CN106995541B - Modified conjugated diene polymer and the rubber composition for tyre for using it - Google Patents
Modified conjugated diene polymer and the rubber composition for tyre for using it Download PDFInfo
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- CN106995541B CN106995541B CN201611163542.6A CN201611163542A CN106995541B CN 106995541 B CN106995541 B CN 106995541B CN 201611163542 A CN201611163542 A CN 201611163542A CN 106995541 B CN106995541 B CN 106995541B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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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
- C08F236/10—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 with vinyl-aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Tires In General (AREA)
Abstract
The present invention relates to modified conjugated diene polymer and use its rubber composition for tyre, there is provided modified conjugated diene high molecular raw material, its using be effectively utilized both sexes initiator anionic polymerization, by with two, specific structure it is terminal-modified to manufacture with the high molecular combined conjugated diene macromolecule of the linear structure and branch shape conjugated diene of the good functional group of silica mixed property to manufacture rubber composite material when, can be improved the dispersibility of inorganic matter caused by the increase of the compatibility with inorganics filled dose.
Description
Technical field
The present invention relates to the conjugated diene macromolecules for increasing degree of modification, are utilizing filler and vulcanizing agent for providing
Rubber composite material manufacture when, sheet processability, low hysteresis loss, wet skidding performance balancing good tire tread
(tread) raw material is used.
Background technique
In the case where the styrene butadiene ribber (SSBR) obtained using polymerisation in solution, it is however generally that will have carbon yin from
The organo-metallic catalyst of sub- property is used as initiator, and referred to as the feature of the polymerization of anionic polymerisation, molecular weight divides
Much less son amount is distributed, not only adjustable high molecular fine structure (micro-structure), but also adjustable huge
Big structure (macro-structure), when being used for tire tread, can design improves the braking on wet road surface
And combustion is than the rubber raw materials of raising.
In 7,915,349 8,426,513 8383711 B2, EP 2045272 in B1 of B2, USP of B2, USP of USP, will have
Organo-metallic catalyst as the lithium alkylide of carboanion is used as initiator and polymerize conjugated diene macromolecule,
As modified compound, the compound synthesis modified conjugated diene macromolecule containing amido and alkoxy silane is used.Synthesis
Modified conjugated diene macromolecule be utilized improve be present in end amido and alkoxy silane with surface have polarity
The compatibility of inorganic additive as the silica of group and the technology of dispersibility.But due to without functional group
Carbon system organo-metallic catalyst initiator carry out initiation polymerization, therefore, have polymerization start whole story end cannot be modified, is only high
The limit that the terminal end of molecule is modified, in addition, in order to improve molecular weight or improve processability, by can be anti-with anion
When the modifying agent more than trivalent answered causes coupling reaction, functional moieties are present in the high molecular center of modified conjugated diene,
Therefore, there are limits in terms of effectively improving compatibility and dispersibility with inorganic additive.With such modified conjugation two
When alkene system manufactures tire tread, by the macromolecule whole story end not being modified fire than be lower or braking and combustion ratio it is flat
Weighing apparatus is lower.
In 8278395 B2 of USP, KR20045225 B1, will also there is the glycidol for being used for terminal-modified multivalence
The modifying agent of base functional group makes an addition to the conjugated diene high score that the organo-metallic catalyst as butyl lithium causes and polymerize
Son manufactures, by the way that the modified conjugated diene macromolecule with such functional group to be directed in inorganic as silica
Additive and want to improve compatibility and dispersibility, but according to reason as described above, effectively improving aspect, there are limits.
In addition, in the high molecular situation of polymerisation in solution conjugated diene manufactured using trivalent coupling agent, molecular weight 200,000~
600,000g/mol, in the case where manufacturing silica and composite material, compared with existing SSBR and carbon black composite material, display
The result being lower significantly to the wear characteristic that tyre life affects.
In 5487848 A, WO 2002008300 of US in A1, to anion lithium catalyst more than effective use divalent
The conjugated diene macromolecule of manufacture multivalence is described.As the initiator used, by 1,3- divinylbenzene (1,3-
Divinylbenzene), 1,3- di isopropenylbenzene (1,3-diisopropenylbenzene), 1,3,5- trivinylbenzene
(1,3,5-trivinylbenzene) and tri- isopropenylbenzene of 1,3,5- (1,3,5-triisopropenylbenzene) etc. with
Butyl lithium (Butyl lithium), s-butyl lithium (secondary butyl lithium) are reacted, and divalent or trivalent are manufactured
Anionic initiator, efficiently used and manufacture conjugated diene macromolecule in polymerization.There is the technology raising end to change
Property rate effect, on the contrary, when coupling reaction, it is possible to can cause gelation (gelation) react, be commercially used aspect
It has difficulties.
