CN104558417A - Modified olefin polymer as well as preparation method and application thereof - Google Patents
Modified olefin polymer as well as preparation method and application thereof Download PDFInfo
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- CN104558417A CN104558417A CN201310513369.8A CN201310513369A CN104558417A CN 104558417 A CN104558417 A CN 104558417A CN 201310513369 A CN201310513369 A CN 201310513369A CN 104558417 A CN104558417 A CN 104558417A
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Abstract
The invention provides a modified olefin polymer, a preparation method of the modified olefin polymer, an olefin polymer prepared by the method, and application of the modified olefin polymer serving as rubber base glue. The molecular chain of the modified modified olefin polymer contains at least one monovinylarene structural unit, at least two conjugated diene structural units, and a silane coupling agent structural unit as shown in a formula (I) in the specification; the average molecular weight of the modified olefin polymer is fifty thousand to 1 million; R1-R4 are linear or branched-chain alkyl with C1-C20 or heteroatom-containing linear or branched-chain alkyl with C1-C20; the heteroatom is selected from one or a plurality of halogen, oxygen, sulphur, silicon and phosphorus. By virtue of the modified olefin polymer, the relationship between wet-skid resistance and rolling resistance can be balanced, and moreover, the unpleasant smell caused by the silane coupling agent used in rubber mixing can be reduced.
Description
Technical field
The present invention relates to the application as rubber-based adhesive of a kind of modified olefine polymer, the preparation method of modified olefine polymer, the modified olefine polymer prepared by aforesaid method and above-mentioned modified olefine polymer.
Background technology
In recent years, along with the development of automotive industry and climbing up and up of oil price, people pay close attention to further to the security of automobile and energy saving, and this just requires that tire is while having compared with high wet-sliding resistant performance, also has lower rolling resistance.But, improve wet-sliding resistant performance and be often difficult to take into account with reduction rolling resistance simultaneously.Therefore, according to different service requirementss, need between high wet-sliding resistant performance and low rolling resistance, seek best balance.
For production low rolling resistance tyre, because anionic solution polymerization can regulate side chain to contain content and the second-order transition temperature of the conjugated diene structural unit of double bond effectively, the solution polymerized butylbenzene of anionoid polymerization has and gathers the more significant advantage of butylbenzene than breast.This advantage is favourable for the relation balanced between the wet-sliding resistant performance of tire and rolling resistance.In addition, research shows, silane coupling agent is added in the mixing process of rubber combination, the dispersion of filler in rubber can be promoted to a certain extent and improve the relation between the wet-sliding resistant performance of rubber and rolling resistance to a certain extent, but in rubber combination mixing process, by the impact of other additives, the reactive behavior of silane coupling agent and rubber and carbon black can reduce.Further, in rubber combination mixing process, add silane coupling agent and also can produce unpleasant stink.The silane that can use and there is structure shown in formula (1) is disclosed as properties-correcting agent to improve the wet-sliding resistant performance of styrene-butadiene rubber(SBR) and to reduce rolling resistance in EP447066:
USi (OR')
jr''
4-i-jformula (1),
Wherein, U is halogen, and R ＇ and R ＇ ＇ is C
1-C
20alkyl, aryl, vinyl or haloalkyl, j is the integer of 1-4, and i is the integer of 0-2, i and j's and be 2-4.The silane with structure shown in formula (1) can be reacted by the catalyst residues of halogen and polymer molecule chain end and key is linked on polymer molecular chain, but, a usual polymer molecular chain can only connect a silane molecule by key, only can produce slight influence to the interaction between polymer molecular chain, can not effectively improve the anti-slippery of rubber and reduce rolling resistance.
Summary of the invention
The object of the invention is to adopt existing method effectively can not improve the defect of the relation between the wet-sliding resistant performance of rubber and rolling resistance to overcome, and provide a kind of and can have the application as rubber-based adhesive of the modified olefine polymer of high wet-sliding resistant performance and low-rolling-resistance, the preparation method of modified olefine polymer and the modified olefine polymer prepared by aforesaid method and above-mentioned modified olefine polymer concurrently.
The invention provides a kind of modified olefine polymer, containing at least one monovinylarene structural unit and at least two kinds of conjugated diene structural units in the molecular chain of described modified olefine polymer, wherein, also containing the silane coupling agent structural unit shown in formula I in the molecular chain of described modified olefine polymer, the number-average molecular weight of described modified olefine polymer is 50,000-100 ten thousand;
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more.
Present invention also offers a kind of preparation method of modified olefine polymer, wherein, the method is included in inert atmosphere and under the existence of initiator, contact containing at least one monovinylarene structural unit with silane coupling agent with the olefin polymer of at least two kinds of conjugated diene structural units, the condition of described contact makes described silane coupling agent chemical bond-linking on described olefin polymer; The number-average molecular weight of described olefin polymer is 50,000-100 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 15-85 % by weight, is preferably 30-60 % by weight, and described silane coupling agent has the structure shown in formula II:
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more.
Present invention also offers the preparation method of another kind of modified olefine polymer, wherein, the method comprises the following steps:
(1) in an inert atmosphere and under the existence of initiator, at least one monovinylarene and at least two kinds of conjugated dienes are carried out polyreaction in the solution, obtain the reaction product containing olefin polymer, the condition of described polyreaction makes the number-average molecular weight of the olefin polymer obtained be 50,000-100 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 15-85 % by weight, is preferably 30-60 % by weight;
(2) in an inert atmosphere and under the existence of initiator, the reaction product containing olefin polymer step (1) obtained contacts with silane coupling agent, the condition of described contact makes described silane coupling agent chemical bond-linking on described olefin polymer, and described silane coupling agent has the structure shown in formula II:
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more.
Present invention also offers the modified olefine polymer prepared by aforesaid method.
In addition, present invention also offers the application of above-mentioned modified olefine polymer as rubber-based adhesive.
