CN115340618A - Preparation method of colorless transparent liquid hydrocarbon polymer - Google Patents
Preparation method of colorless transparent liquid hydrocarbon polymer Download PDFInfo
- Publication number
- CN115340618A CN115340618A CN202211180230.1A CN202211180230A CN115340618A CN 115340618 A CN115340618 A CN 115340618A CN 202211180230 A CN202211180230 A CN 202211180230A CN 115340618 A CN115340618 A CN 115340618A
- Authority
- CN
- China
- Prior art keywords
- organic solvent
- solvent
- monomer
- initiator
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 93
- 239000007788 liquid Substances 0.000 title claims abstract description 66
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 34
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 239000002798 polar solvent Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims abstract description 16
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 14
- -1 alkenyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000003878 thermal aging Methods 0.000 abstract 1
- 239000003292 glue Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000032683 aging Effects 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000010057 rubber processing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical group 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000011414 polymer cement Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004383 yellowing Methods 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers 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
- C08F236/04—Copolymers 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
- C08F236/10—Copolymers 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 with vinyl-aromatic monomers
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
Abstract
The invention provides a preparation method of a colorless transparent liquid hydrocarbon polymer. The preparation method comprises the following steps: a) Under the conditions of protective atmosphere and initiator existence, carrying out anionic polymerization reaction on the monomer in an organic solvent A to obtain a polymer solution; b) Mixing the polymer solution with a terminator to terminate the reaction, then sequentially adding an organic solvent B and activated carbon, then carrying out solid-liquid separation to remove solids, and drying the obtained separation liquid to obtain a colorless transparent liquid hydrocarbon polymer; wherein: the initiator is an organic lithium compound; the monomer is a conjugated diene monomer and/or an alkenyl aromatic hydrocarbon monomer; the organic solvent A is an aprotic polar solvent or a mixed solvent of the aprotic polar solvent and the nonpolar solvent; the terminator is water and/or alcohol; the organic solvent B is a nonpolar organic solvent. The liquid hydrocarbon polymer prepared by the method has high transparency, high thermal aging resistance and low initiator residue.
Description
Technical Field
The invention relates to the field of chemical production, in particular to a preparation method of a colorless transparent liquid hydrocarbon polymer.
Background
The liquid hydrocarbon polymer is a polymer which is composed of only two elements of carbon and hydrogen and is viscous liquid at normal temperature. Compared with solid hydrocarbon polymers, the polymer has a lower number average molecular weight, generally 500 to 20000, so that the polymer has fluidity at normal temperature and is endowed with excellent processing performance. The liquid hydrocarbon polymer is mainly applied to the fields of rubber processing aids, adhesives, coatings, photocuring resins, electronic communication and the like. With the increasing 5G technical requirement, the products are required to have very low dielectric constant, very good water and oil resistance, flexibility and machinability, so that the preparation method of the liquid hydrocarbon polymer meeting the requirements is also important.
The preparation method of the liquid hydrocarbon polymer mainly comprises coordination polymerization, free radical polymerization and anionic polymerization. The molecular weight of the product can be controlled by anionic polymerization, the molecular weight distribution of the obtained product is narrow, but the reaction process is active polymerization, an organic metal compound is used as an initiator, the reaction is terminated after the reaction is finished, the cost of terminating the reaction by water or alcohol is generally low, but glue solutions obtained by different treatment methods have different appearances and performances, such as yellowing of the product, residual metal catalysts or addition of antioxidants and the like, so that the product quality is not high, and the application of the glue solutions in high-end markets such as copper clad laminates or printed circuits is influenced, therefore, how to terminate the reaction to remove the metal compounds in the polymer solution is very important.
