CN106032397B - A kind of preparation method of diene's polymer - Google Patents

Abstract

The present invention provides a kind of preparation methods of diene's polymer.This method includes in an inert atmosphere, the diene polymer containing at least one conjugated diene structural unit being contacted with modifying agent, stabilizer and initiator, the condition of contact makes modifying agent chemical bond be connected on diene polymer；The number-average molecular weight of the diene polymer is 50,000 100 ten thousand, and on the basis of the weight of conjugated diene structural unit, the content that side chain contains the conjugated diene structural unit of double bond is 15 85 weight %, and modifying agent is at least one of the substance simultaneously containing sulfydryl and hydroxyl and the substance simultaneously containing sulfydryl and carboxyl in hydrosulphonyl silane, molecule with structure shown in formula (I)；Stabilizer is one or more in arylamine type antioxidant, hindered phenol type antioxidant and phosphite antioxidant.The method of the present invention makes the relationship that the conversion ratio of modifying agent is substantially completely converted and can be effectively improved between anti-slippery and rolling resistance.

Description

A kind of preparation method of diene's polymer

Technical field

The present invention relates to a kind of preparation methods of diene's polymer.

Background technology

In recent years, climbing up and up with the development of auto industry and oil price, people to the safety of automobile and Energy saving is paid close attention to further, and this requires tires while with compared with high wet-sliding resistant performance, also has lower 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 requirements, It needs to seek best balance between high wet-sliding resistant performance and low rolling resistance.

For producing low rolling resistance tyre, due to anionic solution polymerization can effectively adjust side chain contain it is double The solution polymerized butylbenzene of the content and glass transition temperature of the conjugated diene structural unit of key, anionic polymerisation has fourth more poly- than breast Benzene more significant advantage.Relationship between wet-sliding resistant performance and rolling resistance of the advantage for balancing tire is advantageous.This It outside, can be to a certain extent studies have shown that the modifying agent with sulfhydryl structure is added in the mixing process of rubber composition Promote the relationship between the wet-sliding resistant performance and rolling resistance for disperseing and improving rubber to a certain extent of the filler in raw rubber, But in rubber composition mixing process, influenced by other additives, the reactivity meeting of modifying agent and raw rubber and carbon black It reduces.

Being disclosed in EP447066 can use the silane with structure shown in formula (1) as modifying agent to improve butylbenzene rubber The wet-sliding resistant performance of glue simultaneously reduces rolling resistance：

USi(OR′)_jR″_4-i-jFormula (1),

Wherein, U is halogen, and R ＇ and R " are C₁-C₂₀Alkyl, aryl, vinyl or halogenated alkyl, j be 1-4 integer, i For the integer of 0-2, i and j's and be 2-4.Silane with structure shown in formula (1) can pass through halogen and polymer molecule last-in-chain(LIC) The catalyst residues at end are reacted and key is connected on polymer molecular chain, however, a usual polymer molecular chain can only key connect One silane molecule, the interaction between polymer molecular chain are only capable of generating small effect, cannot effectively improve rubber Anti-slippery and reduce rolling resistance.

CN101821328A discloses a kind of method of modifying being connected to carboxylic acid functional on rubber, and this method includes making two Alkene polymerize in the solution to generate rubber, and then the functional group or their salt of carboxyl or hydroxyl are introduced into the solution rubber, Wherein solvent is removed in a vacuum at 50-200 DEG C with hot water and/steam, and filler and operation oil is then added.It is logical The introducing of percarboxylic acids isopolarity group, to improve dispersion of the white carbon in rubber, so as to improve the dynamic mechanical of rubber, But modifying agent reaction is incomplete, and unconverted modifying agent has niff, and needs to detach from solvent.

Invention content

The purpose of the invention is to overcome the conversion ratio for using existing method that cannot take into account modifying agent and be effectively improved The defect of relationship between the wet-sliding resistant performance and rolling resistance of rubber, and modifying agent conversion ratio can be taken into account and have by providing one kind Effect improves the preparation method of the wet-sliding resistant performance of rubber and diene's polymer of low-rolling-resistance.

According to the first aspect of the invention, the present invention provides a kind of preparation method of diene's polymer, It is characterized in that, this method includes in an inert atmosphere, by the diene polymerization containing at least one conjugated diene structural unit Object is contacted with modifying agent, stabilizer and initiator, and the condition of the contact makes the modifying agent chemical bond be connected to described contain On the diene polymer of at least one conjugated diene structural unit；It is described to contain at least one conjugated diene structural unit The number-average molecular weight of diene polymer be 50,000-100 ten thousand, preferably 100,000-40 ten thousand, and contain at least one be conjugated with described It is described to contain at least one in the diene polymer of alkadienes structural unit on the basis of the weight of conjugated diene structural unit The content that side chain contains the conjugated diene structural unit of double bond in the diene polymer of conjugated diene structural unit is 15- 85 weight %, preferably 30-70 weight %, the modifying agent are same in hydrosulphonyl silane, molecule with structure shown in formula (I) At least one of substance in the substance and molecule of Shi Hanyou sulfydryls and hydroxyl simultaneously containing sulfydryl and carboxyl：

Wherein, R₁-R₄For C₁-C₂₀Linear chain or branched chain alkyl or contain heteroatomic C₁-C₂₀Linear chain or branched chain alkyl, The hetero atom is one or more in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R₁-R₃For C₁-C₅Linear chain or branched chain Alkyl or straight or branched alkoxyl, R₄For C₁-C₅Linear chain or branched chain alkylidene；

The stabilizer is arylamine type antioxidant, hindered phenol type antioxidant and one kind or more in phosphite antioxidant Kind.

According to the second aspect of the invention, the present invention provides a kind of preparation method of diene's polymer, It is characterized in that, this approach includes the following steps：

(1) in an inert atmosphere and in the presence of initiator, by the polymerized monomer containing at least one conjugated diene Polymerisation is carried out in a solvent, obtains the reaction product containing diene polymer, and the condition of the polymerisation makes to obtain Diene polymer number-average molecular weight be 50,000-100 ten thousand, preferably 100,000-40 ten thousand, and in the diene polymer altogether On the basis of the weight of yoke alkadienes structural unit, side chain contains the conjugated diene hydrocarbon structure list of double bond in the diene polymer The content of member is 15-85 weight %, preferably 30-70 weight %；

(2) in an inert atmosphere, the reaction product containing diene polymer that step (1) is obtained and initiator, steady Determine agent and modifying agent, the condition of the contact makes the modifying agent agent chemical bond be connected on the diene polymer, The modifying agent be in hydrosulphonyl silane, molecule with structure shown in formula (I) substance simultaneously containing sulfydryl and hydroxyl and At least one of substance in molecule simultaneously containing sulfydryl and carboxyl：

Wherein, R₁-R₄For C₁-C₂₀Linear chain or branched chain alkyl or contain heteroatomic C₁-C₂₀Linear chain or branched chain alkyl, The hetero atom is one or more in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R₁-R₃For C₁-C₅Linear chain or branched chain Alkyl or straight or branched alkoxyl, R₄For C₁-C₅Linear chain or branched chain alkylidene；

The stabilizer is arylamine type antioxidant, hindered phenol type antioxidant and one kind or more in phosphite antioxidant Kind.

The prior art is usually added after modified-reaction is completed anti-old during preparing modified diene polymer To extend life of product, the present inventor has been surprisingly found that during having carried out numerous studies for agent, anti-old by changing The addition sequence of agent is allowed to the diene of conjugated diene structural unit for containing double bond with side chain together with modifying agent, initiator Hydrocarbon polymer contacts, and modifying agent can be made substantially completely to react.

In addition, as described above, in the prior art, changing with sulfhydryl structure is just added usually in the mixing process of rubber Property agent is to improve the wet-sliding resistant performance of rubber and reduce its rolling resistance, but modifying agent and raw rubber and carbon black react work at this time Property can reduce, and not only be difficult to significantly improve the relationship between the wet-sliding resistant performance of rubber and rolling resistance, but also will produce difficulty The stink of news.And the present inventor has found after further investigation, by by this modifying agent with sulfhydryl structure It learns and is bonded on the diene polymer that number-average molecular weight is 50,000-100 ten thousand, and obtained diene's polymer is whole Body can avoid the anti-of in rubber mixing process caused modifying agent and raw rubber and carbon black as part or all of rubber-based adhesive The problem of answering activity to reduce, and the anti-slippery of tire made of the thus obtained diene polymer of active balance and rolling hinder Relationship between power, while undesirable gas caused by the use in rubber mixing process due to modifying agent can also be improved Taste.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Specific implementation mode

The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

The preparation method of diene's polymer provided by the invention includes that in an inert atmosphere, will contain at least one The diene polymer of kind conjugated diene structural unit is contacted with modifying agent, stabilizer and initiator, the condition of the contact So that the modifying agent chemical bond is connected on the diene polymer containing at least one conjugated diene structural unit；Institute The number-average molecular weight for stating the diene polymer containing at least one conjugated diene structural unit is 50,000-100 ten thousand, preferably 10 Ten thousand-40 ten thousand, more preferable 100,000-20 ten thousand, and with the diene polymer containing at least one conjugated diene structural unit On the basis of the weight of middle conjugated diene structural unit, the alkadienes containing at least one conjugated diene structural unit is poly- Close object in side chain contain double bond conjugated diene structural unit content be 15-85 weight %, preferably 30-70 weight %, More preferable 30-65 weight %, the modifying agent are to contain mercapto simultaneously in hydrosulphonyl silane, molecule with structure shown in formula (I) At least one of substance in the substance and molecule of base and hydroxyl simultaneously containing sulfydryl and carboxyl：

Wherein, R₁-R₄For C₁-C₂₀Linear chain or branched chain alkyl or contain heteroatomic C₁-C₂₀Linear chain or branched chain alkyl, The hetero atom is one or more in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R₁-R₃For C₁-C₅Linear chain or branched chain Alkyl or straight or branched alkoxyl, R₄For C₁-C₅Linear chain or branched chain alkylidene；

The stabilizer is arylamine type antioxidant, hindered phenol type antioxidant and one kind or more in phosphite antioxidant Kind.

According to the present invention, the diene polymer containing at least one conjugated diene structural unit and have formula (I) dosage of the modifying agent of structure shown in can be selected and be changed in a wider scope, for example, with the alkadienes of 100g On the basis of polymer, the dosage of the modifying agent can be 0.01-10g, preferably 0.1-5g, more preferably 0.2-2g.

According to the present invention, the modifying agent is to contain mercapto simultaneously in hydrosulphonyl silane, molecule with structure shown in formula (I) At least one of substance in the substance and molecule of base and hydroxyl simultaneously containing sulfydryl and carboxyl：

Wherein, R₁-R₄For C₁-C₂₀Linear chain or branched chain alkyl or contain heteroatomic C₁-C₂₀Linear chain or branched chain alkyl, The hetero atom is one or more in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R₁-R₃For C₁-C₅Linear chain or branched chain Alkyl or straight or branched alkoxyl, R₄For C₁-C₅Linear chain or branched chain alkylidene.