As mentioned above, in the prior art, usually in the mixing process of rubber, just silane coupling agent is added, to improve the wet-sliding resistant performance of rubber and to reduce its rolling resistance, but now the reactive behavior of silane coupling agent and rubber and carbon black can reduce, not only be difficult to significantly improve the relation between the wet-sliding resistant performance of rubber and rolling resistance, but also unpleasant stink can be produced.And the present inventor finds after deep research, by by silane coupling agent chemical bond-linking on olefin polymer, and using overall as part or all of rubber-based adhesive for the modified olefine polymer obtained, the problem that the reactive behavior of silane coupling agent and rubber and the carbon black caused in rubber mixing process reduces can be avoided, and the relation between the anti-slippery of tire be made up of described modified olefine polymer of active balance and rolling resistance, the undesirable smell caused due to the use of silane coupling agent in rubber mixing process can also be improved simultaneously.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Containing at least one monovinylarene structural unit and at least two kinds of conjugated diene structural units in the molecular chain of modified olefine polymer provided by the invention, wherein, also containing the silane coupling agent structural unit shown in formula I in the molecular chain of described modified olefine polymer, the number-average molecular weight of described modified olefine polymer is 50,000-100 ten thousand;
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more; Preferably, R
1-R
3for C
1-C
5straight or branched alkyl or straight or branched alkoxyl group, R
4for C
1-C
5straight or branched alkylidene group.
Described C
1-C
5the specific examples of straight or branched alkyl include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl; Described C
1-C
5the specific examples of straight or branched alkoxyl group include but not limited to: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, tertiary pentyloxy and neopentyl oxygen; Described C
1-C
5the specific examples of straight or branched alkylidene group include but not limited to: methylene radical, ethylidene, propylidene, butylidene and pentylidene.
On the molecular chain of described modified olefine polymer, monovinylarene structural unit and conjugated diene structural unit form the main chain of polymkeric substance, and the silane coupling agent structural unit key shown in formula I is linked on the conjugated diene structural unit on main chain.
Particularly preferably, in formula I, R
1-R
3for methoxyl group, R
4for propylidene, now, corresponding with the silane coupling agent structural unit shown in formula I silane coupling agent is γ-mercaptopropyl trimethoxysilane; Or, R
1-R
3for oxyethyl group, R
4for propylidene, now, corresponding with the silane coupling agent structural unit shown in formula I silane coupling agent is gamma-mercaptopropyltriethoxysilane; Or, R
1-R
3for methyl, R
4for ethylidene, now, corresponding with the silane coupling agent structural unit shown in formula I silane coupling agent is 2-trimethyl silane sulfur alcohol.
The present invention is to the monovinylarene structural unit in described modified olefine polymer, the content of conjugated diene structural unit and silane coupling agent structural unit is not particularly limited, and can according to monovinylarene in preparation process, the consumption of conjugated diene and silane coupling agent adjusts, but in order to make described modified olefine polymer, there is higher wet-sliding resistant performance and there is lower rolling resistance, with the gross weight of described modified olefine polymer for benchmark, the content of described monovinylarene structural unit and conjugated diene structural unit is preferably 90-99.99 % by weight, be more preferably 98-99.8 % by weight, the content of described silane coupling agent structural unit is preferably 0.01-10 % by weight, be more preferably 0.2-2 % by weight.Further, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit can be 5:95-60:40, be preferably 20:80-40:60.
The present invention is not particularly limited the number-average molecular weight of described modified olefine polymer and molecular weight distribution, and such as, described number-average molecular weight can be 50,000-100 ten thousand, be preferably 150,000-20 ten thousand, and molecular weight distribution can be 1-4, be preferably 1-1.5.Described number-average molecular weight and molecular weight distribution all can adopt the model purchased from Shimadzu Corporation to be that the gel permeation chromatograph (GPC) of LC-10AT records, and wherein, being moving phase with THF, take Narrow distribution polystyrene as standard specimen, and probe temperature is 25 DEG C.
According to the present invention, described monovinylarene structural unit is the structural unit derived from monovinylarene, is namely polymerized the structural unit formed by monovinylarene.With the various aromatic monomers of a vinyl substituent on the aromatic ring that described monovinylarene can be commonly used for this area, as a rule, described monovinylarene has the structure shown in formula III:
Wherein, R
5can be C
6-C
20substituted or unsubstituted aryl, be preferably phenyl and by one or more C
1-C
5alkyl replace phenyl.
According to the present invention, described C
6-C
20the specific examples of substituted or unsubstituted aryl include but not limited to: phenyl, tolyl, ethylbenzene, tert-butyl-phenyl, dodecylphenyl, di-n-butyl phenyl (comprise adjacent di-n-butyl phenyl, a di-n-butyl phenyl and to di-n-butyl phenyl), n-propyl phenyl and diethyl phenyl (comprise adjacent two positive ethylphenyls, a two positive ethylphenyl and to two positive ethylphenyls).
According to the present invention, described monovinylarene is particularly preferably at least two kinds in vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene and 4-vinyl toluene.
According to the present invention, described conjugated diene structural unit be derived from conjugated diene structural unit namely, the structural unit formed by conjugate diene polymerization.Described conjugated diene refers to the various unsaturated acyclic hydrocarbons containing conjugated double bond (that is ,-C=C-C=C-) in molecular structure.Described conjugated diene can be that the routine of this area is selected, be not particularly limited, and choose reasonable can be carried out according to the application scenario of the modified olefine polymer finally obtained, such as, described conjugated diene can be selected from divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2, one or more in 3-dimethylbutadiene, are preferably divinyl and/or isoprene.
The preparation method of modified olefine polymer provided by the invention is included in inert atmosphere and under the existence of initiator, contact containing at least one monovinylarene structural unit with silane coupling agent with the olefin polymer of at least two kinds of conjugated diene structural units, the condition of described contact makes described silane coupling agent chemical bond-linking on described olefin polymer; The number-average molecular weight of described olefin polymer is 50,000-100 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 15-85 % by weight, is preferably 30-60 % by weight, and described silane coupling agent has the structure shown in formula II:
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more; Preferably, R
1-R
3for C
1-C
5straight or branched alkyl or straight or branched alkoxyl group, R
4for C
1-C
5straight or branched alkylidene group.
The content that described side chain contains the conjugated diene structural unit of double bond can adopt the model purchased from Bruker company of Switzerland to be that the nuclear magnetic resonance spectrometer of AVANCE DRX400MHz measures, and wherein, solvent is deuterochloroform.Concrete measuring method is known to the skilled person, and will repeat no more at this.
