CN103374101B - The preparation method of a kind of irregular agent and styrene-butadiene rubber(SBR) - Google Patents
The preparation method of a kind of irregular agent and styrene-butadiene rubber(SBR) Download PDFInfo
- Publication number
- CN103374101B CN103374101B CN201210114260.2A CN201210114260A CN103374101B CN 103374101 B CN103374101 B CN 103374101B CN 201210114260 A CN201210114260 A CN 201210114260A CN 103374101 B CN103374101 B CN 103374101B
- Authority
- CN
- China
- Prior art keywords
- styrene
- consumption
- content
- sbr
- butadiene rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a kind of irregular agent, described irregular agent contains glycol dimethyl ether, alkylsulfonate and/or alkylaryl sulphonate.Present invention also offers a kind of preparation method of styrene-butadiene rubber(SBR), wherein, the method comprises in an inert atmosphere, under anionic polymerization conditions, under the existence of organic lithium initiator and irregular agent, vinylbenzene and divinyl are carried out polyreaction in organic solvent, obtain copolymer solution, and copolymer solution is contacted with terminator, the consumption of described anionic polymerization conditions and irregular agent makes the content of block styrene chain in the styrene-butadiene rubber(SBR) obtained be less than 2 % by weight, the content of described block styrene chain is the content containing continuous more than four and four vinylbenzene chain links on styrene-butadiene rubber(SBR) molecular chain, described irregular agent contains tetrahydrofuran (THF) and irregular agent provided by the invention.Adopt method of the present invention can obtain the lower styrene-butadiene rubber(SBR) of the content of block styrene chain.
Description
Technical field
The present invention relates to the preparation method of a kind of irregular agent and styrene-butadiene rubber(SBR).
Background technology
After the reaction of discovery active anionic polymerization, various types of structure regulator arises at the historic moment, but tetrahydrofuran (THF) (THF) is still industrial comparatively conventional structure regulator so far.THF is adopted to prepare the solution polymerized butylbenzene that vinyl structure content is 15-50 % by weight, the vinyl structure of product can reach control overflow, but because the regulating power of THF is not strong, limited to the regulating power of vinylbenzene sequence distribution, products benzene ethylene block content is higher.
As the butylbenzene copolymer of conventional rubber, the distribution in macromolecular chain of its butadiene unit and styrene units must be random.When containing a small amount of block styrene in solution polymerized butadiene styrene rubber molecular chain, can make to produce Van der Waals force between flexible butadiene molecule chain end and block styrene chain, thus improve tensile strength.And the existence of a large amount of block styrene chain is by the elasticity of grievous injury rubber, intensity and wear resistance, and heat-dissipating can increase, rolling resistance can increase.In industrial solution polymerized butylbenzene, the content general control of block styrene chain is below 2 % by weight.
In order to obtain randomly solution polymerized butylbenzene, usually needing to add irregular agent in preparation process, the relative reactivity of styrene monomer in copolymerization of butylbenzene being increased, thus changes the reactivity ratio of styrene monomer, making it can carry out copolyreaction with divinyl in initial reaction stage.
It is irregular agent that US3294768A discloses a kind of employing alkoxy base metallic compound, copolymerization of butylbenzene is carried out to the adjustment of microtexture, makes the method that the random structure in styrene-butadiene rubber(SBR) improves greatly; Described alkoxy base metallic compound is selected from one or more in tertiary fourth oxygen lithium, tertiary fourth oxygen sodium, tertiary fourth oxygen potassium, potassium t-butoxide (t-BuOK), tertiary fourth oxygen rubidium and tertiary fourth oxygen caesium.Wherein, best with the regulating effect of potassium t-butoxide (t-BuOK), but t-BuOK is insoluble to aliphatic solvents, therefore, must join in reaction system in solid form, be unfavorable for realizing large-scale industrial production.
US6372863B2 discloses a kind of preparation method of random butylbenzene copolymer, and the method takes the mode adding monomer, realizes the control to the micro-block of vinylbenzene.But for batch polymerization process, because rate of polymerization is very fast, each still polymerization process there are differences, monomer additional time not easily accurate assurance, to implement difficulty larger.
Summary of the invention
The object of the invention is to overcome the defect adopting block styrene chain too high levels in the styrene-butadiene rubber(SBR) that obtains of existing method, and a kind of irregular agent that can obtain the lower styrene-butadiene rubber(SBR) of block styrene chain content is provided, and a kind of preparation method of styrene-butadiene rubber(SBR).
