CN110128607A - Monovinylarene-conjugated diene block copolymer and block copolymer composition and vulcanized rubber and its application - Google Patents
Monovinylarene-conjugated diene block copolymer and block copolymer composition and vulcanized rubber and its application Download PDFInfo
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- CN110128607A CN110128607A CN201810134989.3A CN201810134989A CN110128607A CN 110128607 A CN110128607 A CN 110128607A CN 201810134989 A CN201810134989 A CN 201810134989A CN 110128607 A CN110128607 A CN 110128607A
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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Abstract
The invention discloses a kind of monovinylarene-conjugated diene block copolymer, block copolymer composition and vulcanized rubber and its application, the structural unit in the block copolymer presses PS-PSIB1‑PB2Mode connect, PS sections are the block formed by monovinylarene, PSIB1Section is the random copolymerization section formed by the second monovinylarene, the first conjugated diene and the second conjugated diene, PB2Section is the homopolymerization section formed by third conjugated diene, and first conjugated diene and the third conjugated diene are respectively butadiene, and second conjugated diene is isoprene.The material formed by block copolymer of the invention, block copolymer composition or vulcanized rubber not only has preferable damping capacity within the scope of wider temperature, and good damping capacity is all had under the conditions of room temperature and temperature above room temperature, while also there is preferable mechanical property.
Description
Technical field
The present invention relates to a kind of monovinylarene-conjugated diene block copolymer and its application, the invention further relates to
The block copolymer composition formed by the monovinylarene-conjugated diene block copolymer and its application, the present invention
Further to the vulcanized rubber and its application formed by the block copolymer or the block copolymer composition.
Background technique
With the development of sociometric technique and modern industry, mechanical equipment tends to develop to the direction of high speed, top load,
Thus vibration and noise pollution caused by have become global problem.Meanwhile with the enhancing of people's environmental consciousness, to sound ring
The requirement in border is also higher and higher.Therefore, sqouynd absorption lowering noise is gradually evolved into coordinates to send out for a related high-tech, environment and the mankind
The important topic of the urgent need to resolve of exhibition.Vibration and noise reducing is carried out using rubber damping material, it has also become is solved the above problems very
One of effective method.
Sound-absorbing material has two most basic technical requirements: first, the acoustic impedance of material and the acoustic impedance of propagation medium are wanted
Matching, make sound wave in the medium areflexia into people's absorption system；Second, material in-fighting itself is big, and sound wave is made to absorb system
Decay quickly in system.Special Advances in Sound Absorption Polymers can satisfy both requirements, then reasonable sound absorption structure is cooperated to design,
Excellent sound absorption device can be made.New type rubber SIBR (styrene-isoprene-butadiene terpolymer) is a kind of tool
Have specific characteristics can high molecular material, have preferable processing performance and sound absorbing performance, have certain intensity and wider temperature
Stability can bear certain pressure.Meanwhile it has loss characteristic and biggish elastic deformation again, is conducive to damp
It is introduced in material simultaneously with sound absorption mechanism, improves sound absorbing performance, provide wide space for the development of sound absorption and noise reduction material.
The micro molecule structure and sequential structure of polymer, such as the degree of saturation of main chain, polarity, the length of side chain and side chain
Content, monomer distribution etc. in the copolymer, there is significant impact to the molecular motion of polymer, to influence to polymerize
The damping capacity of object material.Therefore, it may be implemented by carrying out selection to type of polymer and molecular structure to damping material
Damping value and effective damping functional areas potential temperature are regulated and controled.
CN102558465A discloses a kind of polymerization for producing solution polymerized butadiene styrene rubber, this method comprises: institute will be reacted
Inert hydrocarbon solvent, butadiene and the nonessential structure regulator needed is added in reactor, is then added a effective amount of organic
Lithium initiator carries out A sections of polymerizations in the presence of initiator, A sections of polymerisation conversions is made to reach 97-100%；Butadiene, benzene is added
Ethylene, structure regulator carry out B sections of polymerizations, and coupling agent is added after B sections of conversion ratios reach 100% and carries out coupling reaction, coupling
After reaction；Terminate reaction.After the vulcanization of rubber by this method preparation, the temperature range of δ >=0.3 fissipation factor tan about-
45 DEG C to 0 DEG C, therefore, the effective efficiency area of the high-damping value of the material is concentrated mainly on low-temperature region, damping more than room temperature
It is worth relatively low, influences the application that product is used as damping shock absorption material at room temperature.
US6,268,427B1 disclose a kind of method for improving rubber damping performance, this method comprises: to vulcanizable group
It closes addition saturation damping material, the damping additive in object and contains dissaving polymer, the dissaving polymer is to pass through
Functionalized polymeric crosslinking is formed with polyfunctional crosslinking agent.But this method is that general elasticity is added by physical blending
Body material improves the damping capacity of product, does not improve to base rubber material internal structure.
Wang Pei etc. (material engineering, 2009, S1:192-195) is prepared for having height using ethoxyethyl group morpholine (EOEM)
The butadiene-styrene rubber damping material of contents of ethylene, product fissipation factor is up to 0.9.But it is damaged by the rubber of this method preparation
The temperature range for consuming δ >=0.3 factor t an is about -1 DEG C to 23 DEG C, and the effective temperature scope of fissipation factor curve is only 24 DEG C, limit
It is made under room temperature conditions as the application in damping material or sound-absorbing material.
Wang Xue etc. (elastomer, 2009,6:35-37) prepares SSBR/IIR damping material, the material using solution co-agglomeration
The maximum loss factor of material is up to 0.8 or more.By the temperature range for δ >=0.3 rubber material fissipation factor tan that this method synthesizes
About -25 DEG C to -4 DEG C, damping value more than room temperature is relatively low, influences the application that product is used as damping shock absorption material at room temperature.
Therefore, it needs to develop one kind not only with preferable mechanical property, but also in low temperature and at room temperature all with excellent
The Novel Damping Materials of damping capacity.
Summary of the invention
The purpose of the present invention is to provide a kind of monovinylarene-conjugated diene block copolymers, are total to by the block
The material that polymers is formed all has good damping capacity under the conditions of room temperature and temperature above room temperature.
