CN113461865B - Star-branched rare earth rubber and preparation method thereof - Google Patents

Star-branched rare earth rubber and preparation method thereof Download PDF

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CN113461865B
CN113461865B CN202110838519.7A CN202110838519A CN113461865B CN 113461865 B CN113461865 B CN 113461865B CN 202110838519 A CN202110838519 A CN 202110838519A CN 113461865 B CN113461865 B CN 113461865B
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rare earth
branched
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rubber
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CN113461865A (en
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李杨
余佳临
牛慧
王艳色
冷雪菲
韩丽
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Dalian University of Technology
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08F4/54—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 other compounds thereof
    • C08F4/545—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 other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate

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Abstract

The invention belongs to the technical field of functionalized high polymer materials, and provides star-shaped branched rare earth rubber and a preparation method thereof in order to solve the problems that star-shaped rubber is difficult to synthesize and low in yield by a rare earth coordination polymerization method in the prior art. The prepared star-branched rare earth rubber can be widely applied to light-cured materials, nonlinear optical materials, drug sustained-release materials, metal nanoparticle packaging, catalytic carriers and the like, and can effectively expand the application field of rare earth rubber materials.

Description

Star-branched rare earth rubber and preparation method thereof
Technical Field
The invention belongs to the technical field of functionalized high polymer materials, and particularly relates to star-shaped branched rare earth rubber and a preparation method thereof.
Background
The rare earth rubber material is an important synthetic rubber, the rare earth catalytic synthetic rubber has been used for over 30 years, and the rare earth is used as a complex and is applied to the rubber as an additive, so that the processability and the physicochemical property of the rubber are improved. The prior rare earth rubber is mostly used as an additive in rubber materials. Since the rare earth coordination polymerization has the characteristics of high activity and easy regulation of polymer structure, some researchers are focusing on the research in the field of rare earth coordination synthesis of rubber. However, most of the rare earth catalytic rubber preparation in the prior art is only limited to the preparation of linear rare earth rubber, and the precise regulation and control of the rubber structure cannot be realized, and most of the prepared rare earth rubber has a disordered structure. Compared with linear rare earth rubber, the star rare earth rubber has unique physical and chemical properties and a branched structure, so that a polymer with high molecular weight can be obtained while the lower melt and solution viscosity is kept, and the unification of physical and mechanical properties and processing properties can be realized. Because the rare earth complex has high catalytic activity for polymerization of conjugated dienes such as isoprene and butadiene, and simultaneously has high stereoselectivity, but due to the limitation of the coordination polymerization mechanism, only a small amount of reports of synthesizing polyisoprene with a star structure by a rare earth coordination polymerization method exist at present, and the yield of the obtained star polymer is low. The polymer with the star-shaped branched structure can be widely applied to photocuring materials, nonlinear optical materials, drug sustained-release materials, metal nanoparticle packaging and catalytic carriers, has important scientific significance in developing and efficiently synthesizing rare earth rubber materials with the star-shaped branched structure, and can also more effectively expand the application field of the rare earth rubber materials.
Disclosure of Invention
The invention provides star-shaped branched rare earth rubber and a preparation method thereof, aiming at solving the problems that the synthesis of star-shaped structure rubber by adopting a rare earth coordination polymerization method is difficult and the yield of star polymers is low in the prior art.
