CN117327219A - Preparation method of high-vinyl liquid polybutadiene rubber - Google Patents
Preparation method of high-vinyl liquid polybutadiene rubber Download PDFInfo
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- CN117327219A CN117327219A CN202311523295.6A CN202311523295A CN117327219A CN 117327219 A CN117327219 A CN 117327219A CN 202311523295 A CN202311523295 A CN 202311523295A CN 117327219 A CN117327219 A CN 117327219A
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- lithium
- liquid polybutadiene
- polybutadiene rubber
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- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 56
- 239000007788 liquid Substances 0.000 title claims abstract description 51
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 68
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 23
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical group C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 16
- 125000001979 organolithium group Chemical group 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- RFVYQWYNYFCXQL-UHFFFAOYSA-N C1=CC=CC2=CC([Li])=CC=C21 Chemical compound C1=CC=CC2=CC([Li])=CC=C21 RFVYQWYNYFCXQL-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- FYOQEFGAZKEPGG-UHFFFAOYSA-N [Li]C1=CC=C(C)C=C1 Chemical compound [Li]C1=CC=C(C)C=C1 FYOQEFGAZKEPGG-UHFFFAOYSA-N 0.000 claims description 2
- SEVZJBPKDJZGFW-UHFFFAOYSA-N [Li]C1=CC=C(CCCC)C=C1 Chemical compound [Li]C1=CC=C(CCCC)C=C1 SEVZJBPKDJZGFW-UHFFFAOYSA-N 0.000 claims description 2
- MENDLKZJBPWBEC-UHFFFAOYSA-N [Li]C1CCC(CCCC)CC1 Chemical compound [Li]C1CCC(CCCC)CC1 MENDLKZJBPWBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 claims description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 claims description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 150000002433 hydrophilic molecules Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 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)
Abstract
The invention relates to a preparation method of high vinyl liquid polybutadiene rubber, under the protection of inert gas, adding solvent oil into a polymerization reaction kettle, adding 1, 3-butadiene, a structure regulator and an organic lithium initiator, mixing, performing polymerization reaction to obtain a reaction mixed solution containing polybutadiene, and separating to obtain a liquid butadiene product; the structure regulator is 2, 2-di (2-tetrahydrofuranyl) propane. The invention adopts a structure regulator to realize the high vinyl content control of the liquid polybutadiene rubber, and the structure regulator can be removed in the solvent stripping process.
Description
Technical Field
The invention belongs to the technical field of synthetic rubber, and relates to a preparation method of high-vinyl liquid polybutadiene rubber.
Background
The liquid polybutadiene rubber is a viscous flowable polymer with a number average molecular weight of 500-10000, and can be divided into medium-vinyl liquid polybutadiene and high-vinyl liquid polybutadiene according to the content of vinyl, wherein the high-vinyl liquid polybutadiene is liquid polybutadiene with a 1, 2-structure content of more than 65% (weight percent), and the high-vinyl liquid polybutadiene is generally prepared by adopting iron-based, cobalt-based and molybdenum-based catalysts, but the preparation of the low-molecular-weight liquid polybutadiene is difficult to realize due to the existence of the catalyst system, the molecular weight distribution is wide, the catalyst contains valence-variable metals, and the stability is poor.
Chinese patent application CN 113698520A discloses a preparation method of liquid polybutadiene with high vinyl content and narrow molecular weight distribution, which is prepared by anionic polymerization, but is unfavorable for reaction regulation, especially unfavorable for realization of industrial production due to the use of more than 2 structure regulators.
Chinese patent application CN1089272a discloses a method for controlling vinyl content in butadiene homopolymer and copolymer, which also uses two regulators to control vinyl content in polybutadiene rubber, and the regulator a described in the patent is a hydrophilic compound, and is not easily soluble in organic solvent, so that it is easy to cause blocking of filter in industrial device pipeline, and the regulator a is easily adsorbed by molecular sieve of industrial device, so that the concentration of regulator is unstable, and is more unfavorable for regulation in production process.
