CN110372819A - A kind of conjugated diene polymer and preparation method thereof and butadiene-styrene rubber - Google Patents
A kind of conjugated diene polymer and preparation method thereof and butadiene-styrene rubber Download PDFInfo
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- CN110372819A CN110372819A CN201810330548.0A CN201810330548A CN110372819A CN 110372819 A CN110372819 A CN 110372819A CN 201810330548 A CN201810330548 A CN 201810330548A CN 110372819 A CN110372819 A CN 110372819A
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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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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Abstract
The present invention relates to rubber processing aids fields, and in particular, to a kind of conjugated diene polymer and preparation method thereof and butadiene-styrene rubber and vulcanizate.The conjugated diene polymer contains the structure and the optional structure provided by mono vinyl arenes monomer provided by conjugated diene monomer, and the side group provided by modifying agent is connected on the strand of the conjugated diene polymer.Conjugated diene polymer provided by the invention enables to white carbon black and the carbon black fine dispersion in butadiene-styrene rubber, and the particle content of bulky grain is lower in the vulcanizate of formation, convenient for providing the reinforcing effect of white carbon black and carbon black.
Description
Technical field
The present invention relates to rubber processing aids fields, and in particular, to a kind of conjugated diene polymer and its preparation side
Method and butadiene-styrene rubber.
Background technique
White carbon black can efficiently reduce the rolling resistance of tire instead of carbon black as the reinforcing agent of tire tread rubber material,
The fuel consumption of automobile is reduced, wet-sliding resistant performance is improved, but white carbon black is difficult to disperse in non-polar rubber, so that white carbon black exists
The filling of big deal is difficult in rubber.In order to improve dispersion of the white carbon black in rubber, people have done a large amount of work, such as logical
It crosses and White carbon black dispersant is added to improve dispersion of the white carbon black in rubber, common hard charcoal is replaced using high-dispersity white carbon black
It is black, chemical surface modification etc. directly is carried out to white carbon black, purpose is all the reunion for weakening white carbon black itself, increases it in rubber
Dispersibility in glue.But so far, the defect due to white carbon black in terms of electrostatic conduction, must be compound suitable in tire
Carbon black, so tire still uses white carbon black and carbon black to mix common reinforced rubber matrix, then find a kind of can promote simultaneously
The processing aid that white carbon black and carbon black disperse in rubber is just particularly important.
Summary of the invention
The purpose of the present invention is to provide the conjugation two that one kind can promote white carbon black and the carbon black fine dispersion in rubber
Olefin polymer and preparation method thereof and butadiene-styrene rubber.
To achieve the goals above, one aspect of the present invention provides a kind of conjugated diene polymer, and the conjugated diene is poly-
It closes object and the structure and the optional structure provided by mono vinyl arenes monomer provided by conjugated diene monomer is provided, and is described
The side group provided by modifying agent is provided on the strand of conjugated diene polymer；
Wherein, with the gross weight of the structure and the structure provided by mono vinyl arenes monomer that are provided by conjugated diene monomer
It should be 70-100 weight % by the content for the structure that conjugated diene monomer provides on the basis of amount, it should be by monovinylarene list
The content for the structure that body provides is 0-30 weight %；
On the basis of the total content of the conjugated diene polymer, being mentioned by conjugated diene monomer containing unsaturated side group
The content of the structure of confession is 10-75 weight %, and the unsaturation side group is provided by the conjugated diene monomer；
The number-average molecular weight of the conjugated diene polymer is 20,000-5 ten thousand；
The modifying agent is one of formula (1) compound represented or a variety of；
Formula (1)
Wherein, R1-R3It is each independently the alkyl of H, C1-C6 or is not present；Alternatively, R1And R2Cyclization is at aromatic rings
Structure；X and Y is each independently carbon, nitrogen or sulphur.
Second aspect of the present invention provides a kind of preparation method of above-mentioned conjugated diene polymer, this method comprises:
(1) in organic solvent, in the presence of organic lithium initiator and optional structure regulator, by the conjugated diene
Hydrocarbon monomer and the optional mono vinyl arenes monomer carry out anionic polymerisation；
(2) in the presence of a free-radical initiator, the product of the anionic polymerisation and the modifying agent are carried out certainly
By base polymerization reaction.
Third aspect present invention provides a kind of butadiene-styrene rubber containing above-mentioned conjugated diene polymer.
Conjugated diene polymer provided by the invention enables to white carbon black and the carbon black fine dispersion in butadiene-styrene rubber,
The particle content of bulky grain is lower in the vulcanizate of formation, convenient for providing the reinforcing effect of white carbon black and carbon black.
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.