The invention provides a kind of irregular agent, wherein, described irregular agent contains glycol dimethyl ether, alkylsulfonate and/or alkylaryl sulphonate.
Present invention also offers a kind of preparation method of styrene-butadiene rubber(SBR), wherein, the method comprises in an inert atmosphere, under anionic polymerization conditions, under the existence of organic lithium initiator and irregular agent, vinylbenzene and divinyl are carried out polyreaction in organic solvent, obtain copolymer solution, and copolymer solution is contacted with terminator, the consumption of described anionic polymerization conditions and irregular agent makes the content of block styrene chain in the styrene-butadiene rubber(SBR) obtained be less than 2 % by weight, the content of described block styrene chain is the content containing continuous more than four and four vinylbenzene chain links on styrene-butadiene rubber(SBR) molecular chain, described irregular agent contains tetrahydrofuran (THF) and irregular agent provided by the invention.
The present inventor surprisingly finds, when being combined described glycol dimethyl ether, alkylsulfonate and/or alkylaryl sulphonate, while ensureing that the irregular agent obtained by said components has better solubility property, effectively can also control the content of block styrene chain in the styrene-butadiene rubber(SBR) obtained, thus obtain random styrene-butadiene rubber, achieve object of the present invention.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the present invention, described irregular agent contains glycol dimethyl ether, alkylsulfonate and/or alkylaryl sulphonate.
According to the present invention, as long as although the irregular agent containing said components just effectively can control the content of block styrene chain in styrene-butadiene rubber(SBR), but, obtain better to make these three kinds of component coordinated, under preferable case, with the gross weight of described irregular agent for benchmark, the content of described glycol dimethyl ether is 10-30 % by weight, and the total content of described alkylsulfonate and alkylaryl sulphonate is 70-90 % by weight.It should be noted that, when containing alkylsulfonate and alkylaryl sulphonate in described irregular agent simultaneously, the total content of described alkylsulfonate and alkylaryl sulphonate refers to the content of alkylsulfonate and the content sum of alkylaryl sulphonate; When only containing alkylsulfonate or alkylaryl sulphonate in described irregular agent, the total content of described alkylsulfonate and alkylaryl sulphonate refers to the content of alkylsulfonate or the content of alkylaryl sulphonate.
According to the present invention, described alkylsulfonate and alkylaryl sulphonate can be existing various alkylsulfonate and alkylaryl sulphonate, and under preferable case, described alkylsulfonate is selected from C
4-C
20alkylsulfonate; It is 1-5 that described alkylaryl sulphonate is selected from aromatic ring number, and on aromatic ring, the carbonatoms of alkyl substituent is the alkylaryl sulphonate of 4-20.Particularly, described alkylsulfonate is preferably selected from one or more in sodium laurylsulfonate, dodecyl sodium sulfonate potassium, sodium cetanesulfonate and hexadecyl potassium sulfonate; Described alkylaryl sulphonate be preferably selected from Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, cetyl benzenesulfonic acid sodium and and cetyl benzenesulfonic acid potassium in one or more.
According to the present invention, the preparation method of described styrene-butadiene rubber(SBR) comprises in an inert atmosphere, under anionic polymerization conditions, under the existence of organic lithium initiator and irregular agent, vinylbenzene and divinyl are carried out polyreaction in organic solvent, obtain copolymer solution, and copolymer solution is contacted with terminator, the consumption of described anionic polymerization conditions and irregular agent makes the content of block styrene chain in the styrene-butadiene rubber(SBR) obtained be less than 2 % by weight, the content of described block styrene chain is the content containing continuous more than four and four vinylbenzene chain links on styrene-butadiene rubber(SBR) molecular chain, described irregular agent contains tetrahydrofuran (THF) and above-mentioned irregular agent provided by the invention.
The use-pattern of described irregular agent provided by the invention is known to the skilled person, such as, can directly described irregular agent be joined in polymerization reaction system, but disperse more even in polymerization system to make above-mentioned irregular agent provided by the invention thus the content of block styrene chain is more effectively controlled, under preferable case, described irregular agent uses with the form of its solution, namely, first irregular agent provided by the invention is dissolved in organic solvent, then the solution containing this irregular agent is carried out mixing and being polymerized with above-mentioned each reactive material.