The C₁-C₅The specific example of linear or branched alkyl group include but not limited to：Methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl and neopentyl；The C₁-C₅Straight chain or The specific example of branched alkoxy includes but 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 specific example of branched alkylidene includes but not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, Isobutylidene, sub- n-pentyl or isoamylidene.

It is particularly preferred that in formula (I), R₁-R₃For methoxyl group, R₄For propylidene, at this point, with functional unit shown in formula (I) Corresponding modifying agent is γ-mercaptopropyl trimethoxysilane；Alternatively, R₁-R₃For ethyoxyl, R₄For propylidene, at this point, and formula (I) the corresponding modifying agent of functional unit shown in is gamma-mercaptopropyltriethoxysilane；Alternatively, R₁-R₃For methyl, R₄For Asia Ethyl, at this point, modifying agent corresponding with functional unit shown in formula (I) is 2- trimethyl silane ethyl mercaptans.

According to the present invention, the substance in the molecule simultaneously containing sulfydryl and hydroxyl is the substance that HS-R-OH is indicated, wherein R be a straight chain, branch or ring C₁-C₃₆Alkylidene or alkylene group or an aryl, wherein these groups are each From tool, there are one other hydroxyls as substituent group, and can be interrupted if appropriate by nitrogen, oxygen or sulphur atom, and such as There are multiple aryl substituents if fruit is appropriate；Preferably, R be carbon atom number be 1-6 linear chain or branched chain alkylidene, by hydroxyl Substituted carbon atom number is one kind in the linear chain or branched chain alkylidene of 1-6；It is highly preferred that R is-(CH₂)_m-CH(OH)- (CH₂)_n, wherein m and n are each independently the integer of 1-2；For example, modifying agent can be 3- sulfydryls -1,2-PD.

According to the present invention, the substance in the molecule simultaneously containing sulfydryl and carboxyl is the substance that HS-R '-COOH is indicated, Wherein R be a straight chain, branch or ring C₁-C₃₆Alkylidene or alkylene group or an aryl, wherein these bases There are one other carboxyls for the respective tool of group as substituent group, and can be interrupted if appropriate by nitrogen, oxygen or sulphur atom, and And there are multiple aryl substituents if appropriate；Preferably, wherein R ' is the linear chain or branched chain alkylene that carbon atom number is 1-6 Base；It is highly preferred that R ' is methylene, ethylidene or propylidene；For example, modifying agent can be thioacetic acid, mercaptopropionic acid.

It is particularly preferred that the modifying agent is trimethoxy propyl hydrosulphonyl silane, triethoxy propyl hydrosulphonyl silane, mercapto third It is one or more in ylmethyl dimethoxysilane, 3- thio propane -1,2- glycol, thioacetic acid, 3- mercaptopropionic acids.

According to the present invention, the dosage of the stabilizer can be this field during preparing polymer after polymerisation The amount for the anti-aging agent being added, for example, relative to the diene for containing at least one conjugated diene structural unit described in 100g The dosage of hydrocarbon polymer, the stabilizer can be 0.001-500mg, preferably 0.1-5mg.

According to the present invention, the stabilizer is in arylamine type antioxidant, hindered phenol type antioxidant and phosphite antioxidant It is one or more.

The arylamine type antioxidant as stabilizer can be selected from naphthylamine derivative, diphenylamine derivatives, p-phenylenediamine At least one of derivative, quinoline.

Wherein naphthylamine derivative includes but not limited to one or more in following substance：

Phenyl-α-naphthylamine (antioxidant T531, antioxidant A)；

Phenyl-β-naphthylamine (antioxidant d)；

N- p-methoxyphenyls alpha-naphthylamine (anti-aging agent 102)；

P-hydroxyphenyl-beta-naphthylamine (antioxidant D-OH)；

Acetaldol-alpha-naphthylamine (antioxidant A P)

Bis- [to (beta-naphthylamine) phenoxy group] propane (anti-aging agent C-49) of 2- hydroxyls -1,3-；

Bis- [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41) of dimethyl；

Bis- [to (beta-naphthylamine) phenoxy group] silane (anti-aging agent C-41- ethyls) of diethyl；

2,2 '-bis- [to (beta-naphthylamine) phenoxy group] diethyl ether (anti-aging agent C-41- ether).

Wherein, the preferred nonox of naphthylamine derivative, such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, N- are to methoxybenzene It is one or more in base alpha-naphthylamine.Particularly preferred phenyl-α-naphthylamine.

Wherein diphenylamine derivatives includes but not limited to one or more in following substance：

4,4 '-diamino-diphenylamines (antioxidant A PA)；

It is right, to '-dimethoxy diphenylamines；

N, N, N ', N '-tetraphenyl diamines methane (anti-aging agent 350)；

N, N '-diphenyl ethylene diamine；

N, N '-diphenylprop diamines；

N, N '-di-o-tolyl-ethylene-diamine；

- 1,3- pairs-(to aniline phenoxy group) propane (anti-aging agent C-47) of 2- hydroxyls；

2,2 '-bis- (to aniline phenoxy group)-diethyl ether (antioxidant H -1)；

Bis- (to aniline-phenoxy group)-silane (anti-aging agent C-1) of dimethyl；

P-isopropoxy-diphenylamine (anti-aging agent ISO)；

It is right, to '-diisopropoxy diphenylamines (antioxidant D ISO)；

4,4 '-bis- (α, α ' '-dimethyl benzyl) diphenylamines (anti-aging agent KY-405)；

Parahydroxydi-phenylamine (antioxidant A O3920)；

Two-(1,1,3,3- tetramethyls ethyl) diphenylamines (anti-aging agent ODA)；

4,4 '-dioctyl diphenylamines；

4,4 '-di-iso-octyldiphenylamines；

4,4 '-diheptyl diphenylamines；

4,4 '-dinonyldiphenylamines；

Octylated diphenylamine (mixture of an octylated diphenylamine and dioctylated diphenylamines, anti-aging agent OD)；

Octyl/butyl diphenylamines (antioxidant L-57)；

Styrenated diphenylamine (antioxidant D FL, DFC-34)；

And the mixture of alkylated diphenylamine, wherein alkyl can be heptyl, octyl, one or more of nonyl, The example of its industrial products has Pennwalt companies of U.S. trade name Pennox A, Pennox A- " S ", U.S. National Polychem companies trade name Wytox ADP, ADP-X, Vanderbilt companies of U.S. trade name Agerite Stalite, Agerite Stalite S, Agerite Nepa, Agerite Gel, Uniroyal companies of U.S. trade name The antioxidant product that Polylite, Antioxidant 445 and domestic code name are T534.

Diphenylamine derivatives type antioxidant optimizing alkyl diphenylamines and its mixture, particularly preferred atomic number of alkyl carbon exist Alkylated diphenylamine between 4-10 and its mixture, such as：4,4 '-dioctyl diphenylamines, 4,4 '-di-iso-octyldiphenylamines, 4, 4 '-diheptyl diphenylamines, 4,4 '-dinonyldiphenylamines, octylated diphenylamine (octylated diphenylamine and dioctylated diphenylamines Mixture), it is octyl/butyl diphenylamines, one or more in commodity antioxidant T534.

Wherein p-phenylene diamine derivative's type antioxidant includes but not limited to one or more in following substance：

N- phenyl-N '-cyclohexyl p-phenylenediamine (antioxidant 4010)；

N, N- (1,3- dimethylbutyls)-N '-diphenyl-para-phenylene diamines (antioxidant 4020)；

N, N '-bis--(1,4- dimethyl amyl groups) p-phenylenediamine (anti-aging agent 4030)；

N- p-methylphenyls-N '-(1,3- dimethylbutyls) p-phenylenediamine (anti-aging agent 4040)；

N, N '-diheptyl p-phenylenediamine (anti-aging agent 788)；

N- isopropyls-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA)；

N- isopropyls-N '-p-methylphenyl p-phenylenediamine (anti-aging agent methyl 4010NA)；

N, N '-DTPD di tolyl p phenylenediamine (anti-aging agent PPD-A)；

N, N '-diphenyl-para-phenylene diamine (antioxidant H)；

N, N '-two-(betanaphthyl) p-phenylenediamine (antioxidant D NP)；

N, N '-di-sec-butyl-p-phenyl enediamine (anti-aging agent U-5)；

N, N '-dioctyl-p-phenylenediamine (anti-aging agent 88)；

N, N '-bis--(1- methylheptyls) p-phenylenediamine (anti-aging agent 288)；

N, N '-bis--(1- ethyl -3- methyl amyls) p-phenylenediamine (anti-aging agent 8L)；

N, N '-bis--(1,4- dimethylbutyls) p-phenylenediamine (anti-aging agent 66)；

N- Octyl-N 's-diphenyl-para-phenylene diamine (anti-aging agent 688)；

N- isobutyl groups-N '-diphenyl-para-phenylene diamine (anti-aging agent 5L)；

N, N '-dimethyl-N, N '-be bis--(1- first propyl) p-phenylenediamine (anti-aging agent 32)；

N- (p-methylphenyl sulfonyl)-N '-diphenyl-para-phenylene diamines (anti-aging agent TPPD)；

N- (3- methylpropenyls acyl-oxygen generation -2- hydroxypropyls)-N '-diphenyl-para-phenylene diamines (anti-aging agent G-1)；

N- (3- aniiinophenyls) Methacrylamide；

N- hexyls-N '-diphenyl-para-phenylene diamine；

The preferred dialkyl-pphenylenediamines of p-phenylene diamine derivative's type antioxidant, particularly preferred atomic number of alkyl carbon 4-10 it Between dialkyl-pphenylenediamines, such as：N, N '-diheptyl p-phenylenediamine；N, N '-di-sec-butyl-p-phenyl enediamine；N, N '-dioctyl pair Phenylenediamine；It is one or more in N, N '-bis--(1- methylheptyls) p-phenylenediamine.

Quinoline therein includes but not limited to：

6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinolines (antioxidant A W)；

6- phenyl -2,2,4- trimethyl -1,2- dihyaroquinolines (anti-aging agent PMQ)；

6- dodecyl -2,2,4- trimethyl -1,2- dihyaroquinolines (antioxidant D D)；

2,2,4- trimethyl -1,2- dihyaroquinolines condensates (anti-aging agent RD, anti-aging agent 124)；

Diphenylamines and acetone low-temp reaction product (anti-aging agent BAS)；

Diphenylamines and acetone high-temperature reaction product (antioxidant BLE)；

The reaction product (anti-aging agent BXA) of diphenylamines and acetone and aldehyde；

The reaction product (antioxidant A PN, antioxidant A M) of phenyl-β-naphthylamine and acetone.

The preferred p-phenylenediamine class arylamine antioxidant of arylamine antioxidant.

Phenol type antioxidant described in stabilizer can be single phenol, bis-phenol, diphenol and polyphenol, can also be their arbitrary proportions Mixture.