According to the first aspect of the invention, the present invention provides a kind of monovinylarene-conjugated diene block is total
Polymers, the structural unit in the block copolymer press PS-PSIB1-PB2Mode connect, wherein
A, PS sections are the homopolymerization section formed by the first monovinylarene；
b、PSIB1Section is to be formed by the second monovinylarene, the first conjugated diene and the second conjugated diene
Random copolymerization section；
c、PB2Section is the homopolymerization section formed by third conjugated diene；
D, on the basis of the total amount of the block copolymer, PS sections of content is 0.8-8 weight %, PSIB1Section content be
80-95 weight %, PB2The content of section is 3-12 weight %, and the content of the structural unit formed by monovinylarene is 30-50
Weight %, the side group content of the block copolymer are 40-65 weight %；And
E, first conjugated diene and the third conjugated diene are respectively butadiene, second conjugated diene
Hydrocarbon is isoprene, and on the basis of the total amount of the block copolymer, the content of the structural unit formed by butadiene is 30-36 weight
% is measured, the content of the structural unit formed by isoprene is 20-30 weight %.
According to the second aspect of the invention, the present invention provides a kind of block copolymer composition, the block copolymers
Composition is obtained from being coupled block copolymer described in first aspect of the present invention with coupling agent.
According to the third aspect of the present invention, the present invention provides a kind of vulcanized rubber, which is will be of the invention
Block copolymer composition described in block copolymer described in first aspect or the second aspect of the present invention vulcanized and
It obtains.
According to the fourth aspect of the present invention, the present invention provides block copolymer described in first aspect of the present invention,
Vulcanized rubber described in terms of block copolymer composition described in the second aspect or third is as damping material or suction
The application of sound material.
By monovinylarene-conjugated diene block copolymer of the invention, block copolymer composition or vulcanization rubber
The material that glue is formed not only has preferable damping capacity within the scope of wider temperature, but also in room temperature and higher than room temperature
Good damping capacity is all had under the conditions of temperature, while also there is preferable mechanical property.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of monovinylarene-conjugated diene block is total
Polymers, the structural unit in the block copolymer press PS-PSIB1-PB2Mode connect, wherein
A, PS sections are the homopolymerization section formed by the first monovinylarene；
b、PSIB1Section is to be formed by the second monovinylarene, the first conjugated diene and the second conjugated diene
Random copolymerization section；
c、PB2Section is the homopolymerization section formed by third conjugated diene.
In the present invention, for purposes of clarity, by PS sections and PSIB1Monovinylarene in section is referred to as " first
Monovinylarene " and " the second monovinylarene ".
In the present invention, term " monovinylarene " refers to that a hydrogen on aromatic ring is replaced the chemical combination to be formed by vinyl
Object.First monovinylarene and second monovinylarene respectively can be in Formulas I compounds represented
One or more,
In Formulas I, R1For C6-C20Substituted or unsubstituted aryl.
In the present invention, the C6-C20The example of substituted or unsubstituted aryl can include but is not limited to: phenyl, neighbour
Tolyl, tolyl, p-methylphenyl, adjacent ethylbenzene, ethylbenzene, to ethylbenzene, o-tert-butyl phenyl, tert-butyl benzene
Base, to tert-butyl-phenyl, to dodecylphenyl, 2,4- di-n-butyl phenyl, to n-propyl phenyl and 2,4- diethylbenzene
Base.
Preferably, first monovinylarene and second monovinylarene, which are respectively, is selected from styrene, 2-
Methyl styrene, 4- methyl styrene, 4- t-butyl styrene, 4- ethyl styrene, 3,5- diethyl, 3,5- bis-
One or more of n-butylstyrene, 4- n-propylbenzene ethylene and 4- dodecylstyrene.
It is highly preferred that first monovinylarene and second monovinylarene be respectively be selected from styrene,
One or more of 2-methyl styrene and 4- methyl styrene.
It is further preferred that first monovinylarene and second monovinylarene are styrene.
In the present invention, for purposes of clarity, by PSIB1Conjugated diene in section is referred to as " the first conjugated diene
Hydrocarbon " and " the second conjugated diene "；By PB2Conjugated diene in section is known as " third conjugated diene ".
Block copolymer according to the present invention, first conjugated diene and third conjugated diene are respectively fourth two
Alkene, second conjugated diene are isoprene.On the basis of the total amount of the block copolymer, the knot that is formed by isoprene
The content of structure unit can be 20-30 weight %, preferably 22-28 weight %, by the content for the structural unit that butadiene is formed
It can be 30-36 weight %, preferably 32-34 weight %.In the present invention, the content of the structural unit formed by isoprene with
And the content of the structural unit formed by butadiene is measured using nuclear magnetic resonance spectroscopy.
Block copolymer according to the present invention is formed on the basis of the total amount of the block copolymer by monovinylarene
The content of structural unit can be 30-50 weight %, preferably 35-48 weight %, more preferably 38-45 weight %.This hair
In bright, the content of the structural unit formed by monovinylarene is measured using nuclear magnetic resonance spectroscopy.
Block copolymer according to the present invention, on the basis of the total amount of the block copolymer, PS sections of content is 0.8-8 weight
Measure %, preferably 1-5 weight %, PSIB1The content of section is 80-95 weight %, preferably 85-94 weight %, PB2The content of section
For 3-12 weight %, preferably 5-10 weight %.In the present invention, PS sections, PSIB1Section and PB2The content of section is true by inventory
It is fixed.
Block copolymer according to the present invention, on the basis of the total amount of the block copolymer, the side group of the block copolymer
Content can be 40-65 weight %, preferably 46-63 weight %.On the basis of the total amount of the block copolymer, as side group
The content of vinyl is preferably 20-38 weight %, more preferably 25-35 weight %；The content of acrylic as side group is preferred
For 18-35 weight %, more preferably 20-32 weight %.
Block copolymer according to the present invention, PSIB1Side group in section contains vinyl and acrylic, with the block copolymerization
On the basis of the total amount of object, the content of the vinyl as side group is preferably 19-26 weight %, the content of the acrylic as side group
Preferably 20-31 weight %.Block copolymer according to the present invention, the PB2Side group in section contains vinyl, with the block
On the basis of the total amount of copolymer, the content of the vinyl as side group is preferably 2-7 weight %.
In the present invention, term " side group content " refers on the basis of the total amount of block copolymer, contains ethylenic bond side group
The content of the structural unit derived from conjugated diene of (that is, side group contains C=C key).Ethylenic bond side group is typically from altogether
The structural unit that the structural unit and conjugated diene that yoke alkadienes is formed with 1,2- polymerization methods are formed with 3,4- polymerization methods.
