CN104558329B - A kind of diene's polymer and its preparation method and application - Google Patents
A kind of diene's polymer and its preparation method and application Download PDFInfo
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- CN104558329B CN104558329B CN201310512794.5A CN201310512794A CN104558329B CN 104558329 B CN104558329 B CN 104558329B CN 201310512794 A CN201310512794 A CN 201310512794A CN 104558329 B CN104558329 B CN 104558329B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a kind of diene's polymer and its preparation method and application.Containing at least one conjugated diene construction unit in the strand of diene's polymer, wherein, also contain formula in the strand of diene's polymer（Ⅰ）Shown silane coupler construction unit, and the number-average molecular weight of diene's polymer is 50,000 100 ten thousand；R1‑R4For C1‑C20Straight or branched alkyl or contain heteroatomic C1‑C20Straight or branched alkyl, one or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.Diene's polymer can not only be effectively improved the relation between anti-slippery and rolling resistance, can also improve in rubber mixing process due to using undesirable smell caused by silane coupler.
Description
Technical field
The present invention relates to a kind of diene's polymer, the preparation method of diene's polymer, by above-mentioned
The diene's polymer and above-mentioned diene's polymer that method is prepared should as rubber-based adhesive
With.
Background technology
In recent years, with the development of auto industry and climbing up and up for oil price, people to the security of automobile and
Energy saving is paid close attention to further, and this requires tire while with compared with high wet-sliding resistant performance, also with relatively low rolling resistance.But
It is to improve between wet-sliding resistant performance and reduction rolling resistance often it is difficult to take into account simultaneously.Therefore, according to different use requirements,
Need to seek optimal balance between high wet-sliding resistant performance and low rolling resistance.
For production low rolling resistance tyre, due to anionic solution polymerization can effectively adjust side chain contain it is double
The content and glass transition temperature of the conjugated diene construction unit of key, the solution polymerized butylbenzene of anionic polymerisation have than newborn poly- fourth
Benzene more significant advantage.Relation between wet-sliding resistant performance and rolling resistance of the advantage for balancing tire is favourable.This
Outside, research shows, silane coupler is added in the mixing process of rubber composition, to a certain extent filler can be promoted to exist
The relation between wet-sliding resistant performance and rolling resistance scattered and that improve rubber to a certain extent in rubber, but in rubber
In composition mixing process, influenceed by other additives, the reactivity of silane coupler and rubber and carbon black can be reduced.And
And, addition silane coupler can also produce unpleasant stink in rubber composition mixing process.Being disclosed in EP447066 can
With using with formula（1）The silane of shown structure is hindered as modifying agent with improving the wet-sliding resistant performance of butadiene-styrene rubber and reducing rolling
Power：
USi(OR′)jR ' ' 4-i-j formulas（1）,
Wherein, U is halogen, and R ＇ and R ＇ ＇ are C1-C20Alkyl, aryl, vinyl or haloalkyl, j be 1-4 integer,
I is 0-2 integer, i and j's and for 2-4.With formula（1）The silane of shown structure can pass through halogen and polymer molecular chain
The catalyst residues of end are reacted and key is connected on polymer molecular chain, however, a usual polymer molecular chain can only key company
A upper silane molecule, is only capable of producing slight influence, it is impossible to effectively improve rubber to the interaction between polymer molecular chain
The anti-slippery of glue simultaneously reduces rolling resistance.
The content of the invention
The invention aims to overcome the wet-sliding resistant performance and the rolling that use existing method not can effectively improve rubber
The defect of relation between dynamic resistance, and providing a kind of can have the functionalization diene of high wet-sliding resistant performance and low-rolling-resistance concurrently
Hydrocarbon polymer, the preparation method of diene's polymer and the diene's polymerization prepared by the above method
The application of thing and above-mentioned diene's polymer in rubber.
The invention provides a kind of diene's polymer, contain in the strand of diene's polymer
There is at least one conjugated diene construction unit, wherein, also contain formula in the strand of diene's polymer（Ⅰ）
Shown silane coupler construction unit, and the number-average molecular weight of diene's polymer is 50,000-100 ten thousand；
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl,
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.
Present invention also offers a kind of preparation method of diene's polymer, wherein, this method is included in inertia
In atmosphere and in the presence of initiator, by diene polymer and silane containing at least one conjugated diene construction unit
Coupling agent is contacted, and the condition of the contact causes the silane coupler chemical bond to be connected on the diene polymer；It is described
The number-average molecular weight of diene polymer is 50,000-100 ten thousand, and with conjugated diene construction unit in the diene polymer
Weight on the basis of, in the diene polymer side chain contain the conjugated diene construction unit of double bond content be 15-85
Weight %, preferably 30-60 weight %, the silane coupler have formula（Ⅱ）Shown structure：
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl,
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.
Present invention also offers the preparation method of another diene's polymer, wherein, this method includes following
Step：
（1）In an inert atmosphere and in the presence of initiator, conjugated diene is subjected to polymerisation in a solvent, obtained
To the reaction product containing diene polymer, the condition of the polymerisation makes the equal molecule of the number of obtained diene polymer
Measure for 50,000-100 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, the alkadienes
It is 15-85 weight %, preferably 30-60 weight % that side chain, which contains the content of the conjugated diene construction unit of double bond, in polymer；
（2）In an inert atmosphere and in the presence of initiator, by step（1）Obtain containing the anti-of diene polymer
Product is answered to be contacted with silane coupler, the condition of the contact causes the silane coupler chemical bond to be connected to the alkadienes and gather
On compound, the silane coupler has formula（Ⅱ）Shown structure：
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl,
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.