Patent CN103087364B discloses a liquid rubber and its preparation method, in which organic lithium compound is used as initiator, the solution obtained by polymerization is contacted with water and/or C1-C6 alcohol and gas containing 10-100 vol% of carbon dioxide, and the contacted product is heated and dried and/or vacuum dried in the presence of anti-aging agent and under stirring condition, so as to obtain colorless and transparent liquid rubber, but the patent does not remove organic metal compound in the product, so that the application is limited. Patents CN102549023A and CN107001490B disclose a method for producing liquid diene rubber, and the disclosed refining method is water washing and acid washing or alcohol washing, which has poor economic benefit, difficult solvent recovery, environmental pollution and is not beneficial to industrial production.
Patent CN102702408B discloses a preparation method of diene liquid rubber, which adopts a linear organic dibasic acid as a reaction terminator in typical anionic polymerization to ensure that the appearance of the polydiene hydrocarbon liquid rubber prepared by the invention is colorless and transparent, and the appearance of the liquid rubber is not obviously changed after the polydiene hydrocarbon liquid rubber is aged for a certain time at a certain temperature. The liquid rubber prepared by the method contains dibasic acid lithium salt generated in termination, a small amount of dibasic acid and an anti-aging agent, so that the product is impure and is limited in application.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a colorless transparent liquid hydrocarbon polymer. The liquid hydrocarbon polymer prepared by the preparation method has high transparency, the glue solution can still be in a colorless transparent state after aging at a certain temperature without adding an antioxidant, and the obtained liquid hydrocarbon polymer has low initiator residue and pure product.
The invention provides a preparation method of a colorless transparent liquid hydrocarbon polymer, which comprises the following steps:
a) Under the conditions of protective atmosphere and initiator existence, carrying out anionic polymerization reaction on the monomer in an organic solvent A to obtain a polymer solution;
b) Mixing the polymer solution with a terminator to terminate the reaction, then adding an organic solvent B and activated carbon, then carrying out solid-liquid separation to remove solids, and drying the obtained separation liquid to obtain a colorless transparent liquid hydrocarbon polymer;
wherein:
the initiator is an organic lithium compound;
the monomer is a conjugated diene monomer and/or an alkenyl aromatic hydrocarbon monomer;
the organic solvent A is an aprotic polar solvent or a mixed solvent of the aprotic polar solvent and an apolar solvent;
the terminator is water and/or alcohol;
the organic solvent B is a nonpolar organic solvent.
Preferably, the concentration of the initiator in the organic solvent A is 0.005-4 mol/L;
the mol ratio of the terminating agent to the initiating agent is (5.0-8.0) to 1.
Preferably, the organic solvent B is selected from one or more of cyclohexane, normal hexane, normal pentane, normal heptane, toluene, xylene and raffinate oil;
the dosage of the organic solvent B is 10-50% of the volume of the polymer solution.
Preferably, the conjugated diene monomer is butadiene and/or isoprene;
the alkenyl aromatic hydrocarbon monomer is styrene and/or alkyl-substituted styrene.
Preferably, in the organic solvent a:
the nonpolar solvent is selected from one or more of cyclohexane, n-hexane, n-pentane, n-heptane, toluene, xylene and raffinate oil;
the aprotic polar solvent is one or more selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and N, N, N, N-tetramethyl ethylenediamine;
the mass fraction of the monomer in the organic solvent A is 8-60%.
Preferably, the temperature of the anionic polymerization reaction is-40 ℃ to 70 ℃ and the time is 2min to 5h.
Preferably, in the mixed solvent, the volume ratio of the nonpolar solvent to the aprotic polar solvent is (0.1-40) to 1;
the initiator is selected from one or more of methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, iso-butyllithium and naphthalene lithium.
Preferably, the step b) specifically comprises:
adding a terminator into the polymer solution, stirring to terminate the reaction, then adding an organic solvent B, fully stirring, then adding activated carbon, stirring, then carrying out solid-liquid separation to remove solids, and drying the obtained separation liquid to obtain the colorless transparent liquid hydrocarbon polymer.
Preferably, the solid-liquid separation is centrifugation or filtration;
the drying is vacuum drying;
the drying temperature is 50-120 ℃ and the drying time is 1-5 h.
Preferably, the temperature for terminating the reaction is-40 ℃ to 60 ℃ and the time is 5 to 30min.
