CN1151412A - Phenylethylene-butadiene block copolymer and prodn. method - Google Patents
Phenylethylene-butadiene block copolymer and prodn. method Download PDFInfo
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Abstract
A process for preparing styrene-butadiene block copolymer used to prepare adhesive or pressure-sensitive glue with better adhesion strength uses styrene (10-29 Wt.%) and butadiene (71-90 Wt.%) as raw materials and features that the concentration of monomer raw material in solvent is 12-20g/100ml, stepwise charge method is used for fractional polymerization, and in final stage, end stopper and coupler are added to obtain linear SBS or star (SB)nR(n=3-4) product which features low cotnent of styrene and high viscosity after being fused or dissolved.
Description
The present invention relates to styrene-butadiene block copolymer and manufacture method thereof.
Existing many reports in the prior art about styrene-butadiene block copolymer and production method thereof, the disclosed technology of CN85102259A has been to reduce the set deformation volume of multipolymer, its product S BS or (SB) ratio (being S/B) of the vinylbenzene of nR and divinyl be 〉=30/70, promptly S section weight percent is greater than 30%.Though technology that also has such as CN1088591A disclose preparation (S-D)
nS (n is 2～4) method for product, its S section weight percent is 20%～45%, D (conjugated diene that contains divinyl) section weight percent is 55%～80%, but its product is a segmented copolymer, with product of the present invention be not with a kind of compound, the initiator that adopts in the building-up process is a dilithium initiator, and is also different with the initiator that the present invention uses.Each trade mark SBS product that above-mentioned technology is produced, because its S section weight percentage is higher, resin property is stronger, is used to prepare tackiness agent and the hot-fusible pressure-sensitive adhesive effect is relatively poor.
The present invention is intended to prepare that S section content is lower, B section (rubber segments) content is higher, make bigger type SBS and star-like (SB) of viscosity after dissolving or the fusion
nTwo kinds of products of R so that improve viscosity after making tackiness agent or pressure sensitive adhesive, and have preferably bonding strength to improve its application performance.
The objective of the invention is to realize by the following technical solutions: adopt the cyclohexane give solvent, n-Butyl Lithium (BuLi) is made initiator, tetrahydrofuran (THF) (THF) is made activator, starting monomer vinylbenzene (S) is respectively 10%～29% and 71%～90% with the weight percent of divinyl (B), the concentration of starting monomer in solvent is 12g～20g/100ml in the system, adopt reinforced stage feeding polymerization of three steps and reinforced coupling process of two steps respectively composite number average molecular weight Mn equal (SB) that 10 ± 20,000 type SBS and number-average molecular weight Mn equal 18 ± 20,000
nR (n is 3～4) product.
In the process of making type SBS, adopt reinforced stage feeding polymerization of three steps.The first step: the solvent hexanaphthene of required total metering 90%～95% and half of monomer styrene are added in the polymeric kettle, again about half times of tetrahydrofuran (THF) molar weight to the initiator mole number added in the still, with chemical purification (n-Butyl Lithium of detrimental impurity equivalent in adding and solvent and the vinylbenzene) remove desolvate and vinylbenzene in detrimental impurity, add the initiator n-Butyl Lithium that doubles the tetrahydrofuran (THF) mole number approximately then, in first section polyreaction of 50～70 ℃ of initiations, under 50～80 ℃ temperature, reacted 25～30 minutes; Second step: after first block polymerization is finished, in the monomer divinyl adding polymeric kettle with required metering,, in 70～120 ℃, reacted under the temperature 25～30 minutes 60～80 ℃ of polymerizations that cause second block down; The 3rd step: after second block polymerization is finished, add all the other metering 5%～10% hexanaphthenes of chemical purification and about 50% vinylbenzene (method of purification is the same), 65～80 ℃ of polymerizations that cause the 3rd block down, and under 70～100 ℃ of temperature, react and got final product discharging in 25～30 minutes, add the antioxidant 264 of terminator water or ethanol (being no less than the BuLi molar weight) and theoretical glue amount 0.6% (weight) during discharging.The number-average molecular weight M of the type SBS product that is obtained
nBe 10 ± 20,000.