The consumption of the present invention to described irregular agent is not particularly limited, as long as the content of block styrene chain in styrene-butadiene rubber(SBR) in the polymeric reaction product obtained can be made to be less than 2 % by weight, such as, the mol ratio of the consumption of described tetrahydrofuran (THF) and the consumption of organic lithium initiator can be 10-40: 1; With total gauge of alkylsulfonate and alkylaryl sulphonate, the mol ratio of the consumption of irregular agent provided by the invention and the consumption of organic lithium initiator can be 0.04-0.6: 1.The present inventor finds, when with total gauge of alkylsulfonate and alkylaryl sulphonate, the mol ratio of the consumption of irregular agent provided by the invention and the consumption of tetrahydrofuran (THF) is preferably 1 × 10
-3-40 × 10
-3: when 1, more effectively can control the content of block styrene chain, obtain the random styrene-butadiene rubber that performance is very excellent.
According to the present invention, the various organic lithium initiators that can cause anionoid polymerization that described organic lithium initiator can be known to the skilled person, such as, the organic lithium initiator of described organic lithium initiator can be molecular formula be RLi, wherein, R is the alkyl of straight or branched, cycloalkyl or aryl; Particularly, described organic lithium initiator can be selected from lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium one or more, be preferably n-Butyl Lithium and/or s-butyl lithium.
The content of the present invention to described organic lithium initiator is not particularly limited, and can select suitable add-on according to actual needs.Those skilled in the art should it is easily understood that when needing to prepare the larger styrene-butadiene rubber(SBR) of molecular weight, can reduce the consumption of organic lithium initiator, now rate of polymerization also can correspondingly reduce; When needing the styrene-butadiene rubber(SBR) preparing molecular weight, can increase the consumption of organic lithium initiator, now rate of polymerization also can correspondingly increase.Therefore, the molecular size range of styrene-butadiene rubber(SBR) considering rate of polymerization and obtain, under preferable case, with total consumption of 100 grams of described vinylbenzene and divinyl for benchmark, the consumption of described organic lithium initiator is 0.3-2.5mmol.
According to the present invention, the content of described vinylbenzene and divinyl can carry out selecting and changing in the larger context, such as, with the total content of described vinylbenzene and divinyl for benchmark, described cinnamic consumption can be 15-50 % by weight, and the consumption of described divinyl can be 50-85 % by weight; Preferably, with the total content of described vinylbenzene and divinyl for benchmark, described cinnamic consumption is 25-45 % by weight, and the consumption of described divinyl is 55-75 % by weight.
As a rule, anionic polymerisation system does not have obvious termination reaction and shift reaction, and after ruing out of whole monomer, active centre still exists.Therefore, after completion of the polymerization reaction, the copolymer solution obtained should be contacted with terminator make active centre inactivation.The consumption of described terminator can be selected according to added organic lithium initiator, and as a rule, the mol ratio of the consumption of described terminator and the consumption of organic lithium initiator can be 0.1-1: 1.Described terminator can be the existing various terminator that can make anion active center inactivation, such as, can be selected from one or more in water, methyl alcohol, ethanol and Virahol, be preferably Virahol.
According to the present invention, described polyreaction can be carried out in a continuous manner, also can carry out with intermittent mode, there is no and limit especially.The condition of described polyreaction comprises the temperature of polyreaction, pressure and time, wherein, as long as the condition of described polyreaction can make the content of block styrene chain in the styrene-butadiene rubber(SBR) obtained be less than 2 % by weight, such as, the temperature of described polyreaction can be 0-130 DEG C, the pressure of polyreaction can be 0.1-1.5MPa, and the time of polyreaction can be 8-25 minute; Preferably, the temperature of described polyreaction is 40-120 DEG C, and the pressure of polyreaction is 0.1-1MPa, and the time of polyreaction is 8-20 minute.Pressure of the present invention is gauge pressure.
As a rule, when carrying out anionic polymerisation, anionic initiator directly gives monomer transfer transport, and all active centre are simultaneous growths, and therefore, the molecular weight distribution of the polymerisate obtained is narrower, processing characteristics is poor.In order to expand the molecular weight distribution of described polymkeric substance, under preferable case, before the preparation method of described styrene-butadiene rubber(SBR) also comprises and to be contacted with terminator by polymeric reaction product, first polymeric reaction product is contacted with coupling agent.The mol ratio of described coupling agent and organic lithium initiator can be 0.1-2: 1.Described coupling agent is conventionally known to one of skill in the art, such as, can be selected from one or more in divinyl phenyl, tetravinyl silane, tetrachloromethane, silicon tetrachloride, tin tetrachloride and dimethyl terephthalate (DMT).
