 is preferably one or more of 1, 4-pentadiene, 1, 5-hexadiene, 1, 6-heptadiene, 1, 7-octadiene, 1, 5-cyclooctadiene, 1, 8-nonadiene, 1, 9-decadiene, 1, 10-undecadiene, 1, 11-dodecadiene, 1, 12-tridecadiene, 1, 13-tetradecadiene, 1, 14-pentadecadiene and corresponding substitutes thereof;
the aromatic diene compound with a linear or branched structure of C4-C30 is preferably one or more of 1, 4-divinylbenzene, 1, 3-divinylbenzene and 1, 2-divinylbenzene;
the cyclic diolefin compound of C4-C30 is preferably one or more of cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, cyclodecadiene and corresponding substitutes thereof.
The diene compound (a) is most preferably one or more of 1, 5-hexadiene, 1, 4-cyclohexadiene, 1, 7-octadiene and 1, 5-cyclooctadiene.
The polyene compound containing the heteroatom (b) is preferably one or more of alpha-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, gamma-linolenic acid and octavinylsilsesquioxane (POSS).
The diene and conjugated diene oligomer (c) is one or more of homopolymer oligomer of diene, copolymer oligomer of diene and functionalized oligomer.
The molecular weight of the diene and the conjugated diene oligomer is 100-20000, and more preferably 200-8000.
The diene and conjugated diene oligomer also comprises a modified polymer thereof, and the preferable modification is as follows: a product modified by a functional group such as hydrogenation modification, epoxidation modification, halogen modification or hydrohalogen modification.
The diene homopolymer oligomer is preferably one or more of 1, 3-butadiene oligomer, 1, 3-isoprene oligomer, 1, 3-piperylene oligomer, 1, 5-hexadiene oligomer and 1, 7-octadiene oligomer;
the copolymerized oligomers of the dienes are preferably: copolymerized oligomers of at least two monomers selected from butadiene, isoprene, myrcene, styrene, substituted styrene, ethylene, alpha-olefin, and acrylonitrile;
more preferably, an oligomer copolymerized with two monomers of butadiene and isoprene, an oligomer copolymerized with two monomers of butadiene and styrene, an oligomer copolymerized with two monomers of butadiene and substituted styrene, an oligomer copolymerized with two monomers of isoprene and styrene, an oligomer copolymerized with two monomers of butadiene and ethylene, an oligomer copolymerized with two monomers of isoprene and ethylene, an oligomer copolymerized with two monomers of butadiene and alpha-olefin, an oligomer copolymerized with two monomers of isoprene and alpha-olefin, the alpha-olefin is one of propylene and butylene, an oligomer copolymerized by two monomers of butadiene-acrylonitrile, and one or more oligomers copolymerized by three monomers of butadiene, isoprene and styrene.
The functionalized oligomer is one of diene oligomers and is classified as an in-chain functionalized oligomer or a chain end functionalized oligomer, and the functionalized group is one or more of hydroxyl, carboxyl, ester group, amidino, silicon group, tin group and halogen.
In molar ratio, the polyene substrate branching agent: the rare earth element in the catalyst system is (0.001-1000): 1.
in the preparation method of the branched high cis-rare earth polymerized diene rubber, the adopted catalyst system comprises a rare earth neodymium compound, an alkyl aluminum compound, a halogen compound and a conjugated diene monomer;
the rare earth neodymium compound is preferably a neodymium carboxylate compound Nd (OCOR) 3 Neodymium phosphate compound Nd (OOOPOR) 3 Alkoxy or phenoxy neodymium compounds Nd (OR) 3 Neodymium chloride and its mixed compound of halogen and acid radical NdCl m (OCOR) 3-m M is one of positive integers of 0-4; wherein R is a linear or branched aliphatic hydrocarbon of C2-C15 or a linear or branched aromatic hydrocarbon of C2-C15;
the neodymium carboxylate compound Nd (OCOR) 3 Preferably one or more of neodymium neodecanoate, neodymium isooctanoate and neodymium naphthenate;
the neodymium phosphate compound Nd (OOOPOR) 3 Preferably neodymium (2-ethylhexyl) phosphonate Nd (P204) 3 Or one or more of (2-ethylhexyl) neodymium phosphonate mono-2-ethylhexyl Nd (P507);
said alkoxy or phenoxide neodymium compound Nd (OR) 3 Preferably one or more of neodymium isopropoxide, neodymium isobutoxide and neodymium n-propoxide;
the neodymium chloride and the mixed compound NdCl of the halogen and the acid radical thereof m (OCOR) 3-m Preferably one or more of neodymium neodecanoate chloride, neodymium naphthenate chloride, neodymium isopropanol chloride and neodymium chloride.
The alkyl aluminum compound is preferably one or a mixture of more of trialkyl aluminum compound, alkyl aluminum hydride compound and alkyl aluminoxane compound;
the trialkyl aluminum compound is preferably one or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and trioctyl aluminum;
the alkyl aluminum hydride compound is preferably one or more of diethyl aluminum hydride, diisobutyl aluminum hydride and dimethyl aluminum hydride;
one or two of the alkyl aluminoxane compound, namely methyl aluminoxane and ethyl aluminoxane;
the alkyl aluminum compound is more preferably one or a mixture of triisobutyl aluminum, triethyl aluminum and diisobutyl aluminum hydride.