Particularly preferably, in formula II, R
1-R
3for methoxyl group, R
4for propylidene, now, corresponding silane coupling agent is γ-mercaptopropyl trimethoxysilane; Or, R
1-R
3for oxyethyl group, R
4for propylidene, now, corresponding silane coupling agent is gamma-mercaptopropyltriethoxysilane; Or, R
1-R
3for methyl, R
4for ethylidene, now, corresponding silane coupling agent is 2-trimethyl silane sulfur alcohol.
According to the present invention, described olefin polymer can adopt existing various method to be prepared, such as, can prepare in accordance with the following methods: in an inert atmosphere and under the existence of initiator, at least one monovinylarene and at least two kinds of conjugated dienes are carried out polyreaction in a solvent, the condition of described polyreaction makes the number-average molecular weight of the olefin polymer obtained be 50,000-100 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 15-85 % by weight, be preferably 30-60 % by weight.
According to the present invention, described inert atmosphere refer to not with any one gas or the gaseous mixture of reactant and product generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.Keep the method for inert atmosphere can for pass in reaction system above-mentioned not with any one gas or the gaseous mixture of reactant and product generation chemical reaction.
According to the present invention, in the preparation process of olefin polymer, described initiator can be the existing various initiator that can cause described monovinylarene and conjugate diene polymerization, such as, can be organic lithium initiator.Single organic lithium initiator of described organic lithium initiator can be such as molecular formula be RLi, wherein, R is the alkyl of straight or branched, cycloalkyl or aryl.Particularly, described single organic lithium initiator can be selected from lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium one or more, be preferably n-Butyl Lithium and/or s-butyl lithium.In addition, the present invention also can adopt dilithium initiator, as trimethylene two lithium and/or tetramethylene two lithium.The consumption of the present invention to described initiator is not particularly limited, and reasonably can select according to the molecular size range of design.Those skilled in the art should it is easily understood that when needing to prepare the larger olefin polymer of molecular weight, can reduce the consumption of initiator, but now rate of polymerization also correspondingly can reduce; When needing the olefin polymer preparing molecular weight, the consumption of initiator can be increased, but now rate of polymerization also correspondingly can increase.Therefore, the molecular size range of olefin polymer considering rate of polymerization and obtain, under preferable case, with the gross weight of 100g monovinylarene and conjugated diene for benchmark, the consumption of described initiator is 0.15-2.5mmol.
According to the present invention, the consumption of described monovinylarene and conjugated diene can carry out selecting and changing in the larger context, and can according to expecting that the olefin polymer that will obtain reasonably is selected, such as, the weight ratio of described monovinylarene and conjugated diene can be 5:95-60:40, be preferably 20:80-40:60.
The condition of the present invention to described polyreaction is not particularly limited, and generally includes polymerization temperature, polymerization pressure and polymerization time.Wherein, in order to more be conducive to the carrying out of polyreaction, described polymerization temperature is preferably 10-160 DEG C, is more preferably 40-80 DEG C, and described polymerization pressure is preferably 0.05-1MPa, is more preferably 0.1-0.3MPa.As a rule, the prolongation of described polymerization time is conducive to the raising of reaction-ure conversion-age and reaction product yield, but the amplitude that polymerization time is long to be improved reaction-ure conversion-age and reaction product yield is also not obvious, therefore, consider polymerization efficiency and effect, described polymerization time is preferably 0.5-10 hour, is more preferably 0.5-2 hour.
In the present invention, described pressure all refers to gauge pressure.
According to the present invention, in the preparation process of olefin polymer, described solvent can be various can, as the material of reaction media, such as, can be varsol and/or ether solvent.Described varsol can be C
5-C
7naphthenic hydrocarbon, one or more in aromatic hydrocarbons and isoparaffin.The specific examples of described varsol can include but not limited to: one or more in benzene, toluene, pentane, heptane, normal hexane and hexanaphthene.Described ether solvent can be C
4-C
15monoether and/or polyether.The specific examples of described ether solvent can include but not limited to: tert-butoxyethoxy ethane and/or tetrahydrofuran (THF).Wherein, these solvents can be used alone, also can be used in combination.The consumption of described solvent reasonably can be selected according to the consumption of monomer, and such as, the consumption of described solvent can make the total concn of described monovinylarene and conjugated diene be 1-30 % by weight, is preferably 5-20 % by weight.
According to the present invention, after polymerization was complete, coupling agent can also be added in polymerization system, to be coupled at together by least part of olefin polymer.The kind of described coupling agent is known to the skilled person, and such as, can be one or more in many vinyl compounds, halogenide, ether, aldehyde, ketone, ester etc.Particularly, described coupling agent can be selected from Vinylstyrene, tetravinyl silane, tetrachloromethane, silicon tetrachloride, tin tetrachloride, dimethyl terephthalate (DMT) and epoxy soybean oil one or more, be preferably in Vinylstyrene, silicon tetrachloride and tin tetrachloride one or more.It should be noted that, when described coupling agent is silane compound, described silane compound is different from the silane coupling agent with structure shown in formula II.
The consumption of the present invention to described coupling agent is not particularly limited, and suitably can select according to the consumption of initiator, and such as, the mol ratio of described coupling agent and described initiator can be 0.1-2:1, is preferably 0.1-1:1.
According to the present invention, under preferable case, can also structure regulator be added in the preparation process of described olefin polymer, effectively can control the microtexture of described olefin polymer like this.Described structure regulator can be the existing various material that can regulate the microtexture of olefin polymer, such as, can be selected from ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, dioxane, crown ether, tetrahydrofurfuryl alcohol ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium and sodium alkyl benzene sulfonate one or more.As a rule, described structure regulator can be 1-100:1, preferably 80-100:1 with the mol ratio preparing olefin polymer initiator used.
As a rule, anionic polymerisation system does not have obvious termination reaction and shift reaction, and after ruing out of whole monomer, active centre still exists.Therefore, after completion of the polymerization reaction, the polymers soln obtained should be contacted with terminator make active centre inactivation.The consumption of described terminator can come according to the consumption preparing olefin polymer initiator used reasonably to select, and as a rule, described terminator can be 0.1-1:1 with the mol ratio preparing olefin polymer initiator used.Described terminator can be the existing various reagent that can make anion active center inactivation, such as, can be selected from one or more in water, methyl alcohol, ethanol and Virahol, be preferably Virahol.