According to the present invention, described organic solvent can be existing various organic solvent of not having an effect with reactant and resultant, and such as, described organic solvent can be selected from organic hydrocarbon solvent, is preferably C
3-C
12organic hydrocarbon solvent; Particularly, described organic solvent can be selected from propane, butane, pentane, normal hexane, heptane, octane, decane, pentamethylene, methylcyclopentane, hexanaphthene, suberane, cyclooctane and one or more in raffinating oil.Described raffinating oil refers in petroleum refining process, and be rich in catalytic reforming gasoline remaining distillate after extraction aromatic hydrocarbons of aromatic hydrocarbons, its main component is C
6-C
8alkane and naphthenic hydrocarbon.Preferably, described organic solvent is selected from pentane, normal hexane, hexanaphthene and one or more in raffinating oil; More preferably, described organic solvent is the mixed solvent of normal hexane and hexanaphthene, and wherein, with the gross weight of described normal hexane and hexanaphthene for benchmark, the content of described normal hexane can be 5-30 % by weight.The consumption of described organic solvent is the conventional amount used of anionic polymerisation, and usually, the consumption of described organic solvent makes the concentration of vinylbenzene and divinyl be 10-20 % by weight.
According to the present invention, the water vapour in air can react by termination of anionic polymerization, and therefore, in order to more be conducive to the carrying out of polyreaction, described polyreaction should preferably be carried out in an inert atmosphere.Described inert atmosphere refer to not with reactant and any one gas or the gaseous mixture of producing thing generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.Keep the method for inert atmosphere can for pass in reaction system above-mentioned not with any one gas or the gaseous mixture of reactant and resultant generation chemical reaction.
Organic solvent removes after being also included in and being contacted with terminator by copolymer solution by the preparation method of styrene-butadiene rubber(SBR) of the present invention.The method removing described organic solvent is known to the skilled person, and this is no longer going to repeat them.In order to obtain the more excellent styrene-butadiene rubber(SBR) of ageing-resistant performance, preferably, the preparation method of described styrene-butadiene rubber(SBR) also comprise copolymer solution is contacted with terminator after, remove organic solvent before, described copolymer solution is contacted with anti-aging agent.The consumption of described anti-aging agent can be the 0.1-2 % by weight of styrene-butadiene rubber(SBR) content usually.Described anti-aging agent can be existing various can as the anti-aging agent of styrene-butadiene rubber(SBR) additive, such as, described anti-aging agent can be phenols and/or amines antioxidants, be preferably selected from 2,6-ditertbutylparacresol (abbreviation antioxidant 264), tert-butyl catechol and 2, one or more in 2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol) (abbreviation antioxidant 2246).
Below will be described the present invention by embodiment.
The molecular weight of styrene-butadiene rubber(SBR) described in embodiment and comparative example, molecular weight distribution and coupling efficiency adopt the model purchased from Japanese Shimadzu Corporation to be that the gel permeation chromatograph of LC-10A measures, mensuration temperature is normal temperature (25 DEG C), and mobile phase solvent is THF; The content of vinyl structure and block styrene chain adopts the model purchased from Bruker company of Switzerland to be that the nuclear-magnetism wave of oscillation spectrometer of AVANCEDRX400MHz measures, and mensuration temperature is normal temperature (25 DEG C), and liquid pool method, solvent is dithiocarbonic anhydride (CS
2).
Embodiment 1
This embodiment is for illustration of the preparation method of styrene-butadiene rubber(SBR) provided by the invention.
(1) preparation of the solution containing irregular agent provided by the invention:
Under room temperature (25 DEG C), 4.8g glycol dimethyl ether, 11.2g Sodium dodecylbenzene sulfonate and 380g are raffinated oil (boiling range is the platformate raffinate of 60-90 DEG C) mixes, and obtains the solution containing irregular agent provided by the invention.
(2) preparation of styrene-butadiene rubber(SBR):
Carry out in the polymeric kettle of 5 liters; under high pure nitrogen protection, in still, add the solution containing irregular agent provided by the invention that 2654g raffinates oil (boiling range is the platformate raffinate of 60-90 DEG C), 162g vinylbenzene, 8.7g tetrahydrofuran (THF) and 3.7g are obtained by step (1) successively.Described polymeric kettle through high pure nitrogen displacement deoxygenation after, toward polymeric kettle in, add 200g divinyl and 0.19g (3mmol) n-Butyl Lithium, temperature be 40 DEG C, pressure be 0.3MPa under be polymerized 20 minutes, transformation efficiency reaches 100%.After polyreaction completes, polymerisate is contacted with 0.13g tin tetrachloride, proceeds linked reaction.After linked reaction completes, then product is contacted with 2.5g anti-aging agent 2,6 ditertiary butyl p cresol with 0.02g terminator Virahol successively, and gained glue devaporation is removed organic solvent.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Comparative example 1
This comparative example is for illustration of the reference preparation method of styrene-butadiene rubber(SBR).