Making star-like (SB)
nIn the process of R, adopt reinforced method coupling process of two steps.The first step: the solvent hexanaphthene and the monomer styrene of required metering are added in the polymeric kettle, in the presence of tetrahydrofuran (THF) (consumption is the same), with chemical purification remove desolvate and vinylbenzene in contained detrimental impurity (method is the same), add initiator n-Butyl Lithium (consumption is the same) then, in first section polyreaction of 50～70 ℃ of initiations, under 50～80 ℃ temperature, reacted 25～30 minutes; Second step: after first block polymerization is finished, in the monomer divinyl adding polymeric kettle with required metering,, under 70～120 ℃ temperature, reacted 25～30 minutes 60～80 ℃ of polymerizations that cause second blocks; The 3rd step: after second block polymerization is finished, add coupling agent SiCl
4Carry out coupling, the total mole number that adds coupling agent is 0.25～0.275 times of initiator mole number, add in two steps, add 70% of about total amount for the first time, add all the other coupling agents after 10 minutes, react and got final product discharging in 20～25 minutes, add the antioxidant 264 of theoretical glue amount 0.6% (weight) during discharging.Star-like (SB) that is obtained
nThe number-average molecular weight Mn of R product is 18 ± 20,000 (n is 3～4).
The present invention's technical scheme preferably can be: starting monomer vinylbenzene (S) and the total concn of divinyl (B) in solvent are 12～20g/100ml in the system, although not finding monomer concentration has a significant effect to product performance, but because of thermal discharge in second section polymerization process bigger, too high restriction of then removing heat energy power because of polymeric kettle causes temperature rise too high as monomer concentration, bring difficulty for operation control, even influence product performance.Therefore, not only want in the strict control system monomer concentration in described scope, and first section of will suitably control in the process of making type SBS add quantity of solvent, preferably adds 90%～95% of required hexanaphthene total amount, control reaction temperature when being beneficial to second section polymerization.
One, two, the scope controlled of three stage polymerization temperature of reaction is respectively 50～80 ℃ the present invention's technical scheme preferably can also be:, 70～120 ℃, 70～100 ℃, the coupling first time temperature range for preparing star-like (SB) nR is 65～80 ℃; In addition, kick off temperature and reaction times are also wanted corresponding being controlled in the aforesaid scope, because the high more then reaction temperature rising of kick off temperature is fast more, temperature of reaction is high more and long more then reaction conversion ratio of time is high more, only mate when reasonable in conditions such as kick off temperature, temperature of reaction, reaction times and relevant material proportions, just can reach best technological effect, make that technology controlling and process is stable, manufacturing cost reduces and constant product quality.
The present invention's technical scheme preferably also can be: the weight percent of preferably controlling starting monomer vinylbenzene and divinyl is 18%～25% and 75%～82%, like this constant product quality, physical and mechanical properties the best.Cinnamic weight percent is not lower than 10%, otherwise the product brute force is low excessively even can cause product to be plasticine sample and even inviscid, and cinnamic consumption runs counter to purpose of the present invention if be higher than 29%.
The present invention has following tangible advantage:
1, product physical and chemical performance excellence:
Adopt the prepared multipolymer of preparation method provided by the invention, through gel permeation chromatography, molecular weight distribution is in 1.05～1.10 scopes, and star-like product coupling degree is between 3.5～3.8; Through the electron microscopic TEM (transmission electron microscope) analysis, the microcosmic phase morphology is significantly " island " structure, and phase-splitting is fairly obvious, is typical segmented copolymer; (GB528-82) carries out mechanics performance determining by relative national standards, has good physical and chemical performance.Use through the user, reaction is good, the product of post-treatment--tackiness agent, and its viscosity, initial bonding strength and stripping strength are all higher, have widened the range of application of SBS series product.(type SBS and star-like (SB)
nR physical and mechanical properties and molecule measuring test result see Table respectively-1 and the table-2).
2, the raw material monomer proportioning of Cai Yonging has reduced the consumption of vinylbenzene (S) widely, and each technic index coupling rationally, successfully solved the heat effect problem of reaction process, and technology is easy to control, reaction time is short, equipment capacity is fully brought into play, reduced production cost.
By the following examples embodiments of the present invention are described in further detail.
(1) embodiment 1～10
The preparation of type SBS
Adopting volume is the polymeric kettle of the Stainless Steel Band chuck of 5 liters, and through being heated to 90～95 ℃, and with high pure nitrogen displacement and vacuum pump drainage three times, cool to room temperature is standby under the protection of high purity nitrogen then.First block polymerization: successively smart hexanaphthene, refining benzene ethene and tetrahydrofuran (THF) (add-on sees Table 3) are added in the polymeric kettle, stirring is warming up to 50～55 ℃, use with solvent and vinylbenzene in the n-Butyl Lithium of detrimental impurity equivalent remove detrimental impurity in the polymerization system.Add the quantitatively initiator n-Butyl Lithium of (seeing Table 3) then, initiated polymerization under 50～70 ℃ temperature, the polymer fluid color becomes orange red, shows that polyreaction begins to carry out, the question response time reach 25～30 minutes after first section reaction promptly accuse and finish.Second block polymerization: with chuck chilled water modulation temperature in the kettle is 60～80 ℃, with high pure nitrogen polymerization-grade divinyl (consumption sees Table 3) is pressed in the polymkeric substance, regulate temperature in the kettle and be not less than 60 ℃, cause two sections polymerizations, polymer fluid is orange red and takes off, and shows little yellow, show that two sections divinyl begin polymerization, control reaction temperature is no more than 120 ℃, and after the reaction times reached 25～30 minutes, second block polymerization was promptly finished.The 3rd block polymerization: with 70～80 ℃ of chuck chilled water modulation temperature in the kettle, (purifying method is with the aforementioned first block) vinylbenzene and the hexanaphthene mixed solution (consumption sees Table 3) that will purify with high pure nitrogen is pressed in the polymeric kettle then, regulate temperature in the kettle and be not less than 60 ℃, cause the 3rd block polymerization, polymer fluid fades to orange red or light yellow, shows the 3rd section beginning polyreaction, and control reaction temperature is not higher than 100 ℃, in 25～30 minutes reaction times, reaction is promptly accused and is finished.Add entry or ethanol terminator during discharging and be equivalent to 0.6% antioxidant 264 of polymer weight, the polymkeric substance that condenses glue white with elutriation method then, takes off light component and gets product at the drying dehydration.
Above-mentioned experimental data is listed in table 3.
(2) embodiment 11～20
The preparation of star-like (SB) nR
The polymerization of first, second block is with the method for embodiment 1～10, and charging capacity sees Table 4.After second block is finished, add the coupling agent silicon tetrachloride and carry out coupled reaction, add-on sees Table 4, divides secondary to add, and after 70%, 10 minute, adds residual content for the second time for the first time, and 25 minutes afterreactions of coupling finish.Add antioxidant 264 during discharging, the anti-aging agent add-on is 0.6% of a theoretical glue amount.Then the polymkeric substance that condenses glue white with elutriation method, drying is taken off light component and is got product.
Reinforced data see Table 4.Table-1 type SBS physical and mechanical properties and molecule measuring test result
| The prescription number | The physical property measurement result | The gpc analysis result | ||||||
| 300% tensile modulus (MPa) | Tensile strength (MPa) | Elongation at break (%) | Tension set (%) | Hardness (Shao A) | ????S/B ????(Wt) | Number-average molecular weight Mn (ten thousand) | Molecular weight distribution D | |
| ??1 | ????1.0 | ???8.5 | ????800 | ????15 | ???45 | ????15/85 | ????9.8 | ????1.05 |