In addition, chinese patent application CN113461837a provides a preparation method of low cis-form, high vinyl hydroxyl-terminated polybutadiene rubber, the added structure regulator in the patent is a mixed solution of tetrahydrofuran and N, N-dimethylformamide, a mixed solution of tetrahydrofuran and tetramethyl ethylenediamine, a mixed solution of tetrahydrofuran and 2, 2-bis (2-tetrahydrofuryl) propane or a mixed solution of 2, 2-bis (2-tetrahydrofuryl) propane and tetrahydrofurfuryl alcohol ethyl ether, the first patent adopts tetrahydrofuran for compounding, the boiling point of the mixed solution is similar to that of solvent oil, and the mixed solution is not easy to separate and remove from the solvent oil; secondly, the vinyl content of the polybutadiene synthesized by the method is low and only reaches 72.5 percent at most.
Disclosure of Invention
The invention aims to provide a preparation method of high vinyl liquid polybutadiene rubber, which can realize the control of the high vinyl content of the liquid polybutadiene rubber by adopting a structure regulator, and meanwhile, the adopted structure regulator can be removed in the solvent stripping process, and the solvent can be recycled after refining.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the high vinyl liquid polybutadiene rubber comprises the steps of adding solvent oil into a polymerization reaction kettle under the protection of inert gas, adding 1, 3-butadiene, a structure regulator and an organic lithium initiator, mixing, performing polymerization reaction to obtain a reaction mixed solution containing polybutadiene, and separating to obtain a liquid butadiene product, namely a target product, wherein the structure regulator is 2, 2-di (2-tetrahydrofuranyl) propane.
Further, the organolithium initiator is selected from one or a combination of several of ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyl lithium and 4-butylcyclohexyl lithium. Preferably, the organolithium initiator is n-butyllithium and/or sec-butyllithium. More preferably, the organolithium initiator is n-butyllithium.
Further, the solvent oil is an organic hydrocarbon solvent that is inert during the polymerization of 1, 3-butadiene. Furthermore, the solvent oil is C5-C8 alkane, C5-C8 cycloalkane or a mixture of C5-C8 alkane and C5-C8 cycloalkane, which provides a good reaction environment for the polymerization reaction of butadiene. It should be noted that the amount of the hydrocarbon solvent to be added in the present invention is not strictly limited, and may be determined according to the conventional amount of the hydrocarbon solvent to be added in the current process for producing a liquid butadiene rubber.
Meanwhile, the addition amount of butadiene is not particularly limited, and can be determined according to the conventional addition amount of butadiene in the existing preparation process of the liquid butadiene rubber.
Furthermore, the polymerization reaction process of butadiene is completed in an inert environment, so that the generated active polymer and oxygen in the air are prevented from reacting, and the reaction progress and the performance of reaction products are prevented from being influenced. The inert environment can be realized by introducing inert gas into the reactor, and concretely, high-purity nitrogen can be introduced into the reaction vessel to isolate air.
Furthermore, the structure regulator does not participate in actual copolymerization reaction in the preparation process of the liquid polybutadiene rubber, and is easy to separate from solvent oil when the liquid polybutadiene rubber is produced in actual industry, and the solvent oil can be recycled. According to the invention, an organic lithium and structure regulator system is adopted to initiate the anionic polymerization reaction of butadiene, and the vinyl content in the polybutadiene structure is precisely controlled by reasonably setting the component proportions in the system, especially the proportion of the structure regulator and n-butyllithium, wherein the molar ratio of the structure regulator to the organic lithium initiator is 1-5:1 in the specific implementation process, and the organic lithium initiator is calculated by lithium element. When the molar ratio of the structure regulator to the organolithium initiator is greater than 5:1, the vinyl content remains substantially unchanged.
Further, the order of addition of the components before the polymerization reaction is not particularly limited in the present invention, and may be reasonably set according to the order of addition in the conventional preparation process of the liquid polybutadiene rubber. In general, a hydrocarbon solvent (i.e., solvent oil), butadiene and a structure regulator, i.e., raw materials except for an organolithium initiator, are uniformly mixed, then the system is heated to the initiation temperature of the organolithium initiator (e.g., the initiation temperature of n-butyllithium is about 20 ℃), and finally the organolithium initiator is added to initiate the polymerization reaction of butadiene. Since the polymerization of butadiene is exothermic, the temperature of the reaction system increases as the polymerization proceeds, and in the practice of the present invention, the polymerization of butadiene can be considered to be completed by controlling the temperature of the reaction system to 5 to 40℃and the reaction time (from the addition of the organolithium initiator to the termination of the reaction) to 1 hour or more.
Further, after the polymerization reaction is completed, a terminator is further added to terminate the reaction. Specifically, the terminator may be selected from solvents such as ethanol, methanol, hydrochloric acid, water or isopropanol.