Wherein single phenol is that there are one the substituted phenol there are one hydroxyl on phenyl ring/and phenyl ring, and in substituent group extremely It is tertiary butyl there are one few, other substituent groups can be alkyl or contain heteroatomic substituent group, and alkyl therein is selected from C₁-C₁₀ Alkyl, such as methyl, ethyl, allyl, normal-butyl, sec-butyl, nonyl etc. are selected from oxygen containing take containing heteroatomic substituent group Dai Jiru methoxyl groups, methoxy-substituted methyl, methylol, nitrogenous substituent group such as alpha, alpha-dimethyl aminomethyl.Such as can be The single phenol of structure below：O-tert-butylphenol, p-tert-butylphenol, 2- tert-butyl-4-methyl-Phenols, 6- tertiary butyl -2- methyl Phenol, 6- tertiary butyl -3- methylphenols；4- tertiary butyl -2,6- xylenols, 6 t butyl 2,4 dimethyl phenol；2,4- DI-tert-butylphenol compounds, 2,5- DI-tert-butylphenol compounds, 2,6 di t butyl phenol；2,5- di-tert-butyl-4-methy phenols, 2,6- bis- Tert-butyl-4-methyl-Phenol (BHT, antioxidant T501), 4,6- di-t-butyl -2- methylphenols；2,4,6- tri-butyl-phenols, 2 allyl 4 methyl 6 tert butyl phenol, 2- sec-butyls -4-TBP, 4- sec-butyls -2,6 di t butyl phenol, 4- nonyls -2,6 di t butyl phenol, 2,6- di-t-butyl -4- ethyl -phenols (antioxidant DBEP), 2,6- di-t-butyls -4- are just Butylphenol (antioxidant 678)；Butylhydroxy anisole (BHA), DBPC 2,6 ditertiary butyl p cresol (antioxidant 264), 2,6- Di-t-butyl-α-methoxyl groups-paracresol (BHT-MO), 4 hydroxymethyl 2,6 di t butyl phenol (antioxidant 754), 2,6- bis- Tertiary butyl-alpha, alpha-dimethyl amino-p-cresol (antioxidant 703), various 3,5- di-tert-butyl-hydroxy phenyls propionic esters and 3,5- bis- Tert-butyl-hydroxy phenyl propionic acid etc..

Wherein be obstructed single phenol of the single phenol antioxidant preferably at least there are one tertiary butyl at phenolic hydroxyl group ortho position, such as：

2- tert-butyl-4-methyl-Phenols, 6 t butyl 2,4 dimethyl phenol, 2,6 di t butyl phenol, bis- uncles of 2,6- Butyl -4- methylphenols (BHT, antioxidant T501), 2,4,6- tri-butyl-phenols, 4- sec-butyls -2,6- DI-tert-butylphenol compounds, 4- nonyls -2,6 di t butyl phenol, 2,6- di-t-butyl -4- ethyl -phenols (antioxidant DBEP), butylhydroxy anisole (BHA), DBPC 2,6 ditertiary butyl p cresol (antioxidant 264), 2,6- di-t-butyls-α-methoxyl group-paracresol (BHT-MO), 4- hydroxyls In methyl -2,6 di t butyl phenol (antioxidant 754), 2,6- di-t-butyls-alpha, alpha-dimethyl amino-p-cresol (antioxidant 703) One or more.

Bis-phenol refers to the phenol type antioxidant being connected by sulphur or carbon atom by two single phenols, such as：

(1) bis-phenol being connected by carbon atom

4,4 '-isopropylidene bis-phenols (bisphenol-A)；

2,2 '-bis--(- 4 hydroxy phenyl of 3- methyl) propane (bisphenol-c)；

4,4 '-dihydroxybiphenyls (antioxidant DOD)；

4,4 '-dihydroxy -3,3 ', 5,5 '-four-tertiary butyl biphenyl (antioxidant 712)；

2,2 '-methylene-bis--(4- methyl-6-tert-butylphenols) (antioxidant 2246)；

4,4 '-methylene-bis--(2- methyl-6-tert-butylphenols) (antioxidant methene 736)；

2,2 '-methylene-bis--(4- ethyl -6- tert-butyl phenols) (antioxidant 425)；

2,2 '-methylene-bis--(4- methyl -6- cyclohexylphenols) (antioxidant ZKF)；

2,2 '-methylene-bis- [4- methyl -6- (Alpha-Methyl cyclohexyl) phenol] (antioxidant WSP)；

2,2 '-methylene-bis--(6- α-methylbenzyls paracresol)；

4,4 '-methylene-bis--(2,6 di t butyl phenol) (antioxidant T511)；

4,4 '-methylene-bis--(2-TBP) (antioxidant 702)；

2,2 '-ethylidene-bis--(4- methyl-6-tert-butylphenols)；

4,4 '-ethylidene-bis--(2- methyl-6-tert-butylphenols)；

4,4 '-ethylidene-bis--(2,6 di t butyl phenol)；

4,4 '-butylidenes-bis--(6- tertiary butyls-metacresol) (antioxidant BBM, antioxidant TCA)；

4,4 '-isobutylidenes-bis--(2,6 di t butyl phenol) etc..

(2) bis-phenol being connected by sulphur atom

4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1)；

2,2 '-thiobis-(4- methyl-6-tert-butylphenols) (antioxidant 2246-S)；

4,4 '-thiobis-(2- methyl-6-tert-butylphenols) (antioxidant 736)；

4,4 '-thiobis-(5- methyl -2-TBP)；

4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300)；

2,2 '-thiobis-(4- octyl phenols) etc..

(3) it is connected by carbon atom but contains heteroatomic bis-phenol

N, N '-hexamethylene pair-(3,5- di-t-butyl -4- hydroxyls hydrocinnamamide) (antioxidant 1098)；

Hexylene glycol is bis- [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic ester] (antioxidant 259)；

Double-(3,5- di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine (antioxidant BPP)；

Double-(3,5- di-tert-butyl-4-hydroxyl benzyls) thioether (antioxidant methene 4426-S)；

2,2 '-sulfurous ethyl glycols are bis- [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic ester] (antioxidant 1035)；

Double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic esters (antioxidant 245) of triethylene glycol etc..

Single phenol of the bisphenol type antioxidant preferably by least one tertiary butyl at phenolic hydroxyl group ortho position passes through methylene or sulphur phase Bis-phenol even, such as：

2,2 '-methylene-bis--(4- methyl-6-tert-butylphenols) (antioxidant 2246)；

4,4 '-methylene-bis--(2- methyl-6-tert-butylphenols) (antioxidant methene 736)；

4,4 '-methylene-bis--(2,6 di t butyl phenol) (antioxidant T511)；

4,4 '-methylene-bis--(2-TBP) (antioxidant 702)；

4,4 '-thiobis-(3 methy 6 tert butyl phenol) (antioxidant 300 or AO-1)；

2,2 '-thiobis-(4- methyl-6-tert-butylphenols) (antioxidant 2246-S)；

4,4 '-thiobis-(2- methyl-6-tert-butylphenols) (antioxidant 736)；

4,4 '-thiobis-(2,6 di t butyl phenol) (Nocrac 300)；

Double-(3,5- di-tert-butyl-4-hydroxyl benzyls) thioether (antioxidant methene 4426-S) etc..

Here diphenol refers to the phenol type antioxidant there are two hydroxyl on a phenyl ring, can be the diphenol of following structure： Hydroquinone, tert-butyl hydroquinone (TBHQ), tert-butyl catechol 2,5 di tert butyl hydroquinone, bis- tertiary pentyls of 2,5- One or more of hydroquinone.

The polyphenol antioxidant refers to the macromolecular antioxidant in molecule by least three single phenol groups preferably by least one A tertiary butyl phenolic hydroxyl group ortho position single phenol group form polyphenol, particularly preferably there are two tertiary butyl phenolic hydroxyl group ortho position by Polyphenol is hindered, such as：

1,3,5- trimethyls -2,4,6- three-(4 '-hydroxyls -3 ', 5 '-di-t-butyls) benzene (antioxidant 330)；

Three [2- (3,5- di-tert-butyl-hydroxy phenyls) propiono oxygen ethyl] isocyanates (antioxidant 3125)；

Four (3,5- di-tert-butyl-hydroxy phenyls propionic acid) pentaerythritol esters (antioxidant 1010)；

3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid stearyl

Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters (anti-aging agent 1010)

1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) guanamine, 4,6- (1H, 3H, 5H) (antioxidant 3114)；

1,1,3- tri--(2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane (antioxidant CA)；

1,3,5- tri- (2,6- dimethyl -4- tertiary butyl -3- hydroxybenzyls) guanamine, 4,6- (1H, 3H, 5H) (antioxygen Agent 1790)；

Bis- [3,3- bis--(3 '-tertiary butyls -4 '-hydroxybenzyl) butyric acid] glycol esters etc..

Here polyphenol can also be that there are three the phenol of hydroxyl, such as pyrogallic acid, gallate for band in phenyl ring As gallicin, progallin A, propylgallate, butyl gallate, gallic acid pentyl ester, gallic acid oneself Ester, gallic acid heptyl ester, octyl gallate, gallic acid nonyl ester, gallic acid last of the ten Heavenly stems ester, lauryl gallate, nutgall Sour 14 esters, gallic acid hexadecyl ester, gallic acid octadecyl ester, gallic acid octadecylene ester etc.；And Chinese Patent Application No. 200810115581.8 disclosed gallamide or ammonia salt.More preferred gallic acid-derivates of phenol type antioxidant are especially Propylgallate.

Bisphenol type antioxidant of the above-mentioned phenol type antioxidant preferably at least there are one tertiary butyl at phenolic hydroxyl group ortho position is especially logical The bisphenol type antioxidant that methylene or sulphur are connected is crossed, tert-butyl hydroquinone, 2,5- di-t-butyls pair in two phenol type antioxidants Gallate, gallamide or ammonia salt in benzenediol and polyphenol antioxidant.

Phosphite antioxidant as stabilizer can be selected from phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, phosphorous acid Three (nonyl phenyl) esters, two different certain herbaceous plants with big flowers ester of pentaerythritol diphosphite, pentaerythrite diphosphorous acid distearyl alcohol ester and season penta 4 It is one or more in alcohol diphosphorous acid octacosanol ester (PKY-618).

Stabilizer can also be above-mentioned arylamine type antioxidant, hindered phenol type antioxidant and the compound antioxygen of phosphite antioxidant Agent.

It is particularly preferred that the stabilizer is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (anti-aging agent 1010), DBPC 2,6 ditertiary butyl p cresol (antioxidant 264), 2,2 '-methylene-bis- (4- methyl-6-tert butyl benzene Phenol) (antioxidant 2246), tert-butyl catechol, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, 3- (3,5- di-t-butyls- 4- hydroxy phenyls) at least one of propionic acid stearyl and phosphorous acid three (nonyl phenyl) ester.