| ??2 | ????1.4 | ???13.8 | ????970 | ????20 | ???50 | ???19.8/80.2 | ????10.0 | ????1.06 |
| ??3 | ????1.4 | ???18.0 | ????950 | ????24 | ???62 | ???25.0/75.0 | ????10.2 | ????1.06 |
| ??4 | ????1.9 | ???22.7 | ????990 | ????30 | ???74 | ???28.8/71.2 | ????9.8 | ????1.05 |
| ??5 | ????1.1 | ???9.8 | ????750 | ????18 | ???52 | ???19.2/80.8 | ????6.2 | ????1.08 |
| ??6 | ????0.8 | ???6.5 | ????970 | ????15 | ???42 | ???11.8/88.2 | ????7.8 | ????1.07 |
| ??7 | ????1.0 | ???9.2 | ????900 | ????14 | ???45 | ???14.3/85.7 | ????12.5 | ????1.05 |
| ??8 | ????1.2 | ???11.5 | ????970 | ????18 | ???48 | ???16.6/83.4 | ????10.4 | ????1.06 |
| ??9 | ????1.6 | ???16.2 | ????1000 | ????20 | ???54 | ???21.5/78.5 | ????9.8 | ????1.09 |
| ?10 | ????1.8 | ???20.4 | ????980 | ????25 | ???70 | ???26.8/73.2 | ????10.2 | ????1.08 |
Annotate: prescription number and table 3 are filled a prescription number corresponding.Table-2 star-like (SB) nR physical and mechanical properties and molecule measuring test results
| The prescription number | The physical property measurement result | The gpc analysis result | ||||||||
| 300% tensile modulus (MPa) | Tensile strength (MPa) | Elongation at break (%) | Tension set (%) | Hardness (Shao A) | ?????S/B ?????(Wt) | Number-average molecular weight Mn (ten thousand) | Molecular weight distribution D | Coupling degree f | Coupling efficiency (%) | |
| ?11 | ??1.0 | ???9.0 | ????750 | ????15 | ???48 | ????14.8/85.2 | ????17.8 | ????1.05 | ????3.6 | ???94.6 |
| ?12 | ??1.4 | ???13.5 | ????850 | ????16 | ???51 | ????19.8/80.2 | ????18.0 | ????1.08 | ????3.8 | ???95.2 |
| ?13 | ??1.4 | ???18.5 | ????950 | ????24 | ???62 | ????25.2/74.8 | ????18.2 | ????1.05 | ????3.5 | ???94.8 |
| ?14 | ??2.1 | ???22.8 | ????950 | ????30 | ???75 | ????29.2/70.8 | ????17.9 | ????1.09 | ????3.9 | ???93.7 |
| ?15 | ??1.6 | ???12.5 | ????810 | ????18 | ???50 | ????19.4/80.6 | ????14.8 | ????1.07 | ????3.7 | ???94.5 |
| ?16 | ??1.8 | ???7.8 | ????850 | ????16 | ???45 | ????12.2/87.8 | ????20.2 | ????1.08 | ????3.5 | ???92.6 |
| ?17 | ??1.8 | ???9.2 | ????800 | ????18 | ???52 | ????13.8/86.2 | ????23.8 | ????1.05 | ????3.6 | ???94.0 |
| ?18 | ??1.8 | ???11.5 | ????820 | ????18 | ???51 | ????17.0/83.0 | ????26.5 | ????1.06 | ????3.6 | ???93.8 |
| ?19 | ??1.6 | ???14.0 | ????810 | ????22 | ???55 | ????21.6/78.4 | ????18.5 | ????1.10 | ????3.5 | ???93.5 |
| ?20 | ??1.8 | ???19.8 | ????830 | ????30 | ???70 | ????27.3/72.7 | ????17.9 | ????1.06 | ????3.8 | ???94.2 |
Annotate: prescription number and table 4 are filled a prescription number corresponding.Table-3 type SBSs formulation Example that feeds intake
Table-4 star-like (SB) nR formulation Example that feeds intake
| The prescription number | ??S/B ??(Wt) | Design Mn (ten thousand) | Monomer concentration g/poml | Monomer total amount (g) | One section | Two sections divinyl (g) | Three sections | ||||
| Solvent (ml) | Vinylbenzene (g) | ?THF(mol) | BuLi(mol) | Solvent (ml) | Vinylbenzene (g) | ||||||
| ?1 | ??15/85 | ???10 | ??15 | ??450 | ??2800 | ????34 | ?0.0022 | ?0.0045 | ????382 | ??200 | ???34 |
| ?2 | ??20/80 | ???10 | ??15 | ??450 | ??2800 | ????45 | ?0.0022 | ?0.0045 | ????360 | ??200 | ???45 |
| ?3 | ??25/75 | ???10 | ??15 | ??450 | ??2800 | ????56 | ?0.0022 | ?0.0045 | ????338 | ??200 | ???56 |
| ?4 | ??29/71 | ???10 | ??15 | ??450 | ??2800 | ????65 | ?0.0022 | ?0.0045 | ????320 | ??200 | ???65 |
| ?5 | ??20/80 | ???6 | ??15 | ??450 | ??2800 | ????45 | ?0.0038 | ?0.0075 | ????360 | ??200 | ???45 |
| ?6 | ??12/88 | ???8 | ??15 | ??450 | ??2800 | ????27 | ?0.0028 | ?0.0056 | ????396 | ??200 | ???27 |
| ?7 | ??14/86 | ???12 | ??15 | ??450 | ??2800 | ????32 | ?0.0019 | ?0.0038 | ????387 | ??200 | ???31 |
| ?8 | ??17/83 | ???10 | ??12 | ??360 | ??2800 | ????31 | ?0.0018 | ?0.0036 | ????299 | ??200 | ???31 |