The preparation method provided by the invention is characterized in that conjugated diene and/or alkenyl arene is used as a monomer, an organic lithium compound is used as an initiator, an aprotic polar solvent is used as a solvent or a mixed solvent of the aprotic polar solvent and the nonpolar solvent is used as a solvent to carry out active polymerization, quantitative water and/or alcohol is used for stopping reaction, then an organic solvent B and active carbon are sequentially added, solid is removed by solid-liquid separation, and devolatilization and drying are carried out to obtain the liquid hydrocarbon polymer with high transparency, the glue solution is still in a colorless transparent state after aging at a certain temperature without adding antioxidants, the liquid hydrocarbon polymer shows high heat resistance and stability, and the amount of initiator residues in a tested product is 5-100 ppm and is relatively pure. And the obtained product has the number average molecular weight of 500-10000 and narrow molecular weight distribution of 1.01-1.40, and can be used in the fields of rubber processing aids, adhesives, coatings, photocuring resins, electronic communication and the like.
Detailed Description
The invention provides a preparation method of a colorless transparent liquid hydrocarbon polymer, which comprises the following steps:
a) Under the conditions of protective atmosphere and initiator existence, carrying out anionic polymerization reaction on the monomer in an organic solvent A to obtain a polymer solution;
b) Mixing the polymer solution with a terminator to terminate the reaction, then adding an organic solvent B and active carbon, performing solid-liquid separation to remove solids, and drying the obtained separation liquid to obtain a colorless transparent liquid hydrocarbon polymer;
wherein:
the initiator is an organic lithium compound;
the monomer is a conjugated diene monomer and/or an alkenyl aromatic hydrocarbon monomer;
the organic solvent A is an aprotic polar solvent or a mixed solvent of the aprotic polar solvent and the nonpolar solvent;
the terminator is water and/or alcohol;
the organic solvent B is a nonpolar organic solvent.
The preparation method provided by the invention is characterized in that conjugated diene and/or alkenyl arene is used as a monomer, an organic lithium compound is used as an initiator, an aprotic polar solvent is used as a solvent or a mixed solvent of the aprotic polar solvent and the nonpolar solvent is used as a solvent to carry out active polymerization, quantitative water and/or alcohol is used for stopping reaction, then an organic solvent B and active carbon are sequentially added, solid is removed by solid-liquid separation, and devolatilization and drying are carried out to obtain the liquid hydrocarbon polymer with high transparency, the glue solution is still in a colorless transparent state after aging at a certain temperature without adding antioxidants, the liquid hydrocarbon polymer shows high heat resistance and stability, and the amount of initiator residues in a tested product is 5-100 ppm and is relatively pure. And the obtained product has the number average molecular weight of 500-10000 and narrow molecular weight distribution of 1.01-1.40, and can be used in the fields of rubber processing aids, adhesives, coatings, photocuring resins, electronic communication and the like.
[ with respect to step a ]:
a) Under the condition of protective atmosphere and initiator, the monomer is processed with anion polymerization reaction in organic solvent A to obtain polymer solution.
In the present invention, the kind of protective gas providing the protective atmosphere is not particularly limited, and may be a conventional protective gas well known to those skilled in the art, such as nitrogen, helium, argon, or the like. The invention forms an anhydrous and anaerobic environment through protective atmosphere, so that the subsequent reaction is carried out under the anhydrous and anaerobic condition.
In the present invention, the initiator is an organolithium compound, preferably one or more of methyllithium, n-butyllithium (i.e., n-BuLi), sec-butyllithium, tert-butyllithium, iso-butyllithium, and naphthyllithium.
In the present invention, the monomer is a conjugated diene monomer and/or an alkenyl aromatic hydrocarbon monomer. Wherein the conjugated diene monomer is preferably butadiene and/or isoprene. The alkenyl aromatic hydrocarbon monomer is styrene and/or alkyl-substituted styrene.