One aspect of the present invention provides a kind of conjugated diene polymer, which contains by conjugated diene
The structure and the optional structure provided by mono vinyl arenes monomer that hydrocarbon monomer provides, and the conjugated diene polymer
The side group provided by modifying agent is provided on strand；
Wherein, with the gross weight of the structure and the structure provided by mono vinyl arenes monomer that are provided by conjugated diene monomer
It should be 70-100 weight % by the content for the structure that conjugated diene monomer provides on the basis of amount, it should be by monovinylarene list
The content for the structure that body provides is 0-30 weight %；
On the basis of the total content of the conjugated diene polymer, being mentioned by conjugated diene monomer containing unsaturated side group
The content of the structure of confession is 10-75 weight %, and the unsaturation side group is provided by the conjugated diene monomer；
The number-average molecular weight of the conjugated diene polymer is 20,000-5 ten thousand；
The modifying agent is one of formula (1) compound represented or a variety of；
Formula (1)
Wherein, R1-R3It is each independently the alkyl of H, C1-C6 or is not present；Alternatively, R1And R2Cyclization is at aromatic rings
Structure；X and Y is each independently carbon, nitrogen or sulphur.
According to the present invention, the conjugated diene polymer can be used as the dispersing aid of butadiene-styrene rubber, to promote by fourth
The dispersion of reinforcing agent i.e. white carbon black and carbon black is added to when benzene rubber system is for vulcanizate.The main chain of the conjugated diene polymer
Structure, which can be, only to be provided by conjugated diene monomer, naturally it is also possible to be by conjugated diene monomer and monovinylarene list
Body provides, it is preferable that with the total of the structure that is provided by conjugated diene monomer and the structure provided by mono vinyl arenes monomer
It should be 80-100 weight % by the content for the structure that conjugated diene monomer provides on the basis of weight, it should be by monovinylarene
The content for the structure that monomer provides is 0-20 weight %.It is highly preferred that the backbone structure of the conjugated diene polymer is by altogether
Yoke diolefinic monomer and mono vinyl arenes monomer provide jointly, for this purpose, it is highly preferred that be provided by conjugated diene monomer
It, should the structure that be provided by conjugated diene monomer on the basis of the total weight of structure and the structure provided by mono vinyl arenes monomer
Content be 80-90 weight %, the content for the structure that should be provided by mono vinyl arenes monomer is 10-20 weight %.
According to the present invention, the conjugated diene monomer can carry out appropriateness from the various of monomer with conjugated double bond
Selection, such as can be selected from the conjugated diene monomer of C4-C6, it is preferable that the conjugated diene monomer is fourth
Diene, isoprene, 1,3-pentadiene, 1,3- hexadiene and 2, one of 3- dimethyl butadiene or a variety of, more preferably
Butadiene and/or isoprene.
In a preferred embodiment of the invention, the conjugated diene monomer is butadiene (i.e. 1,3- fourth two
Alkene).For this purpose, unsaturated vinyl group pendant can be provided when the butadiene carries out 1,2- polymerization.
In a preferred embodiment of the invention, the conjugated diene monomer is butadiene (i.e. 1,3- fourth two
Alkene) and isoprene combination, especially molar ratio be 1:0.4-0.8 butadiene and isoprene combination.For this purpose, the fourth
When diene carries out 1,2- polymerization, unsaturated vinyl group pendant can be provided；The isoprene carries out 1,2- polymerization or 3,4- is poly-
When conjunction, unsaturated side group can be provided.
According to the present invention, the mono vinyl arenes monomer typically refers to the virtue on aromatic ring with a vinyl substituent
Hydrocarbon monomer.Preferably, the mono vinyl arenes monomer is styrene, to vinyltoluene, adjacent vinyltoluene, vinyl
Toluene, α-methylstyrene, 4- t-butyl styrene, 3,5- diethyl, 3,5- di-n-butyl styrene, 4- n-propyl
One of styrene and 4- dodecylstyrene are a variety of, preferably styrene, to vinyltoluene and Alpha-Methyl benzene second
One of alkene is a variety of, more preferably styrene.
In a preferred embodiment of the invention, the conjugated diene monomer is butadiene, the list ethylene
Base aromatic monomer is styrene.
In another preferred embodiment of the invention, the conjugated diene monomer is butadiene and isoprene
Combination, the mono vinyl arenes monomer be styrene.
According to the present invention, the conjugated diene polymer also contains certain unsaturated side group, which is
It is formed when being polymerize by conjugated diene monomer with certain polymerization methods.Preferably, with the conjugated diene polymer
On the basis of total content, the content of the structure provided by conjugated diene monomer containing unsaturated side group is 25-55 weight %.
According to the present invention, the side group provided by modifying agent is provided on the strand of the conjugated diene polymer,
The side group provided by modifying agent is usually by the sulfydryl of modifying agent and the unsaturated side group of conjugated diene polymer through freedom
Base causes connection and obtains.
Wherein, in formula (1), the key that dotted line indicates can be not present, or form double bond with already present key, such as Y can
To form double bond with adjacent C, Y can also be connect in the form of singly-bound with adjacent C, but this also depends on X and Y is specifically selected
The reasonability whether atomic species and double bond selected may be present.Wherein, in R1And R2In the case that cyclization is at aromatic ring structure,
R3It is each independently the alkyl of H, C1-C6 or is not present.
Preferably, R1-R3It is each independently H, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, tert-butyl are not present；Alternatively, R1And R2Cyclization is at benzene ring structure；X is selected from nitrogen or sulphur, and Y is selected from nitrogen or carbon.