In the present invention, the conjugated diene structural unit that the side chain contains double bond includes but not limited to 1,2- ethylene base junctions The model AVANCE DRX purchased from Bruker companies of Switzerland may be used in structure unit and Isosorbide-5-Nitrae-vinyl structure unit, content The nuclear magnetic resonance chemical analyser of 400MHz is measured, wherein solvent is deuterochloroform.Specific assay method is people in the art Known in member, it will not be described in great detail herein.It is conjugated in the diene polymer containing at least one conjugated diene structural unit The content of alkadienes structural unit refer to conjugated diene polymerize in various ways structural unit (including 1,2- polymerization, 1,4- polymerization, 3,4- polymerization) total content.

Preferably, the diene polymer containing at least one conjugated diene structural unit also contains a kind of or more Kind monovinylarene structural unit, the weight ratio of the monovinylarene structural unit and conjugated diene structural unit are 5:95-60:40, it is preferably 20:80-40:60.

According to the present invention, the diene polymer may be used existing various methods and be prepared, for example, it is prepared Method may include：In an inert atmosphere and in the presence of initiator, by the polymerization list containing at least one conjugated diene Body carries out polymerisation in a solvent, and the number-average molecular weight for the diene polymer that the condition of the polymerisation makes is 5 Ten thousand-100 ten thousand, preferably 100,000-40 ten thousand, more preferable 100,000-20 ten thousand, and 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 structural unit of double bond in the diene polymer is 15- 85 weight %, preferably 30-70 weight %, more preferable 30-65 weight %.

According to the present invention, when preparing two simultaneously containing monovinylarene structural unit and conjugated diene structural unit When olefin polymer, the present invention is not particularly limited the dosage of the monovinylarene and conjugated diene, and can be with It is reasonably selected according to the obtained diene polymer of expection, for example, the monovinylarene and conjugated diene Weight ratio can be 5:95-60:40, it is preferably 20:80-40:60.

According to the present invention, the inert atmosphere refers to any one gas not chemically reacted with reactants and products Or admixture of gas, such as one or more of 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 reactants and products into reaction system.

According to the present invention, in the preparation process of the diene polymer containing at least one conjugated diene structural unit In, the initiator can be the existing various initiators that can cause the conjugate diene polymerization, for example, can be to have Machine lithium initiator.The organic lithium initiator for example can be single organic lithium initiator that molecular formula is R " Li, wherein R " is straight The alkyl of chain or branch, naphthenic base or aryl.Specifically, single organic lithium initiator can be selected from ethyl-lithium, propyl lithium, different In propyl lithium, n-BuLi, s-butyl lithium, amyl lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthalene lithium It is one or more, preferably n-BuLi and/or s-butyl lithium.In addition, the present invention can also use Dilithium initiator, such as Sanya Two lithium of two lithium of methyl and/or tetramethylene.The present invention is not particularly limited the dosage of the initiator, and can be according to setting The molecular size range of meter is reasonably selected.Those skilled in the art are it should be readily understood that when needing to prepare molecular weight When larger diene polymer, it is possible to reduce the dosage of initiator, but rate of polymerization also can accordingly reduce at this time；When needing to make When for the smaller diene polymer of molecular weight, the dosage of initiator can be increased, but rate of polymerization also can accordingly increase at this time. Therefore, consider the molecular size range of rate of polymerization and obtained diene polymer, under preferable case, polymerize with 100g On the basis of the total weight of monomer, the dosage of the initiator is 0.15-2.5mmol.

The present invention is not particularly limited the condition of the polymerisation, generally include polymerization temperature, polymerization pressure and Polymerization time.Wherein, in order to be more advantageous to the progress of polymerisation, the polymerization temperature is preferably 10-160 DEG C, is more preferably 50-100 DEG C, the polymerization pressure is preferably 0.05-0.5MPa, more preferably 0.1-0.3MPa.Usually, when 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 turns to reactant The amplitude that rate and reaction product yield improve is not obvious, and therefore, considers polymerization efficiency and effect, the polymerization time Preferably 0.5-10 hours, more preferably 0.5-3 hours.

In the present invention, the pressure refers both to gauge pressure.

According to the present invention, in the preparation process of the diene polymer containing at least one conjugated diene structural unit In, the solvent can be it is various can be as the substance of reaction media, for example, can be hydrocarbon solvent and/or ether solvent. The hydrocarbon solvent can be C₅-C₇Cycloalkane, one or more in aromatic hydrocarbons and isoparaffin.The tool of the hydrocarbon solvent Body example can include but is not limited to：It is one or more in benzene, toluene, pentane, heptane, n-hexane and hexamethylene.The ether Class solvent can be C₄-C₁₅Monoether and/or polyether.The specific example of the ether solvent can include but is not limited to：Tertiary fourth Oxygroup Ethoxyethane and/or tetrahydrofuran.Wherein, these solvents can be used alone, can also be used in mixed way.It is described molten The dosage of agent can reasonably be selected according to the dosage of monomer, for example, the dosage of the solvent can make the conjugation The total concentration of alkadienes can be 1-30 weight %, preferably 5-20 weight %.

According to the present invention, after polymerization was complete, coupling agent can also be added into polymerization system, it will at least portion Diene polymer is divided to be coupled together.The type of the coupling agent is known to the skilled person, for example, can be more second It is 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 It is one or more, it is preferably one or more in divinylbenzene, silicon tetrachloride and butter of tin.It should be noted that working as When the coupling agent is silane compound, the silane compound and the hydrosulphonyl silane class modifying agent with structure shown in formula (I) It is different.

The present invention is not particularly limited the dosage of the coupling agent, can be carried out suitably according to the dosage of initiator Selection, for example, the molar ratio of the coupling agent and the initiator can be 0.1-2:1, preferably 0.1-1:1.

It is poly- in the alkadienes containing at least one conjugated diene structural unit in the case of, according to the invention it is preferred to Structure regulator can also be added by closing in the preparation process of object, can be carried out in this way to the microstructure of the diene polymer It efficiently controls.The structure regulator can be the object of the existing various microstructures that can adjust diene polymer Matter, for example, can be selected from ether, butyl oxide, tetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, crown ether, Tetrahydrofurfuryl alcohol ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoramide, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkane It is one or more in base benzene sulfonic acid potassium and sodium alkyl benzene sulfonate.Usually, the structure regulator contains at least with preparation A kind of molar ratio of initiator used in the diene polymer of conjugated diene structural unit can be 1-100:1, preferably 80-100:1。

Usually, anionic polymerisation system is without significantly terminating reaction and transfer reaction, when ruing out of whole After monomer, activated centre still remains.Therefore, after completion of the polymerization reaction, obtained polymer solution should be connect with terminator It touches so that activated centre inactivates.The dosage of the terminator can be according to the dosage for preparing the initiator used in diene polymer It is reasonably selected, usually, the terminator can with the molar ratio for preparing the initiator used in diene polymer Think 0.1-1:1.The terminator can be the existing various reagents that anion active center can be made to inactivate, for example, can With one or more in water, methanol, ethyl alcohol and isopropanol, preferably isopropanol.

The present invention is to the condition of the diene polymer and modifying agent to be not particularly limited, as long as can make The chemical bond for obtaining the modifying agent is connected on the diene polymer, for example, the condition of the contact generally includes to connect Touch temperature, contact and time of contact.Usually, it is connected to the diene polymerization to be more advantageous to modifying agent chemical bond On object, the Contact Temperature is preferably 20-150 DEG C, more preferably 70-100 DEG C, the contact be 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 by diene polymer and modifying agent, trigger rate and alkadienes are poly- in order to balance The size of adduct molecule amount, on the basis of the weight of diene polymer described in 100g, the dosage of the initiator is preferably 0.01-0.2g, more preferably 0.01-0.08g.The azo that the initiator can be known to the skilled person causes It is one or more in the radical initiators such as agent, peroxide type initiators and redox type initiators.

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 formamide, azo diisopropyl imidazoline hydrochloride, azo dicyan One kind or more in base valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile Kind.

The peroxide type initiators can be selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, peroxide Change 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 it is one or more in ammonium persulfate-fatty amine.Specifically, the sulfate-sulphite can be selected from sodium sulphate-sulfurous It is one or more in sour sodium, potassium sulfate-potassium sulfite and ammonium sulfate-ammonium sulfite；Persulfate-thiocarbamide can be selected from over cure It is one or more in sour sodium-thiocarbamide, potassium peroxydisulfate-thiocarbamide and ammonium persulfate-thiocarbamide；Persulfate-organic salt can be selected from It is 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.

In addition, the present invention also provides the preparation methods of another diene's polymer, which is characterized in that the party Method includes the following steps：

(1) in an inert atmosphere and in the presence of initiator, by the polymerized monomer containing at least one conjugated diene Polymerisation is carried out in a solvent, obtains the reaction product containing diene polymer, and the condition of the polymerisation makes to obtain The number-average molecular weight of diene polymer be 50,000-100 ten thousand, preferably 100,000-40 ten thousand, more preferable 100,000-20 ten thousand, and with described In diene polymer on the basis of the weight of conjugated diene structural unit, side chain contains double bond in the diene polymer The content of conjugated diene structural unit is 15-85 weight %, preferably 30-70 weight %, more preferable 30-65 weight %；

(2) in an inert atmosphere, the reaction product containing diene polymer that step (1) is obtained and initiator, steady Determine agent and modifying agent, the condition of the contact makes the modifying agent agent chemical bond be connected on the diene polymer, The modifying agent be in hydrosulphonyl silane, molecule with structure shown in formula (I) substance simultaneously containing sulfydryl and hydroxyl and At least one of substance in molecule simultaneously containing sulfydryl and carboxyl：

Wherein, R₁-R₄For C₁-C₂₀Linear chain or branched chain alkyl or contain heteroatomic C₁-C₂₀Linear chain or branched chain alkyl, The hetero atom is one or more in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R₁-R₃For C₁-C₅Linear chain or branched chain Alkyl or straight or branched alkoxyl, R₄For C₁-C₅Linear chain or branched chain alkylidene；

The stabilizer is arylamine type antioxidant, hindered phenol type antioxidant and one kind or more in phosphite antioxidant Kind.

The polymerized monomer containing conjugated diene preferably also contains one or more monovinylarenes.

Wherein, in step (1) and (2) type and dosage and polymerisation of each substance condition and contact conditions It is reasonably selected with basis, will not be described in great detail herein above.

According to the present invention, after diene's polymer is prepared and is completed, it is also an option that property to obtaining Diene's polymer in add various additives.The additive can be for example anti-aging agent, enable in this way The diene polymer arrived has good anti-aging property.The type and dosage of the anti-aging agent all can be this field it is normal Rule selection, will not be described in great detail herein.

According to the present invention, after anti-aging agent is added, the diene polymer can by purify precipitation, centrifuge, The methods of filtering, decantation, hot water cohesion are precipitated out from solution, can also be removed the solvent in reaction system using air- extraction It removes, this those skilled in the art can be known, will not be described in great detail herein.

In the present invention,¹HNMR spectrograms use the core of the model AVANCE DRX 400MHz purchased from Bruker companies of Switzerland Resonance spectrometer measures at room temperature, wherein solvent is deuterochloroform.