For example, being directed to butadiene, the structural unit that butadiene is formed with 1,2- polymerization methods is the structural unit containing vinyl group pendant；
For isoprene, the structural unit that isoprene is formed with 1,2- polymerization methods is the structural unit containing vinyl group pendant,
The structural unit that isoprene is formed with 3,4- polymerization methods is then the structural unit containing acrylic side group.In the present invention, side
Base content is measured using nuclear magnetic resonance spectroscopy.
The number-average molecular weight of block copolymer according to the present invention, the block copolymer can be according to the block copolymer
Specifically used occasion is selected.In a preferred embodiment, the number-average molecular weight (M of the block copolymern) preferably
It is 10 × 104-25×104, more preferably 14 × 104-22×104.It is especially suitable according to the block copolymer of the preferred embodiment
It is used in as damping material and/or sound-absorbing material.Block copolymer according to the present invention, the molecular weight point of the block copolymer
Cloth index (Mw/Mn) it can be 1.2-2.5, preferably 1.8-2.In the present invention, molecular weight and molecualr weight distribution index is using solidifying
Glue penetration chromatography is measured using monodisperse polystyrene as standard items.
Block copolymer according to the present invention, the block copolymer can be prepared using method comprising the following steps:
(1) under the first anionic polymerization conditions, in the presence of organic lithium initiator, the first monovinylarene is existed
Polymerize in solvent, the condition of the polymerization make first monovinylarene total conversion be 99 weight % with
On；
(2) under the second anionic polymerization conditions, mixture and the second monovinylarene that step (1) is obtained,
One conjugated diene, the second conjugated diene and structure regulator contact are polymerize, and the condition of the polymerization makes described the
Two monovinylarenes, first conjugated diene and the second conjugated diene hydrocarbon conversion rate are 99 weight % or more；
(3) under third anionic polymerization conditions, mixture that step (2) obtains is contacted with third conjugated diene into
Row polymerization, the condition of the polymerization make the conversion ratio of the third conjugated diene be 99 weight % or more.
First monovinylarene, the second monovinylarene, the first conjugated diene, the second conjugated diene and
Third conjugated diene can be selected according to the composition of expected block copolymer, be become with being able to satisfy previously described group
It is quasi-.It is well known to those skilled in the art according to the method that expected copolymer forms the dosage for determining monomer, herein no longer in detail
It states.
In step (1), the dosage of the organic lithium initiator is can make the molecular weight of the block copolymer finally prepared
Subject to meeting the requirements, such as previously described molecular weight.Specifically, in step (1), relative to the first monovinylarene of 1g,
The dosage of the organic lithium initiator can be 0.05-1mmol, preferably 0.08-0.8mmol, the organic lithium initiator with
Elemental lithium meter.The dosage of the organic lithium initiator refers to the use of the organo-lithium compound as initiator initiated polymerization
Amount, is not included in front of being polymerize, for removing the organo-lithium compound of the impurity in polymerization system.
The organic lithium initiator can gather for the common various monovinylarenes that can cause in anionic polymerisation field
The organo monolithium compounds of conjunction or organic two-lithium compound, are not particularly limited.The organic lithium initiator is preferably organic list
Lithium compound, more preferably Formula II compound represented,
R2Li (Formula II)
In Formula II, R2For C1-C6Alkyl, C3-C12Naphthenic base, C7-C14Aralkyl or C6-C12Aryl.
The C1-C6Alkyl include C1-C6Straight chained alkyl and C3-C6Branched alkyl, specific example may include
But it is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, uncle
Amyl, neopentyl and n-hexyl.
The C3-C12The specific example of naphthenic base can include but is not limited to: cyclopropyl, cyclopenta, cyclohexyl, 4- first
Butylcyclohexyl, 4- ethylcyclohexyl, 4- n-propyl cyclohexyl and 4- normal-butyl cyclohexyl.
The C7-C14The specific example of aralkyl can include but is not limited to: phenyl methyl, phenylethyl, phenyl are just
Propyl, phenyl normal-butyl, phenyl t-butyl, propyloxy phenyl base, phenyl n-pentyl and phenyl normal-butyl.
The C6-C12The specific example of aryl can include but is not limited to: phenyl, naphthalene, 4- aminomethyl phenyl and 4- second
Base phenyl.
The specific example of the organic lithium initiator can include but is not limited to: ethyl-lithium, n-propyl lithium, isopropyl lithium,
N-BuLi, s-butyl lithium, tert-butyl lithium, n-pentyl lithium, hexyllithium, cyclohexyl lithium, phenyl lithium, 2- naphthalene lithium, 4- butyl
One or more of phenyl lithium, 4- tolyl lithium and 4- butylcyclohexyl lithium.Preferably, the organic lithium initiator is
N-BuLi and/or s-butyl lithium.It is highly preferred that the organic lithium initiator is n-BuLi.
The structure regulator can be the common structure regulator in anionic polymerisation field.Generally, the structure tune
Saving agent can be one or more of ether type structure regulator, amine type structure regulator and alcohol salt form structure regulator.
Specifically, the structure regulator can be ether, butyl oxide, tetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, four
Tetrahydrofurfuryl ethylether, tetrahydrofurfuryl butyl ether, 2,2- (double tetrahydrofuran base) propane, dioxane, crown ether, triethylamine, tetramethyl
One or more of base ethylenediamine, hexamethylphosphoramide, potassium tert-butoxide, tert-pentyl alcohol potassium and potassium lauryl.In one kind
In preferred embodiment, the structure regulator is preferably 2,2- (double tetrahydrofuran base) propane.
The dosage of the structure regulator can make appropriate choice according to specific polymerizing condition.Generally, described
The molar ratio of structure regulator and the organic lithium initiator can be 0.1-35:1, and the organic lithium initiator is with elemental lithium
Meter.When the structure regulator is 2,2- (double tetrahydrofuran base) propane, the structure regulator and the organolithium cause
The molar ratio of agent is preferably 0.5-5:1, more preferably 0.8-3:1, further preferably 1-2:1, the organic lithium initiator with
Elemental lithium meter.
The solvent can for it is various can as reaction media and make to react carried out under solution polymerization condition it is organic
Substance, such as can be hydrocarbon solvent.The hydrocarbon solvent can selected from hexamethylene, n-hexane, pentane, normal heptane, benzene and
One or more of raffinate oil.Described raffinate oil is catalytic reformate in petroleum refining process, rich in aromatic hydrocarbons
The remaining distillate after extracting aromatic hydrocarbons.In addition, the solvent can be used alone, can also be used in mixed way.A kind of preferred
Embodiment in, the solvent be hexamethylene and n-hexane mixture.According to the preferred embodiment, hexamethylene and just
The weight ratio of hexane is preferably 4-9:1.