Present invention also offers the diene's polymer prepared by the above method.
In addition, present invention also offers application of the above-mentioned diene's polymer as rubber-based adhesive.
As described above, in the prior art, silane coupler is generally just added in the mixing process of rubber to improve rubber
The wet-sliding resistant performance of glue simultaneously reduces its rolling resistance, but now the reactivity of silane coupler and rubber and carbon black can drop
It is low, not only it is difficult to significantly improve the relation between the wet-sliding resistant performance of rubber and rolling resistance, but also can produce unpleasant smelly
Taste.And the present inventor has found after further investigation, by the way that silane coupler chemistry is bonded in into diene polymer
On, and obtained diene's polymer can be avoided in compounding rubber integrally as part or all of rubber-based adhesive
During caused by the reactivity of silane coupler and rubber and carbon black the problem of reduce, and the thus obtained official of active balance
The relation between the anti-slippery and rolling resistance for the tire that diene polymer is made can be changed, mixed while rubber can also be improved
During refining caused by the use of silane coupler undesirable smell.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Contain at least one conjugated diene hydrocarbon structure list in the strand for diene's polymer that the present invention is provided
Member, wherein, also contain formula in the strand of diene's polymer（Ⅰ）Shown silane coupler construction unit,
And the number-average molecular weight of diene's polymer is 50,000-100 ten thousand；
R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl, it is described miscellaneous
One or more of the atom in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R1-R3For C1-C5Straight or branched alkyl or
Straight or branched alkoxyl, R4For C1-C5Straight or branched alkylidene.
The C1-C5The instantiation of straight or branched alkyl include but is not limited to：Methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl；The C1-C5Straight chain or
The instantiation of branched alkoxy includes but is not limited to：It is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, secondary
Butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy and neopentyl oxygen；The C1-C5Straight chain
Or the instantiation of branched alkylidene includes but is not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl,
Isobutylidene, sub- n-pentyl or isoamylidene.
On diene's polymer molecular chain, conjugated diene construction unit constitutes the main chain of polymer,
And formula（Ⅰ）Shown silane coupler construction unit key is connected on the conjugated diene construction unit for constituting main chain.
It is particularly preferred that formula（Ⅰ）In, R1-R3For methoxyl group, R4For propylidene, now, with formula（Ⅰ）Shown is silane coupled
The corresponding silane coupler of agent construction unit is γ-mercaptopropyl trimethoxysilane；Or, R1-R3For ethyoxyl, R4For Asia
Propyl group, now, with formula（Ⅰ）The corresponding silane coupler of shown silane coupler construction unit is γ-ethoxy of mercapto propyl group three
Base silane；Or, R1-R3For methyl, R4For ethylidene, now, with formula（Ⅰ）Shown silane coupler construction unit is corresponding
Silane coupler be 2- trimethyl silane ethyl mercaptans.
The present invention is to the conjugated diene construction unit in diene's polymer and silane coupler structure
The content of unit is not particularly limited, and can be entered according to the consumption of conjugated diene monomer in preparation process and silane coupler
Row adjustment, but in order that obtaining diene's polymer has higher wet-sliding resistant performance and is hindered with lower rolling
Power, on the basis of the gross weight of diene's polymer, the content of the conjugated diene construction unit is preferably
90-99.99 weight %, more preferably 98-99.8 weight %, the content of the silane coupler construction unit is preferably 0.01-10
Weight %, more preferably 0.2-2 weight %.
The present invention is not particularly limited to the number-average molecular weight and molecular weight distribution of diene's polymer,
For example, the number-average molecular weight can be 50,000-100 ten thousand, preferably 150,000-20 ten thousand, molecular weight distribution can be 1-4, be preferably
1-1.5.The number-average molecular weight and molecular weight distribution can use the gel of the model LC-10AT purchased from Shimadzu Corporation to ooze
Saturating chromatograph（GPC）Measure, wherein, using THF as mobile phase, using Narrow distribution polystyrene as standard specimen, test temperature is 25 DEG C.
According to the present invention, the conjugated diene construction unit is the construction unit derived from conjugated diene, i.e. by altogether
The construction unit of yoke diene polymerization formation.The conjugated diene refers to contain conjugated double bond in molecular structure（That is ,-C=C-C
=C-）Various unsaturated acyclic hydrocarbons.The conjugated diene can be the conventional selection of this area, and can be obtained according to final
To the application scenario of diene's polymer reasonably selected, for example, the conjugated diene can be selected from fourth
One or more in diene, isoprene, 1,3-pentadiene, 1,3- hexadienes and 2,3- dimethyl butadiene, preferably fourth
Diene and/or isoprene.
The preparation method for diene's polymer that the present invention is provided is included in inert atmosphere and in initiator
In the presence of, the diene polymer containing at least one conjugated diene construction unit is contacted with silane coupler, it is described to connect
Tactile condition causes the silane coupler chemical bond to be connected on the diene polymer；The number of the diene polymer is equal
Molecular weight is 50,000-100 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, described two
It is 15-85 weight %, preferably 30-60 weights that side chain, which contains the content of the conjugated diene construction unit of double bond, in olefin polymer
% is measured, the silane coupler has formula（Ⅱ）Shown structure：
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl,
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R1-R3For C1-C5Straight or branched
Alkyl or straight or branched alkoxyl, R4For C1-C5Straight or branched alkylidene.