The present invention is not particularly limited 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 gel that the model LC-10AT purchased from Shimadzu Corporation may be used in the number-average molecular weight and molecular weight distribution oozes Saturating chromatograph (GPC) measures, 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 structural unit is the structural unit derived from conjugated diene, that is, by altogether The structural unit that yoke diene polymerization is formed.The conjugated diene refers to containing 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 field, and can be according to final The application scenario of obtained diene polymer is reasonably selected, for example, the conjugated diene can be selected from butadiene, Isoprene, 1,3-pentadiene, 1,3- hexadienes and 2, one or more in 3- dimethyl butadienes, preferably butadiene And/or isoprene.

According to the present invention, the monovinylarene structural unit is the structural unit derived from monovinylarene, i.e., It polymerize the structural unit formed by monovinylarene.The monovinylarene can be to be carried on aromatic ring commonly used in the art The various aromatic monomers of one vinyl substituent, usually, the monovinylarene have structure shown in formula (II)：

Wherein, R₅Can be C₆-C₂₀Substituted or unsubstituted aryl, preferably phenyl and by one or more C₁-C₅ Alkyl-substituted phenyl.

According to the present invention, the C₆-C₂₀The specific example of substituted or unsubstituted aryl include but not limited to：Phenyl, (including adjacent di-n-butyl phenyl, two are just for tolyl, ethylbenzene, tert-butyl-phenyl, dodecylphenyl, di-n-butyl phenyl Butyl phenyl and to di-n-butyl phenyl), n-propyl phenyl and diethyl phenyl (including adjacent two positive ethylphenyls, two positive second Base phenyl and to two positive ethylphenyls).

According to the present invention, the monovinylarene be particularly preferably styrene, vinyltoluene, α-methylstyrene, It is one or more in 4- t-butyl styrenes and 4- methyl styrenes.

Diene's polymer that preparation method using the present invention is prepared can make as rubber-based adhesive With.

The obtained diene's polymer of preparation method of the present invention when as rubber-based adhesive in use, can be according to The method of this field routine prepares rubber composition, which can contain olefinic rubber, vulcanizing agent, vulcanization promotion Agent, reinforcing agent and activator, and the diene that the preparation method containing the present invention in the olefinic rubber obtains is poly- Close object.Above-mentioned rubber composition is uniformly mixed and vulcanizes available vulcanized rubber.

Preferably, on the basis of the total weight of the olefinic rubber, preparation method of the invention obtains in the olefinic rubber The content of the diene's polymer arrived is 50-100 weight %, preferably 80-100 weight %.

The selection of each ingredient and the method that rubber composition is uniformly mixed and is vulcanized all can be in rubber composition The conventional selection of this field can know this those skilled in the art, will not be described in great detail herein.

The present invention will be described in detail by way of examples below.In following embodiment, modifying agent functional unit contains Amount is calculated in two ways, the first is according to formula；The inventory of content=modifying agent of modifying agent × sulfydryl conversion Rate ÷ (inventory of inventory+modifying agent of inventory+monovinylarene of conjugated diene × sulfydryl conversion ratio) × 100%, the content of the modifying agent functional unit referred to as calculated according to sulfydryl conversion ratio.Unless stated otherwise, modifying agent function list The content of member is the content of the modifying agent functional unit calculated according to sulfydryl conversion ratio.Second is logical according to hydrogen nuclear magnetic spectrogram It crosses calculated by peak area to obtain, referred to as according to the content of the modifying agent functional unit of hydrogen nuclear magnetic spectrogram calculated by peak area.

In following embodiment and comparative example, gas chromatograph is Agilent 7890A type gas chromatographs, test condition packet It includes：Chromatographic column SPB-5 60m × 0.32mm × 1.0um capillary columns, column flow rate 2.0ml/min, 220 DEG C of column temperature, gasify room temperature 220 DEG C of degree detects 250 DEG C of room temperature, split ratio 50：1, sample size 0.3ul.

Side chain contains the content of the conjugated diene structural unit of double bond and the content of modifying agent functional unit using auspicious The nuclear magnetic resonance chemical analyser of the model AVANCE DRX 400MHz of scholar Bruker companies is measured, according to calculated by peak area It obtains.Wherein, solvent is deuterochloroform.In the following Examples and Comparative Examples, side chain contains the conjugated diene hydrocarbon structure of double bond The content of unit be conjugated diene polymerize in various ways structural unit (including 1,2- polymerization, 1,4- polymerization, 3,4- Polymerization) total content.

It is the conjugated diene structural unit that side chain contains double bond.

Before carrying out nuclear-magnetism test, first resulting polymers are stripped, to remove wherein that may be present unreacted change Property agent.Specific extraction procedure includes will be fitted into extract in vessel after samples weighing, solvent use volume ratio for 3/7 toluene/ Alcohol mixture uses acetone extraction 2h again after extracting 4h, and 60 DEG C are dried in vacuo 4h and weigh, and above step are repeated, after drying Until sample weight.

Number-average molecular weight and molecular weight distribution use the gel of the model ALLIANCE2690 of WATERS companies of the U.S. Permeation chromatograph (GPC) measures, wherein THF is mobile phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.

Mooney viscosity is using the SMV-300 type mooney's viscosimeters of Japanese Shimadzu Corporation by side specified in GB/T1232-92 Method measures.

Vulcanized rubber is tested for the property using following method：

(1) test of glass transition temperature (Tg)：

It is measured using differential scanning calorimetry (DSC) instrument of the model MDSC2910 of TA companies of the U.S., wherein adjust Period processed is 60s, and modulated amplitude is ± 1.5 DEG C, and heating rate is 10 DEG C/min, nitrogen protection, flow velocity 50mL/min.

(2) test of mechanical property：

Vulcanized rubber is made to the vulcanized rubber piece of 2mm thickness, and is cut out according to 1 type dumbbell shaped specified in GB/T528-1998 Obtained vulcanized rubber piece is cut into dumbbell shaped standard film by knife, and using rubber puller system, (Japanese Shimadzu Corporation produces, model AG-20KNG) mechanical property of the vulcanized rubber piece is tested, wherein test temperature is 25 DEG C, hauling speed 500 Mm/min obtains the breaking strength and elongation at break of vulcanized rubber.

(3) test of shore a hardness：

It is tested according to method specified in GB/T531-1999.

(4) anti-deformation nature test：

Vulcanized rubber is cut into dumbbell shaped standard film according to 1 type dumbbell shaped cut-off knife specified in GB/T528-92, is being tested Temperature be 25 DEG C, hauling speed be 500 mm/mins under conditions of sample is broken.Sample after tension failure is placed 3min, then two parts of fracture are coincide together, the distance between two parallel lines after coincideing is measured, is calculated as follows and pulls apart forever Long deformation values：

S_b=100 (L_t-L₀)/L₀, wherein S_bTo pull apart permanent deformation, %；L_tAfter coincideing for sample between two parallel lines Distance, mm；L₀For initial trial length, mm.

(5) 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 Degree is 55 DEG C, and the testing time is 25 minutes, and compression frequency is 30 times/second.

(6) test of wet-sliding resistant performance and rolling resistance：

The wet-sliding resistant performance and rolling resistance of vulcanized rubber are carried out using U.S.'s TA companies DMA-2980 types viscoelastic spectrometer It measures, wherein test frequency 2Hz, heating rate are 5 DEG C/min, and test temperature is 100 DEG C, and sample size is 40mm × 5mm ×1mm.Tan δ when with 0 DEG C indicate the wet-sliding resistant performance of vulcanized rubber, and tan δ are bigger, indicate that vulcanized rubber wet-sliding resistant performance is got over It is good；Tan δ when with 60 DEG C indicate the rolling resistance of vulcanized rubber, and tan δ are smaller, indicate that vulcanized rubber rolling resistance is smaller；It fills out Expect that the dispersion in rubber is characterized with the value of Tan δ (0 DEG C)/Tan δ (60 DEG C), value is higher to show that filler disperses better.

Embodiment I-1

(1) in 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 1500g hexamethylenes, 117g butadiene, heating is added The n-BuLi that 1.1g ethyl tetrahydrofurfuryl ethers (ETE) and 3.3mmol are added after to 50 DEG C causes, and obtains containing diene polymerization The solution of object.The number-average molecular weight of the diene polymer is 16.0 ten thousand, and with butadiene knot in the diene polymer On the basis of the weight of structure unit, the content for the conjugated diene structural unit that side chain contains double bond in the diene polymer is 59.5 weight %.

(2) it is anti-that 0.4ml (0.48g) 3- mercaptopropionic acids, 3.8mg is added in the product 78.7g for taking step (1) to obtain thereto Old agent 1010 is added 75.3mg azodiisobutyronitriles, is reacted 1 hour at 80 DEG C and obtain diene after being heated to 80 DEG C Polymer, sampling are dried for 24 hours in 60 DEG C of vacuum.Prove that key is connected on polymer chain modifying agent, is passed through by nuclear magnetic spectrogram Product illustrates that 3- mercaptopropionic acids substantially completely turn wherein not detecting 3- mercaptopropionic acids before gas chromatograph detects above-mentioned drying Change, and the polymer does not have undesirable smell.

Embodiment I-2

(1) in 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 2400g n-hexanes, 274g butadiene, heating is added The sec-butyl of double tetrahydrofuran base propane solution (DTHFP) and 4.4mmol that 0.8ml weight fractions are 57% are added after to 50 DEG C Lithium causes, and obtains diene polymer.The number-average molecular weight of the diene polymer is 16.6 ten thousand, and poly- with the alkadienes It closes in object on the basis of the weight of butadiene structural units, side chain contains the conjugated diene knot of double bond in the diene polymer The content of structure unit is 61.1 weight %.

(2) it is anti-that 2.25ml (2.7g) 3- mercaptopropionic acids, 26.46mg is added in the whole products for taking step (1) to obtain thereto Old agent 264 is added 459.4mg azodicarbonamides, is reacted 1 hour at 85 DEG C and obtain diene after being heated to 85 DEG C Polymer, sampling are dried for 24 hours in 60 DEG C of vacuum.Prove that key is connected on polymer chain modifying agent, is passed through by nuclear magnetic spectrogram Product illustrates that 3- mercaptopropionic acids substantially completely turn wherein not detecting 3- mercaptopropionic acids before gas chromatograph detects above-mentioned drying Change, and the polymer does not have undesirable smell.