In a first aspect, a star-branched rare earth rubber is provided, wherein the star-branched rare earth rubber has a rare earth inner core and a branched chain structure, the inner core is a branched macromonomer containing a plurality of pendant double bonds obtained by homopolymerization of a rare earth catalyst and a bifunctional branching agent containing double bonds, and a branched chain of the star-branched rare earth rubber is one of polybutadiene, polyisoprene and a butadiene-isoprene copolymer; the number of the branched chains is 3-100; the butadiene or isoprene on the branches is polymerized into a star-branched structure through the pendant double bond on the macromonomer;
the weight average molecular weight of the star-shaped branched rare earth rubber is 1 multiplied by 104～100×104g/mol; the weight average molecular weight of the macromonomer is 0.1X 104～10×104g/mol; the molecular weight of each branch is 0.1X 104～5×104g/mol。
Further, the rare earth catalyst is composed of two parts of A and B: a is rare earth complex CpLnR2Xn, wherein: cp is a cyclopentadienyl ligand C5(R1)(R2)(R3)(R4)(R5) Ln is rare earth metal, R is alkyl directly connected with rare earth metal, and X is a coordination group on the rare earth metal. Ln is generally selected from Nd, Sc, Y, Lu, Gd, Sm, preferably from Sc, Y, Lu, preferably from Sc. R is generally selected from CH2SiMe3、CH2C6H4NMe2-o、CH2Ph、CH2CH＝CH2、1,3-C3H4(Me)、1,3-C3H3(SiMe3)2、CH(SiMe3)2、CH3、CH2CH3i-Pr, t-Bu, preferably selected from CH2SiMe3、CH2C6H4NMe2-o、CH2Ph、CH2CH＝CH2(ii) a Most preferably selected from CH2C6H4NMe2-o; wherein Ph is phenyl, Me is methyl, Pr is propyl, and Bu is butyl. R1、R2、R3、R4And R5Is generally selected from H, CH3、CH2CH3、i-Pr、t-Bu、Ph、CH2Ph、SiMe3、CH2SiMe3Wherein Ph is phenyl, Me is methyl, Pr is propyl, and Bu is butyl; r1、R2、R3、R4And R5The same or different; the cyclopentadienyl ligands Cp are selected from C5H5、C5Me5、C5Me4SiMe3、C5HMe4、C5H2Me3、C5Me3(SiMe3)2、C5H3(SiMe3)2、C5Ph5Preferably from C5Me4SiMe3. X is a Lewis acid, generally selected from Lewis acids containing O, N, P, S heteroatoms, more preferably O, N heteroatoms, preferably from Tetrahydrofuran (THF), and n is the number of Lewis acids, selected from 0 or 1.
The rare earth complex CpLnR2Xn has the structural formula:
Figure GDA0003587100080000031
b is an organoboron reagent selected from [ Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]、B(C6F5)3One or more mixtures of [ Ph ], preferably from [ Ph ]3C][B(C6F5)4]。
Further, the bifunctional branching agent containing double bonds is a dialkyl dialkenyl silane.
Further, the double bond-containing bifunctional branching agent is selected from at least one of dimethyldipropenylsilane, dimethyldipentadienylsilane, dimethyldihexyldisilanesilane, diethyldipropenylsilane, diethyldipentadienylsilane, diethyldihexyldisilanesilane, diphenyldipropenylsilane, diphenyldipentadienylsilane, and diphenyldihexylsilane.
Furthermore, the number of branches of the star-shaped branched rare earth rubber is 5-80.
Further, the content of 3, 4-structure isoprene in the star-shaped branched rare earth rubber is 1-70% in terms of mole percentage; the content of 1, 4-structure isoprene is 30-99%, the content of 3, 4-structure butadiene is 1-30%, and the content of 1, 4-structure butadiene is 70-99%.
On the other hand, the preparation method of the star-shaped branched rare earth rubber provided by the invention comprises the following steps: the method comprises the following steps:
(1) preparation of branched macromonomers containing multiple pendant double bonds: adding an organic solvent and the double-bond bifunctional branching agent into a dry deoxygenated polymerization reactor according to a ratio under the protection of inert gas nitrogen or argon, and stirring at room temperature; then adding a rare earth catalyst, wherein the polymerization temperature is 0-60 ℃, the polymerization reaction time is 3-240 min, and drying the polymer by adopting a post-treatment method to obtain a branched macromolecular inner core containing a plurality of pendant double bonds; the molar ratio of the component A to the component B of the rare earth catalyst is 0.5-1, the proportioning concentration of the double-bond bifunctional branching agent is 0.1-20 g/100mL, and the molar ratio of the branching agent to Ln in the rare earth catalyst is 5-4000;
(2) preparing star-shaped branched rare earth rubber: adding an organic solvent and a rare earth catalyst into a dry deoxygenated polymerization reactor, adding the branched macromolecular core containing multiple dangling double bonds prepared in the step (1), carrying out prepolymerization for 1-30 min, adding a branched chain monomer, stirring at room temperature, carrying out polymerization at the temperature of 0-60 ℃ for 0.5-24 h, and drying the polymer by adopting a post-treatment method to obtain star-shaped branched rare earth rubber; the molar ratio of the component A to the component B of the rare earth catalyst is 0.5-1, the concentration of the branched chain monomer is 0.1-20 g/100mL, and the molar ratio of the branched chain monomer to Ln in the rare earth catalyst is 5-4000.
The organic solvent is one or more selected from n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and trichlorobenzene, preferably one selected from n-hexane, cyclohexane, toluene and chlorobenzene.
Furthermore, the proportioning concentration of the double-bond bifunctional branching agent is 0.5-15 g/100mL, and the molar ratio of the branching agent to Ln in the rare earth catalyst is 5-1000; the concentration of the branched chain monomer is 0.5-15 g/100 mL.
Further, the molar ratio of the branching agent to Ln in the rare earth catalyst is 10 to 500.
Furthermore, the molar ratio of the branched chain monomer to Ln in the rare earth catalyst is 100-1000.
Further, the polymerization temperature of the steps (1) and (2) is 0-50 ℃, and the molar ratio of the rare earth catalyst A to the catalyst B is 0.5-0.6.
Further, the polymerization temperature of the steps (1) and (2) is 10-50 ℃.
Further, the polymerization reaction time of the step (1) is 5-15 minutes.
Further, the branched monomer is butadiene, and the prepared star-shaped branched rare earth polybutadiene.
Further, the branched monomer is isoprene, and the prepared star-shaped branched rare earth polyisoprene.
Further, the branched monomer is a mixture of butadiene and isoprene, and the star-branched rare earth butadiene-isoprene copolymer is prepared.
The rare earth catalyst for preparing star-shaped branched rare earth rubber provided by the invention has the following characteristics: the metallocene rare earth complex is used as a main catalyst (component A), the metal center valence state is stable, the structure is simpler, and the synthesis is easy.
The invention has the beneficial effects that:
the preparation method is simple, the reaction condition is mild, and the precise control of the star-shaped branched structure can be realized. The prepared polymer with the star-shaped branched structure can be widely applied to photocuring materials, nonlinear optical materials, drug slow-release materials, metal nanoparticle packaging and catalytic carriers, and can also effectively expand the application field of rare earth rubber materials.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental methods and calculation methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The performance test instrument used in the embodiment of the present invention:
NMR testing of polymers1H NMR, using a Bruker AVANCE 400MHz NMR spectrometer, in deuterated chloroform (CDCl)3) Measured as solvent at room temperature.
The polymer was measured by ordinary temperature GPC using a four-in-one gel permeation chromatograph model markov, Viscotek TDA-305 equipped with four detectors [ differential detector (RI), ultraviolet detector (UV), viscosity detector (VISC), low-angle and right-angle light scattering detectors (7 ° and 90 °, laser wavelength, # 670nm) ]
Glass transition temperature (T) of polymerg) Measured by a TA Q2000 differential scanning calorimeter.
Detecting the content (mol percent, percent) of residual dangling double bond structures on the inner core of the macromonomer by using a nuclear magnetic resonance hydrogen spectrum (1H-NMR), and the content (mol percent, percent) of 1, 4-structures and 3, 4-structures in isoprene monomer units and butadiene monomer units; measuring the weight average molecular weight Mw and molecular weight distribution index Mw/Mn of the polymer by a gel permeation chromatograph (GPC, 30 ℃, tetrahydrofuran is used as a solvent) with a four-detector; the glass transition temperature (Tg) of the polymer was measured by differential thermal scanner (DSC).
EXAMPLE 1 preparation of a trialkyscandia complex Sc (CH)2C6H4NMe2-ο)3
Weighing 1 in a glove box3.500g (100mmol) of N, N-dimethyl o-phenylenediamine is placed into a 100mL round bottom flask with a magnetic stirring bar, 40mL of diethyl ether is added for dissolution and stirring, 40mL (100mmol) of N-butyl lithium hexane solution (2.5mol/L) is taken and added into a reaction bottle dropwise, the reaction is continuously stirred at room temperature for 3 days, after the reaction is finished, the vacuum pumping is carried out to remove the solvent, the solid is washed by N-hexane and then dried by pumping, and LiCH powder which is light yellow is obtained2C6H4NMe2-o。
In a glove box, 1.5134g of ScCl were weighed3(10mmol) was placed in a Schlenk flask with magnetic stirrer and 8mL of tetrahydrofuran was added. 4.2341g of LiCH were weighed2C6H4NMe-o (30mmol) was dissolved in 14mL tetrahydrofuran and added dropwise to ScCl3In THF solution, the reaction was carried out for 30 min. Then, the solvent THF was removed under reduced pressure, 20mL of toluene was added for extraction, and the extract was concentrated and then put into a refrigerator at-35 ℃ for overnight crystallization to give 4.2067g of Sc (CH) as a brown yellow crystal2C6H4NMe2-ο)3。
EXAMPLE 2 preparation of a Monometallocene bis-alkyl scandium Complex (C)5Me4SiMe3)Sc(CH2C6H4NMe2-ο)2
In a glove box, 1.5370g of Sc (CH) were weighed2C6H4NMe-o)3(3.45mmol) was placed in a 100mL Schlenk flask with magnetic stir bar and dissolved by adding 10mL tetrahydrofuran solvent. Weighing 0.6711g C5Me4H(SiMe3) (3.45mmol) was dissolved in 5mL of tetrahydrofuran, and the solution was added to a Schlenk flask at room temperature. The Schlenk flask was closed, taken out of the glove box, reacted at 70 ℃ for 12 hours with stirring, the solvent was removed in vacuo, the residue was washed with diethyl ether and dissolved in toluene, the toluene solution was concentrated and placed in a-35 ℃ freezer overnight, and recrystallized to give 1.4505g of yellow crystals (C)5Me4SiMe3)Sc(CH2C6H4NMe-o)2。
EXAMPLE 3 preparation of Monometallocene bis-alkyl scandium Complex (C)5H5)Sc(CH2C6H4NMe2-ο)2
In glove box1.790g (4mmol) of Sc (CH) were weighed2C6H4NMe2-o)3Put into a Schlenk flask with magnetic stir bar and dissolved by adding 12mL tetrahydrofuran solvent. 0.317g (4.80mmol) of cyclopentadiene (C) was weighed5H5) After dissolving in 6mL of tetrahydrofuran, the mixture was put into a Schlenk flask at room temperature. The Schlenk flask was sealed, taken out of the glove box, heated to 40 ℃ and stirred to react for 1h, taken into the glove box, the solvent was removed in vacuo, the residual solid was washed with diethyl ether and dissolved in toluene, the toluene solution was concentrated and placed in a-35 ℃ freezer overnight, and recrystallized to give 1.271g of yellow crystals (C)5H5)Sc(CH2C6H4NMe2-ο)2。
Example 4 preparation of a macromer core containing multiple pendant double bonds A1
In a glove box, a magnetic stirrer was placed in a 100mL round-bottom flask, and 10.2mg (20. mu. mol) of a rare earth monocyclopentadienyl catalyst (C) dissolved in 2mL of toluene was added5Me4SiMe3)Sc(CH2C6H4NMe2-ο)2Further, 18.5mg (20. mu. mol) of [ Ph ] dissolved in 2mL of toluene was added3C][B(C6F5)4]Adding 2mL of toluene solvent with stirring, adding 0.384g (2mmol) of dimethyl dicyclopentadiene silane with vigorous stirring, reacting at room temperature for 5min, wherein the molar ratio of the dimethyl dicyclopentadiene silane to the rare earth catalyst [ Si]/[Sc]Is 100. After the polymerization is finished, taking the round-bottom flask out of the glove box, adding a small amount of methanol to terminate the reaction, pouring the terminated reaction solution into a large amount of methanol, washing the precipitated polymer with methanol, and then putting the polymer into a vacuum oven at 40 ℃ to dry the polymer to constant weight to obtain the macromonomer inner core A1 containing a plurality of dangling double bonds. The results of the polymer structure analysis are as follows: the yield was 50% (mass percent), molecular weight MwIs 19.6X 103g/mol, molecular weight distribution index Mw/Mn4.30, structural content of pendant double bonds 41% (mole percent) and gel content 0.
Example 5 preparation of a macromer core containing multiple pendant double bonds A2
In the glove box, the glove box is provided with a plurality of grooves,a100 mL round-bottom flask was charged with a magnetic stirrer, and 30.6mg (60. mu. mol) of a monocyclopentadienyl rare earth catalyst (C) dissolved in 2mL toluene was added5Me4SiMe3)Sc(CH2C6H4NMe2-ο)2Further, 55.5mg (60. mu. mol) of [ Ph ] dissolved in 2mL of toluene was added3C][B(C6F5)4]Adding 2mL of toluene solvent with stirring, adding 0.230g (1.2mmol) of dimethyl-dicyclopentadiene-silane with vigorous stirring, reacting at room temperature for 3min, and obtaining the molar ratio of the dimethyl-dicyclopentadiene-silane to the rare earth catalyst [ Si [ ]]/[Sc]Is 20. After the polymerization is finished, taking the round-bottom flask out of the glove box, adding a small amount of methanol to terminate the reaction, pouring the terminated reaction solution into a large amount of methanol, washing the precipitated polymer with methanol, and then putting the polymer into a vacuum oven at 40 ℃ to dry the polymer to constant weight to obtain the macromonomer inner core A2 containing a plurality of dangling double bonds. The results of the polymer structure analysis are as follows: the yield was 82% (mass percent), molecular weight MwIs 8.8 multiplied by 103g/mol, molecular weight distribution index Mw/Mn3.26, structural content of pendant double bonds of 46% (mole percent), gel content of 0.
Example 6 preparation of a macromer core containing multiple pendant double bonds A3
The reaction was carried out at room temperature for 5min under the same other polymerization conditions as in example 5 to obtain a macromonomer core A3 having a plurality of pendant double bonds. The results of the polymer structure analysis are as follows: the yield was 85% (mass percent), molecular weight MwIs 10.0X 103g/mol, molecular weight distribution index Mw/Mn3.69, structural content of pendent double bonds 44% (mole percent), gel content 0.
Example 7 preparation of a macromer core containing multiple pendant double bonds A4
The reaction was carried out at room temperature for 10min under the same other polymerization conditions as in example 5 to obtain a macromonomer core A4 having a plurality of pendant double bonds. The results of the polymer structure analysis are as follows: the yield was 90% (mass percent), molecular weight MwIs 14.3X 103g/mol, molecular weight distribution index Mw/MnOf 3.97, with pendant double bondThe structure content was 41% (mole percent) and the gel content was 10% (mass percent).
Example 8 preparation of a macromer core containing multiple pendant double bonds B1
A100 mL round-bottom flask was charged with a magnetic stirrer, and 30.6mg (60. mu. mol) of a monocyclopentadienyl rare earth catalyst (C) dissolved in 2mL toluene was added5H5)Sc(CH2C6H4NMe2-ο)2And reacted at room temperature for 10min under the same other polymerization conditions as in example 5 to obtain macromonomer core B1 having a plurality of pendant double bonds. The results of the polymer structure analysis are as follows: the yield was 30% (mass percent), molecular weight MwIs 5.0X 103g/mol, molecular weight distribution index Mw/Mn1.31, the structural content of the pendant double bond was 87% (mole percent) and the gel content was 0.
EXAMPLE 9 preparation of Star-shaped Polyisoprene
In a glove box, a magnetic stirrer was placed in a 100mL round-bottom flask, and 10.2mg (20. mu. mol) of a rare earth monocyclopentadienyl catalyst (C) dissolved in 2mL of toluene was added5Me4SiMe3)Sc(CH2C6H4NMe2-ο)2Further, 18.5mg (20. mu. mol) of [ Ph ] dissolved in 2mL of toluene was added3C][B(C6F5)4]Adding 2mL of macromonomer inner core A1 with equivalent weight dissolved in toluene under stirring, reacting at room temperature for 5min, adding 0.136g (2mmol) of isoprene, reacting at room temperature for 120min, wherein the molar ratio of the isoprene to the rare earth catalyst [ Ip ]]/[Sc]Is 100. After the polymerization is finished, taking the round-bottom flask out of the glove box, adding a small amount of methanol to terminate the reaction, pouring the terminated reaction solution into a large amount of methanol, washing the precipitated polymer with methanol, and then putting the polymer into a vacuum oven at 40 ℃ to dry the polymer to constant weight to obtain the star-shaped polyisoprene. The results of the polymer structure analysis are as follows: the yield was 85% (mass percent), molecular weight MwIs 26.2X 103g/mol, molecular weight distribution index Mw/Mn1.53, the 3, 4-structure content of the polyisoprene was 65% (mole percent), the average number of arms of the star-shaped polyisoprene was 42, the number of arms per isoprene armAverage molecular weight of 0.16X 103g/mol, glass transition temperature TgIs-7 ℃.
EXAMPLE 10 preparation of Star-shaped Polyisoprene
2mL of macromonomer core A2 dissolved in toluene and equivalent thereto were added with stirring, and the other polymerization conditions were the same as in example 9, to obtain star-shaped polyisoprene. The results of the polymer structure analysis are as follows: the yield was 94% (mass percent), molecular weight MwIs 48.9 multiplied by 103g/mol, molecular weight distribution index Mw/Mn2.08, the 3, 4-structure content of the polyisoprene was 65% (mole percent), the average number of arms of the star-shaped polyisoprene was 21, and the average molecular weight per isoprene arm was 1.91X 103g/mol, glass transition temperature TgIs-4 ℃.
EXAMPLE 11 preparation of Star-shaped Polyisoprene
2mL of macromonomer core A3 dissolved in toluene and equivalent thereto were added with stirring, and the other polymerization conditions were the same as in example 9, to obtain star-shaped polyisoprene. The results of the polymer structure analysis are as follows: the yield was 87% (mass percent), molecular weight MwIs 48.0X 103g/mol, molecular weight distribution index Mw/Mn2.65, a3, 4-structure content of 65% (mole percent) in the polyisoprene, an average number of arms of the star-shaped polyisoprene of 23, and an average molecular weight per arm of the polyisoprene of 1.65X 103g/mol, glass transition temperature TgIs-4 ℃.
EXAMPLE 12 preparation of Star-shaped Polyisoprene
2mL of macromonomer core A4 dissolved in toluene and equivalent thereto were added with stirring, and the other polymerization conditions were the same as in example 9, to obtain star-shaped polyisoprene. The results of the polymer structure analysis are as follows: the yield was 98% (mass percent), molecular weight MwIs 50.8 multiplied by 103g/mol, molecular weight distribution index Mw/Mn2.12, a3, 4-structure content of 65% (mole percent) in the polyisoprene, an average number of arms of the star-shaped polyisoprene of 31, and an average molecular weight per arm of the polyisoprene of 1.18X 103g/mol, glass transition temperature TgIs-4 ℃.
EXAMPLE 13 preparation of Star-shaped Polyisoprene
2mL of toluene-dissolved equivalent of macromer inner core B1, molar ratio of isoprene to rare earth catalyst [ Ip ] was added with stirring]/[Sc]The other polymerization conditions were the same as in example 9 to obtain star-shaped polyisoprene of 50. The results of the polymer structure analysis are as follows: the yield was 91% (mass percent), molecular weight MwIs 36.2X 103g/mol, molecular weight distribution index Mw/Mn1.78, a3, 4-structure content in the polyisoprene of 65% (mole percent), a mean arm number of the star polyisoprene of 23, and a mean molecular weight per isoprene arm of 1.36X 103g/mol, glass transition temperature TgIs-10 ℃.
EXAMPLE 14 preparation of Star-shaped Polyisoprene
2mL of macromonomer core B1 dissolved in toluene and equivalent thereto were added with stirring under the same polymerization conditions as in example 9 to obtain star-shaped polyisoprene. The results of the polymer structure analysis are as follows: the yield was 90% (mass percent), molecular weight MwIs 88.3X 103g/mol, molecular weight distribution index Mw/Mn1.90, a3, 4-structure content of 65% (mole percent) in the polyisoprene, a flat arm number of the star-shaped polyisoprene of 23, and an average molecular weight per isoprene arm of 3.62X 103g/mol, glass transition temperature TgIs-6 ℃.
EXAMPLE 15 preparation of Star-shaped Polyisoprene
2mL of toluene-dissolved equivalent of macromer inner core B1, molar ratio of isoprene to rare earth catalyst [ Ip ] was added with stirring]/[Sc]To obtain 200, the other polymerization conditions were the same as in example 9 to obtain star-shaped polyisoprene. The results of the polymer structure analysis are as follows: the yield was 89% (mass percent), molecular weight MwIs 112.2X 103g/mol, molecular weight distribution index Mw/Mn1.83, a3, 4-structure content of 65% (mole percent) in the polyisoprene, an average number of arms of the star-shaped polyisoprene of 23, and an average molecular weight per arm of the polyisoprene of 4.67×103g/mol, glass transition temperature TgIs-4 ℃.
EXAMPLE 16 preparation of Star-shaped Polyisoprene
2mL of toluene-dissolved equivalent of macromer inner core B1, molar ratio of isoprene to rare earth catalyst [ Ip ] was added with stirring]/[Sc]To 500, other polymerization conditions were the same as in example 9 to obtain star-shaped polyisoprene. The results of the polymer structure analysis are as follows: the yield was 90% (mass percent), molecular weight MwIs 146.6 multiplied by 103g/mol, molecular weight distribution index Mw/Mn1.83, a3, 4-structure content of 65% (mole percent) in the polyisoprene, an average number of arms of the star-shaped polyisoprene of 23, and an average molecular weight per arm of 4.67X 103g/mol, glass transition temperature TgIs-4 ℃.
Example 17 preparation of Star-shaped Polyisoprene
2mL of toluene-dissolved equivalent of macromer inner core B1, molar ratio of isoprene to rare earth catalyst [ Ip ] was added with stirring]/[Sc]The other polymerization conditions were the same as in example 9 to obtain a star-shaped polyisoprene having a molecular weight of 1000. The polymer structure analysis results were as follows: the yield was 95% (mass percent), molecular weight MwIs 175.8X 103g/mol, molecular weight distribution index Mw/Mn1.64, a3, 4-structure content of 65% (mole percent) in the polyisoprene, an average number of arms of the star-shaped polyisoprene of 23, and an average molecular weight per arm of 7.42X 103g/mol, glass transition temperature TgIs-2 ℃.
EXAMPLE 18 preparation of Star-shaped polybutadiene
2mL of toluene-dissolved equivalent of macromer inner core B1, butadiene to rare earth catalyst molar ratio [ Bd ] was added with stirring]/[Sc]The other polymerization conditions were the same as in example 9 to obtain a star-shaped polybutadiene of 1000. The results of the polymer structure analysis are as follows: the yield was 97% (mass percent), molecular weight MwIs 166.9X 103g/mol, molecular weight distribution index Mw/Mn1.84, the 1, 4-structure content in the polybutadiene was 85% (mol/mol)Fractional) of the butadiene, the average number of arms of the star polybutadiene was 23, and the average molecular weight of each butadiene arm was 7.04X 103g/mol, glass transition temperature TgWas-92 ℃.
EXAMPLE 19 preparation of Star-shaped polybutadiene
2mL of toluene-dissolved equivalent of macromer inner core B1, butadiene to rare earth catalyst molar ratio [ Bd ] was added with stirring]/[Sc]To 500, other polymerization conditions were the same as in example 9 to obtain a star-shaped polybutadiene. The results of the polymer structure analysis are as follows: the yield was 95% (mass percent), molecular weight MwIs 126.9X 103g/mol, molecular weight distribution index Mw/Mn1.85, a1, 4-structure content in the polybutadiene of 86% (mole percent), a mean number of arms of the star polybutadiene of 23, and a mean molecular weight per arm of butadiene of 5.30X 103g/mol, glass transition temperature TgIs-95 ℃.
EXAMPLE 20 preparation of Star-shaped polybutadiene
2mL of toluene-dissolved equivalent of macromonomer core B1, the molar ratio of butadiene to rare earth catalyst [ Bd ] was added with stirring]/[Sc]To 200, other polymerization conditions were the same as in example 9 to obtain a star-shaped polybutadiene. The polymer structure analysis results were as follows: the yield was 93% (mass percent), molecular weight MwIs 55.6 multiplied by 103g/mol, molecular weight distribution index Mw/Mn1.73, a1, 4-structure content in the polybutadiene of 86% (mole percent), a mean number of arms of the star polybutadiene of 23, and a mean molecular weight per arm of 2.20X 103g/mol, glass transition temperature TgIt was-96 ℃.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. The star-branched rare earth rubber is characterized in that the star-branched rare earth rubber has a rare earth inner core and a branched chain structure, the inner core is a branched macromonomer containing a plurality of dangling double bonds obtained by homopolymerizing a rare earth catalyst and a branching agent containing double bonds, and the branched chain of the star-branched rare earth rubber is one of polybutadiene, polyisoprene and a butadiene-isoprene copolymer; the number of the branched chains is 3-100; the butadiene or isoprene on the branches is polymerized into a star-branched structure through the pendant double bond on the macromonomer;
the weight average molecular weight of the star-shaped branched rare earth rubber is 1 multiplied by 104～100×104g/mol; the weight average molecular weight of the macromonomer is 0.1X 104～10×104g/mol; the molecular weight of each branch is 0.1X 104～5×104g/mol；
The rare earth catalyst consists of two parts A and B: a is rare earth complex CpLnR2Xn, wherein:
cp is a cyclopentadienyl ligand C5(R1)(R2)(R3)(R4)(R5) Ln is rare earth metal, R is alkyl directly connected with the rare earth metal, and X is a coordination group on the rare earth metal;
ln is selected from one of Nd, Sc, Y, Lu, Gd and Sm;
r is selected from CH2SiMe3、CH2C6H4NMe2-o、CH2Ph、CH2CH＝CH2、1,3-C3H4(Me)、1,3-C3H3(SiMe3)2、CH(SiMe3)2、CH3、CH2CH3One of i-Pr and t-Bu; wherein Ph is phenyl, Me is methyl, Pr is propyl, and Bu is butyl;
x is selected from Lewis acid containing O, N, P, S heteroatom, n is Lewis acid, and the number of Lewis acid is 0 or 1;
R1、R2、R3、R4and R5Selected from H, CH3、CH2CH3、i-Pr、t-Bu、Ph、CH2Ph、SiMe3、CH2SiMe3One kind of (1); the cyclopentadienyl ligands Cp are selected from C5H5、C5Me5、C5Me4SiMe3、C5HMe4、C5H2Me3、C5Me3(SiMe3)2、C5H3(SiMe3)2、C5Ph5One kind of (1);
the rare earth complex CpLnR2The structural formula of Xn is:
Figure FDA0003587100070000021
b is an organoboron reagent selected from [ Ph3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]、B(C6F5)3At least one of;
the bifunctional branching agent containing double bonds is dialkyl dialkene silane.