The present invention is not particularly limited the condition contacted with silane coupling agent by described olefin polymer, as long as described silane coupling agent chemical bond-linking can be made on olefin polymer, such as, the condition of described contact generally includes Contact Temperature, contact pressure and duration of contact.As a rule, in order to more be conducive to silane coupling agent chemical bond-linking on olefin polymer, described Contact Temperature is preferably 20-150 DEG C, is more preferably 70-90 DEG C, described contact pressure is preferably 0.01-1MPa, is more preferably 0.1-0.5MPa, is preferably 0.1-24 hour described duration of contact, is more preferably 0.5-5 hour.
According to the present invention, when olefin polymer is contacted with silane coupling agent, in order to take into account the size of trigger rate and modified olefine polymer molecular weight, with described olefin polymer and there is structure shown in formula II the gross weight of silane coupling agent for benchmark, the consumption of described initiator is preferably 0.01-0.1 % by weight, is more preferably 0.01-0.08 % by weight.One or more in the radical initiators such as the azo-initiator that described initiator can be known to the skilled person, peroxide type initiators and redox type initiators.
Described azo-initiator can be selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline hydrochloride, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile) one or more.
Described peroxide type initiators can be selected from hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester one or more.
Described redox type initiators can be selected from vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide one or more.Particularly, described vitriol-sulphite can be selected from one or more in sodium sulfate-S-WAT, potassium sulfate-potassium sulfite and ammonium sulfate-ammonium sulphite; Persulphate-thiocarbamide can be selected from Sodium Persulfate-thiocarbamide, Potassium Persulphate-thiocarbamide and ammonium persulphate-thiocarbamide one or more; Persulphate-organic salt can be selected from Sodium Persulfate-Potassium ethanoate, Potassium Persulphate-Potassium ethanoate and ammonium persulphate-ammonium acetate one or more; Ammonium persulphate-aliphatic amide can be selected from ammonium persulphate-N, N-Tetramethyl Ethylene Diamine and/or ammonium persulphate-diethylamine.
The present invention is not particularly limited the consumption of described olefin polymer with the silane coupling agent with structure shown in formula II, such as, with the olefin polymer of 100g for benchmark, the consumption of described silane coupling agent can be 0.01-10g, is preferably 0.1-5g, is more preferably 0.2-2g.
In addition, present invention also offers the method that another kind prepares modified olefine polymer, wherein, the method comprises the following steps:
(1) in an inert atmosphere and under the existence of initiator, at least one monovinylarene and at least two kinds of conjugated dienes are carried out polyreaction in a solvent, obtain the reaction product containing olefin polymer, the condition of described polyreaction makes the number-average molecular weight of the olefin polymer obtained be 50,000-100 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 15-85 % by weight, is preferably 30-60 % by weight;
(2) in an inert atmosphere and under the existence of initiator, the reaction product containing olefin polymer step (1) obtained contacts with silane coupling agent, the condition of described contact makes described silane coupling agent chemical bond-linking on described olefin polymer, and described silane coupling agent has the structure shown in formula II:
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more; Preferably, R
1-R
3for C
1-C
5straight or branched alkyl or straight or branched alkoxyl group, R
4for C
1-C
5straight or branched alkylidene group.
Wherein, in step (1) and (2), the kind of each material and the condition of consumption and polyreaction and contact conditions all according to reasonably selecting above, will be able to repeat no more at this.
According to the present invention, after prepared by described modified olefine polymer, optionally can also add various additive in the modified olefine polymer obtained.Described additive can be such as anti-aging agent, and the modified olefine polymer obtained can be made like this to have good ageing resistance.The kind of described anti-aging agent and consumption can be all that the routine of this area is selected, and will repeat no more at this.
According to the present invention, after adding anti-aging agent, the methods such as described modified olefine polymer can be precipitated by purifying, centrifugation, filtration, decant, hot water cohesion are precipitated out from solution, also air-extraction can be adopted the removal of solvents in reaction system, all can know these those skilled in the art, will repeat no more at this.
Present invention also offers the modified olefine polymer prepared by aforesaid method.
In addition, present invention also offers the application of above-mentioned modified olefine polymer as rubber-based adhesive.
Below will be described the present invention by embodiment.
In following examples and comparative example, sulfydryl transformation efficiency adopts Agilent 7890A type gas chromatograph to measure, test condition comprises: chromatographic column SPB-560m × 0.32mm × 1.0um capillary column, column flow rate 2.0ml/min, column temperature 220 DEG C, vaporizer temperature 220 DEG C, sensing chamber's temperature 250 DEG C, splitting ratio 50:1, sample size 0.3ul.The content that side chain contains the content of the conjugated diene structural unit of double bond, the content of monovinylarene structural unit and conjugated diene structural unit adopts Switzerland Bruker company AVANCE DRX400MHz nuclear magnetic resonance spectrometer to measure, and solvent is deuterochloroform.Number-average molecular weight and molecular weight distribution adopt U.S. WATERS company ALLIANCE2690 type gel permeation chromatograph (GPC) to measure, and THF is moving phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.Mooney viscosity adopts the SMV-300 type mooney's viscosimeter of Japanese Shimadzu Corporation to measure by the method specified in GB/T1232-92.Charging capacity × sulfydryl transformation efficiency the ÷ (charging capacity × sulfydryl transformation efficiency of the charging capacity+silane coupling agent of the charging capacity+conjugated diene of monovinylarene) × 100% of the content=silane coupling agent of silane coupling agent.
Embodiment 1
This embodiment is for illustration of modified olefine polymer provided by the invention and preparation method thereof.
(1) in 5 liters of stainless steel stirring tanks, under High Purity Nitrogen protection, add 2288g hexanaphthene, 31.20g vinylbenzene, 51.60g divinyl, 51.20g isoprene and 1.05g tetrahydrofurfuryl alcohol ether, then add the n-Butyl Lithium of 1.1mmol after being heated to 50 DEG C and by pressure-controlling initiation reaction 2 hours at 0.2 mpa, obtain the solution containing olefin polymer; The number-average molecular weight of described olefin polymer is 18.0 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 41.01 % by weight, the content of styrol structural unit is 23.28 % by weight, the content of butadiene structural units is 38.51 % by weight, and the content of isoprene structures unit is 38.21 % by weight.
(2) 0.8ml(0.836g is added in the product obtained toward step (1)) γ-mercaptopropyl trimethoxysilane, and sulfydryl test is carried out in sampling immediately, then 6.5mg azo-bis-isobutyl cyanide is added after being heated to 75 DEG C, and obtain modified olefine polymer after pressure-controlling is reacted 3 hours at 0.2 mpa, and sulfydryl test is carried out in sampling.In above-mentioned modified olefine polymer, add 0.2g anti-aging agent Irganox1520, and in 60 DEG C of vacuum dry 24h.Wherein, sulfydryl transformation efficiency is 78%, and the mooney viscosity of modified olefine polymer is 43, and number-average molecular weight is 18.0, and molecular weight distribution is 1.08; With the gross weight of described modified olefine polymer for benchmark, the content of γ-mercaptopropyl trimethoxysilane structural unit is 0.49 % by weight.This polymkeric substance does not have undesirable smell.
Embodiment 2
This embodiment is for illustration of modified olefine polymer provided by the invention and preparation method thereof.
(1) in 5 liters of stainless steel stirring tanks, under High Purity Nitrogen protection, add 2288g hexanaphthene, 31.20g Vinyl toluene, 82.30g divinyl, 30.00g isoprene and 0.65g tetrahydrofuran (THF), then add the n-Butyl Lithium of 1.0mmol after being heated to 40 DEG C and by pressure-controlling initiation reaction 2 hours under 0.1MPa, obtain the solution containing olefin polymer; The number-average molecular weight of described olefin polymer is 18.3 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 33.02 % by weight, the content of Vinyl toluene structural unit is 21.74 % by weight, the content of butadiene structural units is 57.35 % by weight, and the content of isoprene structures unit is 20.91 % by weight.
(2) 0.6ml(0.627g is added in the product obtained toward step (1)) γ-mercaptopropyl trimethoxysilane, and sulfydryl test is carried out in sampling immediately, then 29mg azo-bis-isobutyl cyanide is added after being heated to 80 DEG C, and obtain modified olefine polymer after pressure-controlling is reacted 5 hours under 0.1MPa, and sulfydryl test is carried out in sampling.In above-mentioned modified olefine polymer, add 0.2g anti-aging agent Irganox1520, and in 60 DEG C of vacuum dry 2h.Wherein, sulfydryl transformation efficiency is 82%, and the mooney viscosity of modified olefine polymer is 49, and number-average molecular weight is 18.3, and molecular weight distribution is 1.08; With the gross weight of described modified olefine polymer for benchmark, the content of γ-mercaptopropyl trimethoxysilane structural unit is 0.35 % by weight.This polymkeric substance does not have undesirable smell.
Embodiment 3
This embodiment is for illustration of modified olefine polymer provided by the invention and preparation method thereof.
(1) in 5 liters of stainless steel stirring tanks, under High Purity Nitrogen protection, add 2288g hexane, 32.00g vinylbenzene, 42.30g divinyl, 70.00g isoprene and 2.0g tetrahydrofurfuryl ether, then add the n-Butyl Lithium of 1.0mmol after being heated to 45 DEG C and by pressure-controlling initiation reaction 0.5 hour under 0.3MPa, obtain the solution containing olefin polymer; The number-average molecular weight of described olefin polymer is 19.2 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 53.02 % by weight, the content of styrol structural unit is 22.18 % by weight, the content of butadiene structural units is 29.31 % by weight, and the content of isoprene structures unit is 48.51 % by weight.
(2) 1.06ml(1.045g is added in the product obtained toward step (1)) gamma-mercaptopropyltriethoxysilane, and sulfydryl test is carried out in sampling immediately, then 30mg azo-bis-isobutyl cyanide is added after being heated to 90 DEG C, and obtain modified olefine polymer after pressure-controlling is reacted 0.5 hour under 0.5MPa, and sulfydryl test is carried out in sampling.In above-mentioned modified olefine polymer, add 0.2g anti-aging agent Irganox1520, and in 60 DEG C of vacuum dry 24h.Wherein, sulfydryl transformation efficiency is 89%, and the mooney viscosity of modified olefine polymer is 54, and number-average molecular weight is 19.2, and molecular weight distribution is 1.09; With the gross weight of described modified olefine polymer for benchmark, the content of gamma-mercaptopropyltriethoxysilane structural unit is 0.64 % by weight.This polymkeric substance does not have undesirable smell.
Embodiment 4
This embodiment is for illustration of modified olefine polymer provided by the invention and preparation method thereof.
(1) in 5 liters of stainless steel stirring tanks, under High Purity Nitrogen protection, add 2288g tetrahydrofuran (THF), 20.00g vinylbenzene, 110.00g divinyl, 25.00g isoprene and 0.9g tetrahydrofurfuryl alcohol ether, then be heated to add under after 80 DEG C the n-Butyl Lithium of 1.0mmol and by pressure-controlling initiation reaction 1 hour under 0.25MPa, obtain the product containing olefin polymer; The number-average molecular weight of described olefin polymer is 19.6 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 51.01 % by weight, the content of styrol structural unit is 12.90 % by weight, the content of butadiene structural units is 70.97 % by weight, and the content of isoprene structures unit is 16.13 % by weight.
(2) 3.0ml(3.135g is added in the product obtained toward step (1)) γ-mercaptopropyl trimethoxysilane, and sulfydryl test is carried out in sampling immediately, then 30mg azo-bis-isobutyl cyanide is added after being heated to 80 DEG C, and obtain modified olefine polymer after pressure-controlling is reacted 1 hour under 0.3MPa, and sulfydryl test is carried out in sampling.In above-mentioned modified olefine polymer, add 0.2g anti-aging agent Irganox1520, and in 60 DEG C of vacuum dry 24h.Wherein, sulfydryl transformation efficiency is 78%, and the mooney viscosity of modified olefine polymer is 55, and number-average molecular weight is 19.6, and molecular weight distribution is 1.09; With the gross weight of described modified olefine polymer for benchmark, the content of γ-mercaptopropyl trimethoxysilane structural unit is 1.55 % by weight.This polymkeric substance does not have undesirable smell.
Embodiment 5
This embodiment is for illustration of modified olefine polymer provided by the invention and preparation method thereof.