| ?9 | ??22/78 | ???10 | ??18 | ??540 | ??2800 | ????59 | ?0.0027 | ?0.0054 | ????421 | ??200 | ???59 |
| ?10 | ??27/73 | ???10 | ??20 | ??600 | ??2800 | ????81 | ?0.0030 | ?0.0060 | ????438 | ??200 | ???81 |
| The prescription number | ??S/B ??(Wt) | Design Mn (ten thousand) | Monomer concentration g/poml | Monomer total amount (g) | One section | Two sections | Coupling | |||
| Solvent (ml) | Vinylbenzene (g) | ??THF(mol) | ?BuLi(mol) | Divinyl (g) | ?SiCl 4(mol) | |||||
| ?11 | ?15/85 | ???18 | ????15 | ?450 | ??3000 | ????68 | ??0.0050 | ??0.010 | ??382 | ?0.0028 |
| ?12 | ?20/80 | ???18 | ????15 | ?450 | ??3000 | ????90 | ??0.0050 | ??0.010 | ??360 | ?0.0028 |
| ?13 | ?25/75 | ???18 | ????15 | ?450 | ??3000 | ????112 | ??0.0050 | ??0.010 | ??338 | ?0.0028 |
| ?14 | ?29/71 | ???18 | ????15 | ?450 | ??3000 | ????130 | ??0.0050 | ??0.010 | ??320 | ?0.0028 |
| ?15 | ?20/80 | ???16 | ????15 | ?450 | ??3000 | ????90 | ??0.0056 | ??0.0110 | ??360 | ?0.0030 |
| ?16 | ?12/88 | ???20 | ????15 | ?450 | ??3000 | ????54 | ??0.0045 | ??0.0090 | ??396 | ?0.0025 |
| ?17 | ?14/86 | ???24 | ????15 | ?450 | ??3000 | ????63 | ??0.0038 | ??0.0075 | ??387 | ?0.0021 |
| ?18 | ?17/83 | ???28 | ????15 | ?450 | ??3000 | ????77 | ??0.0032 | ??0.0064 | ??374 | ?0.0018 |
| ?19 | ?22/78 | ???18 | ????12 | ?360 | ??3000 | ????79 | ??0.0040 | ??0.0080 | ??281 | ?0.0022 |
| ?20 | ?27/73 | ???18 | ????18 | ?540 | ??3000 | ????146 | ??0.0060 | ??0.0120 | ??395 | ?0.0033 |
Claims (6)
1, a kind of manufacture method of styrene-butadiene block copolymer, with styrenic and alkadiene monomer is raw material, hexanaphthene is a solvent, n-Butyl Lithium is an initiator, tetrahydrofuran (THF) is the activator synthetic segmented copolymer, the invention is characterized in: starting monomer vinylbenzene (S) is respectively 10%～29% and 71%～90% with the weight percent of divinyl (B), the concentration of starting monomer in solvent is 12g～20g/100ml in the system, adopt the reinforced method stage feeding polymerization of substep, and, make line style or star copolymer respectively in latter stage adding terminator or coupling agent.
2, manufacture method according to claim 1 is characterized in that making linear copolymers and adopted for three steps reinforced:
(1) half of 90%～95% and vinylbenzene total amount of adding solvent hexanaphthene total amount adds tetrahydrofuran (THF) and n-Butyl Lithium again, in first section polyreaction of 50～70 ℃ of initiations, reacts under 50～80 ℃ temperature 25～30 minutes, then
(2) add the monomer divinyl,, under 70～120 ℃ temperature, reacted 25～30 minutes, then in 60～80 ℃ of polymerizations that cause second block
(3) add remaining solvent hexanaphthene and monomer styrene, in 65～80 ℃ of polymerizations that cause the 3rd block, under 70～100 ℃ temperature, react and got final product discharging in 25～30 minutes, add terminator water or ethanol during discharging and add the antioxidant 264 of theoretical glue amount 0.6% (weight).
3, manufacture method according to claim 1 is characterized in that making star copolymer and adopts the reinforced coupling of two steps:
(1) adds solvent hexanaphthene and monomer styrene, add tetrahydrofuran (THF) and n-Butyl Lithium again,, under 50～80 ℃ temperature, reacted 25～30 minutes, then in first section polyreaction of 50～70 ℃ of initiations
(2) add the monomer divinyl,, under 70～120 ℃ temperature, reacted 25～30 minutes, then in 60～80 ℃ of polymerizations that cause second block
(3) add coupling agent SiCl
4(add-on is 0.25～0.275 times of initiator mole number) carries out coupling, coupling agent adds in two steps, add earlier add behind 70%, 10 minute of total amount remaining 30%, react and got final product discharging in 20～25 minutes, add the antioxidant 264 of theoretical glue amount 0.6% (weight) during discharging.