Embodiment I-3

(1) in 5 liters of stainless steel stirred tanks, 2200g hexamethylenes, 213g butadiene and 157g is added under High Purity Nitrogen protection Isoprene, be heated to after 50 DEG C be added 0.5ml weight fractions be 57% double tetrahydrofuran base propane solution (DTHFP) and The n-BuLi of 4.4mmol causes, and obtains diene polymer.The number-average molecular weight of the diene polymer is 16.1 ten thousand, And on the basis of the weight of butadiene and isoprene structures unit in the diene polymer, in the diene polymer The content that side chain contains the conjugated diene structural unit of double bond is 50.2 weight %；

(2) 1.15ml (1.38g) 3- mercaptopropionic acids, 13.23mg is added in the whole products for taking step (1) to obtain thereto Antioxidant 2246 is added 227.24mg azo-bis-iso-dimethyls, is reacted 1 hour at 80 DEG C and obtain official after being heated to 80 DEG C Diene polymer can be changed, sampling is dried for 24 hours in 60 DEG C of vacuum.Prove that key is connected to polymer to modifying agent by nuclear magnetic spectrogram On chain, product illustrates 3- mercaptopropionic acid bases wherein not detecting 3- mercaptopropionic acids before detecting above-mentioned drying by gas chromatograph This conversion completely, and the polymer does not have undesirable smell.

Embodiment I-4

Diene's polymer is prepared according to the method for embodiment I-1, unlike, the 3- mercaptopropionic acids phase 2- trimethyl silane ethyl mercaptans with parts by weight substitute, and obtain diene's polymer.It proves to be modified by nuclear magnetic spectrogram Key is connected on polymer chain for agent, product before above-mentioned drying is detected by gas chromatograph, wherein not detecting 2- trimethyl silicanes Alkane ethyl mercaptan illustrates that 2- trimethyl silane ethyl mercaptans substantially completely convert, and the polymer does not have undesirable smell.

Comparative Examples I -1

Diene polymer is prepared according to the method for embodiment I-1, unlike, do not include step (2), obtains alkadienes Polymer.

Comparative Examples I -2

(1) in 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 1500g hexamethylenes, 20g butadiene and 2.7g is added Tetrahydrofurfuryl alcohol ether is then heated to the n-BuLi that 12mmol is added after 40 DEG C and controls pressure and causes instead at 0.4MPa It answers 1 hour, obtains the solution containing diene polymer.The number-average molecular weight of the diene polymer is 1000, and with institute It states in diene polymer on the basis of the weight of conjugated diene structural unit, side chain contains double bond in the diene polymer Conjugated diene structural unit content be 67 weight %.

(2) 20g γ-mercaptopropyl trimethoxysilanes are added into the product that step (1) obtains, and sampling carries out mercapto immediately Base test, after being then heated to 100 DEG C be added 1g dilauroyl peroxides, and by pressure control reacted 5 hours at 0.4MPa after Diene polymer is obtained, sampling carries out sulfydryl test, and samples dry 12h in 60 DEG C of vacuum, is then stripped, 60 DEG C true Aerial dry 12h carries out nuclear-magnetism test.Finally dried for 24 hours in 80 DEG C of vacuum.The mercapto in product is detected by gas chromatograph Base content, it is 72% that sulfydryl conversion ratio, which is calculated,.That is the conversion ratio of 3- mercaptopropionic acids is about 72%.Gained diene polymer Product has apparent bad smell.

Embodiment I-5~I-8

(1) preparation of rubber compound：

35 parts by weight are prepared by embodiment I-1~I-4 respectively diene polymer, the natural rubber of 10 parts by weight Glue, 55 parts of solution polymerized butadiene styrene rubber SSBR2305 (be 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 (Tianjin gold autumn reality carbon black Chemical Co., Ltd.), 60 weight Part white carbon 115GR (goldschmidt chemical corporation) is uniformly mixed and is heat-treated using Haake, wherein heat treatment temperature is 150 DEG C, turns Speed is 30rpm/min, time 7min.After the completion of heat treatment, said mixture is added in open mill, and 2.5 weight are added The zinc oxide (Liuzhou Xin Pin Co., Ltds) of part, stearic acid (the polite Chemical Co., Ltd. in Hong Kong, SA1801), 2 weights of 1 parts by weight Measure the antioxidant 4020 of part, 1.4 parts by weight N- cyclohexyl -2- benzothiazole sulfonamides (Hebi Uhoo Rubber Chemicals Co., Ltd., CZ), 0.75 parts by weight diphenylguanidine (Guangzhou Li great rubber raw materials trade Co., Ltd, DPG) and 6 parts by weight silane coupling agents Si69 (goldschmidt chemical corporation) is kneaded 60 minutes at 50 ± 5 DEG C, obtains rubber compound H-I-1~H-I-4.

(2) preparation of vulcanized rubber：

At 150 DEG C, 12MPa, rubber compound H-I-1~H-I-4 that step (1) is obtained is enterprising in vulcanizing press respectively Row vulcanizing treatment 40 minutes, obtains vulcanized rubber S-I-1~S-I-4.Vulcanized rubber performance is as shown in table 1 below.

Comparative Examples I -3

Rubber is prepared according to the method for embodiment I-5, unlike, the alkadienes being prepared by embodiment I-1 is gathered It closes object to be substituted with the diene polymer obtained by Comparative Examples I -1, and the addition of diene polymer is 34.87 parts by weight, In addition, in the preparation process of rubber compound, it is also added into the γ-mercaptopropyl trimethoxysilane of 0.13 parts by weight, obtains reference Vulcanized rubber DS-I-1.Vulcanized rubber performance is as shown in table 1 below.

Comparative Examples I -4

Vulcanized rubber is prepared according to the method for embodiment I-5, unlike, the diene that will be prepared by embodiment I-3 The diene polymers obtained by Comparative Examples I -1 of 99.17 parts by weight of hydrocarbon polymer and 0.83 parts by weight by Comparative Examples I -2 The mixture replacing of obtained diene polymer obtains vulcanized rubber DS-I-2.Vulcanized rubber performance is as shown in table 1 below.

Table 1

Embodiment II-1

(1) in 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 1500g hexamethylenes, 20g styrene and 97g is added Butadiene is heated to that 1.1g ethyl tetrahydrofurfuryl ethers (ETE) are added after 50 DEG C and the n-BuLi of 3.3mmol causes, contained There is the solution of diene polymer.The number-average molecular weight of the diene polymer is 18.2 ten thousand, and with the diene polymer The quality total amount of middle conjugated diene structural unit is counted for 100%, styryl structures in diene polymer obtained by the step The mass percentage of unit is 17.1%, and 1,2-Bd mass percentage is 46.1%, the mass percentage of Isosorbide-5-Nitrae-Bd It is 36.8%.

(2) it is anti-that 0.4ml (0.48g) 3- mercaptopropionic acids, 2.7mg is added in the product 78.7g for taking step (1) to obtain thereto Old agent 1010 is added 75.3mg azodiisobutyronitriles, is reacted 1 hour at 80 DEG C and obtain diene after being heated to 80 DEG C Polymer, sampling are dried for 24 hours in 60 DEG C of vacuum.Prove that key is connected on polymer chain modifying agent, is passed through by nuclear magnetic spectrogram Product illustrates that 3- mercaptopropionic acids substantially completely turn wherein not detecting 3- mercaptopropionic acids before gas chromatograph detects above-mentioned drying Change, and the polymer does not have undesirable smell.

Embodiment II-2

(1) in 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 2400g n-hexanes, 60g styrene and 214g is added Butadiene, be heated to after 50 DEG C be added 0.8ml weight fractions be 57% double tetrahydrofuran base propane solution (DTHFP) and The s-butyl lithium of 4.4mmol causes, and rises to 80 DEG C and reacts 30min again, the butter of tin of 0.33mmol is then added, and about 75 30min is reacted at DEG C, obtains the diene polymer that coupling efficiency is 39%.The number of diene polymer obtained by the step is divided equally Son amount is 10.1 ten thousand, molecular weight distribution 1.10, and with the quality of conjugated diene structural unit in the diene polymer Total amount is counted for 100%, and the mass percentage of styrol structural unit is 21.8% in diene polymer obtained by the step, 1,2-Bd mass percentage is 48.4%, and the mass percentage of Isosorbide-5-Nitrae-Bd is 29.8%.

(2) it is anti-that 2.25ml (2.7g) 3- mercaptopropionic acids, 46.46mg is added in the whole products for taking step (1) to obtain thereto 459.4mg azodicarbonamides are added in old agent 1010 after being heated to 85 DEG C, reacted at 85 DEG C and obtain within 1 hour functionalization diene Hydrocarbon polymer, sampling are dried for 24 hours in 60 DEG C of vacuum.Prove that key is connected on polymer chain modifying agent, is led to by nuclear magnetic spectrogram It crosses the above-mentioned desciccate of gas chromatograph detection and illustrates that 3- mercaptopropionic acids substantially completely turn wherein not detecting 3- mercaptopropionic acids Change, and the polymer does not have undesirable smell.

Embodiment II-3

(1) in 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 2200g hexamethylenes, 63g styrene, 150g is added It is molten to be heated to the double tetrahydrofuran base propane that addition 0.5ml weight fractions are 57% after 50 DEG C for butadiene and 157g isoprene The n-BuLi of liquid (DTHFP) and 4.4mmol cause, and rise to 75 DEG C and react 1h again, and the butter of tin of 0.22mmol is then added, And 1h is reacted at about 75 DEG C, obtain the diene polymer that coupling efficiency is 30%.Diene polymer obtained by the step Number-average molecular weight is 11.9 ten thousand, molecular weight distribution 1.12, and with conjugated diene structural unit in the diene polymer Quality total amount counted for 100%, the mass percentage of styrol structural unit is in diene polymer obtained by the step 17.1%, 1,2-Bd mass percentage is 20.3%, and the mass percentage of Isosorbide-5-Nitrae-Bd is 20.1%, 3,4-PI% matter It is 21.5% to measure percentage composition, and the mass percentage of Isosorbide-5-Nitrae-PI is 21.0%.

(2) 1.15ml (1.38g) 3- mercaptopropionic acids, 13.23mg is added in the whole products for taking step (1) to obtain thereto Anti-aging agent 1010 is added 227.24mg azo-bis-iso-dimethyls, is reacted 1 hour at 80 DEG C and obtain official after being heated to 80 DEG C Diene polymer can be changed, sampling is dried for 24 hours in 60 DEG C of vacuum.Prove that key is connected to polymer to modifying agent by nuclear magnetic spectrogram On chain, product illustrates 3- mercaptopropionic acid bases wherein not detecting 3- mercaptopropionic acids before detecting above-mentioned drying by gas chromatograph This conversion completely, and the polymer does not have undesirable smell.

Embodiment II-4

Diene's polymer is prepared according to the method for embodiment II-2, unlike, the 3- mercaptopropionic acids Addition is 7.0ml (7.315g), obtains diene's polymer.By nuclear magnetic spectrogram prove modifying agent key be connected to it is poly- It closes on object chain, product illustrates 3- sulfydryls third wherein not detecting 3- mercaptopropionic acids before detecting above-mentioned drying by gas chromatograph Acid substantially completely converts, and the polymer does not have undesirable smell.