In the invention, the organic solvent A is an aprotic polar solvent or a mixed solvent of the aprotic polar solvent and a nonpolar solvent. Wherein, the aprotic polar solvent is preferably one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and N, N, N, N-tetramethyl ethylenediamine; the non-polar solvent is preferably one or more of cyclohexane, n-hexane, n-pentane, n-heptane, toluene, xylene, and raffinate oil. When the organic solvent A is a mixed solvent of an aprotic polar solvent and a nonpolar solvent, the volume ratio of the nonpolar solvent to the aprotic polar solvent is preferably (0.1 to 40) to 1, and in some embodiments of the present invention is 1.5: 1, 2.25: 1, 20: 1, or 40: 1.
In the present invention, the initiator, the monomer and the organic solvent A constitute the material system of step a). The concentration of the initiator in the organic solvent A is preferably 0.005 to 4mol/L, and specifically may be 0.005mol/L, 0.10mol/L, 0.20mol/L, 0.30mol/L, 0.40mol/L, 0.50mol/L, 1mol/L, 2mol/L, 3mol/L, or 4mol/L. The mass fraction of the monomer in the organic solvent a is preferably 8% to 60%, and specifically may be 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%.
In the present invention, the step a) specifically includes: vacuumizing a reaction bottle, filling protective gas for gas replacement to form protective atmosphere in the reaction bottle, adding an organic solvent A and an initiator, stirring and mixing uniformly, adding a monomer, and carrying out anionic polymerization to obtain a polymer solution.
In the present invention, the temperature of the anionic polymerization reaction is preferably-40 ℃ to 70 ℃, and specifically may be-40 ℃, -30 ℃, -20 ℃, -10 ℃, 0 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃. The time of the anionic polymerization reaction is preferably 2min to 5h, and specifically may be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h and 5h. After the above anionic polymerization reaction, a polymer solution is obtained.
[ with respect to step b ]:
b) And mixing the polymer solution with a terminator to terminate the reaction, then adding an organic solvent B and activated carbon, performing solid-liquid separation to remove solids, and drying the obtained separation liquid to obtain the colorless transparent liquid hydrocarbon polymer.
In the invention, the terminator is water and/or alcohol. Wherein the alcohol is preferably one or more of methanol, ethanol, isopropanol and n-propanol. In the present invention, the molar ratio of the terminator to the initiator is (5.0-8.0) to 1, specifically 5.0: 1, 5.2: 1, 5.5: 1, 5.8: 1, 6.0: 1, 6.2: 1, 6.5: 1, 6.8: 1, 7.0: 1, 7.2: 1, 7.5: 1, 7.8: 1, 8.0: 1, more preferably (5.5-7.5) to 1. In the present invention, it is preferable to terminate the reaction by stirring after the addition of the terminator. The temperature of the above operation (i.e., the temperature for terminating the reaction) is preferably-40 ℃ to 60 ℃, specifically-40 ℃, minus 30 ℃, minus 20 ℃, minus 10 ℃, 0 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, and more preferably the same as the temperature of the anionic polymerization reaction, i.e., after the reaction of step a) is completed, the temperature is kept at the same, and the terminator is added and stirred to terminate the reaction. The stirring time is preferably 5-30 min, and specifically may be 5min, 10min, 15min, 20min, 25min, and 30min. In the present invention, the above-mentioned terminator is added in a controlled amount to terminate the anionic polymerization reaction of step a).
In the present invention, after the above treatment, the organic solvent B is added. In the invention, the organic solvent B is a non-polar organic solvent, preferably one or more of cyclohexane, n-hexane, n-pentane, n-heptane, toluene, xylene and raffinate oil. In the invention, the dosage of the organic solvent B is 10-50% of the volume of the polymer solution, namely the volume ratio of the organic solvent B to the polymer solution is (10-50) to 100, and specifically can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% and 50%. In the invention, the organic solvent B is added and stirred; the stirring time is preferably 3-30 min, and specifically may be 5min, 10min, 15min, 20min, 25min, and 30min. In the invention, the letters A and B in the organic solvent A and the organic solvent B do not have special meanings, are not special limits on the types of the organic solvents, and are only used for indicating that the organic solvents are used twice in sequence and are respectively used in different steps.