4, according to the described manufacture method of one of claim 1～3, it is characterized in that: starting monomer vinylbenzene (S) is respectively 18%～25% and 75%～82% with the weight percent of divinyl (B).
5, according to the described manufacture method of one of claim 1～4, it is characterized in that: before polyreaction caused, the n-Butyl Lithium of content of impurities equivalent in first adding and solvent and the vinylbenzene was removed impurity among the two with chemical purification.
6, the product that manufacture method obtained of segmented copolymer according to claim 1.
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| CN1069656C (en) * | 1998-11-05 | 2001-08-15 | 中国石油兰州化学工业公司 | Fragmentation-resisting simplicial spider block copolymer and its preparation |
| CN102558466A (en) * | 2012-01-10 | 2012-07-11 | 宁波科元塑胶有限公司 | Synthesis method of transparent block copolymer |
| CN103030756A (en) * | 2011-10-10 | 2013-04-10 | 中国石油化工股份有限公司 | Styrene-butadiene copolymer as well as preparation and applications thereof |
| CN104987557A (en) * | 2015-07-09 | 2015-10-21 | 安徽嘉阳塑胶有限公司 | Thermoplastic styrene-butadiene rubber |
| CN105237695A (en) * | 2015-10-14 | 2016-01-13 | 中国石油化工股份有限公司 | Preparation method of epoxy group-terminated styrene-butadiene-styrene (SBS) ternary block copolymer |
| CN105801784A (en) * | 2016-03-03 | 2016-07-27 | 中国石油化工股份有限公司 | Linear functionalized SBS prepared from bifunctional coupling agent and process |
| CN107540890A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Coupling agent and the conjugated diene polymer of star line blending and its preparation method and application |
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1996
- 1996-10-23 CN CN 96118387 patent/CN1151412A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069656C (en) * | 1998-11-05 | 2001-08-15 | 中国石油兰州化学工业公司 | Fragmentation-resisting simplicial spider block copolymer and its preparation |
| CN103030756A (en) * | 2011-10-10 | 2013-04-10 | 中国石油化工股份有限公司 | Styrene-butadiene copolymer as well as preparation and applications thereof |
| CN103030756B (en) * | 2011-10-10 | 2015-03-25 | 中国石油化工股份有限公司 | Styrene-butadiene copolymer as well as preparation and applications thereof |
| CN102558466A (en) * | 2012-01-10 | 2012-07-11 | 宁波科元塑胶有限公司 | Synthesis method of transparent block copolymer |
| CN108076641A (en) * | 2015-03-12 | 2018-05-25 | 英力士苯领集团股份公司 | Pipeline styrene-butadiene block copolymer |
| CN104987557A (en) * | 2015-07-09 | 2015-10-21 | 安徽嘉阳塑胶有限公司 | Thermoplastic styrene-butadiene rubber |
| CN105237695A (en) * | 2015-10-14 | 2016-01-13 | 中国石油化工股份有限公司 | Preparation method of epoxy group-terminated styrene-butadiene-styrene (SBS) ternary block copolymer |
| CN105237695B (en) * | 2015-10-14 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of preparation method of epoxy terminated styrene butadiene styrene ternary block polymer |
| CN105801784A (en) * | 2016-03-03 | 2016-07-27 | 中国石油化工股份有限公司 | Linear functionalized SBS prepared from bifunctional coupling agent and process |
| CN105801784B (en) * | 2016-03-03 | 2018-07-17 | 中国石油化工股份有限公司 | A kind of linear functional SBS and technique prepared by difunctional coupling agent |
| CN107540890A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Coupling agent and the conjugated diene polymer of star line blending and its preparation method and application |
| CN114316139A (en) * | 2020-09-30 | 2022-04-12 | 中国石油天然气股份有限公司 | Solution polymerized styrene-butadiene rubber and preparation method and application thereof |
| CN114316139B (en) * | 2020-09-30 | 2024-03-01 | 中国石油天然气股份有限公司 | Solution polymerized styrene-butadiene rubber and preparation method and application thereof |
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