Embodiment II-5

Diene's polymer is prepared according to the method for embodiment II-3, unlike, the 3- mercaptopropionic acids are used The 2- trimethyl silane ethyl mercaptans of identical weight part substitute, and obtain diene's polymer proves to be modified by nuclear magnetic spectrogram Key is connected on polymer chain for agent, product before above-mentioned drying is detected by gas chromatograph, wherein not detecting 2- trimethyl silicanes Alkane ethyl mercaptan illustrates that 2- trimethyl silane ethyl mercaptans substantially completely convert, and the polymer does not have undesirable smell.

Embodiment II-6

Diene's polymer is prepared according to the method for embodiment II-1, unlike, anti-aging agent 1010 is replaced For (2,4- di-tert-butyl-phenyls) ester of phosphorous acid three and 3 times of 1010 mass of anti-aging agent of phase homogenous quantities antioxidant 264 it is mixed Object is closed, diene's polymer is obtained.Prove that key is connected on polymer chain modifying agent, passes through gas phase by nuclear magnetic spectrogram Product illustrates that 3- mercaptopropionic acids substantially completely convert wherein not detecting 3- mercaptopropionic acids before chromatograph detects above-mentioned drying, and The polymer does not have undesirable smell.

Embodiment II-7

Diene's polymer is prepared according to the method for embodiment II-1, unlike, anti-aging agent 1010 is replaced For the antioxidant 4020 of 3 times of 1010 weight of anti-aging agent, diene's polymer is obtained.It proves to be modified by nuclear magnetic spectrogram Key is connected on polymer chain for agent, and product before above-mentioned drying is detected by gas chromatograph, wherein 3- mercaptopropionic acids are not detected, Illustrate that 3- mercaptopropionic acids substantially completely convert, and the polymer does not have undesirable smell.

Comparative Example II -1

Diene's polymer is prepared according to the method for embodiment II-1, unlike, do not include step (2), obtains To diene polymer.

Comparative Example II -2

Diene's polymer is prepared according to the method for embodiment II-1, unlike, identical type and dosage Anti-aging agent 1010 is added after vacuum drying, and further drying for 24 hours, obtains diene polymerization in 60 DEG C of vacuum after the addition Object.

Embodiment II-8

Products therefrom 97.3g is carried out and taken according to the method for (1) the step of embodiment II-1, and 0.1ml is added thereto 18.8mg azodiisobutyronitriles are added, at 90 DEG C in (0.12g) 3- mercaptopropionic acids, 0.66mg anti-aging agents 1010 after being heated to 100 DEG C Lower reaction obtains diene's polymer for 0.3 hour, and sampling is dried for 24 hours in 60 DEG C of vacuum.It is proved by nuclear magnetic spectrogram Key is connected on polymer chain modifying agent, product before above-mentioned drying is detected by gas chromatograph, wherein not detecting 3- sulfydryls Propionic acid illustrates that 3- mercaptopropionic acids substantially completely convert, and the polymer does not have undesirable smell.

Embodiment II-9

Products therefrom 55g is carried out and taken according to the method for (1) the step of embodiment II-1, and 0.08ml is added thereto 10.1mg azodiisobutyronitriles are added, at 85 DEG C in (0.096g) 3- mercaptopropionic acids, 1.0mg anti-aging agents 1010 after being heated to 100 DEG C Lower reaction obtains diene's polymer for 0.6 hour, and sampling is dried for 24 hours in 60 DEG C of vacuum.It is proved by nuclear magnetic spectrogram Key is connected on polymer chain modifying agent, product before above-mentioned drying is detected by gas chromatograph, wherein not detecting 3- sulfydryls Propionic acid illustrates that 3- mercaptopropionic acids substantially completely convert, and the polymer does not have undesirable smell.

Embodiment II-10

(1) in 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 2200g n-hexanes, 60g styrene and 293g is added Isoprene, be heated to after 50 DEG C be added 0.5ml weight fractions be 57% double tetrahydrofuran base propane solution (DTHFP) and The phenyl lithium of 4.84mmol causes, and rises to 90 DEG C and reacts 20min again, the silicon tetrachloride of 0.28mmol is then added, and about 90 20min is reacted at DEG C, obtains the diene polymer that coupling efficiency is 34%.The number of diene polymer obtained by the step is divided equally Son amount is 12.6 ten thousand, molecular weight distribution 1.13, and with mole of conjugated diene structural unit in the diene polymer Total amount is counted for 100%, and the molar content of styrol structural unit is 9.6% in diene polymer obtained by the step, 1,2-Bd molar content is 42.2%, and the molar content of Isosorbide-5-Nitrae-Bd is 48.2%.

(2) it is anti-old that 2.5ml (3g) 3- mercaptopropionic acids, 36.46mg is added in the whole products for taking step (1) to obtain thereto 359.4mg benzoyl peroxides are added in agent 1010 after being heated to 70 DEG C, 45min is reacted under 70 DEG C of pressure and obtains functionalization two Olefin polymer, sampling are dried for 24 hours in 60 DEG C of vacuum.Prove that key is connected on polymer chain modifying agent by nuclear magnetic spectrogram, Product illustrates that 3- mercaptopropionic acids are substantially complete wherein not detecting 3- mercaptopropionic acids before detecting above-mentioned drying by gas chromatograph Full conversion, and the polymer does not have undesirable smell.

Embodiment II-11

Products therefrom 48.8g is carried out and taken according to the method for (1) the step of embodiment II-1, and 0.56ml is added thereto 48.8mg peroxidating is added in (0.56g) (3- mercaptopropyis) triethoxysilane, 1.8mg anti-aging agents 1010 after being heated to 90 DEG C Lauroyl reacts at 80 DEG C and obtains within 1 hour diene's polymer, and sampling is dried for 24 hours in 60 DEG C of vacuum.Pass through core Magnetic spectrum figure proves that key is connected on polymer chain modifying agent, product before above-mentioned drying is detected by gas chromatograph, wherein not examining (3- mercaptopropyis) triethoxysilane is measured, illustrates that (3- mercaptopropyis) triethoxysilane substantially completely converts, and this is poly- Closing object does not have undesirable smell.

Embodiment II-12

Products therefrom 79.5g is carried out and taken according to the method for (1) the step of embodiment II-1, and 0.45ml is added thereto 40.2mg azos two are added in (0.45g) (3- mercaptopropyis) triethoxysilane, 1.1mg anti-aging agents 1010 after being heated to 80 DEG C Isobutyronitrile reacts at 80 DEG C and obtains within 1 hour diene's polymer, and sampling is dried for 24 hours in 60 DEG C of vacuum.Pass through core Magnetic spectrum figure proves that key is connected on polymer chain modifying agent, product before above-mentioned drying is detected by gas chromatograph, wherein not examining (3- mercaptopropyis) triethoxysilane is measured, illustrates that (3- mercaptopropyis) triethoxysilane substantially completely converts, and this is poly- Closing object does not have undesirable smell.

Embodiment II-13

Products therefrom 78.7g is carried out and taken according to the method for (1) the step of embodiment II-1, and 0.2ml is added thereto It is different that 75.3mg azos two are added in (0.2g) (3- mercaptopropyis) triethoxysilane, 2.7mg anti-aging agents 1010 after being heated to 80 DEG C Butyronitrile reacts at 80 DEG C and obtains within 1 hour diene's polymer, and sampling is dried for 24 hours in 60 DEG C of vacuum.Pass through nuclear-magnetism Spectrogram proves that key is connected on polymer chain modifying agent, product before above-mentioned drying is detected by gas chromatograph, wherein not detecting Go out (3- mercaptopropyis) triethoxysilane, illustrates that (3- mercaptopropyis) triethoxysilane substantially completely converts, and the polymerization Object does not have undesirable smell.

Embodiment II-14

Products therefrom 70.8g is carried out and taken according to the method for (1) the step of embodiment II-1, and 0.07ml is added thereto 13.7mg azodiisobutyronitriles are added in (90mg) 3- sulfydryls -1,2-PD, 0.69mg anti-aging agents 1010 after being heated to 80 DEG C, It is reacted at 80 DEG C and obtains within 1 hour diene's polymer, sampling is dried for 24 hours in 60 DEG C of vacuum.Pass through nuclear magnetic spectrogram It proves that key is connected on polymer chain modifying agent, product before above-mentioned drying is detected by gas chromatograph, wherein not detecting 3- Sulfydryl -1,2-PD illustrates that 3- sulfydryls -1,2-PD substantially completely converts, and the polymer does not have undesirable gas Taste.

Embodiment II-15

Products therefrom 62.6g is carried out and taken according to the method for (1) the step of embodiment II-1, and 0.03ml is added thereto 6.0mg azodiisobutyronitriles are added in (37.5mg) 3- sulfydryls -1,2-PD, 0.3mg anti-aging agents 1010 after being heated to 80 DEG C, It is reacted at 80 DEG C and obtains within 1 hour diene's polymer, sampling is dried for 24 hours in 60 DEG C of vacuum.Pass through nuclear magnetic spectrogram Prove that key is connected on polymer chain modifying agent, detects above-mentioned desciccate, wherein not detecting 3- mercaptos by gas chromatograph Base -1,2-PD illustrates that 3- sulfydryls -1,2-PD substantially completely converts, and the polymer does not have undesirable smell.

Embodiment II-16~II-28

(1) preparation of rubber compound：

100 parts by weight are prepared by embodiment II-1~II-15 respectively diene's polymer, 1 weight The stearic acid (the polite Chemical Co., Ltd. in Hong Kong, SA1801), 10 parts by weight medium super abrasion furnace black N220 (Tianjin gold autumn reality charcoals of part Black Chemical Co., Ltd.), 60 parts by weight white carbon 115GR (goldschmidt chemical corporation) be uniformly mixed and using Haake be heat-treated, In, heat treatment temperature is 150 DEG C, rotating speed 30rpm, time 7min.After the completion of heat treatment, mill is added in said mixture In machine, and (the polite chemical industry in Hong Kong has the stearic acid of the zinc oxide (Liuzhou Xin Pin Co., Ltds) of 2.5 parts by weight of addition, 1 parts by weight Limit company, SA1801), the antioxidant 4020 of 2 parts by weight, 1.4 parts by weight N- cyclohexyl -2- benzothiazole sulfonamides (purchase From Hebi Uhoo Rubber Chemicals Co., Ltd., CZ), 0.75 parts by weight diphenylguanidine (Guangzhou Li great rubber raw materials trade Co., Ltd, DPG) and 6 parts by weight silane coupling agent Si69 (goldschmidt chemical corporation), it is kneaded 60 minutes at 50 ± 5 DEG C, obtains rubber compound H-II- 1~H-II-15.

(2) preparation of vulcanized rubber：

At 150 DEG C, 12MPa, the rubber compound H-II-1~H-II-15 for respectively obtaining step (1) is in vulcanizing press Upper progress vulcanizing treatment 45 minutes, obtains vulcanized rubber S-II-1~S-II-15.Vulcanized rubber performance is as shown in table 2 below.