The dosage of the solvent is not particularly limited, and can be the conventional amount used of this field.Generally, in step (1),
The dosage of the solvent makes the concentration of total polymerization monomer be 12-16 weight %.
Step (1), step (2) and step (3) can carry out under the conditions of conventional anionic polymerisation.Generally,
In step (1), the temperature of the polymerization can be 35-80 DEG C, preferably 40-60 DEG C；In step (2) and (3), the polymerization
Temperature can be 60-95 DEG C, preferably 65-90 DEG C, more preferably 70-80 DEG C.Step (1), step (2) and step (3)
In, the duration of the polymerization, which is subject to, can make the conversion ratio for the monomer being polymerize in each step meet the requirements.Generally
Ground, in step (1), step (2) and step (3), the duration of the polymerization respectively can be 10-60min, preferably respectively
For 10-30min.
According to the second aspect of the invention, the present invention provides a kind of block copolymer composition, the block copolymers
Composition is obtained from being coupled block copolymer described in first aspect of the present invention with coupling agent.
Block copolymer composition according to the present invention is coupled the polymer of formation on the basis of the total amount of the composition
Content can be 40-90 weight %, preferably 45-75 weight %, more preferably 50-70 weight %, further preferably
54-65 weight %；After coupling the content of remaining block copolymer can be 10-60 weight %, preferably 25-55 weight %,
More preferably 30-50 weight %, further preferably 35-46 weight %.
The polymer that the coupling is formed refers to the polymer for being reacted and being formed with coupling agent；It is remaining after the coupling
Block copolymer refer in mixture that coupling obtains, the block copolymer not reacted with coupling agent；With block copolymer group
On the basis of the total amount for closing object, the content for the polymer that the coupling is formed is referred to as coupling efficiency.
In the present invention, remaining block after the content (that is, coupling efficiency) and coupling of the polymer that the coupling is formed
The content of copolymer is measured using gel permeation chromatography.Specific test method are as follows: the mixture for obtaining coupling carries out GPC points
Analysis, the peak area for being coupled the polymer of formation and remaining block copolymerization after the peak area of the polymer of coupling formation and coupling
The ratio of the sum of the peak area of object is the content (that is, coupling efficiency) for the polymer that coupling is formed.
The coupling agent can be the conventional selection of this field.Specifically, the coupling agent can be divinylbenzene, two
Dimethyl dichlorosilane (DMCS), methyl trichlorosilane, diethyl oxalate, tetravinyl silane, silicon tetrachloride, tin tetrachloride and to benzene two
One or more of formic acid dimethyl ester；Preferably tin tetrachloride.
The block copolymer can be coupled under normal conditions with coupling agent, to obtain the composition.
It generally, can be by the block copolymer and coupling agent in 20-95 DEG C, preferably 65-90 DEG C, more preferable 70-80 DEG C of temperature
Under contacted.It, can be in step (3) when preparing the block copolymer using method described in first aspect of the present invention
After the completion of polymerization reaction, coupling agent is added in the mixture that obtains to step (3), carries out coupling reaction, to obtain according to this
The block copolymer composition of invention.
Block copolymer composition according to the present invention can also be total to assign block containing one or more kinds of auxiliary agents
The new performance of ionomer compositions and/or the performance for improving block copolymer composition.
Specifically, the auxiliary agent may include anti-aging agent.The type of the anti-aging agent is not particularly limited in the present invention,
It can be conventional selection, for example, the anti-aging agent can be phenols and/or amines antioxidants.Specifically, the anti-aging agent can be with
For 4,6- dioctyl thiomethyl o-cresol, four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, Asia
Tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester, 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid stearyl, bis- uncle of 2,6-
One or both of butyl paracresol, tert-butyl catechol and 2,2 '-methylene-bis- (4- methyl-6-tert-butylphenols)
More than.The dosage of the anti-aging agent can be the conventional amount used of this field.For example, relative to 100 parts of block copolymer groups
Object is closed, the dosage of the anti-aging agent can be 0.005-2 parts by weight, preferably 0.1-1 parts by weight.
According to the third aspect of the present invention, the present invention provides a kind of vulcanized rubber, which is will be of the invention
Block copolymer composition described in block copolymer described in first aspect or the second aspect of the present invention is vulcanized
Obtained from.
The vulcanized rubber can be by by the monovinylarene-conjugated diene block copolymer or block copolymerization
Compositions are mixed with vulcanizing agent, and are vulcanized and obtained.The vulcanizing agent can make single ethylene to be commonly various
Arene-conjugated diene block copolymers or block copolymer composition crosslink reaction, form space network
Substance.Specifically, the vulcanizing agent can be for selected from sulphur, selenium, tellurium, benzoyl peroxide, urethanes and 2,5- bis-
One or more of methyl -2,5- two (t-butylperoxy) hexane.
The dosage of the vulcanizing agent can make appropriate choice according to the application of vulcanized rubber.Generally, relatively
The block copolymer described in 100 parts by weight or the block copolymer composition, the dosage of the vulcanizing agent can be 1-3 weight
Part, thus obtained vulcanized rubber not only intensity with higher, but also toughness with higher.
By monovinylarene-conjugated diene block copolymer of the invention, the block copolymer composition or
The material that the vulcanized rubber is formed has well over a wide temperature range (generally 0 DEG C to 70 DEG C, preferably 5-66 DEG C)
Damping capacity, be suitable for damping material or sound-absorbing material, be particularly suitable as in room temperature and temperature above room temperature condition
The lower damping material or sound-absorbing material used.By monovinylarene-conjugated diene block copolymer of the invention, described embedding
Section copolymer compositions or the vulcanized rubber formed material, by dynamic viscoelasticity spectrum measurement the loss varied with temperature because
The half-peak breadth of sub (that is, tan δ) curve is 40 DEG C or more (such as 45-55 DEG C), and the half-peak breadth refers to that tan δ is maximum value
Difference when half between corresponding two temperature.
According to the fourth aspect of the present invention, the present invention provides monovinylarene-conjugated dienes according to the present invention
The application of hydrocarbon block copolymer, block copolymer composition or vulcanized rubber as damping material or sound-absorbing material.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, number-average molecular weight (Mn), molecular weight distributing index (Mw/Mn) and coupling efficiency adopt
With gel permeation chromatograph (GPC) measurement of the model ALLIANCE 2690 of WATERS company, the U.S., wherein with tetrahydro furan
(THF) is muttered as mobile phase, using Narrow distribution polystyrene as standard specimen, column temperature is 25 DEG C.