2. The star-branched rare earth rubber according to claim 1, wherein the double bond-containing bifunctional branching agent is one selected from the group consisting of dimethyldipropenylsilane, dimethyldipentadienylsilane, dimethyldihexylsilane, diethyldipropenylsilane, diethyldipentadienylsilane, diethyldihexylsilane, diphenyldipropenylsilane, diphenyldipentadienylsilane, and diphenyldihexylsilane.
3. A method of making a star-branched rare earth rubber as claimed in claim 1, comprising: the method comprises the following steps:
(1) preparation of branched macromonomers containing multiple pendant double bonds: adding an organic solvent and the double-bond bifunctional branching agent into a dry deoxygenated polymerization reactor according to a ratio under the protection of inert gas nitrogen or argon, and stirring at room temperature; then adding a rare earth catalyst, wherein the polymerization temperature is 0-60 ℃, the polymerization reaction time is 3-240 min, and drying the polymer by adopting a post-treatment method to obtain a branched macromolecular inner core containing a plurality of pendant double bonds; the molar ratio of the rare earth catalyst component A to the component B is 0.5-1, the proportioning concentration of the double-bond bifunctional branching agent is 0.1-20 g/100mL, and the molar ratio of the branching agent to Ln in the rare earth catalyst is 5-4000;
(2) preparing star-branched rare earth rubber: adding an organic solvent and a rare earth catalyst into a dry deoxygenated polymerization reactor, adding the branched macromolecular core containing multiple dangling double bonds prepared in the step (1), carrying out prepolymerization for 1-30 min, adding a branched chain monomer, stirring at room temperature, carrying out polymerization at the temperature of 0-60 ℃ for 0.5-24 h, and drying the polymer by adopting a post-treatment method to obtain star-shaped branched rare earth rubber; the molar ratio of the component A to the component B of the rare earth catalyst is 0.5-1, the concentration of the branched chain monomer is 0.1-20 g/100mL, and the molar ratio of the branched chain monomer to Ln in the rare earth catalyst is 5-4000.
4. The method for preparing a star-branched rare earth rubber according to claim 3, wherein the organic solvent is at least one selected from the group consisting of n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and trichlorobenzene.
5. The method for preparing a star-branched rare earth rubber according to claim 3, wherein the concentration of the double-bond bifunctional branching agent is 0.5 to 15g/100mL, and the molar ratio of the branching agent to Ln in the rare earth catalyst is 5 to 1000; the concentration of the branched chain monomer is 0.5-15 g/100 mL.
6. The method for preparing star-branched rare earth rubber according to claim 3, wherein the polymerization temperature is 0 to 50 ℃ and the molar ratio of the rare earth catalyst A to the catalyst B is 0.5 to 0.6.
7. The method for preparing star-branched rare earth rubber according to any one of claims 3 to 5, wherein the branched monomer is butadiene, and star-branched rare earth polybutadiene is prepared.
8. The method for preparing star-branched rare earth rubber according to any one of claims 3 to 5, wherein the branched monomer is isoprene, and star-branched rare earth polyisoprene is prepared.
9. The method for preparing star-branched rare earth rubber according to any one of claims 3 to 5, wherein the branched monomer is a mixture of butadiene and isoprene, and a star-branched rare earth butadiene-isoprene copolymer is prepared.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309674A (en) * 1998-07-18 2001-08-22 拜尔公司 Method for polymerizing conjugated diolefins (dienes) with rare-earth catalysts in presence of vinylaromatic solvents
CN103788273A (en) * 2014-02-24 2014-05-14 大连理工大学 Rare earth catalysis system star-branched polyisoprene and preparation method thereof
WO2020208902A1 (en) * 2019-04-12 2020-10-15 株式会社ブリヂストン Polyisoprene production method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10022497A1 (en) * 2000-05-09 2001-11-15 Bayer Ag Copolymerization of conjugated dienes with nonconjugated olefins in the presence of a catalyst comprising a rare earth metal allyl compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309674A (en) * 1998-07-18 2001-08-22 拜尔公司 Method for polymerizing conjugated diolefins (dienes) with rare-earth catalysts in presence of vinylaromatic solvents
CN103788273A (en) * 2014-02-24 2014-05-14 大连理工大学 Rare earth catalysis system star-branched polyisoprene and preparation method thereof
WO2020208902A1 (en) * 2019-04-12 2020-10-15 株式会社ブリヂストン Polyisoprene production method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Copolymerization of Ethylene with 1-Hexene and 1-Octene Catalyzed by Fluorenyl N-Heterocyclic Carbene Ligated Rare-Earth Metal Precursors;Changguang Yao et al.;《Organometallics》;20130319;第32卷;第2204-2209页 *

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