Wherein, it is highly preferred that one of described modifying agent following formula compound represented or a variety of:
(i.e. 3- sulfydryl -1,2,4- triazole),(i.e. 2- mercaptoimidazole),(i.e. 2- sulfydryl-
1,3- sulfur nitrogen indene),(i.e. 2-mercaptobenzimidazole),(i.e. methimazole),
Wherein, the content of the side group provided by modifying agent can change in a wider range, it is preferable that by conjugated diene
On the basis of the mole for the structure that hydrocarbon monomer provides, the content of the side group provided by modifying agent is 0.01-2 moles of %.
According to the present invention, the number-average molecular weight of the conjugated diene polymer needs to meet 20,000-5 ten thousand, in the conjugation
When the number-average molecular weight of diene polymer is less than 20,000, mobility is too strong, and use process is easy loss；When the conjugated diene
When the number-average molecular weight of hydrocarbon polymer is greater than 50,000, excessive rubber properties are showed, the dispersion of filler is not easy to.It is highly preferred that
The molecular weight distributing index of the conjugated diene polymer is 1-2.
Second aspect of the present invention provides a kind of preparation method of above-mentioned conjugated diene polymer, this method comprises:
(1) in organic solvent, in the presence of organic lithium initiator and optional structure regulator, by the conjugated diene
Hydrocarbon monomer and the optional mono vinyl arenes monomer carry out anionic polymerisation；
(2) in the presence of a free-radical initiator, the product of the anionic polymerisation and the modifying agent are carried out certainly
By base polymerization reaction.
According to the present invention, the conjugated diene monomer, mono vinyl arenes monomer and modifying agent are as described above
, details are not described herein by the present invention, wherein this method will make resulting conjugated diene polymer as described above
's.The dosage of the conjugated diene monomer and mono vinyl arenes monomer will so that, the resulting conjugated diene of this method is poly-
It closes in object, the total weight of the structure and the structure provided by mono vinyl arenes monomer that provided by conjugated diene monomer is base
Standard should be 70-100 weight % by the content for the structure that conjugated diene monomer provides, should be provided by mono vinyl arenes monomer
Structure content be 0-30 weight %；Preferably, with the structure that is provided by conjugated diene monomer and by monovinylarene
It should be 80-100 weight by the content for the structure that conjugated diene monomer provides on the basis of the total weight for the structure that monomer provides
% is measured, should be 0-20 weight % by the content for the structure that mono vinyl arenes monomer provides；It is highly preferred that with by conjugated diene
It, should be by conjugated diene monomer on the basis of the structure that monomer provides and the total weight by the structure of mono vinyl arenes monomer offer
The content of the structure of offer is 80-90 weight %, should be 10-20 weight by the content for the structure that mono vinyl arenes monomer provides
Measure %.
Wherein, the modifying agent dosage will so that, in the resulting conjugated diene polymer of this method, with by conjugation two
On the basis of the mole for the structure that olefinic monomer provides, the content of the side group provided by modifying agent is preferably 0.01-2 moles of %.
Wherein, the number-average molecular weight for making resulting conjugated diene polymer is 20,000-5 ten thousand by this method；So that gained
The molecular weight distributing index of conjugated diene polymer be preferably 1-2；So that in resulting conjugated diene polymer, with institute
On the basis of the total content for stating conjugated diene polymer, the structure provided by conjugated diene monomer containing unsaturated side group contains
Amount is 10-75 weight %, preferably 25-55 weight %.
According to the present invention, in step (1), anionic polymerisation will be passed through so that conjugated diene monomer and optional
The mono vinyl arenes monomer carries out initiation polymerization.Used initiator is organic lithium initiator, and the organolithium causes
Agent can be the organic lithium initiator routinely used for anionic polymerisation, and for example, organic single-lithium or double lithiums causes
Agent, preferably single organic lithium initiator.Thus, it is preferable that for the organic lithium initiator as shown in formula RLi, R is selected from alkyl, ring
Alkyl or aryl；Preferably, the organic lithium initiator is ethyl-lithium, n-propyl lithium, isopropyl lithium, n-BuLi, sec-butyl
One of lithium, n-pentyl lithium, hexyllithium, cyclohexyl lithium, phenyl lithium, benzyl lithium and naphthalene lithium are a variety of, are more preferably positive
Butyl lithium and/or s-butyl lithium.
Wherein, the dosage of the initiator can carry out appropriateness according to the molecular weight of required conjugated diene polymer
Selection, it is preferable that described on the basis of the total moles dosage of the conjugated diene monomer and the mono vinyl arenes monomer
The dosage of organic lithium initiator is 0.1-0.4mol%.
According to the present invention, in step (1), the organic solvent can be using the anti-for anionic polymerisation of this field routine
The solvent answered, such as can be one of cycloalkane, aromatic hydrocarbons, isoparaffin of C5-C7 etc. or a variety of.Preferably, step (1)
In, the organic solvent is one of benzene, toluene, n-hexane, hexamethylene, pentane and normal heptane or a variety of.The present invention couple
There is no particular limitation for the dosage of the organic solvent, as long as enabling to the anionic polymerisation successfully i.e.