In the invention, after the treatment, activated carbon is added, wherein the using amount of the activated carbon is 1-5% of the mass of the polymer solution, namely the mass ratio of the activated carbon to the polymer solution is (1-5) to 100, and specifically can be 1%, 2%, 3%, 4% and 5%. In the invention, activated carbon is added and then stirred; the stirring time is preferably 10-60 min, and specifically may be 10min, 20min, 30min, 40min, 50min, 60min.
In the present invention, after the above treatment, solid-liquid separation is performed to remove solids in the solution. The solid-liquid separation mode is not particularly limited in the invention, and the solid-liquid separation mode is a conventional solid-liquid separation mode in the field, such as centrifugal separation or filtration. Solid is removed through solid-liquid separation to obtain separated liquid.
In the present invention, the separated liquid is dried. In the present invention, the drying is preferably vacuum drying. In the present invention, the drying temperature is preferably 50 to 120 ℃, and specifically 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ and 120 ℃. In the present invention, the drying time is preferably 1 to 5 hours, and specifically may be 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours. In the present invention, the degree of vacuum for drying is preferably-60 to-101.325 kPa. After the above treatment, a colorless transparent liquid hydrocarbon polymer is obtained.
The colorless transparent liquid hydrocarbon polymer prepared by the invention has the number average molecular weight of 500-10000 and the molecular weight distribution of 1.01-1.40.
The preparation method provided by the invention comprises the steps of taking conjugated diene and/or alkenyl aromatic hydrocarbon as monomers, taking an organic lithium compound as an initiator, taking an aprotic polar solvent or a mixture of the aprotic polar solvent and the nonpolar solvent as a solvent for active polymerization, stopping reaction by using quantitative water and/or alcohol, sequentially adding the nonpolar solvent and active carbon for stirring, separating solids, devolatilizing and drying to obtain the liquid hydrocarbon polymer with high transparency, wherein a glue solution is still in a colorless transparent state after aging at a certain temperature without adding antioxidants, the liquid hydrocarbon polymer shows high heat-resistant stability, and the amount of initiator residues in a tested product is 5-100 ppm and is relatively pure. And the obtained product has the number average molecular weight of 500-10000 and the molecular weight distribution of 1.01-1.40, and can be used in the fields of rubber processing aids, adhesives, coatings, photocuring resins, electronic communication and the like.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples, the starting material used was a commercially available product, and the n-butyllithium starting material itself was a liquid having a concentration of 2.5mol/L, unless otherwise specified.
Example 1
S1, vacuumizing a system, filling nitrogen for three times for replacement to remove water and oxygen, maintaining a reaction bottle in a nitrogen atmosphere, sequentially adding 160mL of dimethylbenzene and 4mL of tetrahydrofuran as an organic solvent A, adding 40mL of n-butyl lithium (the concentration in the organic solvent A is 0.5 mol/L), and fully stirring and uniformly mixing; then, 200g of butadiene monomer was added thereto, and the mixture was reacted in a cold bath at 15 ℃ for 4 hours to obtain a polymer solution.
S2, adding a certain amount of methanol into the polymer solution, wherein the molar ratio of the methanol to the n-butyllithium is about 5.5: 1, and fully stirring for 10min to obtain a water white solution; then adding 80mL of xylene (which is 19% of the volume of the polymer solution), and stirring for 5min; then, 7.4g of activated carbon (2% by mass of the polymer solution) was added and stirred for 30min; and then filtering, drying the filtrate for 1 hour at 90 ℃ and-0.1 MPa to obtain a low-molecular-weight polybutadiene glue solution which is a colorless transparent glue solution.
Comparative example 1
The procedure is as in example 1, except that the amount of methanol is increased in step S2, no xylene is added, no filtration is performed, etc. The method comprises the following specific steps:
adding a certain amount of methanol into the polymer solution, wherein the molar ratio of the methanol to the n-butyllithium is about 50: 1, fully stirring for 10min, separating out polymer glue solution, washing for 3 times, and drying for 1h at 90 ℃ and-0.1 MPa to obtain the polymer glue solution, wherein the glue solution is yellow.