(1) in 5 liters of stainless steel stirring tanks, under High Purity Nitrogen protection, add 2288g hexanaphthene, 62.40g vinylbenzene, 128.60g divinyl, 120.00g isoprene and 1.5g tetrahydrofurfuryl alcohol ether, then under 70 DEG C of conditions, add the n-Butyl Lithium of 1.1mmol and by pressure-controlling initiation reaction 1.2 hours at 0.2 mpa, obtain the solution containing olefin polymer; The number-average molecular weight of described olefin polymer is 19.1 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 47.30 % by weight, the content of styrol structural unit is 20.06 % by weight, the content of butadiene structural units is 41.35 % by weight, and the content of isoprene structures unit is 38.59 % by weight.
(2) 1.9ml(1.986g is added in the product obtained toward step (1)) γ-mercaptopropyl trimethoxysilane, and sulfydryl test is carried out in sampling immediately, then 10mg azo-bis-isobutyl cyanide is added after being heated to 70 DEG C, and obtain modified olefine polymer after pressure-controlling is reacted 1.2 hours under 0.25MPa, and sulfydryl test is carried out in sampling.In above-mentioned modified olefine polymer, add 0.4g anti-aging agent Irganox1520, and in 60 DEG C of vacuum dry 24h.Wherein, sulfydryl transformation efficiency is 82%, and the mooney viscosity of modified olefine polymer is 49, and number-average molecular weight is 19.1, and molecular weight distribution is 1.08; With the gross weight of described modified olefine polymer for benchmark, the content of γ-mercaptopropyl trimethoxysilane structural unit is 0.53 % by weight.This polymkeric substance does not have undesirable smell.
Embodiment 6
This embodiment is for illustration of modified olefine polymer provided by the invention and preparation method thereof.
Modified olefine polymer is prepared according to the method for embodiment 4, unlike, the 2-trimethyl silane sulfur alcohol of described γ-mercaptopropyl trimethoxysilane identical weight part substitutes, and obtains modified olefine polymer.Wherein, sulfydryl transformation efficiency is 65%, and the mooney viscosity of modified olefine polymer is 51, and number-average molecular weight is 18.9, and molecular weight distribution is 1.09; With the gross weight of described modified olefine polymer for benchmark, the content of 2-trimethyl silane sulfur alcohol structural unit is 1.30 % by weight.This polymkeric substance does not have undesirable smell.
Comparative example 1
This comparative example is for illustration of reference olefin polymer and preparation method thereof.
Olefin polymer is prepared according to the method for embodiment 1, unlike, do not comprise step (2), obtain olefin polymer.In above-mentioned olefin polymer, add 0.4g anti-aging agent Irganox1520, and in 60 DEG C of vacuum dry 24h.Wherein, the mooney viscosity of described olefin polymer is 48, and number-average molecular weight is 18.0, and molecular weight distribution is 1.08; With the gross weight of described olefin polymer for benchmark, the content of styrol structural unit is 23.28 % by weight, and the content of butadiene structural units is 38.51 % by weight, and the content of isoprene structures unit is 38.21 % by weight.
Comparative example 2
This comparative example is for illustration of reference olefin polymer and preparation method thereof.
(1) in 5 liters of stainless steel stirring tanks; under High Purity Nitrogen protection; add 1500g hexanaphthene, 20g divinyl and 2.7g tetrahydrofurfuryl alcohol ether; then add the n-Butyl Lithium of 12mmol after being heated to 40 DEG C and by pressure-controlling initiation reaction 1 hour under 0.4MPa, obtain the solution containing olefin polymer.The number-average molecular weight of described olefin polymer is 1000, and with the weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 67 % by weight.
(2) 20g γ-mercaptopropyl trimethoxysilane is added in the product obtained toward step (1), and sulfydryl test is carried out in sampling immediately, then 1g dilauroyl peroxide is added after being heated to 100 DEG C, and obtain modified olefine polymer after pressure-controlling is reacted 5 hours under 0.4MPa, and sulfydryl test is carried out in sampling.Finally dry 24h in 80 DEG C of vacuum.Wherein, the sulfydryl transformation efficiency of modified olefine polymer is 80%, and number-average molecular weight is 1788.With the gross weight of described modified olefine polymer for benchmark, the content of γ-mercaptopropyl trimethoxysilane structural unit is 44.4 % by weight.
Embodiment 7-12
Embodiment 7-12 is for illustration of the preparation method of the rubber containing modified olefine polymer of the present invention.
(1) preparation of rubber unvulcanizate:
Stearic acid (the polite Chemical Co., Ltd. in Hong Kong of the modified olefine polymer respectively 100 weight parts prepared by embodiment 1-6,1 weight part, SA1801), 10 the weight part high abrasion furnace black(HAF) N330(Tianjin gold autumns real carbon black Chemical Co., Ltd.), 60 weight part white carbon black 115GR(goldschmidt chemical corporation) mix and adopt Haake thermal treatment, wherein, thermal treatment temp is 150 DEG C, rotating speed is 30rpm/min, and the time is 7min.After thermal treatment completes, said mixture is added in mill, and add the zinc oxide (Liuzhou Xin Pin company limited) of 2.5 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong of 1 weight part, SA1801), the antioxidant 4020 of 2 weight parts, N-cyclohexyl-2-benzothiazole sulfonamide (Hebi Uhoo Rubber Chemicals Co., Ltd. of 1.4 weight parts, CZ), 0.75 weight part vulkacit D (Guangzhou Li great rubber raw materials trade Co., Ltd, DPG) and 6 weight part silane coupling agent Si69(goldschmidt chemical corporation), at 50 ± 5 DEG C mixing 60 minutes, obtain rubber unvulcanizate H1-H6.
(2) sulfuration:
150 DEG C, under 12MPa, rubber unvulcanizate H1-H6 step (1) obtained carries out sulfidizing 40 minutes respectively on vulcanizing press, obtains vulcanized rubber S1-S6.
Comparative example 3
This comparative example is for illustration of the preparation method of the rubber containing reference olefin polymer.
Rubber is prepared according to the method for embodiment 7, unlike, the modified olefine polymer prepared by embodiment 1 olefin polymer obtained by comparative example 1 is substituted, and the add-on of olefin polymer is 99.51 weight parts, in addition, in the preparation process of rubber unvulcanizate, also add the γ-mercaptopropyl trimethoxysilane of 0.49 weight part, obtain reference vulcanized rubber DS1.