It can.For example, the dosage of the organic solvent makes the total content of conjugated diene and mono vinyl arenes monomer for 5-30 weight
Measure %, preferably 8-20 weight %.
According to the present invention, the polymerization reaction of step (1) carries out under an inert atmosphere, provides the gas of such inert atmosphere
It such as can be one of nitrogen, argon gas, helium etc. or a variety of.
In the case of, according to the invention it is preferred to, in step (1), the condition of the anionic polymerisation includes: that temperature is
35-80 DEG C, preferably 40-50 DEG C；Time is 30-120min, preferably 50-100min.
According to the present invention, step (1) also carries out in the presence of structure regulator, for this purpose, preferred in one kind of the invention
In embodiment, the process of step (1) includes: by conjugated diene monomer, optional mono vinyl arenes monomer and organic molten
Agent mixing, is then added structure regulator, and carry out the anionic polymerisation in the case where organic lithium initiator is added.
Wherein, the structure regulator being used in polymerization reaction that the structure regulator can be conventional for this field, such as
It may include one of oxygen-containing, nitrogenous, sulfur-bearing and phosphorous compound or a variety of, be preferably selected from ether, butyl oxide, tetrahydro furan
Mutter, glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, crown ether, tetrahydrofurfuryl alcohol ether, tetrahydrofurfuryl alcohol butyl ether, triethylamine,
Tetramethylethylenediamine, hexamethylphosphoramide, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate potassium and benzene sulfonamide
One of sour sodium is a variety of.Such as under using tetrahydrofurfuryl alcohol ether or tetrahydrofurfuryl alcohol butyl ether, with conjugated diene described in 1000g
On the basis of the total weight of hydrocarbon monomer, mono vinyl arenes monomer and organic solvent, the dosage of the structure regulator for example can be with
For 100-550mg, preferably 120-350mg.
According to the present invention, step (2) will make the production of the anionic polymerisation in the presence of a free-radical initiator
The side group provided by modifying agent is provided on the polymer chain in object.Wherein, the modifying agent is as described above,
In, this method will make in resulting conjugated diene polymer, with the mole of the structure provided by conjugated diene monomer
On the basis of, the content of the side group provided by modifying agent is preferably 0.01-2 moles of %.
According to the present invention, the radical initiator can be properly selected from a variety of radical initiators, excellent
Selection of land, the radical initiator are one of azo type free radical initiator and peroxide radical initiator or more
Kind.Wherein, the specific example of the azo type free radical initiator for example can be different for azo-bis-iso-dimethyl, azo two
Butanimidamide, monohydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide, two ring of azo
Hexyl formonitrile HCN, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and azo two
One of different heptonitrile is a variety of.The specific example of the peroxide radical initiator for example can for hydrogen peroxide,
Ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide, benzoyl peroxide and 1,1- di-t-butyl peroxide
One of change -3,3,5- trimethyl-cyclohexane is a variety of.Preferably, the radical initiator is benzoyl peroxide, idol
One of nitrogen bis-isobutyronitrile and 1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexane are a variety of.
Wherein, the dosage of the radical initiator can change in a wider range, it is preferable that with the conjugated diene
On the basis of the total moles dosage of hydrocarbon monomer, the dosage of the radical initiator is 0.002-0.1mol%.
In the case of, according to the invention it is preferred to, the condition of the Raolical polymerizable includes: that temperature is 0-130 DEG C, pressure
For 0.05-0.5MPa, time 0.5-24h；Preferably, it is 50-100 that the condition of the Raolical polymerizable, which includes: temperature,
DEG C, pressure 0.1-0.3MPa, time 2-5h.
Third aspect present invention provides one kind and contains above-mentioned conjugated diene polymer.
According to the present invention, conjugated diene polymer of the invention is mixed in butadiene-styrene rubber using as dispersing aid, it can
To facilitate when butadiene-styrene rubber is prepared vulcanizate as base rubber, convenient for the dispersion of reinforcing agent.Wherein, the butadiene-styrene rubber can
Think the various butadiene-styrene rubber of this field routine, and can be butadiene-styrene rubber made from conventional method in that art, such as described
The preparation process of butadiene-styrene rubber includes: under an inert atmosphere, in organic solvent, and in organic lithium initiator and structure regulator
In the presence of, styrene, butadiene and optional isoprene are subjected to polymerization reaction.Wherein, the organic solvent, organolithium
Initiator and structure regulator are as described above.On the basis of the total weight of butadiene and optional isoprene, institute
The dosage for stating organic lithium initiator for example can be 0.02-0.1 weight %.Such as using tetrahydrofurfuryl alcohol ether or tetrahydrofurfuryl alcohol
Under butyl ether, on the basis of the total weight of styrene, butadiene described in 1000g, optional isoprene and organic solvent, the knot
The dosage of structure regulator for example can be 100-800mg, preferably 180-550mg.With the total weight of butadiene and isoprene
On the basis of, the dosage of the styrene for example can be 20-30 weight %.The condition of the polymerization reaction may include: that temperature is
40-80 DEG C, time 40-120min.
The number-average molecular weight of the butadiene-styrene rubber is preferably 100,000-20 ten thousand.
According to the present invention, the butadiene-styrene rubber is also possible to the rubber after coupling, such as its preparation process includes: in inertia
Under atmosphere, in organic solvent, and in the presence of organic lithium initiator and structure regulator, by styrene, butadiene and appoint
The isoprene of choosing carries out polymerization reaction, and reaction product and coupling agent are then carried out coupling reaction.It is the organic solvent, organic
The type and dosage of lithium initiator and structure regulator are as described above.Wherein, the coupling agent can be polymer
The coupling agent that preparation field routinely uses, such as can be one in more vinyl compounds, halide, ether, aldehyde, ketone, ester etc.
Kind is a variety of, is preferably selected from divinylbenzene, tetravinyl silane, tetrachloromethane, silicon tetrachloride, tin tetrachloride and terephthaldehyde
One of dimethyl phthalate is a variety of.
The Conjugate ratio of the butadiene-styrene rubber is preferably 30-70%.
According to the present invention, the conjugated diene polymer can after polymerization, or include coupling reaction
In the case where just mixed after coupling reaction with product, then by agglomerate be made butadiene-styrene rubber product.Wherein, the conjugation two
The content of olefin polymer is preferably 1-10 weight %, more preferably 2-5 weight %, on the basis of the total weight of butadiene-styrene rubber.
Butadiene-styrene rubber of the invention is when the base rubber as vulcanizate according to the method for this field routine in use, can prepare
Rubber composition, the rubber composition can contain butadiene-styrene rubber, vulcanizing agent, vulcanization accelerator, reinforcing agent and activator etc..Rubber
In glue composition the selection of each ingredient and the method that rubber composition is uniformly mixed and is vulcanized all can be this field it is normal
Rule selection, can know this those skilled in the art, will not be described in great detail herein.
The present invention will be described in detail by way of examples below.
Preparation example 1
Under High Purity Nitrogen protection, 2310g hexamethylene, 62.6g styrene and 249.8g butadiene are mixed, are then added four
(dosage relative to the total amount of the hexamethylene of 1000g, styrene and butadiene, the tetrahydrofurfuryl alcohol ether is hydrogen furfuryl alcohol ether
450mg), the n-BuLi that 1.7mmol is added at 50 DEG C causes, and reacts 60 minutes at 50 DEG C, after take half weight
The glue of amount, as butadiene-styrene rubber base fluid A1, remaining glue obtains butadiene-styrene rubber sample B1 after water vapor accumulation.
Preparation example 2
Under High Purity Nitrogen protection, by 2310g hexamethylene, 62.6g styrene, 117.8g isoprene and 127.7g butadiene
Mixing, be then added tetrahydrofurfuryl alcohol butyl ether (relative to the total amount of the hexamethylene of 1000g, styrene, isoprene and butadiene,
The dosage of the tetrahydrofurfuryl alcohol butyl ether is 210mg), the n-BuLi that 2.17mmol is added at 60 DEG C causes, and reacts at 60 DEG C
60 minutes, add the tin tetrachloride of 0.22mmol, reacted 20 minutes at 60 DEG C, after take the glue of part half weight
Liquid, as butadiene-styrene rubber base fluid A2, remaining glue obtains butadiene-styrene rubber sample B2 after water vapor accumulation.
Embodiment 1
The present embodiment is for illustrating conjugated diene polymer and preparation method thereof and butadiene-styrene rubber.
(1) under High Purity Nitrogen protection, 2010g hexamethylene, 40g styrene and 210g butadiene is mixed, are then added four
(dosage relative to the total amount of the hexamethylene of 1000g, styrene and butadiene, the tetrahydrofurfuryl alcohol ether is hydrogen furfuryl alcohol ether
150mg), it is added at 50 DEG C n-BuLi initiation reaction 60 minutes of 6.9mmol；
(2) the 3- mercapto of 0.095mmol azodiisobutyronitrile and 4.6mmol is added into step (1) resulting reaction product
Base -1,2,4- triazole react 3 hours at 75 DEG C, after obtain glue A3；
Part glue A3 is taken to be added in butadiene-styrene rubber base fluid A1, additional amount makes the conjugated diene polymer in glue A3
Weight be A1 in butadiene-styrene rubber weight 3 weight %, then by dehydrated alcohol agglomerate, obtain butadiene-styrene rubber sample B3.
Embodiment 2
The present embodiment is for illustrating conjugated diene polymer and preparation method thereof and butadiene-styrene rubber.
(1) under High Purity Nitrogen protection, 2010g hexamethylene, 50g styrene and 200g butadiene is mixed, are then added four
(dosage relative to the total amount of the hexamethylene of 1000g, styrene and butadiene, the tetrahydrofurfuryl alcohol butyl ether is hydrogen furfuryl alcohol butyl ether
350mg), it is added at 45 DEG C s-butyl lithium initiation reaction 80 minutes of 9.2mmol；
(2) the first sulphur miaow of 0.18mmol benzoyl peroxide and 6.8mmol is added into step (1) resulting reaction product
Azoles reacts 2.5 hours at 70 DEG C, after obtain glue A4；
Part glue A4 is taken to be added in butadiene-styrene rubber base fluid A1, additional amount makes the conjugated diene polymer in glue A4
Weight be A1 in butadiene-styrene rubber weight 3 weight %, then by dehydrated alcohol agglomerate, obtain butadiene-styrene rubber sample B4.
Embodiment 3
The present embodiment is for illustrating conjugated diene polymer and preparation method thereof and butadiene-styrene rubber.
(1) under High Purity Nitrogen protection, by 1988g hexamethylene, 50.4g styrene, 99.8g isoprene and 112.9g fourth two
Then tetrahydrofurfuryl alcohol butyl ether is added (relative to the total of the hexamethylene of 1000g, styrene, isoprene and butadiene in alkene mixing
Amount, the dosage of the tetrahydrofurfuryl alcohol butyl ether are 180mg), n-BuLi initiation reaction 70 minutes of 7.3mmol are added at 60 DEG C；
(2) the 2- sulfydryl-of 0.122mmol azodiisobutyronitrile and 6mmol is added into step (1) resulting reaction product
1,3- sulfur nitrogen indene reacts 3 hours at 80 DEG C, after obtain glue A5；
Part glue A5 is taken to be added in butadiene-styrene rubber base fluid A2, additional amount makes the conjugated diene of the modification in glue A5
The weight of polymer is 5 weight % of butadiene-styrene rubber weight in A2, then agglomerates by dehydrated alcohol, obtains butadiene-styrene rubber sample
B5。
Comparative example 1
According to method described in embodiment 1, the difference is that, in step (1), the amount of the initiator n-BuLi of addition is
19mmol finally obtains glue DA1；
Part glue DA1 is taken to be added in butadiene-styrene rubber base fluid A1, additional amount makes the conjugate diene polymerization in glue DA1
The weight of object is 3 weight % of butadiene-styrene rubber weight in A1, then agglomerates by dehydrated alcohol, obtains butadiene-styrene rubber sample DB1.
Comparative example 2
According to method described in embodiment 1, the difference is that, in step (1), the amount of the initiator n-BuLi of addition is
3.5mmol finally obtains glue DA2；
Part glue DA2 is taken to be added in butadiene-styrene rubber base fluid A1, additional amount makes the conjugate diene polymerization in glue DA2
The weight of object is 3 weight % of butadiene-styrene rubber weight in A1, then agglomerates by dehydrated alcohol, obtains butadiene-styrene rubber sample DB2.
Comparative example 3
According to method described in embodiment 1, unlike, in step (2), it is added without 3- sulfydryl -1,2,4- triazole, most
Glue DA3 is obtained eventually；
Part glue DA3 is taken to be added in butadiene-styrene rubber base fluid A1, additional amount makes the conjugate diene polymerization in glue DA3
The weight of object is 3 weight % of butadiene-styrene rubber weight in A1, then agglomerates by dehydrated alcohol, obtains butadiene-styrene rubber sample DB3.
Test case
The microstructure of resulting polymers (part of each glue is taken to be condensed to obtain polymer samples) uses Switzerland
The measurement of Bruker company AVANCE DRX 400MHz nuclear magnetic resonance chemical analyser, solvent is deuterated chloroform, to measure in table 1
The data of structural unit content.Wherein, butadiene structure content (weight %), isoprene structures content (weight %) and benzene second
Alkene structural content (weight %) is on the basis of butadiene structure content, isoprene structures content and styryl structures content.
Unsaturated side group content (weight %) refers on the basis of the total content of the conjugated diene polymer, containing unsaturated side group
By the content for the structure that conjugated diene monomer provides.Modifying agent side group content refers to the knot to be provided by conjugated diene monomer
On the basis of the mole of structure, by the content for the side group that modifying agent provides.
The molecular weight and coupling effect of resulting polymers (part of each glue is taken to be condensed to obtain polymer samples)
Rate is measured using U.S. WATERS company ALLIANCE2690 type gel permeation chromatograph (GPC), and THF is mobile phase, narrow ditribution
Polystyrene is standard specimen, and temperature is 25 DEG C, to measure the molecular weight data in table 1.
Filler in the vulcanizate (vulcanizate is obtained by raw rubber using mixer mixing) of gained rubber sample disperses to use
Be U.S. Alpha the test of Disper ' GRADER carbon black dispersion tester, according to " carbon black in GB/T6030-2006 rubber
With carbon black/silica dispersion quick comparison method of assessment " it is evaluated, wherein the particle size distribution such as table 2 in vulcanizate
It is shown.
Wherein, the composition of vulcanized rubber are as follows: raw rubber 100g, high wear-resistant carbon black 15g, white carbon black 55g, zinc oxide 2.5g, firmly
Resin acid 1g, antioxidant 4020 (being purchased from Shandong Sheng'Ao Chemical Co., Ltd, the same below) is 2g, and accelerant CZ (is purchased from Shanghai
It is the same below at bright and beautiful Chemical Co., Ltd.) it is 1.4g, 2,3- diphosphoglyceric acids (DPG) are 0.75g, silane coupling agent KH-Si69
(blocking Chemical Co., Ltd. purchased from Hangzhou Jesse) is 6g, sulphur 1.4g；Filler is heat-treated after being added using Haake, phase condition packet
Include: temperature is 150 DEG C, revolving speed 30rpm, time 7min；Then vulcanized, condition includes: 145 DEG C of temperature, pressure
10MPa or more, time 35min；Wherein, when raw rubber uses B1, vulcanizate DS1 is obtained；When raw rubber uses B3, vulcanized
Glue S1；When raw rubber uses B4, vulcanizate S2 is obtained；When raw rubber uses DB1, vulcanizate DS2 is obtained；When raw rubber uses DB2
When, obtain vulcanizate DS3；When raw rubber uses DB3, vulcanizate DS4 is obtained；
And the composition of vulcanized rubber are as follows: raw rubber (B2 or B4) 100g, aromatic naphtha (are purchased from the limited public affairs of Hengshui Sheng Kang chemical industry
Department) it is 15g, 8# reference black 35g, white carbon black 15g, silane coupling agent KH-Si69 are 4.8g, sulphur 1.5g, diphenylguanidine (purchase
From purchased from Shandong Sheng'Ao Chemical Co., Ltd) it is 1g, accelerator TBBS is (purchased from purchased from the limited public affairs of the holy Austria's chemical industry share in Shandong
Department) it is 1.5g, stearic acid 2g, antioxidant 4020 2g, zinc oxide 3g.Then being vulcanized, condition includes: 145 DEG C of temperature,
Pressure 10MPa or more, time 35min；Wherein, when raw rubber uses B2, vulcanizate DS5 is obtained；When raw rubber uses B5, obtain
Vulcanizate S3.
Table 1
Table 2
| Particle diameter/μm | 2.9-8.6 | 11.5-17.2 | 20.1-28.7 | 31.6-51.7 |
| S1 | 76.7% | 21.7% | 1.6% | 0.0% |
| DS1 | 47.2% | 36.1% | 15.1% | 1.6% |
| DS2 | 60.9% | 32.9% | 6.0% | 0.2% |
| DS3 | 59.9% | 32.1% | 7.2% | 0.8% |
| DS4 | 64.7% | 29.9% | 5.0% | 0.4% |
| S2 | 75.3% | 27.6% | 2.9% | 0.0% |
| S3 | 74.8% | 23.4% | 1.8% | 0.0% |
| DS5 | 41.4% | 35.9% | 19.8% | 2.9% |
Can be seen that conjugated diene polymer of the invention by the data of table 2 enables to white carbon black and carbon black to exist
Fine dispersion in butadiene-styrene rubber, the particle content of bulky grain is lower in the vulcanizate of formation, convenient for providing white carbon black and carbon black
Reinforcing effect.
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, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (15)
1. a kind of conjugated diene polymer, which is characterized in that the conjugated diene polymer contains by conjugated diene monomer
The structure of offer and the optional structure provided by mono vinyl arenes monomer, and the strand of the conjugated diene polymer
On be connected with by modifying agent provide side group；
Wherein, it is with the total weight of the structure and the structure provided by mono vinyl arenes monomer that are provided by conjugated diene monomer
Benchmark should be 70-100 weight % by the content for the structure that conjugated diene monomer provides, should be mentioned by mono vinyl arenes monomer
The content of the structure of confession is 0-30 weight %；
On the basis of the total content of the conjugated diene polymer, containing unsaturated side group by conjugated diene monomer provide
The content of structure is 10-75 weight %, and the unsaturation side group is provided by the conjugated diene monomer；
The number-average molecular weight of the conjugated diene polymer is 20,000-5 ten thousand；
The modifying agent is one of formula (1) compound represented or a variety of；
Formula (1)
Wherein, R1-R3It is each independently the alkyl of H, C1-C6 or is not present；Alternatively, R1And R2Cyclization is at aromatic ring structure；X
Carbon, nitrogen or sulphur are each independently with Y.
2. conjugated diene polymer according to claim 1, wherein with the structure that is provided by conjugated diene monomer and
On the basis of total weight by the structure of mono vinyl arenes monomer offer, the content for the structure that should be provided by conjugated diene monomer
It should be 0-20 weight % by the content for the structure that mono vinyl arenes monomer provides for 80-100 weight %；
Preferably, with the total weight of the structure and the structure provided by mono vinyl arenes monomer that are provided by conjugated diene monomer
On the basis of, it should be 80-90 weight % by the content for the structure that conjugated diene monomer provides, should be mentioned by mono vinyl arenes monomer
The content of the structure of confession is 10-20 weight %.