The content that the side chain contains the conjugated diene construction unit of double bond can use and be purchased from Bruker companies of Switzerland
Model AVANCE DRX400MHz nuclear magnetic resonance chemical analyser be measured, wherein, solvent is deuterochloroform.It is specific to determine
Method is known to the skilled person, and will not be described in great detail herein.
According to the present invention, the diene polymer can be prepared using existing various methods, for example, it is prepared
Method can include：In an inert atmosphere and in the presence of initiator, conjugated diene is subjected to polymerisation in a solvent,
The condition of the polymerisation makes the number-average molecular weight of obtained diene polymer be 50,000-100 ten thousand, and with the alkadienes
In polymer on the basis of the weight of conjugated diene construction unit, side chain contains the conjugation two of double bond in the diene polymer
The content of olefin unit is 15-85 weight %, is preferably 30-60 weight %.
According to the present invention, the inert atmosphere refers to any one gas not chemically reacted with reactant and product
Or admixture of gas, the one or more in such as nitrogen and periodic table of elements zero group gas.Keep the method for inert atmosphere can be with
To be passed through above-mentioned any one gas or admixture of gas not chemically reacted with reactant and product into reaction system.
According to the present invention, in the preparation process of diene polymer, the initiator can for it is existing it is various can
Trigger the initiator of the conjugate diene polymerization, for example, can be organic lithium initiator.The organic lithium initiator for example may be used
Using be molecular formula as RLi single organic lithium initiator, wherein, R is alkyl, cycloalkyl or the aryl of straight or branched.Specifically,
Single organic lithium initiator can selected from ethyl-lithium, propyl lithium, isopropyl lithium, n-BuLi, s-butyl lithium, amyl group lithium, oneself
One or more in base lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium, preferably n-BuLi and/or Zhong Ding
Base lithium.In addition, the present invention can also use Dilithium initiator, such as lithium of trimethylene two and/or the lithium of tetramethylene two.The present invention is right
The consumption of the initiator is not particularly limited, it is possible to reasonably selected according to the molecular size range of design.Ability
Field technique personnel are it should be readily understood that when needing to prepare the larger diene polymer of molecular weight, it is possible to reduce trigger
The consumption of agent, but now rate of polymerization also can accordingly reduce；, can be with when needing to prepare the less diene polymer of molecular weight
Increase the consumption of initiator, but now rate of polymerization also can accordingly increase.Therefore, rate of polymerization and obtain two are considered
Under the molecular size range of olefin polymer, preferable case, on the basis of the gross weight of 100g conjugated dienes, the initiator
Consumption is 0.15-2.5mmol.
The present invention is not particularly limited to the condition of the polymerisation, generally include polymerization temperature, polymerization pressure and
Polymerization time.Wherein, in order to be more beneficial for the progress of polymerisation, the polymerization temperature is preferably 10-160 DEG C, more preferably
40-80 DEG C, the polymerization pressure is preferably 0.05-0.5MPa, more preferably 0.1-0.3MPa.As a rule, during the polymerization
Between extension be conducive to the raising of the conversion ratio of reactant and the yield of reaction product, but polymerization time is long that reactant is turned
The amplitude that rate and reaction product yield are improved is not obvious, therefore, considers polymerization efficiency and effect, the polymerization time
Preferably 0.5-10 hours, more preferably 0.5-2 hours.
In the present invention, the pressure refers both to gauge pressure.
According to the present invention, in the preparation process of diene polymer, the solvent can be used as reaction to be various
The material of medium, for example, can be varsol and/or ether solvent.The varsol can be C5-C7Cycloalkane, virtue
One or more in hydrocarbon and isoparaffin.The instantiation of the varsol can include but is not limited to：Benzene, toluene, penta
One or more in alkane, heptane, n-hexane and hexamethylene.The ether solvent can be C4-C15Monoether and/or polyether.
The instantiation of the ether solvent can include but is not limited to：Tert-butoxyethoxy ethane and/or tetrahydrofuran.Wherein,
These solvents can be used alone, can also be used in mixed way.The consumption of the solvent can be closed according to the consumption of monomer
The selection of reason ground, for example, the consumption of the solvent can allow the total concentration of the conjugated diene to be 1-30 weight %, it is excellent
Elect 5-20 weight % as.
, after polymerization was complete, can also be toward adding coupling agent in polymerization system according to the present invention, will at least portion
Diene polymer is divided to be coupled together.The species of the coupling agent is known to the skilled person, for example, can be many second
One or more in alkenyl compound, halide, ether, aldehyde, ketone, ester etc..Specifically, the coupling agent can be selected from divinyl
In base benzene, tetravinyl silane, tetrachloromethane, silicon tetrachloride, butter of tin, dimethyl terephthalate (DMT) and epoxidized soybean oil
One or more in one or more, preferably divinylbenzene, silicon tetrachloride and butter of tin.It should be noted that working as
When the coupling agent is silane compound, the silane compound is with having formula（Ⅱ）The silane coupler of shown structure is different.
The present invention is not particularly limited to the consumption of the coupling agent, can be carried out suitably according to the consumption of initiator
Selection, for example, the mol ratio of the coupling agent and the initiator can be 0.1-2:1, preferably 0.1-1:1.
, according to the invention it is preferred in the case of, structure tune can also be added in the preparation process of the diene polymer
Agent is saved, the microstructure of the diene polymer can be so effectively controlled.The structure regulator can be
The material of the existing various microstructures that can adjust diene polymer, for example, ether, butyl oxide, tetrahydrochysene can be selected from
Furans, glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, crown ether, tetrahydrofurfuryl alcohol ether, triethylamine, tetramethyl second two
One in amine, HMPA, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate potassium and sodium alkyl benzene sulfonate
Plant or a variety of.As a rule, the structure regulator can be with the mol ratio for preparing the initiator used in diene polymer
1-100:1, preferably 80-100:1.