The present invention provides the high molecular manufacturing method of modified conjugated diene and when using its mixing, can increase and nothing
The compatibility of machine object filler and the modified conjugated diene macromolecule raw material for improving thus caused dispersibility, the system
Method effective use both sexes initiator is made, in the two terminal activating styrene-butadiene conjugated diene macromolecules for anion
Manufacture after, selectively two terminal-modified linear conjugated diene series macromolecules are manufactured using additional modifying agent, by that will make
The conjugated diene macromolecule for the branch shape being polymerize with other reactors is blended with certain ratio, adjustable degree of modification,
Giant molecule structure and content.
Summary of the invention
Problems to be solved by the invention
The present invention provides modified conjugated diene polymer and the rubber composition using it, the modified conjugated diene
Polymer is made two ends by using both sexes initiator while having imparting easy functional group mixed with silica
The structure of linear structure and the branch shape as giant molecule improves the dispersion of the rubber-like of inorganic additive and improves Cross-linked samples
The mechanical performance and abrasivity of piece have high combustion than property, high braking, high abrasivity etc. when being used for tire tread.
Means for solving the problems
The present invention relates to by using both sexes initiator to impart functional group that can be mixed with silica two ends
The mixed type that the high molecular solution blending of branch shape conjugated diene of linear conjugated diene macromolecule and high molecular weight obtains
Conjugated diene polymer and the rubber composition for using it.
Here, the macromolecule that two linear ends are modified refers to: two it is terminal activating be anion in the state of throw
The conjugated diene macromolecule for entering terminal-modified dose and manufacturing.
As the initiator used, can be used 1,3- divinylbenzene (1,3-divinylbenzene), 1,3- bis-
Isopropenylbenzene (1,3-diisopropenylbenzene), 1,3,5- trivinylbenzene (1,3,5-trivinylbenzene)
And it is tri- isopropenylbenzene of 1,3,5- (1,3,5-triisopropenylbenzene) etc. and butyl lithium (butyl lithium), secondary
The initiator that butyl lithium (secondary butyl lithium) is reacted, but in the present invention, refers to: use is by 1,3-
Di isopropenylbenzene (1,3-diisopropenylbenzene) is mixed with tert-butyl lithium (tert- butyl lithium (BuLi)) and is manufactured
The substance of both sexes initiator (DIB-dianion) manufactures the high molecular two end active anion of styrene-butadiene, two
Amine system of the investment as terminal-modified dose, alcoxyl in a terminal activating linear styrene for anion-butadiene-based copolymer
Base silane system, cyano system, hydroxyl system, carboxyl system, sulfone system, phosphate system, ether system, acrylic acid series, methacrylate ester, ester system
Modifying agent manufactures the macromolecule that two ends are modified.
The conjugated diene macromolecule used in the manufacture of rubber composition refers to: being changed by previously fabricated linear pair
Property more than one and branch shape solution blending and the macromolecule that manufactures.
When being illustrated in more details, refer to: manufacturing in the high molecular situation of linear conjugated diene, by monomer, solvent,
Molecular regulation agent (randomizer) is full of after reactor, puts into both sexes initiator and two ends is made to become anion, live
After conjugated diene high molecular polymerization existing for property end, two ends obtained from adding terminal-modified dose by appending change
The property linear macromolecule of conjugated diene.Detailed method can be confirmed by following embodiments expressed.
In addition, the high molecular weight conjugated diene macromolecule of branch shape refers to: for eventually it is terminal activating be anion state
The multivalence branch shape manufactured by the investment of coupling agent down and star-shaped macromolecule.
The conjugated diene macromolecule of branch shape refers to: n-BuLi being used as initiator, terminal end is activated as anion
Styrene-butadiene anion polymerize after, according to functional group number put into anion ratio be 1 equivalent coupling agent, system
Make the 90% conjugated diene macromolecule the above are branch shape.
The conjugated diene macromolecule used in rubber composition manufacture refers to: modified by previously fabricated linear pair
The solution blending of more than one and branch shape and the macromolecule manufactured.
For branch shape conjugated diene macromolecule, in the conjugated diene containing the linear reactive terminal illustrated among the above
In macromolecule, a shape is manufactured using the coupling agent that the functional group that can be reacted with the active anion of activation is 3 or more
Conjugated diene macromolecule.
In general coupling agent can be that can be obtained with any substance of anionic reactive according to functional group's number
And molecular weight increases or the substance that deforms of macromolecular structure, star-shaped branch shape macromolecule in order to obtain, it is necessary to use trivalent
Above coupling agent.