In following embodiment and comparative example, the microstructure of polymer uses the model purchased from Switzerland Bruker company
The nuclear magnetic resonance chemical analyser of AVANCE DRX 400MHz is measured.Test condition are as follows:1The resonant frequency of H core is 400MHz,
Spectrum width is 2747.253Hz, and pulse width is 5.0 μ s, and data point 16K, scanning times are 16 times；Sample pipe diameter is 5mm,
Polymer samples deuterated chloroform (CDCl3) solution for being made into that mass fraction is 2-3% is dissolved, with the chemistry of tetramethylsilane
Displacement is that 0ppm is calibrated.Wherein St% indicates the content of the structural unit formed in polymer by styrene, IP% table
Show the content of the structural unit formed in polymer by isoprene, BD% indicates the structure list formed in polymer by butadiene
The content of member, BSt% indicate the content of styrene block in polymer, and " styrene block " refers to the structural unit in the block
It is derived from styrene, and the number of structural unit is 5 or more in the block.
In following embodiment and comparative example, fissipation factor uses gluing for the model DMA-2980 purchased from U.S. TA company
Play spectrometer measurement, wherein frequency 2Hz, heating rate are 5 DEG C/min, and Range of measuring temp is -120 DEG C to 100 DEG C, sample
Size is 40mm × 5mm × 1mm, is tested using three-point bending mode.When half-peak breadth refers to that tan δ is the half of maximum value
Difference between corresponding two temperature.
In following embodiment and comparative example, mechanical property uses the model SHIMADZU AG-20KNG's of Japanese Shimadzu
Puller system, the measurement of the method according to specified in GB/T528-1998, the sample used is I type sample.
In following embodiment and comparative example, the sample for measuring fissipation factor and mechanical property is according to GB/T8656-
A series formula in 1998 is vulcanized and is prepared, and it is 50 in roller temperature that conditions of vulcanization, which includes: raw rubber using mill mixing,
It is kneaded at ± 5 DEG C；The temperature of vulcanization is 145 DEG C, and pressure is 10MPa or more, and vulcanization time is 35 minutes.
In following embodiment and comparative example, the vulcanization characteristics of vulcanized rubber uses the GT- of the high Inland Steel's production of TaiWan, China
M2000A type is measured without rotor vulcameter according to method specified in GB/T16584-1996.
Embodiment 1-5 is for illustrating the present invention.
Embodiment 1
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 6.24g styrene, first kill with n-butyl lithium initiator it is miscellaneous, then will be warm
Degree is increased to 50 DEG C, and 2.10mmol n-BuLi is added and causes first segment polymerization reaction, is formed the first homopolymerization section (that is, PS sections).
React 10min after, into reaction kettle be added 4.20mmol 2,2- (double tetrahydrofuran base) propane, 114.80g styrene,
86.12g butadiene and 86.12g isoprene carry out second segment polymerization reaction, form random copolymerization section (that is, PSIB1Section), instead
It is 75 DEG C by temperature control during answering.After reacting 30min, it is poly- that 18.72g butadiene progress third section is added into reaction kettle
Reaction is closed, forms the second homopolymerization section (that is, PB2Section), it is 70 DEG C by temperature control in reaction process.After reacting 10min, to anti-
It answers and adds 0.462mmol tin tetrachloride in kettle, carry out coupling reaction.After reacting 40min, 0.4g isopropanol is added and terminates reaction,
2.5g anti-aging agent 1520 (Ciba, Switzerland product) is added later.
Obtained glue obtains monovinylarene of the invention-conjugated diene block copolymerization after water vapor accumulation
Compositions.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Comparative example 1
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio), 124.80g styrene, 93.60g isoprene and 93.60g butadiene, then
4.02mmol 2 is added, 2- (double tetrahydrofuran base) propane first kill with n-butyl lithium initiator miscellaneous, then increases temperature
To 50 DEG C, 2.01mmol n-BuLi initiated polymerization is added.After reacting 30min, 0.442mmol tetra- is added into reaction kettle
Stannic chloride.After reacting 30min, 0.4g isopropanol is added and terminates reaction, (the Switzerland's vapour Bagong of 2.5g anti-aging agent 1520 is added later
Take charge of product).
Obtained glue obtains monovinylarene-conjugated diene copolymer composition after water vapor accumulation.It produces
Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Comparative example 2
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio), 124.04g styrene, 86.12g butadiene, 86.12g isoprene and
4.30mmol 2,2- (double tetrahydrofuran base) propane, first kill with n-butyl lithium initiator miscellaneous, raises the temperature to 50 DEG C,
2.15mmol n-BuLi is added and causes first segment polymerization reaction, forms random copolymerization section.After reacting 30min, into reaction kettle
18.72g butadiene is added and carries out second segment polymerization reaction, forms the second homopolymerization section, is 70 by temperature control in reaction process
℃.After reacting 10min, 0.473mmol tin tetrachloride is added into reaction kettle.After reacting 40min, it is whole that 0.4g isopropanol is added
It only reacts, 2.5g anti-aging agent 1520 (Ciba, Switzerland product) is added later.
Obtained glue obtains monovinylarene-conjugated diene copolymer composition after water vapor accumulation.It produces
Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Comparative example 3
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 6.24g styrene, first kill with n-butyl lithium initiator it is miscellaneous, by temperature liter
Up to 50 DEG C, 2.03mmol n-BuLi is added and causes first segment polymerization reaction, forms the first homopolymerization section.After reacting 10min, to
Be added in reaction kettle 4.06mmol 2,2- (double tetrahydrofuran base) propane, 114.80g styrene, 104.84g butadiene and
86.12g isoprene carries out second segment polymerization reaction, forms random copolymerization section, is 75 DEG C by temperature control in reaction process.
After reacting 30min, 0.447mmol tin tetrachloride is added into reaction kettle.After reacting 40min, 0.4g isopropanol is added and terminates instead
It answers, 2.5g anti-aging agent 1520 (Ciba, Switzerland product) is added later.