Comparative example 4
This comparative example is for illustration of the preparation method of reference vulcanized rubber.
Vulcanized rubber is prepared according to the method for embodiment 7, unlike, by the mixture replacing of the modified olefine polymer prepared by preparation example 3 with the olefin polymer obtained by comparative example 1 of 98.9 weight parts and the modified olefine polymer obtained by comparative example 2 of 1.1 weight parts, obtain vulcanized rubber DS2.
Test case 1-6
Test case 1-6 is for illustration of the test of vulcanized rubber S1-S6 performance provided by the invention.
(1) test of second-order transition temperature (Tg):
Adopt U.S. TA company MDSC2910 type dsc (DSC) instrument to measure, wherein, modulation period is 60s, and modulated amplitude is ± 1.5 DEG C, and temperature rise rate is 10 DEG C/min, nitrogen protection, and flow velocity is 50mL/min.Acquired results is as shown in table 1.
(2) test of mechanical property:
Vulcanized rubber S1-S6 is made the thick vulcanized rubber sheet of 2mm respectively, and according to the 1 type dumbbell shaped cut-off knife specified in GB/T528-1998, the vulcanized rubber sheet obtained is cut into dumbbell shaped standard film, (Japanese Shimadzu Corporation produces to adopt rubber puller system, model is AG-20KNG) mechanical property of described vulcanized rubber sheet is tested, wherein, probe temperature is 25 DEG C, and pulling speed is 500 mm/min, obtain tensile strength at yield and the tensile yield of vulcanized rubber, acquired results is as shown in table 1.
(3) test of shore a hardness:
Method according to specifying in GB/T531-1999 is tested, and acquired results is as shown in table 1.
(4) anti-deformation nature test:
According to the 1 type dumbbell shaped cut-off knife specified in GB/T528-92, vulcanized rubber S1-S6 being cut into dumbbell shaped standard film, is 25 DEG C at probe temperature, and pulling speed is broken by sample under the condition of 500 mm/min.Sample after tension fracture is placed 3min, then two portions of fracture is coincide together, measure the distance of coincideing between rear two parallel lines, be calculated as follows and pull apart permanentset value:
S
b=100(L
t-L
0)/L
0, wherein, S
bfor pulling apart permanentset, %; L
tfor sample coincide the distance between rear two parallel lines, mm; L
0for initial trial length, mm.Acquired results is as shown in table 1.
(5) thermogenesis performance test:
Adopt the Y3000E type compression heat generation test machine of Beijing You Shen Electronic Instrument, Limited to measure, wherein, probe temperature is 55 DEG C, and the test duration is 25 minutes, and compression frequency is 30 times/second.Acquired results is as shown in table 1.
(6) test of wet-sliding resistant performance and rolling resistance:
Adopt U.S. TA company DMA-2980 type viscoelastic spectrometer to measure the wet-sliding resistant performance of vulcanized rubber S1-S6 and rolling resistance, wherein, test frequency is 2Hz, and temperature rise rate is 5 DEG C/min, and probe temperature is 100 DEG C, and sample size is 40mm × 5mm × 1mm.Represent the wet-sliding resistant performance of vulcanized rubber with tan δ when 0 DEG C, tan δ is larger, represents that vulcanized rubber wet-sliding resistant performance is better; Represent the rolling resistance of vulcanized rubber with tan δ when 60 DEG C, tan δ is less, represents that vulcanized rubber rolling resistance is less; The value of the dispersion of filler in rubber Tan δ (0 DEG C)/Tan δ (60 DEG C) characterizes, and the higher fillers of its value disperses better.Acquired results is as shown in table 1.
Contrast test example 1-2
Contrast test example 1-2 is for illustration of the test of the performance of reference rubber.
Test according to the performance of method to reference vulcanized rubber DS1 and DS2 obtained by comparative example 3 and comparative example 4 of test case 1-6, acquired results is as shown in table 1.
Table 1
As can be seen from the result of embodiment and comparative example, modified olefine polymer provided by the invention can not only improve the relation between anti-slippery and rolling resistance effectively, can also improve the undesirable smell caused owing to using silane coupling agent in rubber mixing process.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (16)
1. a modified olefine polymer, containing at least one monovinylarene structural unit and at least two kinds of conjugated diene structural units in the molecular chain of described modified olefine polymer, it is characterized in that, also containing the silane coupling agent structural unit shown in formula I in the molecular chain of described modified olefine polymer, the number-average molecular weight of described modified olefine polymer is 50,000-100 ten thousand;
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more; Preferably, R
1-R
3for C
1-C
5straight or branched alkyl or straight or branched alkoxyl group, R
4for C
1-C
5straight or branched alkylidene group.
2. modified olefine polymer according to claim 1, wherein, with the gross weight of described modified olefine polymer for benchmark, the total content of described monovinylarene structural unit and conjugated diene structural unit is 90-99.99 % by weight, and the content of described silane coupling agent structural unit is 0.01-10 % by weight.
3. modified olefine polymer according to claim 2, wherein, with the gross weight of described modified olefine polymer for benchmark, the total content of described monovinylarene structural unit and conjugated diene structural unit is 98-99.8 % by weight, and the content of described silane coupling agent structural unit is 0.2-2 % by weight.
4. according to the modified olefine polymer in claim 1-3 described in any one, wherein, in formula I, R
1-R
3for methoxyl group, R
4for propylidene; Or,
R
1-R
3for oxyethyl group, R
4for propylidene;
R
1-R
3for methyl, R
4for ethylidene.
5. according to the modified olefine polymer in claim 1-3 described in any one, wherein, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit is 5:95-60:40, is preferably 20:80-40:60.
6. modified olefine polymer according to claim 5, wherein, described monovinylarene structural unit is the structural unit derived from monovinylarene, described monovinylarene be selected from vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene and 4-vinyl toluene one or more; Preferably, described conjugated diene structural unit is the structural unit derived from conjugated diene, and described conjugated diene is selected from least two kinds in divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2,3-dimethylbutadiene.
7. according to the modified olefine polymer in claim 1-3 described in any one, wherein, the number-average molecular weight of described modified olefine polymer is 150,000-20 ten thousand, and molecular weight distribution is 1-4, is preferably 1-1.5.