The halogen compound is a chloroalkyl compound RCl x Aluminum chloride compound, silane chloride SiR 1 4-y Cl y One or more of the above; wherein x is a positive integer of 1-4, R is a linear or branched aliphatic hydrocarbon of C2-C15, or a linear or branched aromatic hydrocarbon of C2-C15; r 1 Is one or more of methyl, ethyl, propyl, butyl and phenyl, and y is a positive integer of 0-4;
the chloroalkyl compound RCl x Preferably one or two of tert-butyl chloride and chloroform;
the aluminum chloride compound is preferably aluminum sesqui-alkyl Al 2 R 2 3 Cl 3 Dialkyl aluminum chloride AlR 2 2 Cl, AlAl alkyl dichloride AlR 2 Cl 2 One or more of the above; wherein R is 2 Is one or more of methyl, ethyl, isobutyl and octyl; more preferably aluminum sesquiethylate chloride;
the chlorosilane SiR 1 4-y Cl y Preferably: one or two of trimethylchlorosilane and dichlorodimethylsilane;
the conjugated diene monomer is one or more of 1, 3-butadiene, 1, 3-isoprene, 1, 3-piperylene and myrcene.
The invention relates to a preparation method of branched high-cis rare earth conjugated diene rubber, which comprises one of the following methods:
the first method comprises the following steps:
(1) mixing and reacting a rare earth neodymium compound, an alkyl aluminum compound, a conjugated diene monomer and a polyene substrate branching agent to obtain a mixed solution A, adding a halogen compound into the mixed solution A, and mixing and reacting to obtain a catalyst system A prepared from the branched high-cis rare earth conjugated diene rubber;
(2) adding a monomer and a catalyst system A into an alkane solvent for polymerization reaction to obtain a reaction solution;
(3) and (3) carrying out reaction polymerization on the reaction solution, and condensing the branched high-cis rare earth conjugated diene rubber in the reaction solution by using a precipitation liquid.
The second method comprises the following steps:
(1) mixing a rare earth neodymium compound, an alkyl aluminum compound and a conjugated diene monomer for reaction to obtain a mixed solution B, adding a halogen compound into the mixed solution B for reaction to obtain a catalyst system B prepared from the branched high-cis rare earth conjugated diene rubber;
(2) adding a monomer and a catalyst system A into an alkane solvent, and then adding a polyene substrate branching agent for polymerization reaction to obtain a reaction solution;
(3) and (3) carrying out reaction polymerization on the reaction solution, and condensing the branched high-cis rare earth conjugated diene rubber in the reaction solution by using a precipitation liquid.
In the first method (1), the mixing temperature of the catalyst system A is 0-100 ℃, preferably 30-80 ℃, and more preferably 40-60 ℃; the mixing reaction time for preparing the mixed solution A is 1-30 minutes, preferably 5-15 minutes, and more preferably 10 minutes; the time for adding the halogen compound into the mixed solution A to mix and react is 10-60 minutes, preferably 20-40 minutes, and more preferably 30 minutes.
In the second method (1), the mixing temperature of the catalyst system B is 0-100 ℃, preferably 30-80 ℃, and more preferably 40-60 ℃; the mixing reaction time for preparing the mixed solution B is 1-30 minutes, preferably 5-15 minutes, and more preferably 10 minutes; and adding the halogen compound into the mixed solution B, and mixing and reacting for 10-60 minutes, preferably 20-40 minutes, and more preferably 30 minutes.
Further, wherein, the molar ratio: rare earth neodymium compound: alkyl aluminum compound: halogen compound: conjugated diene monomer, polyene substrate branching agent ═ 1: (3-50): (0.5-5): (0-30): (0.001 to 1000), preferably 1: (5-40): (1-3): (5-15): (1-500), more preferably 1: (15-30): (1.5-2.5): 10: (5-300); wherein the moles of the rare earth neodymium compound and the polyene substrate branching agent are both moles of double bonds therein.
Further, in terms of molar ratio, monomer: the rare earth neodymium compound in the catalyst (200-50000) is 1.
Further, the educt is preferably ethanol.
Further, the monomer is preferably butadiene or isoprene.
Further, the alkane solvent is selected from pentane, hexane, cyclohexane, heptane, methylcyclohexane, raffinate oil (C) 6 ～C 8 Alkane mixture of (a), one or more of benzene, toluene, xylene, trimethylbenzene.
Further, in the preparation method of the branched high-cis rare earth conjugated diene rubber, the monomer concentration is 5-180 g/L, preferably 20-130 g/L, and more preferably 50-120 g/L.
Further, the branched high-cis rare earth conjugated diene rubber is branched high-cis polybutadiene rubber or branched high-cis polyisoprene rubber.
The cis-1, 4-content of the branched high-cis rare earth conjugated diene rubber prepared by the method is not less than 85 percent, and more preferably not less than 95 percent.
The molecular weight of the branched high cis-rare earth polybutadiene and the branched high cis-polyisoprene prepared by the invention is 0.1 multiplied by 10 4 ～200×10 4 And the branching factor is between 0.40 and 0.95.
The invention relates to an application of branched high-cis rare earth conjugated diene rubber, which is used for tire, shoe making or resin modification. The invention relates to a branched high-cis rare earth conjugated diene rubber, a preparation method and application thereof, and the branched high-cis rare earth conjugated diene rubber has the beneficial effects that:
1. the invention can adjust the branching factor of the prepared rubber by adding the polyene substrate branching agent into a catalyst system or a polymerization system.
2. Compared with linear polymers, the branched high-cis rare earth polybutadiene and polyisoprene rubber provided by the invention have obviously lower solution viscosity and better processing performance, and can be widely applied to the fields of elastomers such as tires and shoes and the like and the aspects of resin modification and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope and practice of the invention.
The microstructure of the branched high cis-rare earth polybutadiene and the branched high cis-polyisoprene provided by the invention passes through FTIR spectrum and nuclear magnetic hydrogen spectrum 1 H NMR and carbon Spectroscopy 13 C NMR measurement and calculation.