Obtained glue obtains monovinylarene-conjugated diene copolymer composition after water vapor accumulation.It produces
Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Comparative example 4
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 6.24g styrene, first kill with n-butyl lithium initiator it is miscellaneous, then will be warm
Degree is increased to 50 DEG C, and 2.10mmol n-BuLi is added and causes first segment polymerization reaction, forms the first homopolymerization section.React 10min
Afterwards, 4.20mmol 2,2- (double tetrahydrofuran base) propane, 114.80g styrene and 172.24g isoamyl two are added into reaction kettle
Alkene carries out second segment polymerization reaction, forms random copolymerization section, is 75 DEG C by temperature control in reaction process.After reacting 30min,
18.72g butadiene is added into reaction kettle and carries out third section polymerization reaction, the second homopolymerization section is formed, in reaction process, by temperature
Control is 70 DEG C.After reacting 10min, 0.462mmol tin tetrachloride is added into reaction kettle, carries out coupling reaction.Reaction
After 40min, 0.4g isopropanol is added and terminates reaction, 2.5g anti-aging agent 1520 (Ciba, Switzerland product) is added later.
Obtained glue obtains monovinylarene-conjugated diene block copolymer combination after water vapor accumulation
Object.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Comparative example 5
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 6.24g styrene, first kill with n-butyl lithium initiator it is miscellaneous, then will be warm
Degree is increased to 50 DEG C, and 2.10mmol n-BuLi is added and causes first segment polymerization reaction, forms the first homopolymerization section.React 10min
Afterwards, 4.20mmol 2,2- (double tetrahydrofuran base) propane, 114.80g styrene and 172.24g butadiene are added into reaction kettle
Second segment polymerization reaction is carried out, random copolymerization section is formed, is 75 DEG C by temperature control in reaction process.After reacting 30min, to
18.72g butadiene is added in reaction kettle and carries out third section polymerization reaction, forms the second homopolymerization section, in reaction process, by temperature control
It is made as 70 DEG C.After reacting 10min, 0.462mmol tin tetrachloride is added into reaction kettle, carries out coupling reaction.React 40min
Afterwards, 0.4g isopropanol is added and terminates reaction, 2.5g anti-aging agent 1520 (Ciba, Switzerland product) is added later.
Obtained glue obtains monovinylarene-conjugated diene block copolymer combination after water vapor accumulation
Object.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Comparative example 6
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 6.24g styrene, first kill with n-butyl lithium initiator it is miscellaneous, then will be warm
Degree is increased to 50 DEG C, and 2.10mmol n-BuLi is added and causes first segment polymerization reaction, forms the first homopolymerization section.React 10min
Afterwards, into reaction kettle be added 4.20mmol 2,2- (double tetrahydrofuran base) propane, 114.80g styrene, 86.12g butadiene and
86.12g isoprene carries out second segment polymerization reaction, forms random copolymerization section, is 75 DEG C by temperature control in reaction process.
After reacting 30min, 18.72g isoprene is added into reaction kettle and carries out third section polymerization reaction, forms the second homopolymerization section, instead
It is 70 DEG C by temperature control during answering.After reacting 10min, 0.462mmol tin tetrachloride is added into reaction kettle, is carried out even
Connection reaction.After reacting 40min, 0.4g isopropanol is added and terminates reaction, (the Switzerland's vapour Bagong of 2.5g anti-aging agent 1520 is added later
Take charge of product).
Obtained glue obtains monovinylarene-conjugated diene block copolymer combination after water vapor accumulation
Object.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Embodiment 2
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 90/10, mass ratio) and 12.48g styrene, first kill with n-butyl lithium initiator miscellaneous, then will
Temperature is increased to 55 DEG C, and 2.04mmol n-BuLi is added and causes first segment polymerization reaction, forms the first homopolymerization section (that is, PS
Section).React 12min after, into reaction kettle be added 3.67mmol 2,2- (double tetrahydrofuran base) propane, 122.15g styrene,
74.65g butadiene and 74.65g isoprene carry out second segment polymerization reaction, form random copolymerization section (that is, PSIB1Section), instead
It is 80 DEG C by temperature control during answering.After reacting 25min, it is poly- that 28.10g butadiene progress third section is added into reaction kettle
Reaction is closed, forms the second homopolymerization section (that is, PB2Section), it is 75 DEG C by temperature control in reaction process.After reacting 12min, to anti-
It answers and adds 0.449mmol tin tetrachloride in kettle.After reacting 40min, 0.4g isopropanol is added and terminates reaction, it is anti-that 2.5g is added later
Old agent 1520 (Ciba, Switzerland product).
Obtained glue obtains monovinylarene of the invention-conjugated diene block copolymerization after water vapor accumulation
Compositions.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Embodiment 3
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 3.12g styrene, first kill with n-butyl lithium initiator it is miscellaneous, by temperature liter
Up to 50 DEG C, 1.92mmol n-BuLi is added and causes first segment polymerization reaction, is formed the first homopolymerization section (that is, PS sections).Reaction
After 10min, 2.88mmol 2,2- (double tetrahydrofuran base) propane, 123.18g styrene, 85.05g fourth are added into reaction kettle
Diene and 85.05g isoprene carry out second segment polymerization reaction, form random copolymerization section (that is, PSIB1Section), reaction process
In, it is 75 DEG C by temperature control.After reacting 30min, 15.60g butadiene is added into reaction kettle and carries out third section polymerization reaction,
The second homopolymerization section is formed (that is, PB2Section), it is 70 DEG C by temperature control in reaction process.After reacting 10min, add into reaction kettle
Add 0.422mmol tin tetrachloride.After reacting 40min, 0.4g isopropanol is added and terminates reaction, 2.5g anti-aging agent 1520 is added later
(Ciba, Switzerland product).
Obtained glue obtains monovinylarene of the invention-conjugated diene block copolymerization after water vapor accumulation
Compositions.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Embodiment 4
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 9.36g styrene, first kill with n-butyl lithium initiator it is miscellaneous, then will be warm
Degree is increased to 50 DEG C, and 1.71mmol n-BuLi is added and causes first segment polymerization reaction, is formed the first homopolymerization section (that is, PS sections).
React 10min after, into reaction kettle be added 2.05mmol 2,2- (double tetrahydrofuran base) propane, 119.40g styrene,
79.14g butadiene and 79.14g isoprene carry out second segment polymerization reaction, form random copolymerization section (that is, PSIB1Section), instead
It is 75 DEG C by temperature control during answering.After reacting 30min, it is poly- that 24.96g butadiene progress third section is added into reaction kettle
Reaction is closed, forms the second homopolymerization section (that is, PB2Section), it is 70 DEG C by temperature control in reaction process.After reacting 10min, to anti-
It answers and adds 0.376mmol tin tetrachloride in kettle.After reacting 40min, 0.4g isopropanol is added and terminates reaction, it is anti-that 2.5g is added later
Old agent 1520 (Ciba, Switzerland product).