3. conjugated diene polymer according to claim 1 or 2, wherein the conjugated diene monomer be butadiene,
Isoprene, 1,3-pentadiene, 1,3- hexadiene and 2, one of 3- dimethyl butadiene or a variety of, preferably butadiene
And/or isoprene；
Preferably, the mono vinyl arenes monomer is styrene, to vinyltoluene, adjacent vinyltoluene, vinyl first
Benzene, α-methylstyrene, 4- t-butyl styrene, 3,5- diethyl, 3,5- di-n-butyl styrene, 4- n-propylbenzene
One of ethylene and 4- dodecylstyrene are a variety of, preferably styrene, to vinyltoluene and α-methylstyrene
One of or a variety of, more preferably styrene.
4. conjugated diene polymer described in any one of -3 according to claim 1, wherein poly- with the conjugated diene
On the basis of the total content for closing object, the content of the structure provided by conjugated diene monomer containing unsaturated side group is 25-55 weight
Measure %.
5. conjugated diene polymer described in any one of -4 according to claim 1, wherein by conjugated diene monomer
On the basis of the mole of the structure of offer, the content of the side group provided by modifying agent is 0.01-2 moles of %.
6. conjugated diene polymer according to claim 1 or 5, wherein R1-R3It is each independently H, methyl, second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl are not present；Alternatively, R1And R2Cyclization is at phenyl ring knot
Structure；X is selected from nitrogen or sulphur, and Y is selected from nitrogen or carbon；
Preferably, one of described modifying agent following formula compound represented or a variety of:
7. conjugated diene polymer described in any one of -6 according to claim 1, wherein the conjugate diene polymerization
The molecular weight distributing index of object is 1-2.
8. the preparation method of conjugated diene polymer described in a kind of any one of claim 1-7, this method comprises:
(1) in organic solvent, in the presence of organic lithium initiator and optional structure regulator, by the conjugated diene list
Body and the optional mono vinyl arenes monomer carry out anionic polymerisation；
(2) in the presence of a free-radical initiator, the product of the anionic polymerisation and the modifying agent are subjected to free radical
Polymerization reaction.
9. according to the method described in claim 8, wherein, for the organic lithium initiator as shown in formula RLi, R is selected from alkyl, cycloalkanes
Base or aryl；Preferably, the organic lithium initiator be ethyl-lithium, n-propyl lithium, isopropyl lithium, n-BuLi, s-butyl lithium,
One of n-pentyl lithium, hexyllithium, cyclohexyl lithium, phenyl lithium, benzyl lithium and naphthalene lithium are a variety of, more preferably normal-butyl
Lithium and/or s-butyl lithium；
Preferably, described on the basis of the total moles dosage of the conjugated diene monomer and the mono vinyl arenes monomer
The dosage of organic lithium initiator is 0.1-0.4mol%.
10. method according to claim 8 or claim 9, wherein the organic solvent is benzene, toluene, n-hexane, hexamethylene, just
One of pentane and normal heptane are a variety of；
Preferably, the dosage of the organic solvent makes the total of the conjugated diene monomer and the mono vinyl arenes monomer
Content is 5-30 weight %, preferably 8-20 weight %.
11. the method according to any one of claim 8-10, wherein the condition packet of the anionic polymerisation
Include: temperature is 35-80 DEG C, preferably 40-50 DEG C；Time is 30-120min, preferably 50-100min.
12. the method according to any one of claim 8-11, wherein the radical initiator is azo type free
One of base initiator and peroxide radical initiator are a variety of；
Preferably, the azo type free radical initiator is azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo
Diformamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide, azo diisopropyl imidazoline hydrochloride, azo two
One of cyanopentanoic acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile or
It is a variety of；The peroxide radical initiator is hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide
One of formyl, benzoyl peroxide and 1,1- di-tert-butyl peroxide -3,3,5- trimethyl-cyclohexane are a variety of；
Preferably, the radical initiator be benzoyl peroxide, azodiisobutyronitrile and 1, di-tert-butyl peroxide -3 1-,
One of 3,5- trimethyl-cyclohexane is a variety of；
Preferably, on the basis of the total moles dosage of the conjugated diene monomer, the dosage of the radical initiator is
0.002-0.1mol%.
13. the method according to any one of claim 8-12, wherein the condition packet of the Raolical polymerizable
Include: temperature is 0-130 DEG C, pressure 0.05-0.5MPa, time 0.5-24h.
14. a kind of butadiene-styrene rubber containing conjugated diene polymer described in any one of claim 1-7.
15. butadiene-styrene rubber according to claim 14, wherein the conjugated diene polymer containing in butadiene-styrene rubber
Amount is 1-10 weight %, preferably 2-5 weight %.
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| CN113402786A (en) * | 2020-03-16 | 2021-09-17 | 中国石油化工股份有限公司 | Modified nitrile rubber composition, mercapto triazole modified nitrile rubber composite material, and preparation method and application thereof |
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| US20120048446A1 (en) * | 2010-08-31 | 2012-03-01 | The Goodyear Tire & Rubber Company | Copolymers of conjugated triene monomers for improved filler interaction |
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