In general, tin series or alkoxy silane or silyl halides can be used, also can be used containing contracting
The glyceryl compound of water.For example, as tin series, can be used stannous phenide dichloride, dibutyl tin dichloride, two oneself
Base tin dichloride, dioctyltin dichloride, phenyltin terchoride, butyl tin terchoride, tin octylate terchoride, four
Dimethylformamide dimethyl oxygroup silicon can be used in chlorine tin, tetramethoxy tin, tin tetraethoxide, four propoxyl group tin etc., alkoxy silane series
Alkane, diethyldimethoxysilane, dipropyl dimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane,
Ethyl trimethoxy silane, propyl trimethoxy silicane, butyl trimethoxy silane, methyltriethoxysilane, three second of ethyl
Oxysilane, propyl-triethoxysilicane, butyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane etc..
Silyl halides series can be used diphenyl dichlorosilane, dihexyl dichlorosilane, dioctyl dichlorosilane,
Dibutyldichlorosilane, dimethyldichlorosilane, methyl trichlorosilane, phenyl trichlorosilane, hexyl trichlorosilane, octyl trichlorine
Silane, butyl trichlorosilane, methyl trichlorosilane, tetrachloro silicane etc..
4,4' methylene bis (N, N- diglycidylaniline), N, N- can be used in compound containing glycidyl
Diglycidyl -4- glycidoxy aniline, N, N- diglycidylaniline, N, N, N', four glycidyl group -3 N'-,
3'- diethyl -4,4'- diaminodiphenyl-methane etc..
Contain as tert. butylacrylate, ((three acryloxypropyls) trimethoxy silane) in addition, also can be used
There is the amino silane derivative of ester group.
The coupling agent illustrated among the above may be used alone or in combination two or more.Exemplary compounds do not limit knot
Structure, alkoxy silane series serial if it is tin, silyl halides series, glycidyl series like that can be with tools
There is the substance of the whole end reaction of anion active, what kind of substance is ok.
The effect of invention
The present invention relates to the conjugated diene macromolecules for being effectively utilized both sexes initiator, it is intended that for providing
When with and both sexes are linear and being blended of branch shape (blend) using the manufacture of filler and the rubber composite material of vulcanizing agent
Sheet processability, low hysteresis loss (Hysteresis loss) property, tire tread (tread) use of wet skidding performance balancing good
Raw material.
Detailed description of the invention
Fig. 1 is for manufacturing containing the general of the two terminal-modified high molecular modified conjugated diene polymers of conjugated diene
Read figure.
Specific embodiment
Numerous variations can be added in the present invention, in the case where can have various embodiments, in order to be beneficial to this
The understanding of invention and show preferred embodiment, but following embodiments only illustrate the present invention, and the scope of the present invention is not limited to
Following embodiments.
Modified conjugated diene macromolecule shown in the present invention can be manufactured by polymerization as described below.
In two respectively different reactors, one manufactures linear structure using both sexes initiator (DIB-dianion)
Two terminal activating conjugated dienes for anion after, investment modifying agent two ends are modified, reaction was completed and
Manufacture two terminal-modified linear conjugated diene series macromolecules；In other reactors, manufacturing the terminal activating of linear structure is
After the conjugated diene of anion, puts into coupling agent and manufacture the conjugated diene macromolecule of a structure.It is to obtain such
After two samples arrived are blended with solution shape, after removing residual solvent using steam stripping tower, it is dried and manufactures and change
The property high molecular method of conjugated diene.
When polymerizeing among the above, polar additive can be according to circumstances added.Polar additive is to control polymer
Fine structure and in order to improve polymerization speed or in order to adjust reactivity and add, purpose of the additive amount because of additive
And type and difference.
As the example of polar additive, tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), diethyl can be used
Ether, ring amyl ether, dipropyl ether, ethylene glycol, triethylamine, ethyl-butyl ether, crown ether, two tetrahydrofuran base propane, ethyl tetrahydro
Furyl ether, triethylamine, Trimethylamine and these derivative.By this polar additive, can be adjusted according to purpose
The disordered structure of polymer and the content of vinyl group, in addition can also be improved polymerization rate.
The solvent used in polymerization can be used as the n-hexane of hydrocarbon solvent, normal heptane, hexamethylene, isooctane, methyl
These can be used alone or two or more is used in mixed way by pentamethylene, benzene,toluene,xylene, tetrahydrofuran etc..Monomer with
Mode in the hydrocarbon solvent as 5~50 weight % is added.It is preferred that with the addition of 15~35 weight % levels.It is lower than 5 weights
Measure % when, polymerization time is elongated sometimes, or is difficult to be reacted, if its be 50 weight % or more, solution viscosity rise and
It is difficult to control molecular weight or reaction heat, or is difficult to uniformly be stirred in polymerization.