Styrene-butadiene rubber(SBR) is prepared according to the method for embodiment 1, unlike, in preparation process, do not add the solution containing irregular agent provided by the invention.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Embodiment 2
This embodiment is for illustration of the preparation method of styrene-butadiene rubber(SBR) provided by the invention.
(1) preparation of the solution containing irregular agent provided by the invention:
Under room temperature (25 DEG C), the mixture (weight ratio of hexanaphthene and normal hexane is 82: 18) of 0.7g glycol dimethyl ether, 6.3g sodium laurylsulfonate and 600g hexanaphthene and normal hexane is mixed, obtains the solution containing irregular agent provided by the invention.
(2) preparation of styrene-butadiene rubber(SBR):
Carry out in the polymeric kettle of 5 liters; under high pure nitrogen protection, add in still successively the mixture (weight ratio of hexanaphthene and normal hexane is 82: 18) of 2654g hexanaphthene and normal hexane, 90g vinylbenzene, 2.2g tetrahydrofuran (THF) and 30.3g by step (1) obtain containing the solution containing irregular agent provided by the invention.Described polymeric kettle through high pure nitrogen displacement deoxygenation after, toward polymeric kettle in, add 272g divinyl and 0.19g (3mmol) n-Butyl Lithium, temperature be 120 DEG C, pressure be 1MPa under be polymerized 8 minutes, transformation efficiency reaches 100%.After polyreaction completes, polymerisate is contacted with 0.5g silicon tetrachloride, proceeds linked reaction.After linked reaction completes, then product is contacted with 2.5g anti-aging agent 2,6 ditertiary butyl p cresol with 0.1g terminator methyl alcohol successively, and gained glue devaporation is removed organic solvent.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Comparative example 2
This comparative example is for illustration of the reference preparation method of styrene-butadiene rubber(SBR).
Styrene-butadiene rubber(SBR) is prepared according to the method for embodiment 2, unlike, in preparation process, do not add the solution containing irregular agent provided by the invention.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Embodiment 3
This embodiment is for illustration of the preparation method of styrene-butadiene rubber(SBR) provided by the invention.
(1) preparation of the solution containing irregular agent provided by the invention:
Under room temperature (25 DEG C), the mixture (weight ratio of hexanaphthene and normal hexane is 82: 18) of 2g glycol dimethyl ether, 12g Sodium dodecylbenzene sulfonate and 680g hexanaphthene and normal hexane is mixed, obtains the solution containing irregular agent provided by the invention.
(2) preparation of styrene-butadiene rubber(SBR):
Carry out in the polymeric kettle of 5 liters; under high pure nitrogen protection, add in still successively the mixture (weight ratio of hexanaphthene and normal hexane is 82: 18) of 2654g hexanaphthene and normal hexane, 130g vinylbenzene, 5.5g tetrahydrofuran (THF) and 35g by step (1) obtain containing the solution of irregular agent provided by the invention.Described polymeric kettle through high pure nitrogen displacement deoxygenation after, toward polymeric kettle in, add 232g divinyl and 0.19g (3mmol) n-Butyl Lithium, temperature be 80 DEG C, pressure be 0.5MPa under be polymerized 15 minutes, transformation efficiency reaches 100%.After polyreaction completes, polymerisate is contacted with 0.9g tetrachloromethane, proceeds linked reaction.After linked reaction completes, then product is contacted with 2.5g anti-aging agent 2,6 ditertiary butyl p cresol with 0.07g terminator ethanol successively, and gained glue devaporation is removed organic solvent.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Comparative example 3
This comparative example is for illustration of the reference preparation method of styrene-butadiene rubber(SBR).
Styrene-butadiene rubber(SBR) is prepared according to the method for embodiment 3, unlike, in preparation process, do not add the solution containing irregular agent provided by the invention.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Embodiment 4
This embodiment is for illustration of the preparation method of styrene-butadiene rubber(SBR) provided by the invention.
(1) preparation of the solution containing irregular agent provided by the invention:
Under room temperature (25 DEG C), 2.8g glycol dimethyl ether, 11.2g Sodium dodecylbenzene sulfonate and 380g are raffinated oil (boiling range is the platformate raffinate of 60-90 DEG C) mixes, and obtains the solution containing irregular agent provided by the invention.