Example 2
S1, vacuumizing a system, filling nitrogen for three times for replacement to remove water and oxygen, maintaining a reaction bottle in a nitrogen atmosphere, sequentially adding 80mL of n-hexane and 4mL of tetrahydrofuran as an organic solvent A, adding 20mL of n-butyllithium (the concentration in the organic solvent A is 0.3 mol/L), and fully stirring and uniformly mixing; then, 100g of butadiene monomer was added thereto, and the mixture was reacted in a cold bath at 10 ℃ for 3 hours to obtain a polymer solution.
S2, adding a certain amount of ethanol into the polymer solution, wherein the molar ratio of the ethanol to the n-butyllithium is about 6: 1, and fully stirring for 15min to obtain a water white solution; then adding 50mL of n-hexane (23% of the volume of the polymer solution), and stirring for 5min; then, 5g of activated carbon (3% by mass of the polymer solution) was added and stirred for 50min; and then filtering, and drying the filtrate for 1h at 80 ℃ and-95 KPa to obtain a low-molecular-weight polybutadiene glue solution which is a colorless transparent glue solution.
Comparative example 2
Example 2 was carried out, except that the ethanol terminator in step S2 was replaced by a solution of adipic acid in tetrahydrofuran (1.6 mol/L), in which the molar ratio of adipic acid to n-butyllithium was about 0.6: 1. The resulting polymer cement was slightly cloudy.
Example 3
S1, vacuumizing a system, filling nitrogen for three times for replacement to remove water and oxygen, maintaining a reaction bottle in a nitrogen atmosphere, adding 150mL of tetrahydrofuran serving as an organic solvent A, adding 20mL of n-butyl lithium (the concentration of the n-butyl lithium in the organic solvent A is 0.29 mol/L), and fully stirring and uniformly mixing; then, 150g of butadiene monomer was added thereto, and the mixture was reacted in a cold bath at-40 ℃ for 1.5 hours to obtain a polymer solution.
S2, adding a certain amount of water into the polymer solution, wherein the molar ratio of the water to the n-butyllithium is about 8: 1, and fully stirring for 15min to obtain a water white solution; then adding 100mL of n-heptane (30% of the volume of the polymer solution), and stirring for 10min; then, 15g of activated carbon (5% of the mass of the polymer solution) is added and stirred for 20min; then filtering, drying the filtrate for 1.5h at 90 ℃ and-0.1 MPa to obtain a low molecular weight polybutadiene glue solution which is a colorless transparent glue solution.
Comparative example 3
The method is implemented according to embodiment 3, except that step S2 is adjusted as follows:
adding a certain amount of water into the polymer solution, wherein the molar ratio of the water to the n-butyllithium is about 2.0: 1, fully stirring for 15min, introducing carbon dioxide gas (with the purity of 99 wt%) for 10min, continuously stirring for 10min, and drying at 90 ℃ and-0.1 MPa for 1.5h to obtain a polymer glue solution which is yellowish.
Example 4
S1, vacuumizing the system, filling nitrogen for three times to remove water and oxygen, maintaining a reaction bottle in a nitrogen atmosphere, sequentially adding 36mL of cyclohexane and 16mL of diethylene glycol dimethyl ether as an organic solvent A, adding 8mL of n-butyl lithium (the concentration in the organic solvent A is 0.33 mol/L), and fully stirring and uniformly mixing; then, 60g of butadiene monomer was added thereto, and the mixture was reacted in a cold bath at 10 ℃ for 1 hour to obtain a polymer solution.