It is blended in sample in production, adjusts the content of linear structure and the reason of linear/high molecular number-average molecular weight of branch shape
By being because sample is blended with the Mooney viscosity manufacture found out in the manufacture of Tire Composites.
The content of two terminal-modified linear structures is preferably 10~60 parts by weight, but its be lower than 10 parts by weight when, be blended sample
The Mooney viscosity of product excessively rises, and not preferably, when more than 60 parts by weight, Mooney viscosity is excessively increased, in Tire Composites
Manufacture when processability can reduce, not preferably.
In the present invention, which is characterized in that the high molecular number-average molecular weight of two terminal-modified linear structures is 100,000
~200,000g/mol, the number of the linear anion active styrene-butadiene system copolymer before the high molecular coupling of branch shape
Average molecular weight is 100,000~400,000g/mol.
Efficiently use carbon black or silica and the Mooney viscosity for the rubber that while manufacturing Tire Composites uses according to
Cooperate purposes and the rubber of Mooney viscosity 30~180 is used to manufacture composite material.This is because the content of linear structure it is excessive,
Or number-average molecular weight cross low land manufacture when, manufactured sometimes in 30 or less Mooney viscosity, on the contrary, the content mistake of linear structure
When low or number-average molecular weight is excessively high, Mooney viscosity is more than 180 sometimes.
Polymerization temperature when polymerization is different due to solvent, it is however generally that can be polymerize at 10~160 DEG C.Fine structure
It is different due to polymerization temperature, polymerization temperature can be adjusted according to purpose.
Before terminal-modified dose of investment, according to the anionic reactive of polymer ends, or in order to make additional modification
Agent and the bonding of polymer are stable or in order to improve efficiency, and can also additionally put into conjugated diene monomer or vinyl
It is that hydrocarbon monomer adds modifying agent later.
Rubber compounding usually can use tire cooperation used, and inorganic particulate additive can be by carbon black, titanium dioxide
Silicon etc. is used alone or two or more cooperates and uses.When especially cooperating, exist as silica in surface of inorganic particles
The high molecular performance of modified conjugated diene that the present invention shows in the inorganic particulate additive of many functional groups is more excellent.
1. the analysis of macromolecule fine structure
The fine structure for the polymer being polymerize uses the 400MHz of Bruker society1H-NMR is confirmed.
2. the measurement of molecular weight
For the measurement of molecular weight, link 5 μm of mixing-C columns of polystyrene of Liang Ge PLgel society in parallel, by polyphenyl
Simultaneously, solvent is measured using THF for ethylene authentic specimen (molecular weight 5000g/mol) and polymer.Detector uses refraction
Rate detector (RI).Method is two columns that connection is filled with silica-based gel (Zorbax PSM) in parallel, and solvent makes
With THF, degree of modification, which refers to the high molecular degree of modification of modified conjugated diene, experimentally to be linked in parallel filled with titanium dioxide
The value that two columns, solvents of Silica hydrogel are calculated using THF, can through the invention in the experimental method shown analyzed.
3. the measurement of degree of modification
Connection is filled with two columns of silica-based gel (Zorbax PSM) in parallel, and solvent uses THF, detector
It is measured with refractive index detector (RI).Polystyrene benchmark sample (molecular weight 5000g/mol) and polymer is molten simultaneously
After solution, it is flowed into column and is measured.
Degree of modification (%)=[1- (A2 × A3)/(A1 × A4)] × 100
A1: being the total peak area of sample in the case where making the area 100 at entire peak obtained in styrene gel column
(not including the peak area of polystyrene benchmark sample)
A2: being polystyrene benchmark sample in the case where making the area 100 at entire peak obtained in styrene gel column
Peak area
A3: in the case where making entire peak area 100 obtained in silica-based gel column, not to be adsorbed in dioxy
The peak area of the sample of SiClx system gel
A4: being polystyrene benchmark sample in the case where making entire peak area 100 obtained in silica-based gel column
The peak area of product
Degree of modification is higher, more excellent by rubber compounding and vulcanization process performance, it is therefore preferable that according to purpose maximum limit
Improve degree of modification in degree ground.In general, degree of modification is necessary for 10% or more, 20% or more must preferably be of.
4. stretching experiment
To sulfureted test film, c-type dumbbell is made according to 412 tension test method of ASTM and uses universal testing machine
(LLOYD UTM) is measured.
5. viscoelastic property
The tan δ of viscoelastic property as sulfureted test film uses DMTA to equip, in 10Hz, 0.1% deformation condition
It is lower to assign temperature change (temperature sweep) on one side, it is measured on one side.When 0 DEG C of tan δ value is high, as braking
It is wet skidding performance excellent, when 60 DEG C of tan δ value is low, show low hysteresis, refer to combustion than good.