Obtained glue obtains monovinylarene of the invention-conjugated diene block copolymerization after water vapor accumulation
Compositions.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Embodiment 5
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 15.60g styrene, first kill with n-butyl lithium initiator miscellaneous, then will
Temperature is increased to 50 DEG C, and 1.42mmol n-BuLi is added and causes first segment polymerization reaction, forms the first homopolymerization section (that is, PS
Section).React 10min after, into reaction kettle be added 1.42mmol 2,2- (double tetrahydrofuran base) propane, 124.64g styrene,
70.28g butadiene and 70.28g isoprene carry out second segment polymerization reaction, form random copolymerization section (that is, PSIB1Section), instead
It is 75 DEG C by temperature control during answering.After reacting 30min, it is poly- that 31.20g butadiene progress third section is added into reaction kettle
Reaction is closed, forms the second homopolymerization section (that is, PB2Section), it is 70 DEG C by temperature control in reaction process.After reacting 10min, to anti-
It answers and adds 0.312mmol tin tetrachloride in kettle.After reacting 40min, 0.4g isopropanol is added and terminates reaction, it is anti-that 2.5g is added later
Old agent 1520 (Ciba, Switzerland product).
Obtained glue obtains monovinylarene of the invention-conjugated diene block copolymerization after water vapor accumulation
Compositions.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
Comparative example 7
In 5 liters of stainless steel stirred autoclaves, high pure nitrogen protection under, be added 2288g mixed solvent (hexamethylene with
The mixed liquor of n-hexane: 82/18, mass ratio) and 1.56g styrene, first kill with n-butyl lithium initiator it is miscellaneous, then will be warm
Degree is increased to 50 DEG C, and 2.13mmol n-BuLi is added and causes first segment polymerization reaction, forms the first homopolymerization section.React 10min
Afterwards, into reaction kettle be added 1.07mmol 2,2- (double tetrahydrofuran base) propane, 72.93g styrene, 109.4g butadiene and
109.4g isoprene carries out second segment polymerization reaction, forms random copolymerization section, is 75 DEG C by temperature control in reaction process.
After reacting 30min, 18.72g butadiene is added into reaction kettle and carries out third section polymerization reaction, forms the second homopolymerization section, reaction
It in the process, is 70 DEG C by temperature control.After reacting 10min, 0.469mmol tin tetrachloride is added into reaction kettle.React 40min
Afterwards, 0.4g isopropanol is added and terminates reaction, 2.5g anti-aging agent 1520 (Ciba, Switzerland product) is added later.
Obtained glue obtains monovinylarene-conjugated diene block copolymer combination after water vapor accumulation
Object.Molecular weight, microstructure, physical mechanical property and the dynamic mechanical data of product are shown in Table 1.
From the results shown in Table 1, by monovinylarene according to the present invention-conjugated diene copolymer composition
Vulcanize obtained material, not only there is good mechanical property, but also the loss varied with temperature measured by dynamic viscoelasticity spectrum
The half-peak breadth of factor curve is 45 DEG C or more, thus is suitable for damping material or sound-absorbing material.
Specifically, the half-peak breadth of the material formed by block copolymer of the invention prepared by embodiment 1 is 52.8 DEG C,
And the half-peak breadth of the material formed by random copolymer prepared by comparative example 1 is only 36.5 DEG C, the diblock prepared by comparative example 2
The half-peak breadth of material made from copolymer is also only 40.9 DEG C, material made from the diblock copolymer prepared as comparative example 3
Half-peak breadth is also only 40.0 DEG C.
Embodiment 1- embodiment 5 is compared with comparative example 7, it can be seen that although in polymer structural unit company
It is identical to connect mode, but if in copolymer styrene block content and side group structural content not within the scope of the present invention when,
Also it is difficult to obtain the material that half-peak breadth is 40 DEG C or more.Specifically, the half-peak breadth of material made from embodiment 1 to embodiment 5 is equal
Greater than 45 DEG C, and the half-peak breadth of material made from comparative example 4 is 32.9 DEG C.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, two or more simple variants, including each technical characteristic can be carried out to technical solution of the present invention to appoint
What other suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination,
It belongs to the scope of protection of the present invention.
Claims (19)
1. a kind of monovinylarene-conjugated diene block copolymer, the structural unit in the block copolymer presses PS-
PSIB1-PB2Mode connect, wherein
A, PS sections are the homopolymerization section formed by the first monovinylarene；
b、PSIB1Section is random total to be formed by the second monovinylarene, the first conjugated diene and the second conjugated diene
Poly- section；
c、PB2Section is the homopolymerization section formed by third conjugated diene；
D, on the basis of the total amount of the block copolymer, PS sections of content is 0.8-8 weight %, PSIB1The content of section is 80-95
Weight %, PB2The content of section is 3-12 weight %, and the content of the structural unit formed by monovinylarene is 30-50 weight
% is measured, the side group content in the block copolymer is 40-65 weight %；And
E, first conjugated diene and the third conjugated diene are respectively butadiene, and second conjugated diene is
Isoprene, on the basis of the total amount of the block copolymer, the content of the structural unit formed by butadiene is 30-36 weight
% is measured, the content of the structural unit formed by isoprene is 20-30 weight %.
2. block copolymer according to claim 1, wherein on the basis of the total amount of the block copolymer, PS sections contain
Amount is 1-5 weight %, PSIB1The content of section is 85-94 weight %, PB2The content of section is 5-10 weight %.
3. block copolymer according to claim 1 or 2, wherein the structural unit formed by monovinylarene contains
Amount is 35-48 weight %, preferably 38-45 weight %.
4. block copolymer described in any one of -3 according to claim 1, wherein the side group content in the block copolymer
For 46-63 weight %；
Preferably, on the basis of the total amount of the block copolymer, the content of the vinyl as side group is 20-38 weight %, excellent
It is selected as 25-35 weight %.
5. block copolymer described in any one of -4 according to claim 1, wherein using the total amount of the block copolymer as base
Standard, PSIB1Duan Zhong, the content of the vinyl as side group are 19-26 weight %, and the content of the acrylic as side group is 20-
31 weight %.
6. block copolymer described in any one of -5 according to claim 1, wherein using the total amount of the block copolymer as base
Standard, PB2Duan Zhong, the content of the vinyl as side group are 2-7 weight %.