Comparative Example II -3 is to Comparative Example II -4

Rubber is prepared according to the method for embodiment II-16, unlike, the alkadienes that will be prepared by embodiment II-1 Polymer is substituted with the diene polymer that is obtained by Comparative Example II -1 and Comparative Example II -2 respectively, and diene polymer plus It is that 99.54 parts by weight are also added into γ-mercapto propyl front three of 0.46 parts by weight in addition, in the preparation process of rubber compound to enter amount Oxysilane obtains reference vulcanized rubber DS-II-1 and DS-II-2.Vulcanized rubber performance is as shown in table 2 below.

Table 2

Continued 2

As can be seen from the above results, modified in diene's polymer that preparation method provided by the invention obtains Agent substantially completely converts, and the relationship that can be effectively improved between anti-slippery and rolling resistance, and it is mixed can also to improve rubber Due to the use of undesirable smell caused by modifying agent during refining.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.

Claims (31)

1. a kind of preparation method of diene's polymer, which is characterized in that this method includes that in an inert atmosphere, will contain There is the diene polymer of at least one conjugated diene structural unit to be contacted with modifying agent, stabilizer and initiator, it is described to connect It is poly- that tactile condition so that the modifying agent chemical bond is connected to the alkadienes containing at least one conjugated diene structural unit It closes on object；The number-average molecular weight of the diene polymer containing at least one conjugated diene structural unit is 50,000-100 Ten thousand, and with conjugated diene structural unit in the diene polymer containing at least one conjugated diene structural unit On the basis of weight, side chain contains being total to for double bond in the diene polymer containing at least one conjugated diene structural unit The content of yoke alkadienes structural unit is 15-85 weight %, and the modifying agent is the sulfydryl silicon with structure shown in formula (I) At least one in substance in substance and molecule in alkane, molecule simultaneously containing sulfydryl and hydroxyl simultaneously containing sulfydryl and carboxyl Kind：

Wherein, R₁-R₄For C₁-C₂₀Linear chain or branched chain alkyl or contain heteroatomic C₁-C₂₀Linear chain or branched chain alkyl, it is described Hetero atom is one or more in halogen, oxygen, sulphur, silicon and phosphorus；

The stabilizer is one or more in arylamine type antioxidant, hindered phenol type antioxidant and phosphite antioxidant.

2. preparation method according to claim 1, wherein it is described containing at least one conjugated diene structural unit two The number-average molecular weight of olefin polymer is 100,000-40 ten thousand.

3. preparation method according to claim 1, wherein it is described containing at least one conjugated diene structural unit two The content that side chain contains the conjugated diene structural unit of double bond in olefin polymer is 30-70 weight %.

4. preparation method according to claim 1, wherein R₁-R₃For C₁-C₅Linear or branched alkyl group or linear chain or branched chain Alkoxy, R₄For C₁-C₅Linear chain or branched chain alkylidene.

5. preparation method according to claim 1, wherein relative to containing at least one conjugated diene described in 100g The dosage of the diene polymer of structural unit, the modifying agent is 0.01-10g, and the dosage of the stabilizer is 0.001- 500mg。

6. according to the preparation method described in any one of claim 1-5, wherein contain sulfydryl and hydroxyl in the molecule simultaneously The substance of base be HS-R-OH indicate substance, wherein R be carbon atom number be 1-6 linear chain or branched chain alkylidene, be optionally substituted by a hydroxyl group Carbon atom number be 1-6 linear chain or branched chain alkylidene in one kind；

Substance in the molecule simultaneously containing sulfydryl and carboxyl is the substance that HS-R '-COOH is indicated, wherein R ' is carbon atom number For the linear chain or branched chain alkylidene of 1-6.

7. preparation method according to claim 6, wherein R is-(CH₂)_m-CH(OH)-(CH₂)_n, wherein m and n are respectively only It is on the spot the integer of 1-2.

8. preparation method according to claim 6, wherein R ' is methylene, ethylidene or propylidene.

9. according to the preparation method described in any one of claim 1-5, wherein the modifying agent is trimethoxy propyl mercapto Base silane, triethoxy propyl hydrosulphonyl silane, mercapto hydroxypropyl methyl dimethoxysilane, 3- thio propane -1,2- glycol, sulfydryl second It is one or more in acid, 3- mercaptopropionic acids.

10. according to the preparation method described in any one of claim 1-5, wherein the stabilizer is four [β-(3,5- bis- Tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, DBPC 2,6 ditertiary butyl p cresol, 2,2 '-methylene-bis- (4- methyl -6- Tert-butyl phenol), tert-butyl catechol, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, 3- (3,5- di-t-butyl -4- hydroxyls Base phenyl) at least one of propionic acid stearyl and phosphorous acid three (nonyl phenyl) ester.

11. according to the preparation method described in any one of claim 1-5, wherein the condition of the contact includes, relative to The diene polymer containing at least one conjugated diene structural unit of 100g, the dosage of the initiator are The temperature of 0.01-0.2g, contact are 20-150 DEG C, and the time of contact is 0.2-24 hours.

12. preparation method according to claim 11, wherein the temperature of contact is 70-100 DEG C, and the time of contact is 0.5-5 hours.

13. according to the preparation method described in any one of claim 1-5, wherein described to contain at least one conjugated diene The diene polymer of hydrocarbon structure unit is prepared by the following method to obtain：In an inert atmosphere and in the presence of initiator, Polymerized monomer containing at least one conjugated diene is subjected to polymerisation in a solvent, the condition of the polymerisation makes The number-average molecular weight of the diene polymer containing at least one conjugated diene structural unit arrived is 50,000-100 ten thousand, and with The weight of conjugated diene structural unit is in the diene polymer containing at least one conjugated diene structural unit Benchmark, side chain contains the conjugated diene of double bond in the diene polymer containing at least one conjugated diene structural unit The content of hydrocarbon structure unit is 15-85 weight %.

14. preparation method according to claim 13, wherein what the condition of the polymerisation made contains at least one The number-average molecular weight of the diene polymer of kind conjugated diene structural unit is 100,000-40 ten thousand, described total containing at least one The content that side chain contains the conjugated diene structural unit of double bond in the diene polymer of yoke alkadienes structural unit is 30-70 Weight %.

15. preparation method according to claim 13, wherein the polymerized monomer also contains monovinylarene, and institute It states in polymerized monomer, the weight ratio of the monovinylarene and conjugated diene is 5:95-60:40.

16. preparation method according to claim 15, wherein the weight ratio of the monovinylarene and conjugated diene It is 20:80-40:60.

17. a kind of preparation method of diene's polymer, which is characterized in that this approach includes the following steps：

(1) in an inert atmosphere and in the presence of initiator, by the polymerized monomer containing at least one conjugated diene molten Carry out polymerisation in agent, obtain the reaction product containing diene polymer, the condition of the polymerisation make two The number-average molecular weight of olefin polymer is 50,000-100 ten thousand, and with conjugated diene structural unit in the diene polymer On the basis of weight, side chain contains the content of the conjugated diene structural unit of double bond for 15-85 weights in the diene polymer Measure %；

(2) in an inert atmosphere, the reaction product containing diene polymer step (1) obtained and initiator, stabilizer And modifying agent, the condition of the contact makes the modifying agent chemical bond be connected on the diene polymer, described to change Property agent be in hydrosulphonyl silane, molecule with structure shown in formula (I) in substance and molecule simultaneously containing sulfydryl and hydroxyl At least one of substance simultaneously containing sulfydryl and carboxyl：

Wherein, R₁-R₄For C₁-C₂₀Linear chain or branched chain alkyl or contain heteroatomic C₁-C₂₀Linear chain or branched chain alkyl, it is described Hetero atom is one or more in halogen, oxygen, sulphur, silicon and phosphorus；

The stabilizer is one or more in arylamine type antioxidant, hindered phenol type antioxidant and phosphite antioxidant.

18. preparation method according to claim 17, wherein the diene polymerization that the condition of the polymerisation makes The number-average molecular weight of object is 100,000-40 ten thousand, and side chain contains the conjugated diene structural unit of double bond in the diene polymer Content be 30-70 weight %.

19. preparation method according to claim 17, wherein R₁-R₃For C₁-C₅Linear or branched alkyl group or straight chain or branch Chain alkoxy, R₄For C₁-C₅Linear chain or branched chain alkylidene.

20. preparation method according to claim 17, wherein relative to containing at least one conjugated diene described in 100g The dosage of the diene polymer of hydrocarbon structure unit, the modifying agent is 0.01-10g, and the dosage of the stabilizer is 0.001- 500mg。

21. according to the preparation method described in any one of claim 17-20, wherein contain sulfydryl simultaneously in the molecule Be the substance that HS-R-OH is indicated with the substance of hydroxyl, wherein R be carbon atom number be 1-6 linear chain or branched chain alkylidene, by hydroxyl Substituted carbon atom number is one kind in the linear chain or branched chain alkylidene of 1-6；

Substance in the molecule simultaneously containing sulfydryl and carboxyl is the substance that HS-R '-COOH is indicated, wherein R ' is carbon atom number For the linear chain or branched chain alkylidene of 1-6.

22. preparation method according to claim 21, wherein R is-(CH₂)_m-CH(OH)-(CH₂)_n, wherein m and n are respectively It independently is the integer of 1-2.

23. preparation method according to claim 21, wherein R ' is methylene, ethylidene or propylidene.

24. according to the preparation method described in any one of claim 17-20, wherein the modifying agent is trimethoxy third Base hydrosulphonyl silane, triethoxy propyl hydrosulphonyl silane, mercapto hydroxypropyl methyl dimethoxysilane, 3- thio propane -1,2- glycol, mercapto It is one or more in guanidine-acetic acid, 3- mercaptopropionic acids.

25. according to the preparation method described in any one of claim 17-20, wherein the stabilizer is four [β-(3,5- Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, DBPC 2,6 ditertiary butyl p cresol, 2,2 '-methylene-bis- (4- methyl- 6- tert-butyl phenols), tert-butyl catechol, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, 3- (3,5- di-t-butyls -4- Hydroxy phenyl) at least one of propionic acid stearyl and phosphorous acid three (nonyl phenyl) ester.

26. according to the preparation method described in any one of claim 17-20, wherein by the diene polymer with change Property agent contact condition include, relative to described in 100g contain at least one conjugated diene structural unit diene polymerization The dosage of object, the initiator is 0.01-0.2g, and the temperature of contact is 20-150 DEG C, and the time of contact is 0.2-24 hours.

27. preparation method according to claim 26, wherein the temperature of contact is 70-100 DEG C, and the time of contact is 0.5-5 hours.

28. according to the preparation method described in any one of claim 17-20, wherein also contain in the polymerized monomer single The weight ratio of vinyl-arene, the monovinylarene and conjugated diene is 5:95-60:40.

29. preparation method according to claim 28, wherein the weight ratio of the monovinylarene and conjugated diene It is 20:80-40:60.

30. according to the preparation method described in any one of claim 17-20, wherein the condition of the polymerisation includes Polymerization temperature is 10-160 DEG C, and polymerization time is 0.5-10 hours.

31. preparation method according to claim 30, wherein polymerization temperature is 50-100 DEG C, and polymerization time is that 0.5-3 is small When.