(2) preparation of styrene-butadiene rubber(SBR):
Carry out in the polymeric kettle of 5 liters; under high pure nitrogen protection, in still, add the solution containing irregular agent provided by the invention that 2654g raffinates oil (boiling range is the platformate raffinate of 60-90 DEG C), 72g vinylbenzene, 9.9g tetrahydrofuran (THF) and 1.8g are obtained by step (1) successively.Described polymeric kettle through high pure nitrogen displacement deoxygenation after, toward polymeric kettle in, add 290g divinyl and 0.19g (3mmol) n-Butyl Lithium, temperature be 30 DEG C, pressure be 1.5MPa under be polymerized 25 minutes, transformation efficiency reaches 100%.After polyreaction completes, polymerisate is contacted with 0.13g tin tetrachloride, proceeds linked reaction.After linked reaction completes, then product is contacted with 2.5g anti-aging agent 2,6 ditertiary butyl p cresol with 0.12g terminator Virahol successively, and gained glue devaporation is removed organic solvent.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Comparative example 4
This comparative example is for illustration of the reference preparation method of styrene-butadiene rubber(SBR).
Styrene-butadiene rubber(SBR) is prepared according to the method for embodiment 4, unlike, in preparation process, do not add the solution containing irregular agent provided by the invention.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Embodiment 5
This embodiment is for illustration of the preparation method of styrene-butadiene rubber(SBR) provided by the invention.
Styrene-butadiene rubber(SBR) is prepared according to the method for embodiment 1, unlike, the add-on of the described solution containing irregular agent provided by the invention is 0.57g.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Comparative example 5
This comparative example is for illustration of the reference preparation method of styrene-butadiene rubber(SBR).
Styrene-butadiene rubber(SBR) is prepared according to the method for embodiment 5, unlike, in preparation process, do not add the solution containing irregular agent provided by the invention.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
Embodiment 6
This embodiment is for illustration of the preparation method of styrene-butadiene rubber(SBR) provided by the invention.
Styrene-butadiene rubber(SBR) is prepared according to the method for embodiment 1, unlike, do not add coupling agent after completion of the polymerization reaction and carry out linked reaction.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency vinyl structure and block styrene chain is as table 1.
Comparative example 6
This comparative example is for illustration of the reference preparation method of styrene-butadiene rubber(SBR).
Styrene-butadiene rubber(SBR) is prepared according to the method for embodiment 6, unlike, in preparation process, do not add the solution containing irregular agent provided by the invention.The content of the molecular weight and molecualr weight distribution of polymerisate, coupling efficiency, vinyl structure and block styrene chain is as table 1.
The molecular parameter of table 1 polymerisate and structure
| Sequence number | Mn (ten thousand) | CE％ | Mw/Mn | Bv％ | Macro-St-block(％) |
| Embodiment 1 | 12.0 | 74.7 | 1.465 | 32.4 | 1.3 |
| Comparative example 1 | 12.1 | 74.5 | 1.428 | 33.3 | 4.3 |
| Embodiment 2 | 11.9 | 76.1 | 1.423 | 15.2 | 1.1 |
| Comparative example 2 | 12.0 | 76.2 | 1.478 | 15.7 | 5.3 |
| Embodiment 3 | 12.5 | 74.3 | 1.416 | 27.5 | 1.2 |
| Comparative example 3 | 12.6 | 75.4 | 1.469 | 27.5 | 3.8 |
| Embodiment 4 | 12.7 | 75.7 | 1.428 | 36.3 | 0.8 |
| Comparative example 4 | 12.0 | 77.3 | 1.446 | 36.1 | 4.1 |
| Embodiment 5 | 12.5 | 75.7 | 1.428 | 31.3 | 1.9 |
| Comparative example 5 | 12.3 | 77.3 | 1.446 | 32.4 | 5.1 |
| Embodiment 6 | 12.1 | 0.0 | 1.04 | 30.4 | 1.9 |
| Comparative example 6 | 12.6 | 0.0 | 1.04 | 31.2 | 4.5 |
Note: Mn is number-average molecular weight; Mw is weight-average molecular weight; CE% is coupling efficiency; Mw/Mn is molecular weight distribution; Bv% is the content of 1，2-butadiene structural unit in styrene-butadiene rubber(SBR); Macro-St-block (%) is the content containing continuous more than four and four vinylbenzene chain links on styrene-butadiene rubber(SBR) molecular chain.