6. the dispersibility of inorganic particles
For the dispersibility of modified conjugated diene and inorganic particles, after being blended with Hakke, before vulcanization, in sample
The RPA2000 that Alpha Technology society is used in product, is confirmed according to Penn (Payne) effect.
Penn effect refers to: being indicated to deform 0.7% and 14% difference in 0.1Hz, 60 DEG C with kPa, is worth smaller, inorganic matter grain
The dispersibility of son is the better.
7. Mooney viscosity
For the Mooney viscosity of modified conjugated diene macromolecule itself, the Mooney of Alpha Technology society is used
Viscometer, at 100 DEG C to be measured on the basis of ML (1+4).
Embodiment 1
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into herein
The linear SBR that weight average molecular weight (Mw) is about 150,000g/mol is polymerize by DIB-diamion by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, setting two ends of polymer through 5 minutes
It is changed to butadiene active anion.It puts into 2.2 moles of mole ratio herein and has put into modifying agent di ethoxy di methyl-monosilane
(diethoxydimethylsilane) DIB-dianion reacts 10 minutes.Then, second of the addition as reaction terminating agent
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, manufacture linear SBR solution.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 300,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.Here, 1/3 mole of mole ratio of investment has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) on the basis of 100 parts by weight of total solid, with 1) 20 parts by weight (40g), 2) 80 weight
It after the ratio mixing of part (160g), stirs 30 minutes and manufactures uniform mixed solution, thereafter, efficiently use steam stripping tower
And remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufacture
The polymer blended coupons of unmodified conjugated diene of 200g.
Embodiment 2
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into herein
The linear SBR that weight average molecular weight (Mw) is about 150,000g/mol is polymerize by DIB-diamion by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, setting two ends of polymer through 5 minutes
It is changed to butadiene active anion.It puts into 2.2 moles of mole ratio herein and has put into modifying agent (3- cyanopropyl) dimethyl
The DIB-diamion of chlorosilane ((3-Cyanopropyl) dimethylchlorosilane) reacts 10 minutes.Then, it adds
As reaction terminating agent ethyl alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant,
Manufacture linear SBR solution.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 300,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1/3 mole of mole ratio herein and has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) on the basis of 100 parts by weight of total solid, with 1) 20 parts by weight (40g), 2) 80 weight
It after the ratio mixing of part (160g), stirs 30 minutes and manufactures uniform mixed solution, thereafter, efficiently use steam stripping tower
And remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufacture
The polymer blended coupons of unmodified conjugated diene of 200g.
Embodiment 3
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into herein
The linear SBR that weight average molecular weight (Mw) is about 150,000g/mol is polymerize by DIB-diamion by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, setting two ends of polymer through 5 minutes
It is changed to butadiene active anion.It puts into 2.2 moles of mole ratio herein and has put into modifying agent 1- (2- chloroethyl) -2,2,5,
Two silacyclopentan (1- (2-chloroethyl) -2,2,5,5-tetramethyl-1-aza- of 5- tetramethyl -1- azepine -2,5-
2,5-disilacyclopentane) DIB-diamion reacts 10 minutes.Then, ethyl alcohol of the addition as reaction terminating agent
And stopping polymerization, the I-1076 relative to polymer addition 0.2wt% as antioxidant manufactures linear SBR solution.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 300,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.Here, 1/3 mole of mole ratio of investment has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) on the basis of 100 parts by weight of total solid, with 1) 20 parts by weight (40g), 2) 80 weight
It after the ratio mixing of part (160g), stirs 30 minutes and manufactures uniform mixed solution, thereafter, efficiently use steam stripping tower
And remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufacture
The polymer blended coupons of unmodified conjugated diene of 200g.
Embodiment 4
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into herein
The linear SBR that weight average molecular weight (Mw) is about 120,000g/mol is polymerize by DIB-diamion by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, setting two ends of polymer through 5 minutes
It is changed to butadiene active anion.It puts into 2.2 moles of mole ratio herein and has put into modifying agent di ethoxy di methyl-monosilane
(diethoxydimethylsilane) DIB-dianion reacts 10 minutes.Then, second of the addition as reaction terminating agent
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, manufacture linear SBR solution.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 350,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1/3 mole of mole ratio herein and has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) on the basis of 100 parts by weight of total solid, with 1) 40 parts by weight (80g), 2) 60 weight
It after the ratio mixing of part (120g), stirs 30 minutes and manufactures uniform mixed solution, thereafter, efficiently use steam stripping tower
And remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufacture
The polymer blended coupons of unmodified conjugated diene of 200g.
