WO2022185132A1 - Process and compositions for preparing high cis and high linear polybutadiene rubber - Google Patents
Process and compositions for preparing high cis and high linear polybutadiene rubber Download PDFInfo
- Publication number
- WO2022185132A1 WO2022185132A1 PCT/IB2022/051032 IB2022051032W WO2022185132A1 WO 2022185132 A1 WO2022185132 A1 WO 2022185132A1 IB 2022051032 W IB2022051032 W IB 2022051032W WO 2022185132 A1 WO2022185132 A1 WO 2022185132A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polybutadiene rubber
- butadiene
- mixture
- solvent
- group
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 82
- 230000008569 process Effects 0.000 title claims abstract description 75
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000003426 co-catalyst Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 239000004411 aluminium Substances 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 229920001971 elastomer Polymers 0.000 claims description 17
- 239000005060 rubber Substances 0.000 claims description 17
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 16
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000002798 polar solvent Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 10
- HWVKIRQMNIWOLT-UHFFFAOYSA-L cobalt(2+);octanoate Chemical group [Co+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HWVKIRQMNIWOLT-UHFFFAOYSA-L 0.000 claims description 10
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 claims description 6
- 230000000704 physical effect Effects 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- 229920003194 trans-1,4-polybutadiene polymer Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000012190 activator Substances 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000009862 microstructural analysis Methods 0.000 description 1
- 238000013365 molecular weight analysis method Methods 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present disclosure is in the chemical sciences and material sciences. The present disclosure generally relates to a process for preparing polybutadiene rubber by employing a composition comprising co-catalyst as active species without water as activator. In particular, the disclosure relates to a process for preparing cobalt-based polybutadiene rubber with specific microstructure configuration by employing chloroethylalumioxane as a novel co-catalyst as active species. Thus, the disclosure relates to a process for butadiene polymerization and improvement in the resultant product properties like high cis content, lower gel content and high linearity with improved physical product properties.
Description
PROCESS AND COMPOSITIONS FOR PREPARING HIGH CIS AND HIGH LINEAR POLYBUTADIENE RUBBER
TECHNICAL FIELD
[001]. The present disclosure is in the chemical sciences and material sciences. The present disclosure generally relates to a process for preparing polybutadiene rubber by employing a composition comprising co-catalyst as active species without water as activator. In particular, the disclosure relates to a process for preparing cobalt-based polybutadiene rubber with specific microstructure configuration by employing chloroethylalumioxane as a co-catalyst which is active species. Thus, the disclosure relates to a process for butadiene polymerization and improvement in the resultant product properties like high cis content, lower gel content and high linearity with improved physical product properties.
BACKGROUND OF THE DISCLOSURE
[002]. Butadiene Rubber (BR) is a synthetic rubber prepared by solution polymerization method using butadiene monomer. BR is widely used for tires, shoes and golf balls due to its excellent wear resistance, bend resistance, rebound resilience and cold resistance. Properties of polydienes mainly governed by their microstructures generated during polymerization process. BR is typically categorized according to the polymerization technology and an initiator or a catalyst used during the process of preparation.
[003]. PBR grades can be categorized based on method of preparation, viz., radical polymerization using emulsion method, anionic polymerization using lithium catalyst and coordination polymerization using transition metal-based Ziegler-Natta catalyst system.
[004]. Amongst above methods PBR synthesis using cobalt based catalyst system has received considerable attention due to control over molecular structure and other physical properties of resultant polymer.
[005]. During polymerization process cross linking of chains takes place results in gel formation and is non-desirable component of the process. Such gel formation can reduce the efficiency of the process mainly by disturbing smoothness of hardware operations and the quality of polybutadiene rubber is reduced. It is believed that one of the components, water in this catalyst system is found to disperse non uniformly in the organic solvent medium thus uneven activation of co-catalyst and catalyst system. This leads to rapid cross linking in polymer back bone resulting in gel formation.
[006]. Accordingly, there has been a continuing need in the art to provide compositions or process which could provide cis-polybutadiene rubber with narrow molecular weight and with high molecular weight with lower branching.