The number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn) and branching factor (g is the ratio of the mean square radius of rotation of the same molecular weight branching to the linear polymer) of the branched high-cis rare earth polybutadiene and the branched high-cis polyisoprene provided by the invention are measured by three-detector (viscosity, light scattering and difference) Gel Permeation Chromatography (GPC).
The formula of the vulcanized rubber of the branched high cis-rare earth polybutadiene and the branched high cis-polyisoprene provided by the invention is as follows: 100 parts of polymer (same as other components in mass), 4 parts of zinc oxide, 2 parts of stearic acid, 1 part of anti-aging agent, 50 parts of carbon black, 1.5 parts of sulfur and 0.9 part of accelerator. And mixing on a double-roller open mill, wherein the roller temperature is 40-60 ℃, the mixed rubber is remilled after standing for 4.0h, the obtained rubber material is vulcanized on a flat vulcanizing machine after standing for 0.5h, and the conditions are that the temperature is 145 ℃ for 25 min.
The vulcanized rubber of the branched high-cis rare earth polybutadiene and the branched high-cis polyisoprene provided by the invention is tested for tensile strength, stress at definite elongation, elongation at break and tearing property at a tensile rate of 500mm/min according to GB/T528-2009 standard.
In the following examples, polybutadiene comprises a polymer of cis-1,4-, trans-1, 4-, 1, 2-structure; a polymer comprising cis-1,4-, trans-1, 4-, 1, 2-structure, 3, 4-structure for isoprene; for piperylene, polymers comprising cis-1,4-, trans-1, 4-, 1, 2-structures, 3, 4-structures are included.
The following ratios of the respective raw materials are molar ratios unless otherwise specified.
Example 1:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (polyene substrate branching agent E1 has the structure shown below) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride: the branching agent E1 was reacted at 50 ℃ for 10 minutes at 1:10:25:0.1, and then dimethyldichlorosilane (Cl/Nd ═ 2) was added to the reaction mixture to react at 50 ℃ for 30 minutes, thereby obtaining a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 95%, the cis-1, 4-structure was 97.3%, and the number-average molecular weight was 14.5 × 10 ═ Mn 4 The molecular weight distribution was 2.3 and the branching factor was 0.72.
Wherein the polyene substrate branching agent E1 has the formula:
Figure BDA0003538381720000071
example 2:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (polyene substrate branching agent E1 has the same structure as in example 1) were added in one portion under nitrogen protection, in a molar ratio, neodymium neodecanoate: butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 were 1:10:25:0.2, reacted at 50 ℃ for 10 minutes, and then dimethyldichlorosilane (Cl/Nd ═ 2) was added, reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 92%, the cis-1, 4-structure was 96.5%, and the number-average molecular weight was 16.5 × 10 ═ Mn 4 The molecular weight distribution was 2.6 and the branching factor was 0.60.
Example 3:
under the protection of nitrogen, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (the structure of polyene substrate branching agent E1 is the same as that in example 1) were added at once to a dry catalyst reaction flask in a molar ratio of 1:10:25:0.25, and after reacting at 50 ℃ for 10 minutes, dimethyldichlorosilane (Cl/Nd ═ 2) was added to react at 50 ℃ for 30 minutes, to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 90%, the cis-1, 4-structure was 96.1%, and the number-average molecular weight was 18.5 × 10 ═ Mn 4 The molecular weight distribution was 2.7 and the branching factor was 0.55.
Examples 1-3 show that the branching factor of the branched high cis rare earth butadiene rubber produced can be adjusted by adjusting the amount of polyene substrate branching agent.
Example 4:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E2 (polyene substrate branching agent E2 has the structure shown below) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride; the polyene substrate branching agent E2 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 94%, the cis-1, 4-structure was 96.9%, and the number-average molecular weight was Mn ═ 12.5 × 10 4 The molecular weight distribution was 2.4 and the branching factor was 0.75.
The polyene substrate branching agent E2 has the following structural formula:
Figure BDA0003538381720000081
example 5:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E3 (polyene substrate branching agent E3 has the structure shown below) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E3 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing at 50 deg.C for 4h, and terminating with ethanol solution containing 1% of antioxidant 264And condensing with ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 85%, the cis-1, 4-structure was 95.2%, and the number average molecular weight was 10.5 × 10 ═ Mn 4 The molecular weight distribution was 2.8 and the branching factor was 0.79.
The polyene substrate branching agent E3 has the formula:
Figure BDA0003538381720000082
example 6:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E4 (polyene substrate branching agent E4 has the structure shown below) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E4 was 1:10:25:0.05, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 86%, the cis-1, 4-structure was 95.9%, and the number-average molecular weight was 11.2 × 10 ═ Mn 4 The molecular weight distribution was 2.6 and the branching factor was 0.66.
The polyene substrate branching agent E4 has the formula:
Figure BDA0003538381720000091
example 7:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride, triisobutylaluminum, and polyene substrate branching agent E1 (structure example 1 of polyene substrate branching agent E1) were added in one portion under nitrogen protection in a molar ratio of neodymium neodecanoate: butadiene: diisobutylaluminum hydride: triisobutylaluminum: the polyene substrate branching agent E1 was reacted at 50 ℃ for 10 minutes at 1:10:20:15:0.1, and then dimethyldichlorosilane (Cl/Nd ═ 2) was added to react at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 93%, the cis-1, 4-structure was 96.0%, and the number-average molecular weight was 15.5 × 10 ═ Mn 4 The molecular weight distribution was 2.8 and the branching factor was 0.76.
Example 8:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and a polyene substrate branching agent E1 (structural example 1 of polyene substrate branching agent E1) were added at a time to a dry catalyst reaction flask under nitrogen protection in a molar ratio of 1:10:25:0.1, followed by reaction at 50 ℃ for 10 minutes, addition of dimethyldichlorosilane (Cl/Nd ═ 2) and reaction at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used was Bd/Nd 12000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 85%, the cis-1, 4-structure was 96.1%, and the number-average molecular weight was 19.2 × 10 ═ Mn 4 The molecular weight distribution was 2.6 and the branching factor was 0.79.
Example 9:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (shown in structural example 1 of polyene substrate branching agent E1) were added at once to a dry catalyst reaction flask under nitrogen protection in a molar ratio such that neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 ═ 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, and then dimethyldichlorosilane (Cl/Nd ═ 2) was added thereto and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The dosage of the catalyst is Bd/Nd 5000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 99%, the cis-1, 4-structure was 95.3%, and the number-average molecular weight was 8.2 × 10 ═ Mn 4 The molecular weight distribution was 2.0 and the branching factor was 0.68.
Example 10:
to a dry catalyst reaction flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (shown in structural example 1 of polyene substrate branching agent E1) were added at once under nitrogen protection in a molar ratio of neodymium neodecanoate: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E1 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used was Bd/Nd 2000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 100%, the cis-1, 4-structure was 92.3%, and the number-average molecular weight was 2.5 × 10 ═ Mn 4 The molecular weight distribution was 1.8 and the branching factor was 0.64.
Example 11:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (structure example 1 of polyene substrate branching agent E1) were added in one portion under nitrogen protection, in molar ratio neodymium neodecanoate: butadiene: diisobutylaluminum hydride; the polyene substrate branching agent E1 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used was Bd/Nd 500. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 100%, the cis-1, 4-structure was 86.3%, and the number-average molecular weight was Mn ═ 0.6 × 10 4 The molecular weight distribution was 1.3.
Example 12:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, triisobutylaluminum and polyene substrate branching agent E1 (structure example 1 of polyene substrate branching agent E1) were added in one portion under nitrogen protection, in a molar ratio, neodymium neodecanoate: butadiene: triisobutylaluminum: the polyene substrate branching agent E1 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
40ml (concentration: 0.1g/ml) of an isoprene monomer solution was added to a dry 50ml reaction flask under nitrogen protection, and then the prepared catalyst solution was added. The dosage of the catalyst is Bd/Nd 5000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 85%, the cis-1, 4-structure was 98.3%, and the number-average molecular weight was 95.5 × 10 ═ Mn 4 The molecular weight distribution was 5.6 and the branching factor was 0.79.
Example 13:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, triisobutylaluminum and polyene substrate branching agent E1 (polyene substrate branching agent E1 has the same structure as in example 1) were added in one portion under nitrogen protection, in a molar ratio, neodymium neodecanoate: butadiene: triisobutylaluminum; the polyene substrate branching agent E1 was 1:10:25:0.2, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
40ml (concentration: 0.1g/ml) of an isoprene monomer solution was added to a dry 50ml reaction flask under nitrogen protection, and then the prepared catalyst solution was added. The dosage of the catalyst is Bd/Nd 5000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 76%, the cis-1, 4-structure was 97.4%, and the number-average molecular weight was 84.3 × 10 ═ Mn 4 The molecular weight distribution was 4.9 and the branching factor was 0.70.
Example 14:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, triisobutylaluminum, diisobutylaluminum hydride and polyene substrate branching agent E1 (structure example 1 of polyene substrate branching agent E1) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: triisobutylaluminum: diisobutylaluminum hydride: the polyene substrate branching agent E1 was 1:10:15:10:0.1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2) and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
40ml (concentration: 0.1g/ml) of an isoprene monomer solution was added to a dry 50ml reaction flask under nitrogen protection, and then the prepared catalyst solution was added. The dosage of the catalyst is Bd/Nd 5000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 81%, the cis-1, 4-structure was 97.3%, and the number-average molecular weight was 65.5 × 10 4 The molecular weight distribution was 4.9 and the branching factor was 0.75.
Example 15:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (polyene substrate branching agent E1 is structured as shown in example 1) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride; the polyene substrate branching agent E1 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, added with aluminum sesquidiethyl chloride (Cl/Nd ═ 2), and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 96%, the cis-1, 4-structure was 96.9%, and the number-average molecular weight was 13.1 × 10 ═ Mn 4 The molecular weight distribution was 2.5 and the branching factor was 0.76.
Example 16:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (polyene substrate branching agent E1 is structured as shown in example 1) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E1 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, added with diethyl aluminum chloride (Cl/Nd ═ 2), and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 93%, the cis-1, 4-structure was 96.5%, and the number-average molecular weight was Mn 12.9 × 10 4 The molecular weight distribution was 2.6.
Example 17:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, triisobutylaluminum, and polyene substrate branching agent E1 (shown in structural example 1 of polyene substrate branching agent E1)) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: triisobutylaluminum: the polyene substrate branching agent E1 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, added with aluminum sesquidiethyl chloride (Cl/Nd ═ 2), and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
40ml (concentration: 0.1g/ml) of an isoprene monomer solution was added to a dry 50ml reaction flask under nitrogen protection, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 79%, the cis-1, 4-structure was 96.5%, and the number-average molecular weight was 102.6 × 10 4 The molecular weight distribution was 7.0 and the branching factor was 0.79.
Example 18:
under the protection of nitrogen, neodymium neodecanoate, butadiene and diisobutylaluminum hydride are added into a dry catalyst reaction bottle in one step, and the molar ratio of neodymium neodecanoate: butadiene: diisobutylaluminum hydride at a ratio of 1:10:25 was reacted at 50 ℃ for 10 minutes, and then dimethyldichlorosilane (Cl/Nd ═ 2) was added thereto, and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under nitrogen protection, 40ml of a butadiene monomer solution (concentration of 0.1g/ml) was added to a dry 50ml reaction flask, and then a hexane solution (E1/Nd ═ 0.01) of a polyene substrate branching agent E1 (polyene substrate branching agent having the same structure as in example 1) was added and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 93%, the cis-1, 4-structure was 96.9%, and the number-average molecular weight was 10.5 × 10 ═ Mn 4 The molecular weight distribution was 2.3 and the branching factor was 0.45.
Example 19:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E5 (polyene substrate branching agent E5 is 1, 5-hexadiene) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene; diisobutylaluminum hydride; the polyene substrate branching agent E5 was 1:10:25:1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 88%, the cis-1, 4-structure was 94.2%, and the number-average molecular weight was 11.5 × 10 ═ Mn 4 The molecular weight distribution was 2.9 and the branching factor was 0.86.
Example 20:
to a dry catalyst reaction flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E6 (polyene substrate branching agent E6 is 1, 7-octadiene) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E6 was 1:10:25:1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 80%, the cis-1, 4-structure was 93.2%, and the number-average molecular weight was 9.5 × 10 ═ Mn 4 The molecular weight distribution was 3.1 and the branching factor was 0.85.
Example 21:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E7 (polyene substrate branching agent E7 has the structure shown below) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E7 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 76%, the cis-1, 4-structure was 96.3%, and the number-average molecular weight was Mn ═ 10.5 × 10 4 The molecular weight distribution was 2.9 and the branching factor was 0.80.
The polyene substrate branching agent E7 has the following structural formula:
Figure BDA0003538381720000141
example 22:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E8 (polyene substrate branching agent E8 is liquid polybutadiene, molecular weight 2.6X 10) were added in one portion to a dry catalyst reactor under nitrogen protection 3 Distribution 1.1, 1, 2-content: 51%, cis-1, 4-content 26%), neodymium neodecanoate in molar ratio: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E8 was 1:10:25:50, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 93%, and the cis-1, 4-structure was 96.2%, a numberAverage molecular weight Mn 14.8X 10 4 The molecular weight distribution was 2.9 and the branching factor was 0.83.
Example 22:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E9 (polyene substrate branching agent E9 is liquid polybutadiene, molecular weight 7.1X 10) were added in one portion to a dry catalyst reactor under nitrogen protection 3 Distribution 1.2, 1, 2-content: 55 percent of cis-1, 4-content 32 percent, by mole, 1:10:25:50 of neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E9, and after reacting at 50 ℃ for 10 minutes, dimethyldichlorosilane (Cl/Nd ═ 2) was added and reacted at 50 ℃ for 30 minutes, a catalyst solution was obtained.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 94%, the cis-1, 4-structure was 95.8%, and the number-average molecular weight was 13.8 × 10 ═ Mn 4 The molecular weight distribution was 2.6 and the branching factor was 0.85.
Example 23:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E10 (polyene substrate branching agent E10 is liquid polybutadiene, molecular weight 4.1X 10) were added in one portion to a dry catalyst reactor under nitrogen protection 3 Distribution 1.2, 1, 2-content: 97% with cis-1, 4-content 1%), neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E10 in a molar ratio of 1:10:25:50, reacted at 50 ℃ for 10 minutes, then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, and then a catalyst solution was obtained.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerization at 50 ℃ for 4h, after whichTerminating by using an ethanol solution containing 1 percent of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 90%, the cis-1, 4-structure was 95.8%, and the number-average molecular weight was 11.3 × 10 ═ Mn 4 The molecular weight distribution was 2.6 and the branching factor was 0.75.
Example 24:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E11 (polyene substrate branching agent E11 is liquid polybutadiene, molecular weight 4.1X 10) were added in one portion to a dry catalyst reactor under nitrogen protection 3 Distribution 1.2, 1, 2-content: 3% and cis-1, 4-content 81%), in a molar ratio, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E11 were 1:10:25:50, reacted at 50 ℃ for 10 minutes, then dimethyldichlorosilane (Cl/Nd ═ 2) was added, and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 88%, the cis-1, 4-structure was 95.1%, and the number-average molecular weight was 10.5 × 10 ═ Mn 4 The molecular weight distribution was 2.3 and the branching factor was 0.89.
Example 23:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E12 (polyene substrate branching agent E12 is liquid polyisoprene, molecular weight 3.6X 10) were added in one portion to a dry catalyst reactor under nitrogen blanket 3 Distribution 1.2, 3.4-content: 43%, 1, 4-content 51%), neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E12 in a molar ratio of 1:10:25:50, reacted at 50 ℃ for 10 minutes, then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
To a dry 50ml reaction flask under nitrogen protectionTo this was added 40ml (concentration: 0.1g/ml) of a butadiene monomer solution, followed by addition of the above-prepared catalyst solution. The amount of catalyst used is 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 85%, the cis-1, 4-structure was 95.8%, and the number-average molecular weight was 9.8 × 10 ═ Mn 4 The molecular weight distribution was 3.2 and the branching factor was 0.95.
Example 24:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E13 (polyene substrate branching agent E13 is a liquid butadiene styrene copolymer, molecular weight 4.1X 10) were added at once to a dry catalyst reaction flask under nitrogen blanket 3 Distribution 1.2, butadiene content: 68 percent, wherein the 1, 2-content is 60 percent, the cis-1, 4-content is 21 percent), and the molar ratio is as follows: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E13 was 1:10:25:50, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 80%, the cis-1, 4-structure was 92.8%, and the number-average molecular weight was 8.8 × 10 ═ Mn 4 The molecular weight distribution was 3.6 and the branching factor was 0.92.
Example 25:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E14 (polyene substrate branching agent E14 is hydroxyl-terminated liquid polybutadiene, molecular weight 3.0X 10) were added in one portion to a dry catalyst reaction flask under nitrogen protection 3 Distribution 1.2, 1, 2-content 78%, cis-1, 4-content 10%), in mol ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride: polyene substrate branching agent E14 was 1:10:25:50, after reacting at 50 ℃ for 10 minutes, dimethyldichlorosilane (Cl/Nd ═ 2) was added and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under the protection of nitrogen, 40ml (concentration: 0.1g/ml) of a butadiene monomer solution was added to a dry 50ml reaction flask, and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 75%, the cis-1, 4-structure was 88.6%, and the number-average molecular weight was 7.8 × 10 ═ Mn 4 The molecular weight distribution was 3.0 and the branching factor was 0.94.
Example 26:
to a dry catalyst reactor flask, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E1 (polyene substrate branching agent E1 is structured as shown in example 1) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E1 was 1:10:25:0.1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes, to obtain a catalyst solution.
4000ml of butadiene monomer solution (concentration 0.1g/ml) was added to a dry 5000ml reaction flask under nitrogen protection, followed by the above prepared catalyst solution. The dosage of the catalyst is Bd/Nd 10000. Polymerizing for 5h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 90%, the cis-1, 4-structure was 96.9%, and the number-average molecular weight was Mn ═ 12.6 × 10 4 The molecular weight distribution was 2.4 and the branching factor was 0.80.
Vulcanizing the obtained branched rare earth butadiene rubber, wherein the vulcanization formula is as follows: 100 parts of polymer (same as other components in mass), 4 parts of zinc oxide, 2 parts of stearic acid, 1 part of anti-aging agent, 50 parts of carbon black, 1.5 parts of sulfur and 0.9 part of accelerator. And mixing on a double-roller open mill, wherein the roller temperature is 40-60 ℃, the mixed rubber is remilled after standing for 4.0h, the obtained rubber material is vulcanized on a flat vulcanizing machine after standing for 0.5h, and the conditions are that the temperature is 145 ℃ for 25 min. The mechanical properties of the vulcanized rubber were evaluated, and the tensile strength was 19.4MPa and the elongation at break was 492%.
Comparative example 1:
under the protection of nitrogen, neodymium neodecanoate, butadiene and diisobutylaluminum hydride are added into a dry catalyst reaction bottle in one step, and the molar ratio of neodymium neodecanoate: butadiene: diisobutylaluminum hydride at a ratio of 1:10:25:0.1 was reacted at 50 ℃ for 10 minutes, and then dimethyldichlorosilane (Cl/Nd ═ 2) was added thereto and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
4000ml of butadiene monomer solution (concentration 0.1g/ml) was added to a dry 5000ml reaction flask under nitrogen protection, followed by the above prepared catalyst solution. The dosage of the catalyst is Bd/Nd 10000. Polymerizing for 5h at 50 ℃, and then terminating by using ethanol solution containing 1% of antioxidant 264 and condensing by using ethanol to obtain the rare earth butadiene rubber.
The yield of the polymer was 93%, the cis-1, 4-structure was 97.1%, and the number-average molecular weight was 14.2 × 10 ═ Mn 4 The molecular weight distribution was 2.2, the polymer was linear, the branching factor was 1.0.
Comparing this comparative example with example 26, it is shown that the introduction of the branching agent significantly increases the degree of branching of the polymer.
Example 27:
neodymium neodecanoate, butadiene, diisobutylaluminum hydride and polyene substrate branching agent E8 (polyene substrate branching agent E8 is liquid polybutadiene, molecular weight 2.6X 10) were added in one portion to a dry catalyst reactor under nitrogen protection 3 Distribution 1.1, 1, 2-content: 51%, cis-1, 4-content 26%), neodymium neodecanoate in molar ratio: butadiene: diisobutylaluminum hydride: the polyene substrate branching agent E8 was 1:10:25:50, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
4000ml of butadiene monomer solution (concentration 0.1g/ml) was added to a dry 5000ml reaction flask under nitrogen protection, followed by the above prepared catalyst solution. The amount of catalyst used is Bd/Nd 8000.Polymerizing for 5h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 86%, the cis-1, 4-structure was 96.4%, and the number-average molecular weight Mn was 15.6 × 10 4 The molecular weight distribution was 2.8 and the branching factor was 0.88.
Vulcanizing the obtained branched rare earth butadiene rubber, wherein the vulcanization formula is as follows: 100 parts of polymer (same as other components in mass), 4 parts of zinc oxide, 2 parts of stearic acid, 1 part of anti-aging agent, 50 parts of carbon black, 1.5 parts of sulfur and 0.9 part of accelerator. And mixing on a double-roller open mill, wherein the roller temperature is 40-60 ℃, the mixed rubber is remilled after standing for 4.0h, the obtained rubber material is vulcanized on a flat vulcanizing machine after standing for 0.5h, and the conditions are that the temperature is 145 ℃ for 25 min. The mechanical properties of the vulcanized rubber were evaluated, and the tensile strength was 18.4MPa and the elongation at break was 444%.