Embodiment 5
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into herein
The linear SBR that weight average molecular weight (Mw) is about 120,000g/mol is polymerize by DIB-diamion by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, setting two ends of polymer through 5 minutes
It is changed to butadiene active anion.Here, 2.2 moles of mole ratio of investment has put into modifying agent (3- cyanopropyl) dimethyl
The DIB-diamion of chlorosilane ((3-Cyanopropyl) dimethylchlorosilane) reacts 10 minutes.Then, it adds
As reaction terminating agent ethyl alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant,
Manufacture linear SBR solution.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 350,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.Here, 1/3 mole of mole ratio of investment has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) with 100 parts by weight benchmark of total solid, with 1) 40 parts by weight (80g), 2) 60 parts by weight
(120g) ratio mixing after, stirring 30 minutes and manufacture uniform mixed solution, thereafter, efficiently use steam stripping tower and
Remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufactures 200g
The polymer blended coupons of unmodified conjugated diene.
Embodiment 6
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into herein
The linear SBR that weight average molecular weight (Mw) is about 120,000g/mol is polymerize by DIB-diamion by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, setting two ends of polymer through 5 minutes
It is changed to butadiene active anion.It puts into 2.2 moles of mole ratio herein and has put into modifying agent 1- (2- chloroethyl) -2,2,5,
Two silacyclopentan (1- (2-chloroethyl) -2,2,5,5-tetramethyl-1-aza- of 5- tetramethyl -1- azepine -2,5-
2,5-disilacyclopentane) DIB-diamion reacts 10 minutes.Then, ethyl alcohol of the addition as reaction terminating agent
And stopping polymerization, the I-1076 relative to polymer addition 0.2wt% as antioxidant manufactures linear SBR solution.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 350,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1/3 mole of mole ratio herein and has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) with 100 parts by weight benchmark of total solid, with 1) 40 parts by weight (80g), 2) 60 parts by weight
(120g) ratio mixing after, stirring 30 minutes and manufacture uniform mixed solution, thereafter, efficiently use steam stripping tower and
Remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufactures 200g
The polymer blended coupons of unmodified conjugated diene.
Comparative example 1
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 150,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1.2 moles of mole ratio herein and has put into modifying agent di ethoxy di methyl-monosilane
(diethoxydimethylsilane) butyl lithium (BuLi) reacts 10 minutes.Then, second of the addition as reaction terminating agent
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, manufacture an end and be modified
For the SBR solution of Ethoxysilane.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 300,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1/3 mole of mole ratio herein and has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) with 100 parts by weight benchmark of total solid, with 1) 20 parts by weight (40g), 2) 80 parts by weight
(160g) ratio mixing after, stirring 30 minutes and manufacture uniform mixed solution, thereafter, efficiently use steam stripping tower and
Remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufactures 200g
The polymer blended coupons of end list modified conjugated diene.
Comparative example 2
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 150,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1.2 moles of mole ratio herein and has put into modifying agent (3- cyanopropyl) dimethyl chloride
The butyl lithium (BuLi) of silane ((3-Cyanopropyl) dimethylchlorosilane) reacts 10 minutes.Then, it adds
As reaction terminating agent ethyl alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant,
Manufacture the SBR solution that an end is modified as cyano.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 300,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1/3 mole of mole ratio herein and has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) with 100 parts by weight benchmark of total solid, with 1) 20 parts by weight (40g), 2) 80 parts by weight
(160g) ratio mixing after, stirring 30 minutes and manufacture uniform mixed solution, thereafter, efficiently use steam stripping tower and
Remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufactures 200g
The polymer blended coupons of end list modified conjugated diene.
Comparative example 3
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 150,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.Here, 1.2 moles of mole ratio of investment has put into modifying agent 1- (2- chloroethyl) -2,2,5,
Two silacyclopentan (1- (2-chloroethyl) -2,2,5,5-tetramethyl-1-aza- of 5- tetramethyl -1- azepine -2,5-
2,5-disilacyclopentane) butyl lithium (BuLi) reacts 10 minutes.Then, second of the addition as reaction terminating agent
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, manufacture an end and be modified
For the SBR solution of nitrogen and silicon compound.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 300,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1/3 mole of mole ratio herein and has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) with 100 parts by weight benchmark of total solid, with 1) 20 parts by weight (40g), 2) 80 parts by weight
(160g) ratio mixing after, stirring 30 minutes and manufacture uniform mixed solution, thereafter, efficiently use steam stripping tower and
Remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufactures 200g
The polymer blended coupons of end list modified conjugated diene.