From the results shown in Table 1, method provided by the invention is adopted can to obtain the lower styrene-butadiene rubber(SBR) of block styrene chain content.
Claims (10)
1. an irregular agent, is characterized in that, described irregular agent contains glycol dimethyl ether, alkylsulfonate and/or alkylaryl sulphonate; With the gross weight of described irregular agent for benchmark, the content of described glycol dimethyl ether is 10-30 % by weight, and the total content of described alkylsulfonate and alkylaryl sulphonate is 70-90 % by weight.
2. irregular agent according to claim 1, wherein, described alkylsulfonate is selected from C
4-C
20alkylsulfonate; The aromatic ring number of described alkylaryl sulphonate is 1-5, and on aromatic ring, the carbonatoms of alkyl substituent is 4-20.
3. irregular agent according to claim 2, wherein, described alkylsulfonate be selected from sodium laurylsulfonate, dodecyl sodium sulfonate potassium, sodium cetanesulfonate and hexadecyl potassium sulfonate one or more; Described alkylaryl sulphonate be selected from Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, cetyl benzenesulfonic acid sodium and and cetyl benzenesulfonic acid potassium in one or more.
4. the preparation method of a styrene-butadiene rubber(SBR), it is characterized in that, the method comprises in an inert atmosphere, under anionic polymerization conditions, under the existence of organic lithium initiator and irregular agent, vinylbenzene and divinyl are carried out polyreaction in organic solvent, obtain copolymer solution, and copolymer solution is contacted with terminator, the consumption of described anionic polymerization conditions and irregular agent makes the content of block styrene chain in the styrene-butadiene rubber(SBR) obtained be less than 2 % by weight, the content of described block styrene chain is the content containing continuous more than four and four vinylbenzene chain links on styrene-butadiene rubber(SBR) molecular chain, described irregular agent contains the irregular agent in tetrahydrofuran (THF) and claim 1-3 described in any one.
5. method according to claim 4, wherein, with total consumption of 100 grams of described vinylbenzene and divinyl for benchmark, the consumption of described organic lithium initiator is 0.3-2.5mmol; With the total content of described vinylbenzene and divinyl for benchmark, described cinnamic content is 15-50 % by weight, and the content of described divinyl is 50-85 % by weight.
6. method according to claim 5, wherein, the mol ratio of the consumption of described tetrahydrofuran (THF) and the consumption of organic lithium initiator is 10-40:1; With total gauge of alkylsulfonate and alkylaryl sulphonate, the mol ratio of the consumption of the irregular agent described in claim 1-3 and the consumption of organic lithium initiator is 0.04-0.6:1.
7. method according to claim 6, wherein, with total gauge of alkylsulfonate and alkylaryl sulphonate, the mol ratio of the consumption of the irregular agent described in claim 1-3 and the consumption of tetrahydrofuran (THF) is 1 × 10
-3-40 × 10
-3: 1.
8. method according to claim 4, wherein, the mol ratio of the consumption of described terminator and the consumption of organic lithium initiator is 0.1-1:1; Described terminator be selected from water, methyl alcohol, ethanol and Virahol one or more.
9. method according to claim 4, wherein, the temperature that described anionic polymerization conditions comprises polyreaction is 0-130 DEG C, and the pressure of polyreaction is 0.1-1.5MPa, and the time of polyreaction is 8-25 minute.