[007]. BRIEF DESCRIPTION OF THE ACCOMPANYING FIGURES [008]. The novel features and characteristics of the disclosure are set forth in the appended description. The disclosure itself, however, as well as a preferred mode of use, further objectives, and advantages thereof, will best be understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying figures. One or more embodiments are now described, by way of example only, with reference to the accompanying figures wherein like reference numerals represent like elements and in which: [009]. Figure 1 shows NMR analysis of CEAO-PBR with cis 99 %, trans 0.6 %, vinyl 0.4 %
[0010]. Figure 2 shows NMR analysis of Commercial PBR with cis 97.1 %, trans 1,8 %, vinyl 1,2 %
DESCRIPTION OF THE DISCLOSURE
[0011]. The present disclosure aims to overcome the aforesaid drawbacks by providing an efficient process or composition(s) comprising organocobalt salt, alkyl halo aluminium component and chain terminating agent.
[0012]. In an embodiment, the present disclosure includes a process for preparing polybutadiene rubber, wherein said process comprising polymerization of butadiene in the presence of organocobalt salt, alkyl halo aluminium component and chain terminating agent.
[0013]. The present disclosure relates to a process for preparing polybutadiene rubber, wherein said process comprising the steps:
- adding dried solvent into a reactor followed by purging with inert gas;
- adding co-catalyst followed by addition of cobalt catalyst to the dried solvent containing reactor to obtain mixture -I;
- adding chain transfer agent to the mixture I to obtain mixture- II; and
- adding butadiene monomer to the mixture-III to obtain polybutadiene rubber mixture.
[0014]. In a non-limiting embodiment of the present disclosure, the above process further comprising the step of coagulation of polymer from solvent medium by adding polar solvent(s).
[0015]. In a non-limiting embodiment of the present disclosure, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber, high cis -1,4-polybutadiene rubber, low cis 1,4 polybutadiene, high trans- 1,4 polybutadiene and combination thereof.
[0016]. In a non-limiting embodiment of the present disclosure, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber with high linearity compared to standard DEAC (diethyl aluminium chloride) process and combination thereof,
[0017]. non-limiting embodiment of the present disclosure, wherein the polybutadiene rubber is selected from a group comprising 1,3 -polybutadiene rubber has high solution viscosity
[0018]. non-limiting embodiment of the present disclosure, wherein the polybutadiene rubber is selected from a group comprising 1,3 -polybutadiene rubber with improved physical properties of high tensile strength.
[0019]. In a non-limiting embodiment of the present disclosure, wherein the butadiene is 1,3 -butadiene.
[0020]. In a non-limiting embodiment of the present disclosure, the organocobalt salt is Cobalt octanoate and combination thereof.
[0021]. In a non-limiting embodiment of the present disclosure, the alkyl halo aluminium component is selected from a group comprising alkyl chloro aluminium component, diethyl aluminum chloride , methyl aluminoxane, triisobutyl aluminium, and combination thereof.
[0022]. In a non-limiting embodiment of the present disclosure, the alkyl chloro aluminium component is selected from a group comprising chloroethyl aluminoxane, diethyl aluminium chloride, methyl aluminoxane, triisobutyl aluminium, and combination thereof.
[0023]. In a non-limiting embodiment of the present disclosure, the chain terminating agent is butadiene, 1,2 butadiene, and combination thereof.
[0024]. In a non-limiting embodiment of the present disclosure, the concentration of organocobalt salt ranges from 1 x 105 to 2 x 105 mole per mole of 1,3 butadiene.
[0025]. In a non-limiting embodiment of the present disclosure, the concentration of alkyl halo aluminium component in ratio amount of 155 per mole of organocobalt salt.
[0026]. In a non-limiting embodiment of the present disclosure, the concentration of chain terminating agent ranges from an amount of 1 to 100 ppm per 100 g of butadiene.
[0027]. In a non-limiting embodiment of the present disclosure, the process is carried out at temperature ranging from 10 to 50 °C preferably 20 to 35 °C.
[0028]. In a non-limiting embodiment of the present disclosure, the process is carried out at temperature ranging from 10 to 30°C preferably 15 to 25 °C.
[0029]. In a non-limiting embodiment of the present disclosure, the concentration of monomer ranges from 10 to 60 wt % of the dry feed more precisely 20 to 30 wt%.
[0030]. In a non-limiting embodiment of the present disclosure, the process is carried for a time period ranging from 10 minutes to 300 minutes, preferably for a time period ranging from 20 minutes to 60 minutes.
[0031]. In a non-limiting embodiment of the present disclosure, the process is carried out in presence of a solvent, wherein the solvent is at least one or mixture of aromatic and non-aromatic solvent with C6 units.
[0032]. In a non-limiting embodiment of the present disclosure, the coagulation of polymer from the solvent medium is carried using polar solvents.
[0033]. In a non-limiting embodiment of the present disclosure, a polar solvent is selected from a group comprising water, alcohol containing Cl to C5 chain units and combinations thereof.
[0034]. The present disclosure also provides a catalyst composition for preparing cis-polybutadiene rubber with narrow molecular weight and with high molecular weight with lower branching, wherein said composition comprising organocobalt salt, alkyl chloro aluminium component, chain terminating agent.
[0035]. In a non-limiting embodiment of the present disclosure, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber, high cis -1,4-polybutadiene rubber, low cis-1, 4-polybutadiene rubber, high trans -1,4-polybutadiene rubber, and combination thereof.
[0036]. In a non-limiting embodiment of the present disclosure, wherein the butadiene is selected from a group comprising 1,3 -butadiene, cis- 1,3 -butadiene, 1,2-butadiene and combination thereof.
[0037]. In a non-limiting embodiment of the present disclosure, the organocobalt salt is cobalt octanoate.
[0038]. In a non-limiting embodiment of the present disclosure, the alkyl halo aluminium component is selected from a group comprising alkyl chloro aluminium component, diethyl alumiunium chloride, methyl aluminoxane, triisobutyl aluminium, and combination thereof.
[0039]. In a non-limiting embodiment of the present disclosure, the alkyl chloro aluminium component is selected from a group comprising chloroethyl aluminoxane, diethyl aluminium chloride, methyl aluminoxane, triisobutyl aluminium, and combination thereof.
[0040]. In a non-limiting embodiment of the present disclosure, the chain terminating agent is selected from a group comprising butadiene, 1,2 butadiene, and combination thereof.
[0041]. In a non-limiting embodiment of the present disclosure, a composition comprises about 0.5% wt/wt to 50% wt/wt of organocobalt salt, about 0.5% wt/wt to 50% wt/wt of alkyl chloro aluminium component; and about 1 ppm to 1 % chain terminating agent.
[0042]. In a non-limiting embodiment of the present disclosure, a composition comprises about 1 %wt/wt to 20 %wt/wt of organocobalt salt, about 1 %wt/wt to 30 %wt/wt of alkyl chloro aluminium component; and about 1 %wt/wt to 100 %wt/wt chain terminating agent.
[0043]. The present disclosure provides process for preparing cis-polybutadiene rubber, wherein said process comprising the steps:
- adding dried benzene into a reactor followed by purging with nitrogen gas;
- adding alkyl halo aluminium component followed by Cobalt octanoate to the dried solvent containing reactor to obtain mixture -I;
- adding 1,2-butadiene to the mixture I to obtain mixture-II; and
- adding 1, 3-butadiene monomer to the mixture-III to obtain cis- polybutadiene rubber mixture.
- wherein the concentration of organocobalt salt ranges from 1 x 105 to 2 x 105 mole per mole of 1,3 -butadiene.
[0044]. In a non-limiting embodiment of the present disclosure, the concentration of alkyl halo aluminium component in ratio amount of 155 per mole of organocobalt salt.
[0045]. In a non-limiting embodiment of the present disclosure, the concentration of chain terminating agent ranges from an amount of 1 to 100 ppm per 100 g of butadiene.
[0046]. In a non-limiting embodiment of the present disclosure, the reaction is carried out at temperature ranging from 10 to 50 °C preferably 20 to 35 °C.
[0047]. In a non-limiting embodiment of the present disclosure, the reaction is carried out at temperature ranging from 10 to 30°C preferably 15 to 25 °C.
[0048]. In a non-limiting embodiment of the present disclosure, the concentration of monomer ranges from 10 to 60 wt % of the dry feed more precisely 20 to 30 wt%.
[0049]. In a non-limiting embodiment of the present disclosure, the process is carried for a time period ranging from 10 minutes to 300 minutes, preferably for a time period ranging from 20 minutes to 60 minutes.
[0050]. In a non-limiting embodiment of the present disclosure, the process is carried out in presence of a solvent, wherein the solvent is at least one or mixture of aromatic and non-aromatic solvent with C6 units.
[0051]. In a non-limiting embodiment of the present disclosure, the coagulation of polymer from the solvent medium is carried using polar solvents.
[0052]. In a non-limiting embodiment of the present disclosure, a polar solvent is selected from a group comprising water, alcohol containing Cl to C5 chain units and combinations thereof.
[0053]. The present disclosure also provides a catalyst composition for preparing cis-polybutadiene rubber with narrow molecular weight and with high molecular weight with lower branching, wherein said composition comprising organocobalt salt, alkyl chloro aluminium component, chain terminating agent.
[0054]. In a non-limiting embodiment of the present disclosure, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber, high cis -1,4-polybutadiene rubber, low cis-1, 4-polybutadiene rubber, high trans -1,4-polybutadiene rubber, and combination thereof.
[0055]. In a non-limiting embodiment of the present disclosure, wherein the butadiene is selected from a group comprising 1,3 -butadiene, cis- 1,3 -butadiene, 1,2-butadiene and combination thereof.
[0056]. In a non-limiting embodiment of the present disclosure, the PBR product obtained in the present invention has high linearity and low gel content.
[0057]. The process disclosed in the present application reduces gel content in the polymerization process thus improving the smooth operation of plant as well as superior grade PBR product.
[0058]. In an embodiment, the foregoing descriptive matter is illustrative of the disclosure and not a limitation. While considerable emphasis has been placed herein on the particular features of this disclosure, it will be appreciated that various modifications can be made, and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. Those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
[0059]. Additional embodiments and features of the present disclosure will be apparent to one of ordinary skill in art based upon description provided herein. The embodiments herein provide various features and advantageous details thereof in the description. Descriptions of well-known/conventional methods/steps and techniques are omitted so as to not unnecessarily obscure the embodiments herein. Further, the disclosure herein provides for examples illustrating the above described embodiments, and in order to illustrate the embodiments of the present disclosure certain aspects have been employed. The examples used herein for such illustration are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the following examples should not be construed as limiting the scope of the embodiments herein.
EXAMPLES:
[00601. EXAMPLE 1:
[0061]. A composition comprising organocobalt salt, alkyl chloro aluminium component; and chain terminating agent.
100621. EXAMPLE 2:
[0063]. A composition comprising organocobalt salt 0.5 to 50 wt.wt %, alkyl chloro aluminium component 0.5 to 30 wt/wt %; and chain terminating agent 1 to 100 ppm.
100641. EXAMPLE 3:
[0065]. A composition comprising cobalt octanoate, chloroethyl aluminoxane (CEAO) and 1,2 butadiene.
100661. EXAMPLE 4:
[0067]. A composition comprising cobalt octanoate at a concentration ranging from about 1 to 100 ppm, CEAO at a concentration ranging from about 50 to 500 ppm; and 1,2 butadiene at a concentration ranging from about 1 to 100 ppm.
[0068] .EXAMPLE 5: General process for preparing high cis-polvbutadiene rubber:
[0069]. Polybutadiene polymerization was prepared in solution polymerization technique and using benzene as solvent. Benzene was dried over molecular sieves overnight prior to experiment. Moisture content to be kept as low as 30 50 ppm which was measured by Karl Fisher titration method.
Dry solvent was charged to reactor vessel by means of nitrogen pressure in order to prevent any atmospheric moisture exposure. Solvent was purged with nitrogen in the reactor prior to begin polymerization. Co-catalyst containing alkyl halo aluminium component was charged in dilute form (7%) followed by organic ester based cobalt salts as catalyst in solvent (5%). Reaction mixture was subjected to stirring followed by addition of 1,2 butadiene as chain transfer agent [Chain transfer agent contributes in terminating growing chain after specific growth of
chain length], and then by the addition of 1,3 butadiene. Reaction initiation was indicated by exothermicity in the reaction and reaction was performed for 1-2 hours. Reaction was terminated by adding polar solvent to reaction mixture and polymer was coagulated using polar solvent. Polymer was dried in vacuum oven and weighed.
[0070] .EXAMPLE 6: Specific process for preparing high cis-polvbutadiene rubber:
[0071]. In a typical reaction condition, benzene dried over molecular sieves was taken in glass reactor as a solvent, to which chloroethyl aluminoxane was added and the mixture is stirred for 5 mins. A catalyst Cobalt octanoate is added to the above mixture and allowed to react for 10 mins. 1,2 butadiene was added as a chain transfer/terminating agent and the reaction was initiated by adding 1,3 butadiene as monomer at 25 °C. Reaction temperature is controlled by using oil circulator. Reaction was allowed to proceed for 60 mins and methanol was used to quench the reaction followed by coagulation with methanol and dried under vacuum to get high cis-polybutadiene rubber.
[0072] .EXAMPLE 7: Specific Application of Composition:
[0073] .Halogen based aluminoxane reagents mentioned are important component in preparing high cis nolvbtudiene rubber with higher linearity. Such rubber products find application in high performance tyre due to improved product properties.
Table 1: Reaction conditions and composition of experiments performed.
Polybutadiene rubber synthesis performed by two methods, a. conventional method by utilizing DEAC-water system as co-catalvst; b. halogen based aluminoxane -CEAO co-catalvst system. Polymerization process conducted with general procedure mentioned in earlier section with below shown components.
Experimental Data
Table 2: Microstructural analysis of PBR product a. Gel content
From the above provided Gel content analysis, it is evident that the gel content of CEAO-PBR is less than that of commercial PBR and DEAC-PBR. b. Cis content & molecular weight analysis
From the above provided cis content analysis, it is evident that the cis content of CEAO-PBR is less than that of commercial PBR and DEAC-PBR.
c. Branching by RPA Studies: Higher value indicates higher linearity
From the above provided RPA Studies, it is evident that the RPA Molecular Weight Distribution of CEAO-PBR is less than that of commercial PBR and DEAC-PBR. d. Linearity study by Fluid Viscosity
From the above provided fluid viscosity Studies, it is evident that the fluid viscosity of CEAO-PBR is less than that of commercial PBR and DEAC-PBR.
Table 3: Rubber processing analysis and rheology studies of PBR
From the above provided rubber processing analysis and rheology studies of PBR, it is evident that the CEAO-PBR is highly linear than that of commercial PBR and DEAC-PBR.
Table 4: Physical Properties
From the above provided physical property Studies, it is evident that the CEAO-
PBR has high tensile strength than that of commercial PBR and DEAC-PBR.
[00741. EXAMPLE 9:
[0075]. The invention is further described by the following numbered paragraphs:
1) A Process for preparing polybutadiene rubber, wherein said process comprising polymerization of butadiene in the presence of organocobalt salt, alkyl halo aluminium component and chain terminating agent.
2) A process for preparing polybutadiene rubber, wherein said process comprising the steps:
- adding dried solvent into a reactor followed by purging with inert gas;
- adding co-catalyst followed by addition of cobalt catalyst to the dried solvent containing reactor to obtain mixture -I;
- adding chain transfer agent to the mixture I to obtain mixture- II; and
- adding butadiene monomer to the mixture-III to obtain polybutadiene rubber mixture.
3) The process of paragraphs 1 and 2, further comprising the step of coagulation of polymer from solvent medium by adding polar solvent(s).
) The process of paragraph 1, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber, high cis -1,4- polybutadiene rubber, low cis -1,4-polybutadiene rubber, trans -1,4- polybutadiene rubber, and combination thereof. ) The process of paragraph 1, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber, high linear-1,4- polybutadiene rubber and combinations thereof. ) The process of paragraph 1, wherein the polybutadiene rubber is 1,4- polybutadiene rubber with high solution viscosity. ) The process of paragraph 1, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber with improved physical properties such as high tensile strength. ) The process of paragraph 1, wherein the butadiene is selected from a group comprising 1,3 -butadiene, cis- 1,3 -butadiene, 1,2 butadiene, and combination thereof. ) The process of paragraph 1, wherein the organocobalt salt is cobalt octanoate. 0) The process of paragraph 1, wherein the alkyl halo aluminium component is selected from a group comprising alkyl chloro aluminium component, diethyl aluminium chloride, methyl aluminoxane, triisobutyl aluminium and combination thereof. 1) The process of paragraph 1, wherein the alkyl chloro aluminium component is selected from a group comprising chloroethyl aluminoxane, diethyl aluminium chloride, methyl aluminoxane, triisobutyl aluminium, and combination thereof. 2) The process of paragraph 1, wherein the chain terminating agent is selected from a group comprising butadiene, 1,2 butadiene, and combination thereof. 3) A process for preparing cis-polybutadiene rubber, wherein said process comprising the steps:
- adding dried benzene into a reactor followed by purging with nitrogen gas;
- adding alkyl halo aluminium component followed by Cobalt octanoate to the dried solvent containing reactor to obtain mixture -I;
- adding 1,2-butadiene to the mixture I to obtain mixture-II; and
- adding 1, 3-butadiene monomer to the mixture-III to obtain cis- polybutadiene rubber mixture. ) The process of paragraph 1, wherein the concentration of organocobalt salt ranges from 1 x 105 to 2 x 105 mole per mole of 1,3 -butadiene. ) The process of paragraph 1, wherein the concentration of alkyl halo aluminium component in an ratio amount of 155 per mole of organocobalt salt. ) The process of paragraph 1, wherein the concentration of chain terminating agent ranges from an amount of 1 to 100 ppm per 100 g of butadiene. ) The process of paragraph 1, wherein the process is carried out at temperature ranging from 10 to 50 °C preferably 20 to 35 °C. ) The process of paragraph 1, wherein the process is carried out at temperature ranging from 10 to 30°C preferably 15 to 25 °C. ) The process of paragraph 1, wherein the concentration of the monomer ranges from 10 to 60 wt % of the dry feed more precisely 20 to 30 wt%.) The process of paragraph 1, wherein the process is carried for a time period ranging from 10 minutes to 300 minutes, preferably for a time period ranging from 20 minutes to 60 minutes. ) The process of paragraph 1, wherein the process is carried out in presence of a solvent, wherein the solvent is at least one or mixture of aromatic and non-aromatic solvent with C6 units. ) The process of paragraph 1, wherein the coagulation of polymer from the solvent medium is carried using polar solvents.
23) The process of paragraph 1, wherein said polar solvent is selected from a group comprising water, alcohol containing Cl to C5 chain units and combinations thereof.
24) The catalyst composition for preparing cis-polybutadiene rubber with narrow molecular weight and with high molecular weight with lower branching, wherein said composition comprising organocobalt salt, alkyl chloro aluminium component, chain terminating agent.
[0076]. Additional embodiments and features of the present disclosure will be apparent to one of ordinary skill in art based on the description provided herein. The embodiments herein provide various features and advantageous details thereof in the description. Descriptions of well-known/conventional methods and techniques are omitted so as to not unnecessarily obscure the embodiments herein.
[0077]. The foregoing description of the specific embodiments fully reveals the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments in this disclosure have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
[0078]. Throughout this specification, the word “comprise”, or variations such as “comprises” or “comprising” wherever used, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
[0079]. With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.
[0080]. Any discussion of documents, acts, materials, devices, articles and the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.
[0081]. While considerable emphasis has been placed herein on the particular features of this disclosure, it will be appreciated that various modifications can be made, and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and other modifications in the nature of the disclosure or the preferred embodiments will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.
Claims
We Claim:
1) A Process for preparing polybutadiene rubber, wherein said process comprising polymerization of butadiene in the presence of organocobalt salt, alkyl halo aluminium component and chain terminating agent.
2) A process for preparing polybutadiene rubber, wherein said process comprising the steps:
- adding dried solvent into a reactor followed by purging with inert gas;
- adding co-catalyst followed by addition of cobalt catalyst to the dried solvent containing reactor to obtain mixture -I;
- adding chain transfer agent to the mixture I to obtain mixture- II; and
- adding butadiene monomer to the mixture-III to obtain polybutadiene rubber mixture.
3) The process as claimed in claims 1 and 2, further comprising the step of coagulation of polymer from solvent medium by adding polar solvent(s).
4) The process as claimed in claim 1, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber, high cis -1,4- polybutadiene rubber, low cis -1,4-polybutadiene rubber, trans -1,4- polybutadiene rubber, and combination thereof.
5) The process as claimed in claim 1, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber, high linear-1,4- polybutadiene rubber and combinations thereof.
6) The process as claimed in claim 1, wherein the polybutadiene rubber is 1,4- polybutadiene rubber with high solution viscosity
7) The process as claimed in claim 1, wherein the polybutadiene rubber is selected from a group comprising 1,4-polybutadiene rubber with improved physical properties such as high tensile strength.
8) The process as claimed in claim 1, wherein the butadiene is selected from a group comprising 1,3 -butadiene, cis- 1,3-butadiene, 1,2 butadiene, and combination thereof.
9) The process as claimed in claim 1, wherein the organocobalt salt is cobalt octanoate.
10) The process as claimed in claim 1, wherein the alkyl halo aluminium component is selected from a group comprising alkyl chloro aluminium component, diethyl aluminium chloride, methyl aluminoxane, triisobutyl aluminium and combination thereof.
11) The process as claimed in claim 1, wherein the alkyl chloro aluminium component is selected from a group comprising chloroethyl aluminoxane, diethyl aluminium chloride, methyl aluminoxane, triisobutyl aluminium, and combination thereof.
12) The process as claimed in claim 1, wherein the chain terminating agent is selected from a group comprising butadiene, 1,2 butadiene, and combination thereof.
13) A process for preparing cis-polybutadiene rubber, wherein said process comprising the steps:
- adding dried benzene into a reactor followed by purging with nitrogen gas;
- adding alkyl halo aluminium component followed by Cobalt octanoate to the dried solvent containing reactor to obtain mixture -I;
- adding 1,2-butadiene to the mixture I to obtain mixture-II; and
- adding 1, 3-butadiene monomer to the mixture-III to obtain cis- polybutadiene rubber mixture.
14) The process as claimed in claim 1, wherein the concentration of organocobalt salt ranges from 1 x 105 to 2 x 105 mole per mole of 1 ,3- butadiene .
15) The process as claimed in claim 1, wherein the concentration of alkyl halo aluminium component in an ratio amount of 155 per mole of organocobalt salt.
16) The process as claimed in claim 1, wherein the concentration of chain terminating agent ranges from an amount of 1 to 100 ppm per 100 g of butadiene.
17) The process as claimed in claim 1, wherein the process is carried out at temperature ranging from 10 to 50 °C preferably 20 to 35 °C.
18) The process as claimed in claim 1, wherein the process is carried out at temperature ranging from 10 to 30°C preferably 15 to 25 °C.
19) The process as claimed in claim 1, wherein the concentration of the monomer ranges from 10 to 60 wt % of the dry feed more precisely 20 to 30 wt%.
20) The process as claimed in claim 1, wherein the process is carried for a time period ranging from 10 minutes to 300 minutes, preferably for a time period ranging from 20 minutes to 60 minutes.
21) The process as claimed in claim 1, wherein the process is carried out in presence of a solvent, wherein the solvent is at least one or mixture of aromatic and non-aromatic solvent with C6 units.
22) The process as claimed in claim 1, wherein the coagulation of polymer from the solvent medium is carried using polar solvents.
23) The process as claimed in claim 1, wherein said polar solvent is selected from a group comprising water, alcohol containing Cl to C5 chain units and combinations thereof.
24) The catalyst composition for preparing cis-polybutadiene rubber with narrow molecular weight and with high molecular weight with lower branching, wherein said composition comprising organocobalt salt, alkyl chloro aluminium component, chain terminating agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN202121009230 | 2021-03-05 | ||
| IN202121009230 | 2021-03-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022185132A1 true WO2022185132A1 (en) | 2022-09-09 |
Family
ID=83153914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2022/051032 WO2022185132A1 (en) | 2021-03-05 | 2022-02-07 | Process and compositions for preparing high cis and high linear polybutadiene rubber |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2022185132A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4255543A (en) * | 1978-08-21 | 1981-03-10 | Japan Synthetic Rubber Co., Ltd. | Process for the preparation of 1,2-polybutadiene |
| WO2003102041A1 (en) * | 2002-05-31 | 2003-12-11 | Dow Global Technologies Inc. | A two-step butadiene polymerization process for manufacturing high-cis 1,4-ploybutadiene |
| EP1842875B1 (en) * | 2004-12-20 | 2013-10-09 | Ube Industries, Ltd. | Process for production of polybutadiene rubber and rubber compositions |
-
2022
- 2022-02-07 WO PCT/IB2022/051032 patent/WO2022185132A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4255543A (en) * | 1978-08-21 | 1981-03-10 | Japan Synthetic Rubber Co., Ltd. | Process for the preparation of 1,2-polybutadiene |
| WO2003102041A1 (en) * | 2002-05-31 | 2003-12-11 | Dow Global Technologies Inc. | A two-step butadiene polymerization process for manufacturing high-cis 1,4-ploybutadiene |
| EP1842875B1 (en) * | 2004-12-20 | 2013-10-09 | Ube Industries, Ltd. | Process for production of polybutadiene rubber and rubber compositions |
Non-Patent Citations (1)
| Title |
|---|
| WANG QIANG, LIAO MINGYI, WANG YURONG, ZHANG CHUNQING: "Effects of 1,2-butadiene on the anionic copolymerization of styrene and 1,3-butadiene in the presence of polar additives", POLYMER INTERNATIONAL, BARKING, GB, vol. 56, no. 8, 1 August 2007 (2007-08-01), GB , pages 1021 - 1028, XP055967345, ISSN: 0959-8103, DOI: 10.1002/pi.2236 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4924026B2 (en) | Method for producing vinyl cis-polybutadiene rubber and vinyl cis-polybutadiene rubber | |
| US5448002A (en) | Synthesis of trans-1,4-polybutadiene having controlled molecular weight | |
| RU2638960C2 (en) | Butadiene rubber with drawfully increased viscosity by mooney received with use of inodimic catalyst | |
| JP4131625B2 (en) | Elastomeric, high trans-1,4-polybutadiene | |
| US5834573A (en) | Synthesis of trans-1,4-polybutadiene | |
| KR940004722B1 (en) | Direct method for preparing syndiotactic 1,2-polybutadiene | |
| US6617406B2 (en) | Synthesis of elastomeric high trans-1,4-polybutadiene | |
| CN104628963A (en) | Polyisoprene, preparation method thereof and vulcanized rubber | |
| EP0936242B1 (en) | Metal deactivator for cobalt catalyzed polymers | |
| JP6701763B2 (en) | Vinyl cis-polybutadiene rubber and method for producing the same | |
| WO2022185132A1 (en) | Process and compositions for preparing high cis and high linear polybutadiene rubber | |
| Behera et al. | Insights into the preparation of vinyl polybutadiene via cobalt-based catalyst: tuning its properties by thiol-ene modification of vinyl group | |
| JP5962139B2 (en) | Method for producing diene rubber | |
| CN107286296B (en) | Application of butadiene-b-isoprene polymer | |
| US3573249A (en) | Polymerization of butadiene | |
| CN106977667B (en) | Branched polydiene branched regulator and preparation method thereof | |
| US6013736A (en) | Metal deactivator for cobalt catalyzed polymers | |
| JP2004511589A (en) | Catalyst system for high cis polybutadiene | |
| US3448095A (en) | Process and catalytic compositions for the polymerization and copolymerization of conjugated dienes and the products thereof | |
| WO2003102041A1 (en) | A two-step butadiene polymerization process for manufacturing high-cis 1,4-ploybutadiene | |
| RU2374270C1 (en) | Butadiene rubber and method of producing said rubber | |
| JP7027564B2 (en) | Vinyl cis-polybutadiene rubber and its manufacturing method | |
| RU2666724C1 (en) | Method for producing butadiene polymers or butadiene copolymers with styrene with low content of 1,2-units in butadiene part | |
| JP6269867B2 (en) | Method for producing diene rubber | |
| JPS6128684B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22762678 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 22762678 Country of ref document: EP Kind code of ref document: A1 |