As a rule, anionic polymerisation system does not have obvious terminating reaction and transfer reaction, when ruing out of whole
After monomer, activated centre is still present.Therefore, after completion of the polymerization reaction, obtained polymer solution and terminator should be connect
Touch so that activated centre is inactivated.The consumption of the terminator can be according to used in preparing diene polymer initiator consumption
Reasonably to be selected, as a rule, the terminator can with preparing the mol ratio of the initiator used in diene polymer
Think 0.1-1:1.The terminator can be the existing various reagents that can inactivate anion active center, for example, can
With the one or more in water, methanol, ethanol and isopropanol, preferably isopropanol.
The present invention is not particularly limited to the condition for contacting the diene polymer with silane coupler, as long as energy
Enough so that the silane coupler chemical bond is connected on the diene polymer, for example, the condition of the contact is usual
Including Contact Temperature, contact and time of contact.As a rule, in order to be more beneficial for silane coupler chemical bond be connected to it is described
On diene polymer, the Contact Temperature is preferably 20-150 DEG C, more preferably 40-90 DEG C, and the contact is preferably
0.01-1MPa, more preferably 0.1-0.5MPa, the time of contact are preferably 0.2-24 hours, more preferably 0.5-5 hours.
According to the present invention, when diene polymer is contacted with silane coupler, in order to take into account trigger rate and function
Change the size of diene polymer molecular weight, with the diene polymer and with formula（Ⅱ）The silane coupler of shown structure
Gross weight on the basis of, the consumption of the initiator is preferably 0.01-0.1 weight %, more preferably 0.01-0.08 weight %.Institute
Azo-initiator, peroxide type initiators and the redox class that stating initiator can be known to the skilled person are drawn
Send out the one or more in the radical initiators such as agent.
The azo-initiator can be selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo two
Formamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo dicyan
One kind or many in base valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and ABVN
Kind.
The peroxide type initiators can be selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, peroxide
Change the one or more in benzoyl and the benzoyl peroxide tert-butyl ester.
The redox type initiators are selected from sulfate-sulphite, persulfate-thiocarbamide, persulfate-organic salt
With the one or more in ammonium persulfate-fatty amine.Specifically, the sulfate-sulphite can be selected from sodium sulphate-sulfurous
One or more in sour sodium, potassium sulfate-potassium sulfite and ammonium sulfate-ammonium sulfite；Persulfate-thiocarbamide can be selected from over cure
One or more in sour sodium-thiocarbamide, potassium peroxydisulfate-thiocarbamide and ammonium persulfate-thiocarbamide；Persulfate-organic salt can be selected from
One or more in sodium peroxydisulfate-potassium acetate, potassium peroxydisulfate-potassium acetate and ammonium persulfate-ammonium acetate；Ammonium persulfate-fat
Amine can be selected from ammonium persulfate-N, N- tetramethylethylenediamine and/or ammonium persulfate-diethylamine.
According to the present invention, the diene polymer and with formula（Ⅱ）The consumption of the silane coupler of shown structure can be with
Selected and changed in wider scope, for example, on the basis of 100g diene polymer, the silane coupler
Consumption can be 0.01-10g, preferably 0.1-5g, more preferably 0.2-2g.
In addition, present invention also offers the method for another preparation diene's polymer, wherein, this method includes
Following steps：
（1）In an inert atmosphere and in the presence of initiator, conjugated diene is subjected to polymerisation in a solvent, obtained
To the reaction product containing diene polymer, the condition of the polymerisation makes the equal molecule of the number of obtained diene polymer
Measure for 50,000-100 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, the alkadienes
It is 15-85 weight %, preferably 30-60 weight % that side chain, which contains the content of the conjugated diene construction unit of double bond, in polymer；
（2）In an inert atmosphere and in the presence of initiator, by step（1）Obtain containing the anti-of diene polymer
Product is answered to be contacted with silane coupler, the condition of the contact causes the silane coupler chemical bond to be connected to the alkadienes and gather
On compound, the silane coupler has formula（Ⅱ）Shown structure：
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl,
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R1-R3For C1-C5Straight or branched
Alkyl or straight or branched alkoxyl, R4For C1-C5Straight or branched alkylidene.
Wherein, step（1）With（2）In each material species and the condition and contact conditions of consumption and polymerisation
According to reasonably being selected above, will not be described in great detail herein.
According to the present invention, after diene's polymer is prepared and completed, it is also an option that property to obtaining
Diene's polymer in add various additives.The additive can be for example age resistor, so enable to
To diene's polymer there is good ageing resistace.The species and consumption of the age resistor can be ability
The conventional selection in domain, will not be described in great detail herein.
According to the present invention, after age resistor is added, diene's polymer can be by purifying precipitation, centrifugation
The methods such as separation, filtering, decantation, hot water cohesion are precipitated out from solution, it would however also be possible to employ air- extraction is by reaction system
Solvent is removed, and this those skilled in the art can be known, be will not be described in great detail herein.
Present invention also offers the diene's polymer prepared by the above method.