8. the preparation method of a modified olefine polymer, it is characterized in that, the method is included in inert atmosphere and under the existence of initiator, contact containing at least one monovinylarene structural unit with silane coupling agent with the olefin polymer of at least two kinds of conjugated diene structural units, the condition of described contact makes described silane coupling agent chemical bond-linking on described olefin polymer; The number-average molecular weight of described olefin polymer is 50,000-100 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 15-85 % by weight, is preferably 30-60 % by weight, and described silane coupling agent has the structure shown in formula II:
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more; Preferably, R
1-R
3for C
1-C
5straight or branched alkyl or straight or branched alkoxyl group, R
4for C
1-C
5straight or branched alkylidene group.
9. preparation method according to claim 8, wherein, described olefin polymer prepares by the following method: in an inert atmosphere and under the existence of initiator, at least one monovinylarene and at least two kinds of conjugated dienes are carried out polyreaction in a solvent, the condition of described polyreaction makes the number-average molecular weight of the olefin polymer obtained be 50,000-100 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 15-85 % by weight, be preferably 30-60 % by weight.
10. a preparation method for modified olefine polymer, is characterized in that, the method comprises the following steps:
(1) in an inert atmosphere and under the existence of initiator, at least one monovinylarene and at least two kinds of conjugated dienes are carried out polyreaction in a solvent, obtain the reaction product containing olefin polymer, the condition of described polyreaction makes the number-average molecular weight of the olefin polymer obtained be 50,000-100 ten thousand, and with the gross weight of conjugated diene structural unit in described olefin polymer for benchmark, the content that in described olefin polymer, side chain contains the conjugated diene structural unit of double bond is 15-85 % by weight, is preferably 30-60 % by weight;
(2) in an inert atmosphere and under the existence of initiator, the reaction product containing olefin polymer step (1) obtained contacts with silane coupling agent, the condition of described contact makes described silane coupling agent chemical bond-linking on described olefin polymer, and described silane coupling agent has the structure shown in formula II:
Wherein, R
1-R
4for C
1-C
20straight or branched alkyl or containing heteroatomic C
1-C
20straight or branched alkyl, described heteroatoms be selected from halogen, oxygen, sulphur, silicon and phosphorus one or more; Preferably, R
1-R
3for C
1-C
5straight or branched alkyl or straight or branched alkoxyl group, R
4for C
1-C
5straight or branched alkylidene group.
Preparation method described in 11. according to Claim 8,9 or 10, wherein, described silane coupling agent be selected from γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane and 2-trimethyl silane sulfur alcohol one or more.
12. preparation methods according to claim 9 or 10, wherein, the condition of described polyreaction comprises polymerization temperature and is 10-160 DEG C, is preferably 40-80 DEG C, and polymerization pressure is 0.05-1MPa, is preferably 0.1-0.3MPa, and polymerization time is 0.5-10 hour, is preferably 0.5-2 hour.
Preparation method described in 13. according to Claim 8,9 or 10, wherein, the condition that described olefin polymer contacts with silane coupling agent is comprised Contact Temperature to be 20-150 DEG C, to be preferably 70-90 DEG C, contact pressure is 0.01-1MPa, is preferably 0.1-0.5MPa, and duration of contact is 0.1-24 hour, is preferably 0.5-5 hour.
Preparation method described in 14. according to Claim 8,9 or 10, wherein, with the described olefin polymer of 100g for benchmark, the consumption of described silane coupling agent is 0.01-10g, is preferably 0.1-5g, is more preferably 0.2-2g.
15. modified olefine polymers prepared by the method in claim 8-14 described in any one.
Modified olefine polymer in 16. claim 1-7 and 15 described in any one is as the application of rubber-based adhesive.
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| CN201310513369.8A CN104558417B (en) | 2013-10-25 | 2013-10-25 | Modified olefin polymer as well as preparation method and application thereof |
| FR1460262A FR3012455B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENE POLYMER, PROCESS FOR PREPARING THE SAME, AND RUBBER COMPOSITION COMPRISING SAME |
| 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 |
| BE2014/0796A BE1022183B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
| US14/523,113 US9296840B2 (en) | 2013-10-25 | 2014-10-24 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
| 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107586362A (en) * | 2016-07-08 | 2018-01-16 | 中国石油化工股份有限公司 | Modified conjugated diene polymer and preparation method thereof and butadiene-styrene rubber |
| CN108239225A (en) * | 2016-12-23 | 2018-07-03 | 中国石油天然气股份有限公司 | A kind of butadiene-styrene rubber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212218A (en) * | 2010-04-05 | 2011-10-12 | 住友橡胶工业株式会社 | Tire rubber composition and pneumatic tire |
| CN102391424A (en) * | 2011-09-01 | 2012-03-28 | 上海交通大学 | Method for modifying styrene-butadiene-styrene (SBS) block copolymer |
| CN102731723A (en) * | 2011-04-13 | 2012-10-17 | 住友橡胶工业株式会社 | Diene polymer and production method thereof |
-
2013
- 2013-10-25 CN CN201310513369.8A patent/CN104558417B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212218A (en) * | 2010-04-05 | 2011-10-12 | 住友橡胶工业株式会社 | Tire rubber composition and pneumatic tire |
| CN102731723A (en) * | 2011-04-13 | 2012-10-17 | 住友橡胶工业株式会社 | Diene polymer and production method thereof |
| CN102391424A (en) * | 2011-09-01 | 2012-03-28 | 上海交通大学 | Method for modifying styrene-butadiene-styrene (SBS) block copolymer |
Cited By (4)
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| CN107586362A (en) * | 2016-07-08 | 2018-01-16 | 中国石油化工股份有限公司 | Modified conjugated diene polymer and preparation method thereof and butadiene-styrene rubber |
| CN107586362B (en) * | 2016-07-08 | 2021-03-16 | 中国石油化工股份有限公司 | Modified conjugated diene polymer, preparation method thereof and styrene butadiene rubber |
| CN108239225A (en) * | 2016-12-23 | 2018-07-03 | 中国石油天然气股份有限公司 | A kind of butadiene-styrene rubber and preparation method thereof |
| CN108239225B (en) * | 2016-12-23 | 2020-04-10 | 中国石油天然气股份有限公司 | Styrene butadiene rubber and preparation method thereof |
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