Example 28:
to a dry catalyst reactor flask, neodymium neodecanoate, isoprene, diisobutylaluminum hydride and polyene substrate branching agent E15 (polyene substrate branching agent E15 is 1, 4-divinylbenzene) were added in one portion under nitrogen protection, in molar ratio, neodymium neodecanoate: isoprene: diisobutylaluminum hydride: the polyene substrate branching agent E15 was 1:10:25:1, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
4000ml (0.1 g/ml) of an isoprene monomer solution was added to a dry 5000ml reaction flask under nitrogen protection, and then the prepared catalyst solution was added. The amount of catalyst used is Ip/Nd 10000. Polymerizing for 5h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth isoprene rubber with a branched structure. The yield of the polymer was 61%, the cis-1, 4-structure was 94.0%, and the number-average molecular weight was 6.8 × 10 ═ Mn 4 The molecular weight distribution was 3.2 and the branching factor was 0.95.
Example 29:
to a dry catalyst reactor flask, neodymium chloride, diisobutylaluminum hydride and polyene substrate branching agent E16 (polyene substrate branching agent E16 is cyclopentadiene) were added in one portion under nitrogen protection, in molar ratio, neodymium chloride: diisobutylaluminum hydride: the polyene substrate branching agent E16 was 1:25:500, reacted at 50 ℃ for 10 minutes, and then added with dimethyldichlorosilane (Cl/Nd ═ 2), reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
4000ml (0.1 g/ml) of a butadiene monomer solution was added to a dry 5000ml reaction flask under nitrogen, followed by the above prepared catalyst solution. The dosage of the catalyst is Bd/Nd 10000. Polymerizing for 5 hours at 50 ℃, then terminating by using ethanol solution containing 1 percent of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 43%, the cis-1, 4-structure was 92.6%, and the number-average molecular weight was 4.6 × 10 ═ Mn 4 The molecular weight distribution was 3.6 and the branching factor was 0.94.
Example 30:
nd (P204) was added to the dried catalyst reaction flask in one portion under nitrogen protection 3 Butadiene and diisobutylaluminum hydride in molar ratio, Nd (P204) 3 : butadiene: diisobutylaluminum hydride at a ratio of 1:10:25 was reacted at 50 ℃ for 10 minutes, and then dimethyldichlorosilane (Cl/Nd ═ 2) was added thereto, and reacted at 50 ℃ for 30 minutes to obtain a catalyst solution.
Under nitrogen protection, 40ml of a butadiene monomer solution (concentration of 0.1g/ml) was added to a dry 50ml reaction flask, and then a hexane solution of a polyene substrate branching agent E17 (polyene substrate branching agent 17 is α -linolenic acid) (E17/Nd ═ 0.01) was added and then the prepared catalyst solution was added. The amount of catalyst used is Bd/Nd 8000. Polymerizing for 4h at 50 ℃, then terminating by using ethanol solution containing 1% of antioxidant 264, and condensing by using ethanol to obtain the rare earth butadiene rubber with a branched structure. The yield of the polymer was 62%, the cis-1, 4-structure was 96.9%, and the number-average molecular weight was 3.5 × 10 4 The molecular weight distribution was 2.9 and the branching factor was 0.96.

Claims (10)

1. A preparation method of branched high-cis rare earth conjugated diene rubber is characterized in that a polyene substrate branching agent is added into a catalyst system or a polymerization system in the process of preparing the branched high-cis rare earth conjugated diene rubber.
2. The process for producing a branched high-cis rare earth conjugated diene rubber according to claim 1, wherein the polyene substrate branching agent is a polyfunctional polyene substrate, and is classified into (i) a polyfunctional conjugated polyene substrate and (ii) a polyfunctional nonconjugated polyene substrate, depending on whether or not they are conjugated;
the structural formula of the (i) polyfunctional conjugated polyene substrate is as follows:
Figure FDA0003538381710000011
wherein X is an aliphatic hydrocarbon group or an aromatic hydrocarbon group;
the (ii) polyfunctional non-conjugated polyene substrate is selected from one or more of (a) diene compounds, (b) polyene compounds containing hetero atoms, and (c) diene and conjugated diene oligomers.
3. The method for preparing a branched high-cis rare earth conjugated diene rubber according to claim 2, wherein the diene compound (a) is one or more of an aliphatic diene compound having a linear or branched structure of C4-C30, an aromatic diene compound having a linear or branched structure of C4-C30, and a cyclic diene compound having a linear or branched structure of C4-C30;
the polyene compound containing the heteroatom (b) is one or more of alpha-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, gamma-linolenic acid and octavinylsilsesquioxane (POSS);
the diene and conjugated diene oligomer (c) is one or more of homopolymer oligomer of diene, copolymer oligomer of diene and functionalized oligomer.
4. The method for preparing a branched high-cis rare earth conjugated diene rubber according to any one of claims 1 to 3, wherein the polyene substrate branching agent: the rare earth element in the catalyst system is (0.001-1000): 1.
5. the preparation method of the branched high-cis rare earth conjugated diene rubber according to any one of claims 1 to 3, wherein in the preparation method of the branched high-cis rare earth polymerized diene rubber, a catalyst system adopted comprises a rare earth neodymium compound, an alkyl aluminum compound, a halogen compound and a conjugated diene monomer;
the rare earth neodymium compound is a carboxylic acid neodymium compound Nd (OCOR) 3 Neodymium phosphate compound Nd (OOOPOR) 3 Alkoxy or phenoxy neodymium compounds Nd (OR) 3 Neodymium chloride and its mixed compound of halogen and acid radical NdCl m (OCOR) 3-m M is one of positive integers of 0-4; wherein R is a linear or branched aliphatic hydrocarbon of C2-C15 or a linear or branched aromatic hydrocarbon of C2-C15;
the alkyl aluminum compound is one or a mixture of more of trialkyl aluminum compound, alkyl aluminum hydride compound and alkyl aluminoxane compound;
the halogen compound is a chloroalkyl compound RCl x Aluminum chloride compound, silane chloride SiR 1 4-y Cl y One or more of the above; wherein x is a positive integer of 1-4, R is a linear or branched aliphatic hydrocarbon of C2-C15, or a linear or branched aromatic hydrocarbon of C2-C15; r 1 Is one or more of methyl, ethyl, propyl, butyl and phenyl, and y is a positive integer of 0-4;
the conjugated diene monomer is one or more of 1, 3-butadiene, 1, 3-isoprene, 1, 3-piperylene and myrcene.