Further, the separation process specifically comprises: adding water and acid into the reaction mixture containing polybutadiene, stirring, standing for layering, and separating out water phase and oil phase, wherein the oil phase is distilled under reduced pressure to obtain the final product.
Further, the high vinyl liquid polybutadiene rubber prepared by the invention has a number average molecular weight of 500-5000, a molecular weight distribution index of 1.0-1.1 and a vinyl content of 65-95%.
Compared with the prior art, the invention has the following advantages:
(1) The structure regulator is adopted to control the vinyl content, which is beneficial to industrialized regulation and control, and the used structure regulator is easy to separate from the solvent oil, thereby being beneficial to recycling the solvent oil;
(2) The liquid polybutadiene rubber prepared by the invention not only has high vinyl content, but also has narrow molecular weight distribution and proper molecular weight and dynamic viscosity, and can be applied to the fields of electronic coating, electronic insulation, encapsulation, resin modification and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the liquid polybutadiene product obtained in example 9.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the butadiene used was 1, 3-butadiene, the structure-controlling agent used was 2, 2-bis (2-tetrahydrofuranyl) propane, DTHFP for short, and the catalyst used was n-butyllithium.
The remainder, unless specifically stated, is indicative of a conventional commercially available feedstock or conventional processing technique in the art.
Example 1
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 200mmol of 2, 2-di (2-tetrahydrofuranyl) propane is then added, the polymerization kettle is kept at 5 ℃ after stirring for 10min, and 200mmol of n-butyllithium is then added, wherein the specific raw material proportions are shown in table 1. In the polymerization reaction process, the temperature is maintained at 5 ℃ for reaction for 60min.
After the polymerization is finished, adding ethanol for reaction termination to obtain a polymerization reaction mixed solution, adding 1L of water and 2mL of sulfuric acid into the mixed solution, stirring for 20 minutes, standing for layering, separating out a water phase, then continuously washing an oil phase with 1L of water for 2 times, and carrying out reduced pressure distillation on the obtained oil phase to obtain a liquid polybutadiene product.
Example 2
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 98mmol of 2, 2-di (2-tetrahydrofuranyl) propane is then added, the polymerization kettle is kept at 10 ℃ after stirring for 10min, and 65mmol of n-butyllithium is then added, wherein the specific raw material proportions are shown in table 1. In the polymerization reaction process, the temperature is maintained at 10 ℃ for reaction for 70min.
After the polymerization is finished, ethanol is added for reaction termination to obtain a polymerization reaction mixed solution, 1L of water and 1mL of sulfuric acid are added into the mixed solution, stirring is carried out for 10 minutes, standing delamination is carried out, a water phase is separated, then the oil phase is continuously washed with 1L of water for 2 times, and the obtained oil phase is subjected to reduced pressure distillation to obtain a liquid polybutadiene product.
Example 3
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 120mmol of 2, 2-di (2-tetrahydrofuranyl) propane is then added, the polymerization kettle is kept at 10 ℃ after stirring for 10min, and 60mmol of n-butyllithium is then added, wherein the specific raw material proportions are shown in table 1. In the polymerization reaction process, the temperature is maintained at 15 ℃ for reaction for 90min.
After the polymerization is finished, ethanol is added for reaction termination, a polymerization reaction mixed solution is obtained, 1L of water and 1mL of sulfuric acid are added into the mixed solution, stirring is carried out for 20 minutes, standing delamination is carried out, a water phase is separated, and the obtained oil phase is subjected to reduced pressure distillation, so that a liquid polybutadiene product is obtained.
Example 4
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, then 100mmol of 2, 2-di (2-tetrahydrofuranyl) propane is added, the temperature of the polymerization kettle is kept at 15 ℃ after stirring for 10min, and 50mmol of n-butyllithium is added, wherein the specific raw material ratio is shown in table 1. During the polymerization reaction, the temperature was maintained at 25℃for 90 minutes.
After the polymerization is finished, adding ethanol for reaction termination to obtain a polymerization reaction mixed solution, adding 1L of water and 1mL of sulfuric acid into the mixed solution, stirring for 20 minutes, standing for layering, separating out a water phase, then continuously washing an oil phase with 1L of water for 2 times, and carrying out reduced pressure distillation on the obtained oil phase to obtain a liquid polybutadiene product.
Example 5
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 111mmol of 2, 2-di (2-tetrahydrofuranyl) propane is added, the polymerization kettle is kept at 30 ℃ after stirring for 10min, and 37mmol of n-butyllithium is added, wherein the specific raw material ratio is shown in table 1. In the polymerization reaction process, the temperature is maintained at 40 ℃ for reaction for 80min.
After the polymerization is finished, adding ethanol for reaction termination to obtain a polymerization reaction mixed solution, adding 1L of water and 1mL of sulfuric acid into the mixed solution, stirring for 20 minutes, standing for layering, separating out a water phase, then continuously washing an oil phase with 1L of water for 2 times, and carrying out reduced pressure distillation on the obtained oil phase to obtain a liquid polybutadiene product.
Example 6
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 116mmol of 2, 2-di (2-tetrahydrofuranyl) propane is then added, the polymerization kettle is kept at 30 ℃ after stirring for 10min, and 33mmol of n-butyllithium is further added, wherein the specific raw material proportions are shown in table 1. In the polymerization reaction process, the temperature is maintained at 40 ℃ for reaction for 90min.
After the polymerization is finished, adding ethanol for reaction termination to obtain a polymerization reaction mixed solution, adding 1L of water and 1mL of sulfuric acid into the mixed solution, stirring for 20 minutes, standing for layering, separating out a water phase, then continuously washing an oil phase with 1L of water for 2 times, and carrying out reduced pressure distillation on the obtained oil phase to obtain a liquid polybutadiene product.
Example 7
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 165mmol of 2, 2-di (2-tetrahydrofuranyl) propane is added, the temperature of the polymerization kettle is kept at 5 ℃ after stirring for 10min, and 33mmol of n-butyllithium is added, wherein the specific raw material ratio is shown in table 1. In the polymerization reaction process, the temperature is maintained at 5 ℃ for reaction for 90min.
After the polymerization is finished, adding ethanol for reaction termination to obtain a polymerization reaction mixed solution, adding 1L of water and 1mL of sulfuric acid into the mixed solution, stirring for 20 minutes, standing for layering, separating out a water phase, then continuously washing an oil phase with 1L of water for 2 times, and carrying out reduced pressure distillation on the obtained oil phase to obtain a liquid polybutadiene product.
Example 8
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 200mmol of 2, 2-di (2-tetrahydrofuranyl) propane is then added, the polymerization kettle is kept at 5 ℃ after stirring for 10min, and 25mmol of n-butyllithium is then added, wherein the specific raw material proportions are shown in table 1. In the polymerization reaction process, the temperature is maintained at 10 ℃ for reaction for 90min.
After the polymerization is finished, ethanol is added for reaction termination to obtain a polymerization reaction mixed solution, 1L of water and 1mL of sulfuric acid are added into the mixed solution, stirring is carried out for 20 minutes, standing delamination is carried out, a water phase is separated, then the oil phase is continuously washed with 1L of water for 2 times, and the obtained oil phase is subjected to reduced pressure distillation to obtain a liquid polybutadiene product.
Example 9
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 120mmol of 2, 2-di (2-tetrahydrofuranyl) propane is then added, the polymerization kettle is kept at 20 ℃ after stirring for 10min, and 30mmol of n-butyllithium is then added, wherein the specific raw material proportions are shown in table 1. In the polymerization reaction process, the temperature is maintained at 30 ℃ for reaction for 90min.
After the polymerization is finished, adding ethanol for reaction termination to obtain a polymerization reaction mixed solution, adding 1L of water and 1mL of sulfuric acid into the mixed solution, stirring for 20 minutes, standing for layering, separating out a water phase, then continuously washing an oil phase with 1L of water for 2 times, and carrying out reduced pressure distillation on the obtained oil phase to obtain a liquid polybutadiene product.
Example 10
9000g of cyclohexane and 100g of butadiene are added into a 2L polymerization kettle under the protection of high-purity nitrogen, 125mmol of 2, 2-di (2-tetrahydrofuranyl) propane is added, the temperature of the polymerization kettle is kept at 15 ℃ after stirring for 10min, and 25mmol of n-butyllithium is added, wherein the specific raw material ratio is shown in table 1. In the polymerization reaction process, the temperature is maintained at 20 ℃ for reaction for 90min.
After the polymerization is finished, adding ethanol for reaction termination to obtain a polymerization reaction mixed solution, adding 1L of water and 1mL of sulfuric acid into the mixed solution, stirring for 20 minutes, standing for layering, separating out a water phase, then continuously washing an oil phase with 1L of water for 2 times, and carrying out reduced pressure distillation on the obtained oil phase to obtain a liquid polybutadiene product.
Comparative example 1
Liquid polybutadiene was prepared by the same procedures as in example 4, except that the amount of 2, 2-bis (2-tetrahydrofuranyl) propane as a structure regulator in the step was adjusted to 25mmol.
Comparative example 2
Liquid polybutadiene was prepared by the same procedures as in example 6, except that the temperature of the polymerization in the step was adjusted to 70℃to conduct the reaction.
Comparative example 3
Liquid polybutadiene was prepared by the same procedures as in example 10, except that the amount of 125mmol of the structure-adjusting agent 2, 2-bis (2-tetrahydrofuranyl) propane polymerized in the step was adjusted to 150mmol.
Comparative example 4
Liquid polybutadiene was prepared by the same procedures as in example 5, except that the structure-adjusting agent polymerized in the step was increased by one kind of tetrahydrofuran, and the addition amount of 2, 2-bis (2-tetrahydrofuryl) propane was reduced to 56mmol, and the addition amount of tetrahydrofuran was 56mmol.
FIG. 1 is a nuclear magnetic resonance spectrum of the liquid polybutadiene product obtained in example 9.
The above examples 1-9 and comparative examples 1-3 were tested and the performance data obtained are as follows.
TABLE 1 raw material ratios and reaction conditions
Table 2 microstructure test structures of samples of various examples
Example 4 reduced the amount of structure modifier added compared to comparative example 1, the molar ratio of structure modifier to n-butyllithium was calculated from 2:1 to 0.5:1, vinyl is reduced from 80.2% to 63.4%; example 6 compared to comparative example 2, the reaction temperature was increased from 40 ℃ to 70 ℃ and the vinyl group was reduced from 75.9% to 61.2%; in example 10, compared with comparative example 3, the addition amount of the regulator was increased from 125mmol to 150mmol, and the ether lithium ratio was increased from 5:1 to 6:1, the vinyl group of which is substantially unchanged. From the cost point of view, the preferred conditions for the structure modifier and n-butyllithium are up to 5:1, while the temperature decrease is favorable for the rise of vinyl groups, the temperature is preferably 5-40 ℃ in view of energy saving, the temperature is too low, and the energy consumption is excessive.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. A preparation method of high vinyl liquid polybutadiene rubber is characterized in that solvent oil is added into a polymerization reaction kettle under the protection of inert gas, 1, 3-butadiene, a structure regulator and an organic lithium initiator are added, the mixture is mixed and polymerized to obtain a reaction mixed solution containing polybutadiene, and a liquid butadiene product is obtained through separation, namely a target product, wherein the structure regulator is 2, 2-di (2-tetrahydrofuranyl) propane.
2. The method for preparing high vinyl liquid polybutadiene rubber according to claim 1, wherein said organolithium initiator is selected from one or a combination of several of ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyl lithium and 4-butylcyclohexyl lithium.
3. The method for preparing high vinyl liquid polybutadiene rubber according to claim 1, wherein said organolithium initiator is n-butyllithium and/or sec-butyllithium.
4. The method for producing a high vinyl liquid polybutadiene rubber according to claim 1, wherein said solvent oil is an organic hydrocarbon solvent inert during the polymerization of 1, 3-butadiene.
5. The method for producing a high vinyl liquid polybutadiene rubber according to claim 4, wherein said solvent oil is a C5-C8 alkane, or a C5-C8 cycloalkane, or a mixture of a C5-C8 alkane and a C5-C8 cycloalkane.
6. The method for preparing high-vinyl liquid polybutadiene rubber according to claim 1, wherein the molar ratio of the structure regulator to lithium element in the organolithium initiator is 1-5:1.
7. The method for preparing high vinyl liquid polybutadiene rubber according to claim 1, wherein the temperature of the reaction system is controlled to be 5-40 ℃ and the reaction time is more than 1h in the polymerization reaction process.
8. The process for producing a high vinyl liquid polybutadiene rubber according to claim 1, wherein a terminator is further added to terminate the reaction after the completion of the polymerization reaction.
9. The method for preparing the high-vinyl liquid polybutadiene rubber according to claim 1, wherein the separation process is specifically as follows: adding water and acid into the reaction mixture containing polybutadiene, stirring, standing for layering, and separating out water phase and oil phase, wherein the oil phase is distilled under reduced pressure to obtain the final product.
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