Comparative example 4
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 120,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1.2 moles of mole ratio herein and has put into modifying agent di ethoxy di methyl-monosilane
(diethoxydimethylsilane) butyl lithium (BuLi) reacts 10 minutes.Then, second of the addition as reaction terminating agent
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, manufacture an end and be modified
For the SBR solution of Ethoxysilane.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 350,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.Here, 1/3 mole of mole ratio of investment has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) with 100 parts by weight benchmark of total solid, with 1) 40 parts by weight (80g), 2) 60 parts by weight
(120g) ratio mixing after, stirring 30 minutes and manufacture uniform mixed solution, thereafter, efficiently use steam stripping tower and
Remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufactures 200g
The polymer blended coupons of end list modified conjugated diene.
Comparative example 5
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 120,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1.2 moles of mole ratio herein and has put into modifying agent (3- cyanopropyl) dimethyl chloride
The butyl lithium (BuLi) of silane ((3-Cyanopropyl) dimethylchlorosilane) reacts 10 minutes.Then, it adds
As reaction terminating agent ethyl alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant,
Manufacture the SBR solution that an end is modified as cyano.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 350,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1/3 mole of mole ratio herein and has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) with 100 parts by weight benchmark of total solid, with 1) 40 parts by weight (80g), 2) 60 parts by weight
(120g) ratio mixing after, stirring 30 minutes and manufacture uniform mixed solution, thereafter, efficiently use steam stripping tower and
Remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufactures 200g
The polymer blended coupons of end list modified conjugated diene.
Comparative example 6
1) manufacture of linear SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
Base lithium (BuLi) makes the linear SBR polymerization that weight average molecular weight (Mw) is about 120,000g/mol by polymerization reaction.Reaction
Temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, the terminal end of polymer being replaced into fourth through 5 minutes
Diene co anion.Here, 1.2 moles of mole ratio of investment has put into modifying agent 1- (2- chloroethyl) -2,2,5,5- tetra-
Methyl-1-two silacyclopentan of azepine-2,5- (1- (2-chloroethyl)-2,2,5,5-tetramethyl-1-aza-2,5-
Disilacyclopentane butyl lithium (BuLi)) reacts 10 minutes.Then, relative to polymer addition 0.2wt% addition
As reaction terminating agent ethyl alcohol and make polymerization stop, as the I-1076 of antioxidant, manufacture an end and be modified as nitrogen
With the SBR solution of silicon compound.
2) manufacture of branch shape SBR
It is put into styrene 170g, 1,3-butadiene 630g, hexane 4150g in 10L autoclave reactor, puts into tetramethyl
After ethylenediamine (TMEDA) 10ml, temperature of reactor is rotated with blender on one side, is warming up to 50 DEG C on one side.It is put into fourth herein
The linear SBR that weight average molecular weight (Mw) is about 350,000g/mol is polymerize by base lithium (BuLi) by polymerization reaction.
Reaction temperature reaches maximum temperature and by after ten minutes, putting into butadiene 50g, and the terminal end through 5 minutes by polymer is replaced
For butadiene active anion.It puts into 1/3 mole of mole ratio herein and has put into 3- glycidoxypropyl trimethoxy silicon
The butyl lithium (BuLi) of alkane (3-glycidoxypropyltrimethoxysilane) reacts 10 minutes.After reaction, second is added
Alcohol and stop polymerization, relative to polymer addition I-1076 of the 0.2wt% as antioxidant, the SBR solution of manufacture branch shape.
3) manufacture of SBR is blended
By previously fabricated 1) and 2) with 100 parts by weight benchmark of total solid, with 1) 40 parts by weight (80g), 2) 60 parts by weight
(120g) ratio mixing after, stirring 30 minutes and manufacture uniform mixed solution, thereafter, efficiently use steam stripping tower and
Remove the hexane as solvent.Moisture is dried using 100 DEG C of processing roller for the moisture of obtained solids, manufactures 200g
The polymer blended coupons of end list modified conjugated diene.
The mixing transitivity measurement experiment of experimental example and polymer and inorganic matter
The mixing method of the rubber composition of polymer obtained in above-mentioned uses Thermo Scientific society
Haake Polylab OS Rheodrive, uses Banbury rotor.With formed shown in following tables the cooperation embodiment and
Polymer obtained in comparative example.
Cooperation is with the progress of 2 stages.For being kneaded, 75% is filled in the 1st mixing, under the conditions of rotor speed 60rpm
It is put into polymer, filler (silica), oil, zinc oxide (ZnO), stearic acid (stearic acid), silane coupling agent
(Si-69), antioxidant (6-PPD) and temperature is controlled, 1 rubber composition is obtained at 150~160 DEG C.It will in being kneaded the 2nd
Complex is cooled to room temperature, in 90 DEG C or less addition sulphur (sulfur) and DPG (Diphenyl Guanidine, diphenylguanidine), CBS
(N-cyclohexyl-2-benzothiazole sulfonamide, N- cyclohexyl -2-[4-morpholinodithio sulfonamide) and it is kneaded 5 points
Clock.