6. The method for preparing a branched high-cis rare earth conjugated diene rubber according to claim 5, wherein the neodymium carboxylate compound Nd (OCOR) 3 Is one or more of neodecanoic acid neodymium, isooctanoic acid neodymium and naphthenic acid neodymium;
the neodymium phosphate compound Nd (OOOPOR) 3 Is (2-ethylhexyl) neodymium phosphonate Nd (P204) 3 Or one or more of (2-ethylhexyl) neodymium phosphonate mono-2-ethylhexyl Nd (P507);
said alkoxy or phenoxide neodymium compound Nd (OR) 3 Is one or more of neodymium isopropoxide, neodymium isobutoxide and neodymium n-propoxide;
the neodymium chloride and the mixed compound NdCl of the halogen and the acid radical thereof m (OCOR) 3-m Is one or more of neodymium neodecanoate chloride, neodymium naphthenate chloride, neodymium isopropanol chloride and neodymium chloride;
the trialkyl aluminum compound is one or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and trioctyl aluminum;
the alkyl aluminum hydride compound is one or more of diethyl aluminum hydride, diisobutyl aluminum hydride and dimethyl aluminum hydride;
one or two of the alkyl aluminoxane compound, namely methyl aluminoxane and ethyl aluminoxane;
the chloroalkyl compound RCl x Is one or two of tert-butyl chloride and chloroform;
the aluminum chloride compound is aluminum sesqui-alkyl Al 2 R 2 3 Cl 3 Dialkyl aluminum chloride AlR 2 2 Cl, AlAl alkyl dichloride AlR 2 Cl 2 One or more of the above; wherein R is 2 Is one or more of methyl, ethyl, isobutyl and octyl;
the chlorosilane SiR 1 4-y Cl y Comprises the following steps: one or two of trimethylchlorosilane and dichlorodimethylsilane.
7. The process for preparing a branched high-cis rare earth conjugated diene rubber according to claim 1, comprising one of the following processes:
the first method comprises the following steps:
(1) mixing and reacting a rare earth neodymium compound, an alkyl aluminum compound, a conjugated diene monomer and a polyene substrate branching agent to obtain a mixed solution A, adding a halogen compound into the mixed solution A, and mixing and reacting to obtain a catalyst system A prepared from the branched high-cis rare earth conjugated diene rubber;
(2) adding a monomer and a catalyst system A into an alkane solvent for polymerization reaction to obtain a reaction solution;
(3) carrying out reaction polymerization on the reaction solution, and condensing the branched high-cis rare earth conjugated diene rubber in the reaction solution by using a precipitation liquid;
the second method comprises the following steps:
(1) mixing a rare earth neodymium compound, an alkyl aluminum compound and a conjugated diene monomer for reaction to obtain a mixed solution B, adding a halogen compound into the mixed solution B for reaction to obtain a catalyst system B prepared from the branched high-cis rare earth conjugated diene rubber;
(2) adding a monomer and a catalyst system A into an alkane solvent, and then adding a polyene substrate branching agent for polymerization reaction to obtain a reaction solution;
(3) and (3) carrying out reaction polymerization on the reaction solution, and condensing the branched high-cis rare earth conjugated diene rubber in the reaction solution by using a precipitation liquid.
8. The method for preparing the branched high-cis rare earth conjugated diene rubber according to claim 7, wherein in the first method (1), the mixing temperature of the catalyst system A is 0 to 100 ℃, the mixing reaction time for preparing the mixed solution A is 1 to 30 minutes, and the mixing reaction time for adding the halogen compound into the mixed solution A is 10 to 60 minutes;
in the second method (1), the mixing temperature of the catalyst system B is 0-100 ℃; the mixing reaction time for preparing the mixed solution B is 1-30 minutes; adding a halogen compound into the mixed solution B, and mixing for 10-60 minutes;
wherein, the molar ratio is as follows: rare earth neodymium compound: alkyl aluminum compound: halogen compound: conjugated diene monomer, polyene substrate branching agent ═ 1: (3-50): (0.5-5): (0-30): (0.001-1000); wherein the moles of rare earth neodymium compound and polyene substrate branching agent are both moles of double bonds therein;
according to molar ratio, monomer: the rare earth neodymium compound in the catalyst (200-50000) is 1.
9. A branched high cis-rare earth conjugated diene rubber is characterized in that the cis-1, 4-content of the prepared branched high cis-rare earth conjugated diene rubber is more than or equal to 85 percent, and the rubber is prepared by the preparation method of any one of claims 1 to 8; the branched high cis-rare earth conjugated diene rubber is branched high cis-polybutadiene rubber or branched high cis-polyisoprene rubber;
the molecular weight of the branched high cis-rare earth polybutadiene is 0.1 multiplied by 10 4 ～200×10 4 The branching factor is 0.40-0.95;
the molecular weight of the branched high cis-polyisoprene is 0.1X 10 4 ～200×10 4 The branching factor is 0.40 to 0.95.
10. Use of the branched high-cis rare earth conjugated diene rubber of claim 9 in tire, shoe, or resin modification.
CN202210231077.4A 2022-03-09 2022-03-09 Branched high-cis rare earth conjugated diene rubber and preparation method and application thereof Pending CN114853948A (en)

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