In addition, present invention also offers application of the above-mentioned diene's polymer as rubber-based adhesive.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, sulfydryl conversion ratio is measured using Agilent 7890A type gas chromatographs, is surveyed
Strip part includes：Chromatographic column SPB-560m × 0.32mm × 1.0um capillary columns, column flow rate 2.0ml/min, 220 DEG C of column temperature, gas
Change 220 DEG C of room temperature, detect 250 DEG C of room temperature, split ratio 50：1, sample size 0.3ul.Side chain contains the conjugated diene of double bond
The content of construction unit is carried out using the model AVANCE DRX400MHz of Bruker companies of Switzerland nuclear magnetic resonance chemical analyser
Determine, wherein, solvent is deuterochloroform.Number-average molecular weight and molecular weight distribution use the model of WATERS companies of the U.S.
ALLIANCE2690 gel permeation chromatograph（GPC）Determine, wherein, THF is mobile phase, and Narrow distribution polystyrene is standard specimen,
Temperature is 25 DEG C.Mooney viscosity is using the SMV-300 type mooney's viscosimeters of Japanese Shimadzu Corporation as specified in GB/T1232-92
Method is determined.The inventory ÷ of content=conjugated diene of conjugated diene construction unit（Inventory+tool of conjugated diene
There is formula（Ⅱ）The inventory of the silane coupler of shown structure × sulfydryl conversion ratio）×100%；Content=silicon of silane coupler
The inventory of alkane coupling agent × sulfydryl conversion ratio ÷（Inventory × sulfydryl of inventory+silane coupler of conjugated diene turns
Rate）×100%.
Embodiment 1
The embodiment is used to illustrate diene's polymer of the invention provided and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, add 2288g hexamethylenes, 180.00g butadiene and
1.0g tetrahydrofurfuryl alcohol ether, be then heated to after 50 DEG C add 1.2mmol n-BuLi and by Stress control at 0.2 mpa
Initiation reaction 2 hours, obtains the solution containing diene polymer.The number-average molecular weight of the diene polymer is 160,000,
And on the basis of the weight of butadiene structural units in the diene polymer, side chain contains double in the diene polymer
The content of the conjugated diene construction unit of key is 55.40 weight %.
（2）Toward step（1）0.8ml is added in obtained product（0.836g）γ-mercaptopropyl trimethoxysilane, and immediately
Sampling carries out sulfydryl test, is then heated to addition 6.7mg azo-bis-isobutyl cyanides after 75 DEG C, and by Stress control at 0.2 mpa
Reaction obtains diene's polymer after 3 hours, and samples progress sulfydryl test.Toward above-mentioned diene's polymer
Middle addition 0.2g age resistor Irganox1520, and the dry 24h in 60 DEG C of vacuum.Wherein, sulfydryl conversion ratio is 80%, functionalization
The Mooney viscosity of diene polymer is 45, and number-average molecular weight is 160,000, and molecular weight distribution is 1.1；With the functionalization diene
On the basis of the gross weight of hydrocarbon polymer, the content of butadiene structural units is 99.63 weight %, γ-mercaptopropyl trimethoxysilane
The content of construction unit is 0.37 weight %.The polymer does not have undesirable smell.
Embodiment 2
The embodiment is used to illustrate diene's polymer of the invention provided and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, add 2288g hexamethylenes, 200.00g butadiene and
0.65g tetrahydrofurfuryl alcohol ether, is then heated to after 40 DEG C and adds 1.0mmol n-BuLi and by Stress control under 0.1MPa
Initiation reaction 2 hours, obtains the solution containing diene polymer.The number-average molecular weight of the diene polymer is 16.6
Ten thousand, and on the basis of the weight of butadiene structural units in the diene polymer, side chain contains in the diene polymer
The content for having the conjugated diene construction unit of double bond is 39.90 weight %.
（2）Toward step（1）0.6ml is added in obtained product（0.627g）γ-mercaptopropyl trimethoxysilane, and immediately
Sampling carries out sulfydryl test, is then heated to addition 13mg azo-bis-isobutyl cyanides after 40 DEG C, and by Stress control 5 under 0.1MPa
Diene's polymer is obtained after hour, and samples progress sulfydryl test.Add into above-mentioned diene's polymer
Enter 0.2g age resistor Irganox1520, and the dry 24h in 60 DEG C of vacuum.Wherein, sulfydryl conversion ratio is 82%, functionalization diene
The Mooney viscosity of hydrocarbon polymer is 49, and number-average molecular weight is 16.6 ten thousand, and molecular weight distribution is 1.3；With the diene
On the basis of the gross weight of polymer, the content of butadiene structural units is 99.74 weight %, γ-mercaptopropyl trimethoxysilane knot
The content of structure unit is 0.26 weight %.The polymer does not have undesirable smell.
Embodiment 3
The embodiment is used to illustrate diene's polymer of the invention provided and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, add 2288g hexanes, 52.00g isoprene and
5ml tetrahydrofurans, are then heated to the n-BuLi that 0.4mmol is added after 75 DEG C and Stress control are triggered into anti-under 0.3MPa
Answer 0.5 hour, obtain the solution containing diene polymer.The number-average molecular weight of the diene polymer is 16.1 ten thousand, and
On the basis of the weight of isoprene structures unit in the diene polymer, side chain contains double in the diene polymer
The content of the conjugated diene construction unit of key is 35.00 weight %；
（2）Toward step（1）1.06ml is added in obtained product（1.045g）Gamma-mercaptopropyltriethoxysilane, exists side by side
I.e. sampling carries out sulfydryl test, is then heated to addition 30mg azo-bis-isobutyl cyanides after 90 DEG C, and by Stress control in 0.5MPa
Lower reaction obtains diene's polymer after 0.5 hour, and samples progress sulfydryl test.Gather toward above-mentioned diene
0.08g age resistor Irganox1520, and the dry 24h in 60 DEG C of vacuum are added in compound.Wherein, sulfydryl conversion ratio is 89%,
The Mooney viscosity of diene's polymer is 46, and number-average molecular weight is 16.1, and molecular weight distribution is 1.05；With the function
On the basis of the gross weight for changing diene polymer, the content of isoprene structures unit is 98.24 weight %, the γ-second of mercapto propyl group three
The content of TMOS construction unit is 1.76 weight %.The polymer does not have undesirable smell.
Embodiment 4
The embodiment is used to illustrate diene's polymer of the invention provided and preparation method thereof.
Diene's polymer is prepared according to the method for embodiment 1, unlike, the γ-mercapto propyl group trimethoxy
Base silane is substituted with the 2- trimethyl silanes ethyl mercaptan of identical weight part, obtains diene's polymer.Wherein, sulfydryl turns
Rate is 72%, and the Mooney viscosity of diene's polymer is 41, and number-average molecular weight is 15.6, and molecular weight distribution is 1.03；
On the basis of the gross weight of diene's polymer, the content of butadiene structural units is 99.67 weight %, 2- tri-
The content of methyl-monosilane ethyl mercaptan construction unit is 0.33 weight %.The polymer does not have undesirable smell.
Comparative example 1
The comparative example is used to illustrate reference diene polymer and preparation method thereof.
Method according to embodiment 1 prepares diene polymer, unlike, not including step（2）, obtain alkadienes and gather
Compound.Wherein, Mooney viscosity is 45, and number-average molecular weight is 160,000, and molecular weight distribution is 1.09.
Comparative example 2
The comparative example is used to illustrate reference diene's polymer and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 1500g hexamethylenes, 20g butadiene and 2.7g are added
Tetrahydrofurfuryl alcohol ether, is then heated to the n-BuLi that 12mmol is added after 40 DEG C and Stress control is triggered into anti-under 0.4MPa
Answer 1 hour, obtain the solution containing diene polymer.The number-average molecular weight of the diene polymer is 1000, and with institute
State in diene polymer on the basis of the weight of conjugated diene construction unit, side chain contains double bond in the diene polymer
Conjugated diene construction unit content be 67 weight %.
（2）Toward step（1）20g γ-mercaptopropyl trimethoxysilane is added in obtained product, and sampling carries out mercapto immediately
Base is tested, and is then heated to after 100 DEG C addition 1g dilauroyl peroxides, and after Stress control is reacted 5 hours under 0.4MPa
Diene's polymer is obtained, and samples progress sulfydryl test.24h is finally dried in 80 DEG C of vacuum.Wherein, functionalization
The sulfydryl conversion ratio of diene polymer is 80%, and number-average molecular weight is 1788.With the gross weight of diene's polymer
On the basis of amount, the content of γ-mercaptopropyl trimethoxysilane construction unit is 44.4 weight %.
Embodiment 5-8
Embodiment 5-8 is used for the preparation method for illustrating the rubber containing diene's polymer.
（1）The preparation of elastomeric compound：
35 parts by weight are prepared by embodiment 1-4 respectively diene's polymer, the natural rubber of 10 parts by weight
Glue, 55 parts of solution polymerized butadiene styrene rubber SSBR2305（Purchased from Dongguan Hua Xiang trading companies）, 1 parts by weight stearic acid（Hong Kong is polite
Chemical Co., Ltd., SA1801）, 10 parts by weight abrasion furnace blacks N330（The Tianjin gold autumn reality carbon black Chemical Co., Ltd.）, 60 weight
Part white carbon 115GR（Goldschmidt chemical corporation）It is well mixed and uses Haake to be heat-treated, wherein, heat treatment temperature is 150 DEG C, turns
Speed is 30rpm/min, and the time is 7min.After the completion of heat treatment, said mixture is added in mill, and adds 2.5 weight
The zinc oxide of part（Liuzhou Xin Pin Co., Ltds）, 1 parts by weight stearic acid（The polite Chemical Co., Ltd. in Hong Kong, SA1801）, 2 weights
Measure the antioxidant 4020, the N- cyclohexyl -2- benzothiazole sulfonamides of 1.4 parts by weight of part（Hebi Uhoo Rubber Chemicals Co., Ltd.,
CZ）, 0.75 parts by weight diphenylguanidine（Guangzhou Li great rubber raw materials trade Co., Ltd, DPG）With 6 parts by weight silane couplers
Si69（Goldschmidt chemical corporation）, kneaded 60 minutes at 50 ± 5 DEG C, obtain elastomeric compound H1-H4.
（2）Vulcanization：
Under 150 DEG C, 12MPa, by step（1）Obtained elastomeric compound H1-H4 is vulcanized on vulcanizing press respectively
Processing 40 minutes, obtains vulcanization rubber S1-S4.
Comparative example 3
The comparative example is used for the preparation method for illustrating the rubber containing reference diene polymer.
Method according to embodiment 5 prepares rubber, unlike, the diene that will be prepared by embodiment 1
Polymer is substituted with the diene polymer obtained by comparative example 1, and the addition of diene polymer is 34.87 parts by weight,
In addition, in the preparation process of elastomeric compound, being also added into γ-mercaptopropyl trimethoxysilane of 0.13 parts by weight, obtaining reference
Vulcanize rubber DS1.
Comparative example 4
The comparative example is used for the preparation method for illustrating that reference vulcanizes rubber.
Method according to embodiment 5 prepares vulcanization rubber, unlike, the functionalization two that will be prepared by preparation example 3
The olefin polymer diene polymer obtained by comparative example 1 of 99.17 parts by weight and being obtained by comparative example 2 for 0.83 parts by weight
The mixture replacing of the diene's polymer arrived, obtains vulcanization rubber DS2.
Test case 1-4
Test case 1-4 is used for the test for illustrating the vulcanization rubber S1-S4 performances that the present invention is provided.
（1）The test of mechanical property：
Rubber S1-S4 will be vulcanized respectively the thick vulcanization sheet rubbers of 2mm are made；And according to specified in GB/T528-1998 1
Obtained vulcanization sheet rubber is cut into dumbbell shaped standard film by type dumbbell shaped cut-off knife, using rubber puller system（Japanese Shimadzu Corporation's life
Production, model AG-20KNG）Mechanical property to the vulcanization sheet rubber is tested, wherein, test temperature is 25 DEG C, traction
Speed is 500 mm/mins, obtains vulcanizing the breaking strength and elongation at break of rubber, and acquired results are as shown in table 1.
（2）The test of shore a hardness：
Method is tested according to specified in GB/T531-1999, and acquired results are as shown in table 1.
（3）Anti- deformation nature test：
Dumbbell shaped standard film is cut into by rubber S1-S4 is vulcanized according to 1 type dumbbell shaped cut-off knife specified in GB/T528-92,
Test temperature be 25 DEG C, hauling speed be 500 mm/mins under conditions of sample is broken.Sample after tension failure is put
3min is put, then two parts of fracture are coincide together, the distance after measurement coincide between two parallel lines is calculated as follows and pulled apart
Set value：
Sb=100（Lt-L0）/L0, wherein, SbFor setafter break, %；LtAfter being coincide for sample between two parallel lines away from
From mm；L0For initial trial length, mm.Acquired results are as shown in table 1.
（4）Thermogenesis performance is tested：
It is measured using the Y3000E type compression heat generation test machines of Beijing You Shen Electronic Instrument, Limiteds, wherein, test temperature
Spend for 55 DEG C, the testing time is 25 minutes, compression frequency is 30 times/second.Acquired results are as shown in table 1.
（5）The test of wet-sliding resistant performance and rolling resistance：
Using wet-sliding resistant performance and rolling resistance of U.S.'s TA companies DMA-2980 types viscoelastic spectrometer to vulcanization rubber S1-S4
It is measured, wherein, test frequency is 2Hz, and heating rate is 5 DEG C/min, and test temperature is 100 DEG C, and sample size is 40mm
×5mm×1mm.Represent to vulcanize the wet-sliding resistant performance of rubber with tan δ at 0 DEG C, tan δ are bigger, represent that vulcanization rubber is anti-slippery
Performance is better；Represent to vulcanize the rolling resistance of rubber with tan δ at 60 DEG C, tan δ are smaller, represent that vulcanization rubber rolling resistance is got over
It is small；Scattered in rubber of filler uses Tan δ（0℃）/Tanδ（60℃）Value characterize, its value is higher show that filler is scattered must be more
It is good.Acquired results are as shown in table 1.
Contrast test example 1-2
Contrast test example is used for the test for illustrating to vulcanize containing reference the performance of rubber.
Vulcanize rubber DS1 and DS2 property to the reference obtained by comparative example 2 and comparative example 3 according to test case 1-4 method
It can be tested, acquired results are as shown in table 1.
Table 1
As can be seen from the above results, diene's polymer that the present invention is provided can not only be effectively improved moisture-resistant
Relation between slip and rolling resistance, can also improve in rubber mixing process and be made caused by using silane coupler
The unhappy smell of people.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. contain at least one conjugation in a kind of diene's polymer, the strand of diene's polymer
Alkadienes construction unit, it is characterised in that also containing changing shown in formula (I) in the strand of diene's polymer
Property agent construction unit, and diene's polymer number-average molecular weight be 50,000-100 ten thousand；
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl, it is described
Hetero atom is oxygen；
On the basis of the gross weight of diene's polymer, the content of the conjugated diene construction unit is 98-
99.8 weight %, the content of the structure of modifier unit is 0.2-2 weight %.
2. diene's polymer according to claim 1, wherein, R1-R3For C1-C5Straight or branched alkyl or
Straight or branched alkoxyl, R4For C1-C5Straight or branched alkylidene.
3. diene's polymer according to claim 1 or 2, wherein, in formula (I), R1-R3For methoxyl group, R4For
Propylidene；Or,
R1-R3For ethyoxyl, R4For propylidene；
R1-R3For methyl, R4For ethylidene.
4. diene's polymer according to claim 1 or 2, wherein, the conjugated diene construction unit is
Construction unit derived from conjugated diene, the conjugated diene is selected from butadiene, isoprene, 1,3-pentadiene, 1,3-
One or more in hexadiene and 2,3 dimethyl butadiene.
5. diene's polymer according to claim 1 or 2, wherein, diene's polymer
Number-average molecular weight is 150,000-20 ten thousand, and molecular weight distribution is 1-4.
6. diene's polymer according to claim 5, wherein, the molecule of diene's polymer
Amount is distributed as 1-1.5.
7. a kind of preparation method of diene's polymer, it is characterised in that this method be included in inert atmosphere and
In the presence of initiator, by diene polymer and modifying agent containing at least one conjugated diene construction unit, institute
The condition of contact is stated so that the modifying agent chemical bond is connected on the diene polymer；The number of the diene polymer is equal
Molecular weight is 50,000-100 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, described two
It is 15-85 weight % that side chain, which contains the content of the conjugated diene construction unit of double bond, in olefin polymer, the modifying agent tool
There is the structure shown in formula (II)：
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl, it is described
Hetero atom is oxygen；
The consumption of the modifying agent causes on the basis of the gross weight of diene's polymer, the conjugated diene
The content of construction unit is 98-99.8 weight %, and the content of the structure of modifier unit derived from modifying agent is 0.2-2 weights
Measure %.
8. preparation method according to claim 7, wherein, with conjugated diene construction unit in the diene polymer
Weight on the basis of, in the diene polymer side chain contain the conjugated diene construction unit of double bond content be 30-60
Weight %.
9. preparation method according to claim 7, wherein, R1-R3For C1-C5Straight or branched alkyl or straight or branched
Alkoxy, R4For C1-C5Straight or branched alkylidene.
10. preparation method according to claim 7, wherein, the diene polymer, which is prepared by the following method, to be obtained：
In an inert atmosphere and in the presence of initiator, conjugated diene is subjected to polymerisation, the polymerisation in a solvent
Condition make obtained diene polymer number-average molecular weight be 50,000-100 ten thousand, and with the diene polymer be conjugated
On the basis of the weight of alkadienes construction unit, side chain contains the conjugated diene construction unit of double bond in the diene polymer
Content be 15-85 weight %.
11. preparation method according to claim 10, wherein, with conjugated diene hydrocarbon structure list in the diene polymer
On the basis of the weight of member, the content that side chain contains the conjugated diene construction unit of double bond in the diene polymer is 30-
60 weight %.
12. a kind of preparation method of diene's polymer, it is characterised in that this method comprises the following steps：
(1) conjugated diene in an inert atmosphere and in the presence of initiator, is subjected to polymerisation in a solvent, contained
There is a reaction product of diene polymer, the condition of the polymerisation makes the number-average molecular weight of obtained diene polymer be
50000-100 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, the diene polymerization
The content that side chain contains the conjugated diene construction unit of double bond in thing is 15-85 weight %；
(2) in an inert atmosphere and in the presence of initiator, the reaction containing diene polymer that step (1) is obtained is produced
Thing and modifying agent, the condition of the contact cause the modifying agent chemical bond to be connected on the diene polymer, described
Modifying agent has the structure shown in formula (II)：
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl, it is described
Hetero atom is oxygen；
The consumption of the modifying agent causes on the basis of the gross weight of diene's polymer, the conjugated diene
The content of construction unit is 98-99.8 weight %, and the content of the structure of modifier unit derived from modifying agent is 0.2-2 weights
Measure %.
13. preparation method according to claim 12, wherein, with conjugated diene hydrocarbon structure list in the diene polymer
On the basis of the weight of member, the content that side chain contains the conjugated diene construction unit of double bond in the diene polymer is 30-
60 weight %.
14. preparation method according to claim 12, wherein, R1-R3For C1-C5Straight or branched alkyl or straight chain or branch
Chain alkoxy, R4For C1-C5Straight or branched alkylidene.
15. the preparation method according to any one in claim 10-14, wherein, the condition of the polymerisation includes
Polymerization temperature is 10-160 DEG C, and polymerization pressure is 0.05-0.5MPa, and polymerization time is 0.5-10 hours.
16. preparation method according to claim 15, wherein, it is 40- that the condition of the polymerisation, which includes polymerization temperature,
80 DEG C, polymerization pressure is 0.1-0.3MPa, and polymerization time is 0.5-2 hours.
17. the preparation method according to any one in claim 7-14, wherein, by the diene polymer and modification
It is 20-150 DEG C that the condition of agent contact, which includes Contact Temperature, and contact is 0.01-1MPa, and time of contact is 0.2-24 hours.
18. preparation method according to claim 17, wherein, by the condition of the diene polymer and modifying agent
It it is 40-90 DEG C including Contact Temperature, contact is 0.1-0.5MPa, time of contact is 0.5-5 hours.
19. the diene's polymer prepared as the method described in any one in claim 7-18.
20. diene's polymer in claim 1-6 and 19 described in any one is used as the application of rubber-based adhesive.
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| CN201310512794.5A CN104558329B (en) | 2013-10-25 | 2013-10-25 | A kind of diene's polymer and its preparation method and application |
| DE201410221690 DE102014221690A1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
| RU2014142923/04A RU2599641C2 (en) | 2013-10-25 | 2014-10-24 | Functional polydiene, method for production thereof and rubber composition containing same |
| US14/523,113 US9296840B2 (en) | 2013-10-25 | 2014-10-24 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
| FR1460262A FR3012455B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENE POLYMER, PROCESS FOR PREPARING THE SAME, AND RUBBER COMPOSITION COMPRISING SAME |
| BE2014/0796A BE1022183B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
| KR1020140146390A KR101660856B1 (en) | 2013-10-25 | 2014-10-27 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
| SG10201407122YA SG10201407122YA (en) | 2013-10-25 | 2014-10-31 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
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| CN111032763A (en) * | 2017-09-01 | 2020-04-17 | 株式会社可乐丽 | Rubber composition for high grip tire |
| CN114773514A (en) * | 2022-05-26 | 2022-07-22 | 青岛科技大学 | Macromolecular coupling agent for improving performance of rubber material vulcanized rubber and application thereof |
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| FR2940302B1 (en) * | 2008-12-22 | 2012-07-27 | Michelin Soc Tech | RUBBER COMPOSITION COMPRISING A BLOCKED MERCAPTOSILANE COUPLING AGENT |
| KR20110131217A (en) * | 2009-03-11 | 2011-12-06 | 제이에스알 가부시끼가이샤 | Rubber composition and pneumatic tire |
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