Rubber through cooperating is vulcanized at 160 DEG C by T90+5min pressurization, sulfureted rubber is manufactured.
[table 1]
| Substance name | Content (Phr) |
| Polymer (SSBR) | 100 |
| Silica (Silica) | 50 |
| Oily (Oil) (TDAE) | 5 |
| Zinc oxide (ZnO) | 3 |
| Stearic acid (Stearic acid) | 2 |
| Si69 | 4 |
| 6-PPD(A/O) | 1 |
| Sulphur (Sulfur) | 1.5 |
| Diphenylguanidine (DPG) | 1.5 |
| N- cyclohexyl -2-[4-morpholinodithio sulfonamide (CBS) | 1.8 |
The polymer manufactured through the invention and oligometric comples and evaluation performance are analyzed, 2~table of table 9 is shown in.
[table 2]
* styrene-content, contents of ethylene are the result calculated with H-NMR
* GPTMS:3- glycidoxypropyl trimethoxy silane
[table 3]
* styrene-content, contents of ethylene are the result calculated with H-NMR
* GPTMS:3- glycidoxypropyl trimethoxy silane
[table 4]
* styrene-content, contents of ethylene are the result calculated with H-NMR
* GPTMS:3- glycidoxypropyl trimethoxy silane
[table 5]
* styrene-content, contents of ethylene are the result calculated with H-NMR
* GPTMS:3- glycidoxypropyl trimethoxy silane
[table 6]
[table 7]
[table 8]
[table 9]
Claims (4)
1. modified conjugated diene polymer, to use with intermittent two or more reactors linked side by side point
Two terminal-modified linear conjugated diene series macromolecules and branch shape conjugated diene Polymer Solution are not polymerize, by two end
Modified linear conjugated diene series macromolecule and the branch shape conjugated diene Polymer Solution shape are blended and what is manufactured is modified conjugation
Diene polymer, wherein
1) described two terminal-modified linear conjugated diene series macromolecules are to use end to linear styrene-butadiene-based copolymer
Modifying agent make two it is terminal-modified and manufacture, two terminal-modified linear conjugated two described in the modified conjugated diene polymer
The high molecular content of alkene system is 10~60 parts by weight, and the linear styrene-butadiene-based copolymer is using 1,3- bis- is different
Propenylbenzene is mixed with tert-butyl lithium and the both sexes initiator that manufactures, and high molecular two end of linear styrene-butadiene is used
The linear styrene that anion has activated-butadiene-based copolymer,
2) the described two terminal-modified linear conjugated high molecular number-average molecular weights of diene series are 100,000~200,000g/mol,
Linear anion active styrene-butadiene system copolymer before the high molecular coupling of conjugated diene of the branch shape structure
Number-average molecular weight be 100,000~400,000g/mol,
It 3) is 20% or more as the degree of modification of modified conjugated diene polymer.
2. modified conjugated diene polymer according to claim 1, which is characterized in that when manufacturing branch shape structure,
Tin series, alkoxy silane, monosilane are used in the one terminal activating linear styrene for anion-butadiene-based copolymer
Either one or two of base halide, compound containing glycidyl are used as coupling agent above.
3. modified conjugated diene polymer according to claim 1 is styrene-butadiene system copolymer, special
Sign is that Mooney viscosity is 30~180.
4. rubber composition for tyre contains modified conjugated diene polymer according to any one of claims 1 to 3.
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| KR1020160009094A KR101830492B1 (en) | 2016-01-26 | 2016-01-26 | Modified conjugated diene-based polymer and a tire rubber composition using the same |
| KR10-2016-0009094 | 2016-01-26 |
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| KR102139528B1 (en) | 2018-02-05 | 2020-07-30 | 주식회사 엘지화학 | Method for preparing conjugated diene based polymer and apparatus for preparing conjugated diene based polymer |
| CN113166315B (en) * | 2018-12-21 | 2023-08-01 | 株式会社Lg化学 | Process for producing modified conjugated diene polymer |
| CN113166314B (en) * | 2018-12-21 | 2023-08-01 | 株式会社Lg化学 | Modified conjugated diene polymer and rubber composition containing the same |
| KR102255801B1 (en) * | 2021-02-16 | 2021-05-26 | 금호석유화학 주식회사 | A rubber composition comprising carbon nanotubes |
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| JP2017132986A (en) | 2017-08-03 |
| KR101830492B1 (en) | 2018-02-20 |
| CN106995541A (en) | 2017-08-01 |
| KR20170089112A (en) | 2017-08-03 |
| JP6615739B2 (en) | 2019-12-04 |
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