10. method according to claim 4, wherein, before the method also comprises and to be contacted with terminator by polymeric reaction product, first contacts polymeric reaction product with coupling agent; The mol ratio of the consumption of described coupling agent and the consumption of organic lithium initiator is 0.1-2:1; Described coupling agent be selected from divinyl phenyl, tetravinyl silane, tetrachloromethane, silicon tetrachloride, tin tetrachloride and dimethyl terephthalate (DMT) one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210114260.2A CN103374101B (en) | 2012-04-18 | 2012-04-18 | The preparation method of a kind of irregular agent and styrene-butadiene rubber(SBR) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210114260.2A CN103374101B (en) | 2012-04-18 | 2012-04-18 | The preparation method of a kind of irregular agent and styrene-butadiene rubber(SBR) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103374101A CN103374101A (en) | 2013-10-30 |
| CN103374101B true CN103374101B (en) | 2015-11-25 |
Family
ID=49459982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210114260.2A Active CN103374101B (en) | 2012-04-18 | 2012-04-18 | The preparation method of a kind of irregular agent and styrene-butadiene rubber(SBR) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103374101B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106715501B (en) | 2014-05-16 | 2019-08-16 | 科腾聚合物美国有限责任公司 | The wide MWD conjugated diolefin polymer of branching |
| US10358430B2 (en) | 2017-08-25 | 2019-07-23 | Thomas Swan & Co. Ltd | Oligomeric (TH)FP, production and uses therefor |
| CN109627382B (en) | 2017-10-06 | 2022-03-18 | 台橡股份有限公司 | Conjugated diene polymer, composition thereof, and method for producing same |
| CN117567686A (en) * | 2024-01-16 | 2024-02-20 | 新疆独山子石油化工有限公司 | Solution polymerized styrene-butadiene rubber with fixed block styrene content, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814630A (en) * | 2005-01-31 | 2006-08-09 | 中国石化北京燕化石油化工股份有限公司 | Star high-vinyl-content poly-conjugated-diolefin rubber and preparing method |
| CN1844169A (en) * | 2006-05-22 | 2006-10-11 | 北京化工大学 | Regulator and method for controlling microstructure of butadiene homopolymer and copolymer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5734104A (en) * | 1980-08-08 | 1982-02-24 | Japan Synthetic Rubber Co Ltd | Production of low-molecular weight polymer |
| JPS61293212A (en) * | 1986-05-09 | 1986-12-24 | Bridgestone Corp | Styrene/butadiene copolymer rubber |
-
2012
- 2012-04-18 CN CN201210114260.2A patent/CN103374101B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814630A (en) * | 2005-01-31 | 2006-08-09 | 中国石化北京燕化石油化工股份有限公司 | Star high-vinyl-content poly-conjugated-diolefin rubber and preparing method |
| CN1844169A (en) * | 2006-05-22 | 2006-10-11 | 北京化工大学 | Regulator and method for controlling microstructure of butadiene homopolymer and copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103374101A (en) | 2013-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103374101B (en) | The preparation method of a kind of irregular agent and styrene-butadiene rubber(SBR) | |
| CN102101902A (en) | Method for preparing irregular copolymer of conjugated diene and vinyl arene | |
| CN103382241B (en) | Star-shaped isoprene-b-butadiene styrene terpolymer and preparation method thereof | |
| JP2017508859A (en) | Novel anionic polymerization initiator and method for producing conjugated diene copolymer using the same | |
| CN103788273A (en) | Rare earth catalysis system star-branched polyisoprene and preparation method thereof | |
| CN103833945B (en) | Star-shaped isoprene-styrene block copolymer and preparation method thereof | |
| CN103450373B (en) | Rare earth catalyst composition and rare earth catalyst and application thereof | |
| CN103304717A (en) | Method for preparing high-viscosity-index synthetic lubricating oil through copolymerization of ethylene and alpha-olefin and applications thereof | |
| CN107200797B (en) | Preparation method of polymer | |
| CN104098726B (en) | A kind of polybutadiene rubber and preparation method thereof | |
| CN110357997A (en) | Conjugated diene and monovinylarene random copolymer and preparation method thereof | |
| CN104628918B (en) | A kind of conjugated diene polymer and preparation method thereof | |
| CN105754055A (en) | Star-shaped hydrogenated styrene diene copolymer and preparation method thereof | |
| CN107337755A (en) | Conjugated diene polymer and preparation method thereof and polybutadiene and polyisoprene | |
| CN105199028A (en) | High vinyl polybutadiene rubber capable of adjusting microstructure and preparation method thereof | |
| CN103360516A (en) | Neodymium homogeneous phase rare earth catalyst composition and neodymium homogeneous phase rare earth catalyst as well as preparation method and application of neodymium homogeneous phase rare earth catalyst | |
| CN107337754A (en) | Conjugated diene polymer and preparation method thereof and polybutadiene and polyisoprene | |
| CN103360525A (en) | Polymerization method | |
| CN103183758B (en) | Modified high-cis conjugated diene polymer and method for producing same | |
| CN102603950B (en) | Preparation method of polyisobutene with low molecular weight and high activity | |
| CN102532356B (en) | Rare earth catalyst and controllable polymerization method for conjugated diene in arene medium | |
| CN101255203B (en) | Method for restraining gelatin during preparation of conjugated diolefin and monovinyl aromatic hydrocarbons random polymers | |
| CN106256843B (en) | A kind of olefin copolymer and its preparation method and application | |
| CN105732920A (en) | Star-shaped hydrogenated styrene diene copolymer and preparation method thereof | |
| CN104628951A (en) | Structure regulator for anionic polymerization and anionic polymerization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |