CN106977667A - Dendritic branched conditioning agent of poly double-olefin and preparation method thereof - Google Patents
Dendritic branched conditioning agent of poly double-olefin and preparation method thereof Download PDFInfo
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- CN106977667A CN106977667A CN201610031220.XA CN201610031220A CN106977667A CN 106977667 A CN106977667 A CN 106977667A CN 201610031220 A CN201610031220 A CN 201610031220A CN 106977667 A CN106977667 A CN 106977667A
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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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
Abstract
The present invention relates to branched polydiene rubber with branched conditioning agent field, a kind of branched conditioning agent of dendritic poly double-olefin and preparation method thereof is disclosed.The number-average molecular weight of the branched conditioning agent of dendritic poly double-olefin is 5000~50000, and the molecular weight distribution of the dendritic branched conditioning agent of poly double-olefin is 1~2；The content of Isosorbide-5-Nitrae construction unit is not higher than 50 weight % in the structure of the dendritic poly double-olefin, and the main chain average branch number of the dendritic poly double-olefin is not less than 1.The present invention obtains the dendritic branched conditioning agent of poly double-olefin, and is further used for the polymerization of dendritic polydiene rubber, can adjust the molecular structure of polydiene rubber, improves the processability of polydiene rubber.The method for synthesizing the branched conditioning agent of dendritic poly double-olefin is simple, and the degree of branching for the dendritic polydiene rubber that the branched conditioning agent of dendritic poly double-olefin of preparation is further obtained is high and mechanical property is improved.
Description
Technical field
The present invention relates to branched polydiene rubber with branched conditioning agent field, in particular it relates to a kind of dendritic poly bis alkene
Branched conditioning agent of hydrocarbon and preparation method thereof.
Background technology
Synthetic rubber is a kind of important elastomeric material, is widely used in the every field of people's production and life.But
Be some catalyst preparations synthetic rubber exist in molecular weight height, narrow molecular weight distribution, polymerization process solution viscosity it is big and
The poor defect of the processability of obtained product, the processed and applied to synthetic rubber brings very big difficulty.
CN101068839A discloses a kind of copolymer, includes the reaction product of following material：(a) at least one ethylenic
Unsaturated monomer；(b) maleimide monomer of at least one N- substitutions；(c) the unsaturated function of at least two ethylenics is included
At least one crosslinking agent of group；(d) at least one radical initiator；At least one chain-transferring agent (e)；Wherein described reaction
Product is branched.Crosslinking agent is used in this method.
CN1919893A discloses a kind of hyperbranched polymeric monomer, and it has the branched structure of three or more than three, and extremely
It is few to contain vinyl on a side chain, there are multiple hydroxyls or carboxyl to be distributed along side chain.Specifically disclosed preparation method is use
The method of fed batch, is obtained through multistep reaction, including：A, will contain double bond, functional group's number be more than or equal to 2 A monomers with
The B monomer that degree of functionality is more than or equal to 2 reacts, and obtains the molecular weight bigger and C performed polymers containing double bond；B, C performed polymer and B monomer
Polycondensation reaction is further carried out, is increased the degree of branching of molecule, through many one-step polycondensations, hyperbranched polymeric monomer is finally obtained.Tool
Body, the A monomers are：Containing double bond, functional group's number is more than or equal to 2 maleic acid, maleic anhydride；The B
Monomer is：N,N-dimethylformamide of functional group's number more than or equal to 2, diethanol amine, maleic acid, glycerine, season penta
Tetrol, trimethylolpropane, phthalic acid, phthalic anhydride, maleic anhydride, trimellitic anhydride.Described over-expense
Change polymeric monomer and be mainly polyester type hyperbranched polymeric monomer and the hyperbranched polymeric monomer of polyamide type, applied in high solid coating.
CN1946754A discloses branched polyphenylene polymers, with formula
Wherein P is polyvalent arylene branching repeat unit, and D is divalent arylene repeat unit, and M is monovalence arylene endcapping unit, a, b
It is P, D and M relative mole fraction respectively with c, x represents the number of the key in addition to two keys that P is connected on polymer
Amount, wherein x >=1.
CN101007750A discloses a kind of method for preparing branched olefin, including by percent of aliphatic quaternary carbon atoms content 0.5%
Or lower isoparaffinic composition only dehydrogenation reaction on appropriate catalyst, the isoparaffinic composition is by chain
What the hygrogenating isomerization reaction of alkane composition was obtained, and the isoparaffinic composition includes the alkane of C7-C18 scopes
Hydrocarbon, at least a portion molecule of alkane is branched, and the average branch number of each paraffin molecules is 0.5-2.5, branched bag
Include methyl-branched and optionally include ethyl branched, the aliphatic quaternary carbon content of the branched olefin is 0.5% or lower.
US2002/0016423A1 discloses a kind of method for controlling high Isosorbide-5-Nitrae-cis polybutadiene degree of branching, by 1,3-
Butadiene polymerize in non-polar solven, and the catalyst used is by by organo-nickel compounds, boron trifluoride compounds and organic
Mixture ageing of the aluminium compound together with optional conjugated diene compound and prepare, the method is characterized in that by following formula I
The dialkyl zinc compounds of expression add mixture as the reagent of control degree of branching, and Formulas I is R1-Zn-R2Wherein R1And R2It is
Identical or different, including the alkyl containing C1~C5.
CN104650362A discloses a kind of preparation method of the branched conjugated diene polymer of rare-earth catalysis system, bag
Include：Under rare earth catalyst effect, polymerisation occurs in organic inert solvent for conjugated diene, and reaction to be polymerized terminates
Afterwards, branching agent is added, continues to react 0.1h~1h at 50-90 DEG C, then adds the second of BHT
Alcoholic solution terminating reaction, obtains branched conjugated diene polymer, wherein, branching agent is the liquid polymers of nitrile group-containing.It is branched
The consumption of agent is measured as 5~50 with the nitrile group and the mol ratio of rare earth carboxylate in branching agent.
The content of the invention
The invention aims to solve how to obtain the branched conditioning agent of dendritic poly double-olefin to obtain degree of branching raising
Polydiene rubber so that the problem of improving the processability and mechanical property of polydiene rubber is dendritic poly- there is provided one kind
Branched conditioning agent of diolefin and preparation method thereof.
To achieve these goals, the present invention provides a kind of dendritic branched conditioning agent of poly double-olefin, wherein, it is described dendritic poly-
The number-average molecular weight of the branched conditioning agent of diolefin is 5000~50000, the molecular weight of the dendritic branched conditioning agent of poly double-olefin
It is distributed as 1~2；The content of Isosorbide-5-Nitrae construction unit is not higher than 50 weight % in the structure of the branched conditioning agent of dendritic poly double-olefin,
The main chain average branch number of the branched conditioning agent of dendritic poly double-olefin is not less than 1.
Present invention also offers preparing a kind of method of the branched conditioning agent of dendritic poly double-olefin, including：(1) in the first polymerization
In the presence of catalyst and the first organic solvent containing tetrahydrofuran, diolefinic monomer A is subjected to the first polymerisation in solution, obtained
Polymer fluid containing straight chain poly double-olefin；(2) depositing in the second polymerization catalyst and the second organic solvent containing tetrahydrofuran
Under, the polymer fluid and diolefinic monomer B are subjected to the second polymerisation in solution, the branched conditioning agent of dendritic poly double-olefin is obtained.
The present invention can also provide a kind of dendritic polydiene rubber, wherein, the polydiene rubber in polymerization by urging
In the presence of agent and organic solvent, the raw material containing diolefinic monomer and branched conditioning agent is subjected to polymerisation in solution and obtained, it is described
Branched conditioning agent is the branched conditioning agent of dendritic poly double-olefin of the invention.
By above-mentioned technical proposal, the present invention can obtain the branched conditioning agent of dendritic poly double-olefin, change dendritic poly double-olefin
The content of Isosorbide-5-Nitrae construction unit is 4~17 weight % in the structure of branched conditioning agent, and main chain average branch number is 1~2.Further
For the polymerization of dendritic polydiene rubber, the molecular structure of the dendritic polydiene rubber can be adjusted, increases the degree of branching, changes
The processability of kind polydiene rubber, the polydiene rubber such as obtained have be more suitable for processing plasticate, the door that numerical value is 65-70
Buddhist nun's viscosity, higher tensile strength and elongation at break.
The method of the dendritic branched conditioning agent of poly double-olefin of synthesis provided by the present invention is simple, the dendritic poly double-olefin of preparation
The degree of branching for the dendritic polydiene rubber that branched conditioning agent progress is obtained is high.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of dendritic branched conditioning agent of poly double-olefin, wherein, the dendritic branched conditioning agent of poly double-olefin
Number-average molecular weight be 5000~50000, the molecular weight distribution of the dendritic branched conditioning agent of poly double-olefin is 1~2；The branch
The content of Isosorbide-5-Nitrae construction unit is not higher than 50 weight %, the dendritic poly double-olefin in the structure of the branched conditioning agent of shape poly double-olefin
The main chain average branch number of branched conditioning agent is not less than 1.
Preferably, the content of Isosorbide-5-Nitrae construction unit is 4~17 weights in the structure of the branched conditioning agent of dendritic poly double-olefin
Measure %.
Preferably, the main chain average branch number of the branched conditioning agent of dendritic poly double-olefin is 1~2.
In accordance with the present invention it is preferred that, the dendritic branched conditioning agent of poly double-olefin is C4~C10Diolefin it is aggregated
The dendritic polymer arrived.
Preferably, the branched conditioning agent of dendritic poly double-olefin is dendritic polyisoprene or dendritic polybutadiene.
Present invention also offers a kind of method for preparing the branched conditioning agent of dendritic poly double-olefin, including：(1) in the first polymerization
In the presence of catalyst and the first organic solvent containing tetrahydrofuran, diolefinic monomer A is subjected to the first polymerisation in solution, obtained
Polymer fluid containing straight chain poly double-olefin；(2) depositing in the second polymerization catalyst and the second organic solvent containing tetrahydrofuran
Under, the polymer fluid and diolefinic monomer B are subjected to the second polymerisation in solution, the branched conditioning agent of dendritic poly double-olefin is obtained.
, according to the invention it is preferred in the case of, first polymerization catalyst is the olefin polymerization catalysis containing metal M,
Mol ratio using metal M first polymerization catalysts counted and the diolefinic monomer A is 0.001~0.1, and preferably 0.01
~0.08, most preferably 0.03~0.06；Metal M is lithium, titanium, rare earth or molybdenum, preferably lithium, titanium or rare earth, most preferably lithium
Or rare earth.
When first polymerization catalyst is the Titanium series catalyst containing titanium and the rare earth series catalysts containing rare earth, may be used also
With alkyl aluminum containing cocatalyst and electron donor chlorination alkyl aluminum.For example can be carboxylic acid neodymium, alkyl aluminum, halide, conjugation
The rare earth catalyst of alkadienes complexing, the mol ratio of four kinds of components can be 1:(5~15):(1~3):(10~20).It is excellent
The first polymerisation in solution is selected to use the rare earth catalyst.
Specifically, first polymerization catalyst can be for butyl lithium, containing neodymium catalyst or titanium-containing catalyst.
, according to the invention it is preferred in the case of, the diolefinic monomer A is C4~C10Diolefin, preferably butadiene or
Isoprene.
Preferably, the mass ratio of the diolefinic monomer A and first organic solvent is 50：50~10：90, be preferably
30：70~15：85.
, according to the invention it is preferred in the case of, first organic solvent also contains alkane, and the alkane is C5~C8 alkane
At least one of, preferably described alkane is hexane, pentane, isopentane, methyl cyclopentane, 2- methylpentanes, 3- methylpents
At least one of alkane, n-hexane, hexamethylene, normal heptane and normal octane.
Preferably, in first organic solvent, the weight ratio of tetrahydrofuran and the alkane is 99:1~1:99 is excellent
Select 90:10~50:50.
, according to the invention it is preferred in the case of, the temperature of first polymerisation in solution is 0~80 DEG C, preferably 40~60 DEG C；
The time of first polymerisation in solution is 5~10h, preferably 1~3h.
, according to the invention it is preferred in the case of, the number-average molecular weight of the straight chain poly double-olefin is 500~2000, described straight
The content of 1,4 structures is not higher than 20 weight % in the structure of chain poly double-olefin.The main chain average branch of the straight chain poly double-olefin
Number is 0.
, according to the invention it is preferred in the case of, second polymerization catalyst is the olefin polymerization catalysis containing metal L,
Mol ratio using metal L second polymerization catalysts counted and the diolefinic monomer B is 0.0001~0.05, preferably
0.001~0.04, most preferably 0.002~0.03；Metal L is lithium, titanium, rare earth or molybdenum, preferably lithium or rare earth, is most preferably
Lithium.
When second polymerization catalyst is the Titanium series catalyst containing titanium and the rare earth series catalysts containing rare earth, may be used also
With alkyl aluminum containing cocatalyst and electron donor chlorination alkyl aluminum.E.g. carboxylic acid neodymium, alkyl aluminum, halide, conjugated diene
The rare earth catalyst of hydrocarbon complexing, the mol ratio of four kinds of components can be 1:(5~15):(1~3):(10~20).It is preferred that the
Two polymerisation in solutions use the rare earth catalyst.
Specifically, second polymerization catalyst can be for butyl lithium, containing neodymium catalyst or titanium-containing catalyst.
, according to the invention it is preferred in the case of, the diolefinic monomer B is C4~C10Diolefin, preferably butadiene or
Isoprene.
Preferably, the mass ratio of the diolefinic monomer B and second organic solvent is 5：95~30：70, be preferably
10：90~25：75.
, according to the invention it is preferred in the case of, in step (2), the mass ratio of the polymer fluid and the diolefinic monomer B is
1：1000~5：100, preferably 5：1000~4：100, most preferably 7：1000~3.5：100.
, according to the invention it is preferred in the case of, second organic solvent also contains alkane, and the alkane is C5~C8 alkane
At least one of, preferably described alkane is hexane, pentane, isopentane, methyl cyclopentane, 2- methylpentanes, 3- methylpents
At least one of alkane, n-hexane, hexamethylene, normal heptane and normal octane.
Preferably, in second organic solvent, the weight ratio of tetrahydrofuran and the alkane is 99:1~1:99 is excellent
Select 90:10~50:50.
, according to the invention it is preferred in the case of, the temperature of second polymerisation in solution is 0~80 DEG C, preferably 40~60 DEG C；
The time of second polymerisation in solution is 5~10h, preferably 1~3h.
In the present invention, prepare in the branched regulation agent method of dendritic poly double-olefin, the diolefinic monomer A and diolefinic monomer
B can be simultaneously identical or different；First polymerization catalyst can be simultaneously identical or different with the second polymerization catalyst；First is organic
In solvent in the ratio and the second organic solvent of tetrahydrofuran and alkane tetrahydrofuran and alkane can be simultaneously identical or different.
The present invention can also provide a kind of dendritic polydiene rubber, wherein, the dendritic polydiene rubber by
In the presence of polymerization catalyst and organic solvent, the raw material containing diolefinic monomer and branched conditioning agent is subjected to polymerisation in solution and obtained
Arrive, the branched conditioning agent is the branched conditioning agent of dendritic poly double-olefin of the invention.
, according to the invention it is preferred in the case of, the number-average molecular weight of the dendritic polydiene rubber is 500,000~600,000, described
The molecular weight distribution of dendritic polydiene rubber is 3~4.
Preferably, cis-Isosorbide-5-Nitrae structural content is more than 98% in the structure of the dendritic polydiene rubber.
Preferably, the main chain average branch number of the dendritic polydiene rubber is not less than 1.
Preferably, the dendritic polydiene rubber is dendritic polybutadiene rubber or dendritic polyisoprene rubber.
According to the present invention, Mooney viscosity ML of the dendritic polydiene rubber at 100 DEG C1+4For 65-70.
Preferably, the elongation at break of the dendritic polydiene rubber is 620~630%.
Preferably, the tensile strength of the dendritic polydiene rubber is 29~30MPa.
The dendritic polydiene rubber that the present invention is provided, adds branched regulation into diolefinic monomer in the course of the polymerization process
Agent, realizes the high polydiene rubber of the obtained degree of branching.Preferably, the main chain average branch of the dendritic polydiene rubber
Number is more than 4, it is further preferred that the main chain average branch number of the dendritic polydiene rubber is 4~5.
In the present invention, the diolefinic monomer is butadiene or isoprene.
In the present invention, the mass ratio of the branched conditioning agent and the diolefinic monomer is 1：1000 to 5：100, be preferably
5：1000 to 3：100.
In the present invention, the polymerization catalyst is the olefin polymerization catalysis containing metal J, described poly- in terms of metal J
The mol ratio for closing catalyst and the diolefinic monomer is 0.00001~0.1, preferably 0.0001~0.05；Metal J be lithium,
Titanium, rare earth, molybdenum or iron, preferably lithium, titanium or rare earth.Its middle rare earth is preferably neodymium.
In the present invention, the polymerization catalyst can also contain cocatalyst alkyl aluminum and electron donor chlorination alkyl aluminum.
For example can be carboxylic acid neodymium, alkyl aluminum, halide, the rare earth catalyst of conjugated diene complexing, mole of four kinds of components
Than that can be 1:(5~15):(1~3):(10~20).It is preferred that the raw material containing diolefinic monomer and branched conditioning agent is carried out
Polymerisation in solution uses the rare earth catalyst.
In the present invention, in the raw material, the concentration of the diolefinic monomer is the weight % of 5 weight %~30, preferably 10
The weight % of weight %~20.
In the present invention, the organic solvent is C5~C8 alkanes.
In the present invention, the pressure of the polymerisation in solution is 0.1~3MPa, preferably 0.2~1MPa；The polymerisation in solution
Temperature is 0~200 DEG C, more preferably preferably 30~100 DEG C, 40~80 DEG C；The time of the polymerisation in solution is 1~10h, excellent
Elect 2~6h as.
In the present invention, it is gauge pressure to be related to pressure.
The present invention will be described in detail by way of examples below.
In following examples, the molecular weight and molecular weight of the dendritic branched conditioning agent of poly double-olefin and dendritic polydiene rubber
Distribution is measured using 1515 type gel permeation chromatographs (GPC) of Waters companies：Using tetrahydrofuran as mobile phase, flow velocity
For 1mL/min.
Structure in the dendritic branched conditioning agent of poly double-olefin and dendritic polydiene rubber passes through Fourier transform infrared light
Compose (FTIR) analysis：Using toluene as solvent, polymer is made into glue, with coating method Nicolet companies BRUKER
Determined on VERTEX70 type analysis instrument.
Branched structure is characterized, and the dendritic branched conditioning agent of poly double-olefin and dendritic polydiene are determined by three detection GPC datas
The main chain average branch number of rubber；Wherein, three detection GPC datas are joined by gel permeation chrommatograph-laser light scattering instrument-in-line viscometer
Measured with system, gel permeation chromatograph is the 1100Series of Agilent companies；Laser light scattering instrument is Wyatt companies
DAWN HELEOS；In-line viscometer is the ViscoStar viscometer of Wyatt companies；Solvent is THF, and flow velocity is 1ml/
min。
Mooney viscosity uses the SMV-201 mooney's viscosimeters of Shimadzu Corporation, is carried out according to GB/T1232.1-2000 regulation
Determine, wherein, test condition includes：Preheating time is 1min, and rotation time is 4min, and test temperature is 100 DEG C.
The tensile property of dendritic polydiene rubber, elongation at break are determined according to GB/T528-2009 method.
The consumption that miscellaneous required initiator is killed in following examples is determined by the following method：
By glass polymerization bottle through vacuum pump drainage, high temperature barbecue and high-purity N2Miscellaneous experiment is killed in displacement, progress：Add into polymerization bottle
Enter 2 drop 2- vinylpyridines to develop the color；N-BuLi is slowly added dropwise with syringe, while polymerization bottle is constantly shaken, until 2- second
Alkenyl pyridine and n-BuLi composition are killed untill miscellaneous liquid is changed into faint yellow and colour-fast, as titration end-point, are write down now just
The volume 0.1ml of butyl lithium consumption, as kills the consumption of miscellaneous initiator used.
Embodiment 1
This example demonstrates that preparation and the dendritic polydiene rubber of the branched conditioning agent of dendritic poly double-olefin of the present invention.
(1) the branched conditioning agent of dendritic poly double-olefin is prepared：Butadiene 3g is added into polymerization bottle, solvent 25ml (is wherein wrapped
Tetrahydrofuran containing 22ml and 3ml hexane fractions)；By polymerization bottle in water bath with thermostatic control after after 50 DEG C, miscellaneous required initiator will be killed
With carry out the common 0.4ml of n-BuLi needed for the first polymerisation in solution, be added in polymerization bottle that the first solution is carried out at 50 DEG C is poly-
Close, polymer fluid is obtained after 1 hour, by the polymer fluid sampling analysis, it is determined that wherein containing straight chain polybutadiene, number-average molecular weight is
600, Isosorbide-5-Nitrae structural content is 16.2 weight %, the main chain average branch number of straight chain polybutadiene in the structure of straight chain polybutadiene
For 0；
0.4ml above-mentioned polymer fluid is taken to be added to equipped with 3g butadiene and 30ml solvents (wherein comprising 15ml tetrahydrofurans
With 15ml hexane fractions) 60 DEG C of polymerization bottle in, add n-BuLi 0.12ml, the second polymerisation in solution carried out at 60 DEG C
6h, is designated as TJ-1 by obtained product, is tested, the results are shown in Table 1.
(2) dendritic polydiene rubber is prepared：1ml TJ-1 is taken to be added to equipped with 10g isoprene and 80g hexane solvents
Polymerization bottle in, while add contain 2.2 × 10-5The rare earth catalyst of mol neodymiums, polymerisation in solution is carried out under 60 DEG C and 0.1MPa
2h, obtains polymerizate and is designated as XJ-1, tested, the results are shown in Table 1.
Polymerizate XJ-1 is subjected to Mooney viscosity and Mechanics Performance Testing.Test result is shown in Table 2.
Embodiment 2
This example demonstrates that preparation and the dendritic polydiene rubber of the branched conditioning agent of dendritic poly double-olefin of the present invention.
(1) the branched conditioning agent of dendritic poly double-olefin is prepared：Iso-amylene 6g is added into polymerization bottle, solvent 25ml (is wherein wrapped
Tetrahydrofuran containing 20ml and 5ml hexane fractions)；By polymerization bottle in water bath with thermostatic control after after 55 DEG C, miscellaneous required initiator will be killed
With carry out the common 0.6ml of n-BuLi needed for the first polymerisation in solution, be added in polymerization bottle that the first solution is carried out at 55 DEG C is poly-
Close, polymer fluid is obtained after 1 hour, by the polymer fluid sampling analysis, it is determined that wherein containing straight chain polybutadiene, number-average molecular weight is
1500, cis-structure content is 10.3 weight %, the main chain average branch of straight chain polybutadiene in the structure of straight chain polybutadiene
Number is 0；
0.4ml above-mentioned polymer fluid is taken to be added to equipped with 5.3g isoprene and 25ml solvents (wherein comprising 20ml tetrahydrochysenes
Furans and 5ml hexane fractions) 60 DEG C of polymerization bottle in, add n-BuLi 0.15ml, the second solution carried out at 60 DEG C
It polymerize 6h, obtained product is designated as TJ-2, tested, 1 is the results are shown in Table.
(2) dendritic polydiene rubber is prepared：1ml TJ-2 is taken to be added to equipped with 10g isoprene and 80g hexane solvents
Polymerization bottle in, while add contain 2.2 × 10-5The rare earth catalyst of mol neodymiums, polymerisation in solution is carried out under 60 DEG C and 0.1MPa
2h, obtains polymerizate and is designated as XJ-2, tested, the results are shown in Table 1.
Polymerizate XJ-2 is subjected to Mooney viscosity and Mechanics Performance Testing.Test result is shown in Table 2.
Embodiment 3
This example demonstrates that preparation and the dendritic polydiene rubber of the branched conditioning agent of dendritic poly double-olefin of the present invention.
(1) the branched conditioning agent of dendritic poly double-olefin is prepared：Butadiene 4.2g is added into polymerization bottle, solvent 25ml is (wherein
Include 13ml tetrahydrofurans and 12ml hexane fractions)；By polymerization bottle in water bath with thermostatic control after after 50 DEG C, miscellaneous required initiation will be killed
The common 0.6ml of n-BuLi needed for the first polymerisation in solution of agent and progress, is added in polymerization bottle at 50 DEG C and carries out the first solution
Polymerization, polymer fluid is obtained after 1 hour, by the polymer fluid sampling analysis, it is determined that wherein containing straight chain polybutadiene, number-average molecular weight
For 2000, Isosorbide-5-Nitrae structural content is 12.4 weight %, the main chain average branch of straight chain polybutadiene in the structure of straight chain polybutadiene
Number is 0；
0.4ml above-mentioned polymer fluid is taken to be added to equipped with 5.3g isoprene and 25ml solvents (wherein comprising 22ml tetrahydrochysenes
Furans and 3ml hexane fractions) 60 DEG C of polymerization bottle in, add n-BuLi 0.15ml, the second solution carried out at 60 DEG C
It polymerize 6h, obtained product is designated as TJ-3, tested, 1 is the results are shown in Table.
(2) dendritic polydiene rubber is prepared：1ml TJ-3 is taken to be added to equipped with 10g isoprene and 80g hexane solvents
Polymerization bottle in, while add contain 2.2 × 10-5The rare earth catalyst of mol neodymiums, polymerisation in solution is carried out under 60 DEG C and 0.1MPa
2h, obtains polymerizate and is designated as XJ-3, tested, the results are shown in Table 1.
Polymerizate XJ-3 is subjected to Mooney viscosity and Mechanics Performance Testing.Test result is shown in Table 2.
Comparative example 1
Into the polymerization bottle equipped with 10g isoprene and 80g hexane solvents, add and contain 2.2 × 10-5The rare earth of mol neodymiums
Catalyst, polymerisation in solution 2h is carried out under 60 DEG C and 0.1MPa, polymerizate is obtained and is designated as DXJ-1, tested, be the results are shown in Table
1。
Polymerizate DXJ-1 is subjected to Mooney viscosity and Mechanics Performance Testing.Test result is shown in Table 2.
Table 1
Table 2
| Project | Mooney viscosity | Tensile strength, MPa | Elongation at break, % |
| XJ-1 | 70 | 29.6 | 625 |
| XJ-2 | 67 | 29.9 | 620 |
| XJ-3 | 65 | 30.0 | 630 |
| DXJ-1 | 90 | 27.2 | 570 |
The method that can be seen that the present invention by the data structure of above example and comparative example and table 1 can be provided
The high branched conditioning agent of dendritic poly double-olefin of the degree of branching, is further prepared using the dendritic branched conditioning agent of poly double-olefin
Dendritic polydiene rubber, it is 500,000~600,000 that can have number-average molecular weight, and the Mooney viscosity scope of rubber is more suitable for processing
Plasticate, and mechanical property is improved.
Claims (10)
1. a kind of branched conditioning agent of dendritic poly double-olefin, it is characterised in that the number of the dendritic branched conditioning agent of poly double-olefin is equal
Molecular weight is 5000~50000, and the molecular weight distribution of the dendritic branched conditioning agent of poly double-olefin is 1~2；It is described dendritic poly bis
The content of Isosorbide-5-Nitrae construction unit is not higher than 50 weight % in the structure of the branched conditioning agent of alkene, and the dendritic poly double-olefin is branched to be adjusted
The main chain average branch number for saving agent is not less than 1.
2. the branched conditioning agent of dendritic poly double-olefin according to claim 1, wherein, the branched regulation of dendritic poly double-olefin
The content of Isosorbide-5-Nitrae construction unit is 4~17 weight % in the structure of agent, and the main chain of the dendritic branched conditioning agent of poly double-olefin is averaged
Side chain number is 1~2.
3. the branched conditioning agent of dendritic poly double-olefin according to claim 1 or 2, wherein, the dendritic poly double-olefin is branched
Conditioning agent is C4~C10The aggregated obtained dendritic polymer of diolefin, the preferably described branched conditioning agent of dendritic poly double-olefin is
Dendritic polyisoprene or dendritic polybutadiene.
4. a kind of method for preparing the branched conditioning agent of dendritic poly double-olefin, including：
(1) in the presence of the first polymerization catalyst and the first organic solvent containing tetrahydrofuran, diolefinic monomer A is carried out
First polymerisation in solution, obtains the polymer fluid containing straight chain poly double-olefin；
(2) in the presence of the second polymerization catalyst and the second organic solvent containing tetrahydrofuran, by the polymer fluid and two
Olefinic monomer B carries out the second polymerisation in solution, obtains the branched conditioning agent of dendritic poly double-olefin.
5. method according to claim 4, wherein, first polymerization catalyst is that the olefinic polymerization containing metal M is urged
Agent, the mol ratio using metal M first polymerization catalysts counted and the diolefinic monomer A is 0.001~0.1, preferably
For 0.01~0.08, most preferably 0.03~0.06；Metal M is lithium, titanium, rare earth or molybdenum, and preferably lithium, titanium or rare earth are optimal
Elect lithium or rare earth as；
Preferably, the diolefinic monomer A is C4~C10Diolefin, preferably butadiene or isoprene；The alkadienes
The mass ratio of monomer A and first organic solvent is 50：50~10：90, preferably 30：70~15：85.
6. the method according to claim 4 or 5, wherein, first organic solvent also contains alkane, and the alkane is C5
At least one of~C8 alkane；The weight ratio of tetrahydrofuran and the alkane is 99:1~1:99, preferably 90:10~50:
50。
7. method according to claim 4, wherein, the number-average molecular weight of the straight chain poly double-olefin is 500~2000, institute
The content for stating 1,4 structures in the structure of straight chain poly double-olefin is not higher than 20 weight %.
8. method according to claim 4, wherein, second polymerization catalyst is that the olefinic polymerization containing metal L is urged
Agent, the mol ratio using metal L second polymerization catalysts counted and the diolefinic monomer B is excellent as 0.0001~0.05
Elect 0.001~0.04, most preferably 0.002~0.03 as；Metal L is lithium, titanium, rare earth or molybdenum, and preferably lithium or rare earth are optimal
Elect lithium as；
Preferably, the diolefinic monomer B is C4~C10Diolefin, preferably butadiene or isoprene；The alkadienes
The mass ratio of monomer B and second organic solvent is 5：95~30：70, preferably 10：90~25：75；
Preferably, the polymer fluid and the diolefinic monomer B mass ratio are 1：1000~5：100, preferably 5：1000~
4：100, most preferably 7：1000~3.5：100.
9. method according to claim 4, wherein, second organic solvent also contains alkane, the alkane be C5~
At least one of C8 alkane；The weight ratio of tetrahydrofuran and the alkane is 99:1~1:99, preferably 90:10~50:50.
10. method according to claim 4, wherein, the temperature of first polymerisation in solution is 0~80 DEG C, preferably 40
~60 DEG C；The time of first polymerisation in solution is 5~10h, preferably 1~3h；The temperature of second polymerisation in solution be 0~
80 DEG C, preferably 40~60 DEG C；The time of second polymerisation in solution is 5~10h, preferably 1~3h.
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| CN111019053A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Preparation method of modified butadiene rubber for tire sidewall |
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| CN1884328A (en) * | 2006-06-06 | 2006-12-27 | 青岛科技大学 | Method for preparing branched high vinyl polybutadiene rubber using molybdenum series catalysis |
| CN104628963A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Polyisoprene, preparation method thereof and vulcanized rubber |
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| CN1884328A (en) * | 2006-06-06 | 2006-12-27 | 青岛科技大学 | Method for preparing branched high vinyl polybutadiene rubber using molybdenum series catalysis |
| CN104628963A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Polyisoprene, preparation method thereof and vulcanized rubber |
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