7. block copolymer described in any one of -6 according to claim 1, wherein first monovinylarene and institute
It is identical or different to state the second monovinylarene, is respectively selected from one or more of Formulas I compound represented,
In Formulas I, R1For C6-C20Substituted or unsubstituted aryl；
Preferably, the monovinylarene is styrene.
8. block copolymer according to any one of claims 1-7, wherein the number-average molecular weight of the block copolymer
It is 10 × 104-25×104, preferably 14 × 104-22×104。
9. block copolymer described in any one of -8 according to claim 1, wherein it includes following that the block copolymer, which uses,
It is prepared by the method for step:
(1) under the first anionic polymerization conditions, in the presence of organic lithium initiator, by the first monovinylarene in solvent
In polymerize, the condition of the polymerization make first monovinylarene total conversion be 99 weight % or more；
(2) mixture and the second monovinylarene that step (1) is obtained, first total under the second anionic polymerization conditions
Yoke alkadienes, the second conjugated diene and structure regulator contact are polymerize, and the condition of the polymerization makes second list
Vinyl-arene, first conjugated diene and the second conjugated diene hydrocarbon conversion rate are 99 weight % or more；
(3) under third anionic polymerization conditions, the mixture that step (2) obtains is contacted with third conjugated diene and is gathered
It closes, the condition of the polymerization makes the conversion ratio of the third conjugated diene be 99 weight % or more.
10. block copolymer according to claim 9, wherein in step (1), relative to the first monovinylarene of 1g,
The dosage of the organic lithium initiator is 0.05-1mmol, and preferably 0.08-0.8mmol, the organic lithium initiator is with lithium member
Element meter.
11. block copolymer according to claim 9, wherein the structure regulator and the organic lithium initiator
Molar ratio is 0.1-35:1, and the organic lithium initiator is in terms of elemental lithium.
12. the block copolymer according to claim 9 or 11, wherein the structure regulator is selected from ether type structure tune
Save one or more of agent, amine type structure regulator and alcohol salt form structure regulator, preferably 2,2- (double tetrahydrofuran
Base) propane.
13. the block copolymer according to any one of claim 9-12, wherein the organic lithium initiator is Formula II
Compound represented,
R2Li (Formula II)
In Formula II, R2For C1-C6Alkyl, C3-C12Naphthenic base, C7-C14Aralkyl or C6-C12Aryl；
Preferably, the organic lithium initiator is n-BuLi and/or s-butyl lithium.
14. block copolymer according to claim 9, wherein in step (1), the initiation temperature of the polymerization is 35-80
℃；
In step (2) and step (3), the temperature of the polymerization is respectively 60-95 DEG C.
15. a kind of block copolymer composition, which is will be described in any one of claim 1-14
Block copolymer be coupled with coupling agent obtained from.
16. block copolymer composition according to claim 15, wherein on the basis of the total amount of the composition, coupling
The content of the polymer of formation be 40-90 weight %, preferably 45-75 weight %, more preferably 50-70 weight %, further
Preferably 54-65 weight %；The content of remaining block copolymer is 10-60 weight %, preferably 25-55 weight after coupling
Measure %, more preferably 30-50 weight %, further preferably 35-46 weight %.
17. block copolymer composition according to claim 15 or 16, wherein the coupling agent be divinylbenzene,
Dimethyldichlorosilane, methyl trichlorosilane, diethyl oxalate, tetravinyl silane, tetrachloromethane, silicon tetrachloride, tetrachloro
Change one or more of tin and dimethyl terephthalate (DMT).
18. a kind of vulcanized rubber, which is by block copolymer or power described in any one of claim 1-14
Obtained from benefit requires block copolymer composition described in any one of 15-17 to be vulcanized.
19. embedding described in any one of block copolymer described in any one of claim 1-14, claim 15-17
Application of the vulcanized rubber as damping material or sound-absorbing material described in section copolymer compositions or claim 18.
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| CN113307911A (en) * | 2021-05-31 | 2021-08-27 | 大连理工大学 | Nitrogen/silicon-oxygen-containing functionalized SIBR (silicon-oxide-rubber) integrated rubber and composite material with linear coupling structure and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5096973A (en) * | 1988-02-13 | 1992-03-17 | Huels Aktiengesellschaft | Abc block copolymers based on butadiene, isoprene and styrene, process for their production and their use |
| CN1350012A (en) * | 2000-10-19 | 2002-05-22 | 中国石油化工股份有限公司 | Star-shaped butadiene, isopene and styrene block copolymer and its prepn |
| JP2004131707A (en) * | 2002-10-10 | 2004-04-30 | Kumho Petrochemical Co Ltd | Block terpolymer and method for producing the same |
| CN1640903A (en) * | 2004-01-17 | 2005-07-20 | 中国石化北京燕化石油化工股份有限公司 | Phenylethylene-isoprene/butadiene-phenylethylene ternary block copolymer and its preparation method |
| JP2010270314A (en) * | 2009-04-22 | 2010-12-02 | Bridgestone Corp | Rubber composition and tire using the same |
| CN102020757A (en) * | 2010-10-24 | 2011-04-20 | 大连理工大学 | Linear high-impact butadiene/isoprene/styrene terpolymer resin and preparation method thereof |
-
2018
- 2018-02-09 CN CN201810134989.3A patent/CN110128607B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5096973A (en) * | 1988-02-13 | 1992-03-17 | Huels Aktiengesellschaft | Abc block copolymers based on butadiene, isoprene and styrene, process for their production and their use |
| CN1350012A (en) * | 2000-10-19 | 2002-05-22 | 中国石油化工股份有限公司 | Star-shaped butadiene, isopene and styrene block copolymer and its prepn |
| JP2004131707A (en) * | 2002-10-10 | 2004-04-30 | Kumho Petrochemical Co Ltd | Block terpolymer and method for producing the same |
| CN1640903A (en) * | 2004-01-17 | 2005-07-20 | 中国石化北京燕化石油化工股份有限公司 | Phenylethylene-isoprene/butadiene-phenylethylene ternary block copolymer and its preparation method |
| JP2010270314A (en) * | 2009-04-22 | 2010-12-02 | Bridgestone Corp | Rubber composition and tire using the same |
| CN102020757A (en) * | 2010-10-24 | 2011-04-20 | 大连理工大学 | Linear high-impact butadiene/isoprene/styrene terpolymer resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113307911A (en) * | 2021-05-31 | 2021-08-27 | 大连理工大学 | Nitrogen/silicon-oxygen-containing functionalized SIBR (silicon-oxide-rubber) integrated rubber and composite material with linear coupling structure and preparation method thereof |
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