S2, adding a certain amount of water into the polymer solution, wherein the molar ratio of the water to the n-butyllithium is about 7: 1, fully stirring for 10min, and then adding 0.3mL of methanol to obtain a water white solution; then adding 30mL of cyclohexane (which is 24% of the volume of the polymer solution), and stirring for 10min; then, 3.3g of activated carbon (3% of the mass of the polymer solution) is added and stirred for 20min; and then, centrifugally separating, and drying the separated solution at 95 ℃ and under the pressure of-0.1 MPa for 1 hour to obtain a low-molecular-weight polybutadiene glue solution which is a colorless transparent glue solution.
Comparative example 4
The method is implemented according to embodiment 4, except that step S2 is adjusted as follows:
the polymer solution is directly washed with 200mL of pure water for 2 times, then washed with 200mL of hydrochloric acid solution (with the concentration of 0.2%) once, then washed with 300mL of pure water for 3 times, an organic layer is separated, 10g of anhydrous magnesium sulfate is added, standing is carried out for 30min, then filtering is carried out, and the filtrate is dried for 1h at 95 ℃ and-0.1 MPa to obtain polymer glue solution which is colorless and transparent.
Example 5
S1, vacuumizing a system, filling nitrogen for three times for replacement to remove water and oxygen, maintaining a reaction bottle in a nitrogen atmosphere, sequentially adding 60mL of n-hexane and 40mL of ethylene glycol dimethyl ether as an organic solvent A, adding 5mL of n-butyllithium (the concentration in the organic solvent A is 0.12 mol/L), and fully and uniformly stirring; then, 40g of butadiene monomer and 10g of styrene monomer were added thereto, and the mixture was reacted in a cold bath at-10 ℃ for 1 hour to obtain a polymer solution.
S2, adding a certain amount of isopropanol into the polymer solution, wherein the molar ratio of the isopropanol to the n-butyl lithium is about 6: 1, and fully stirring for 10min to obtain a water white solution; then adding 30mL of n-hexane (19% of the volume of the polymer solution), and stirring for 10min; then, 5g of activated carbon (4% by mass of the polymer solution) was added and stirred for 10min; and then, centrifugally separating, and drying the separated solution for 1 hour at 95 ℃ and-0.1 MPa to obtain a low-molecular-weight polymer glue solution which is a colorless transparent glue solution.
Comparative example 5
The method is implemented according to embodiment 5, except that step S2 is adjusted as follows:
adding a certain amount of isopropanol into the polymer solution, wherein the molar ratio of the isopropanol to the n-butyllithium is about 1.5: 1, fully stirring for 10min, adding 2, 6-di-tert-butyl-p-methylphenol serving as an antioxidant (accounting for 0.1 percent of the mass of the polymer), and drying for 1h at 95 ℃ and under-0.1 MPa to obtain a polymer glue solution, wherein the glue solution is yellow.
Example 6: product testing
The content of Li contained in the polymer dope obtained after drying was measured using an ICP emission spectrometer for quantitative analysis of inorganic elements, and the analysis results are shown in table 1. Meanwhile, the product appearance statistics are in table 1. In addition, the product was tested for high temperature aging stability, specifically, the glue solution product was placed in an oven at 95 ℃ for 5 hours, after which the appearance of the glue solution was observed, and the results are shown in table 1.
Table 1: test effect of product
| Residual amount of catalyst, ppm | Initial appearance | Appearance after high temperature aging | |
| Example 1 | 93 | Colorless and transparent | Colorless and transparent |
| Example 2 | 67 | Colorless and transparent | Colorless and transparent |
| Example 3 | 36 | Colorless and transparent | Colorless and transparent |
| Example 4 | 83 | Colorless and transparent | Colorless and transparent |
| Example 5 | 25 | Colorless and transparent | Colorless and transparent |
| Comparative example 1 | 387 | Yellow colour | Yellow colour |
| Comparative example 2 | 860 | Turbidity | Yellow turbidity |
| Comparative example 3 | 949 | Light yellow | Yellow colour |
| Comparative example 4 | 173 | Colorless and transparent | Light yellow |
| Comparative example 5 | 985 | Yellow colour | Yellow colour |
As can be seen from the test results in Table 1, the liquid hydrocarbon polymer prepared by the invention is a colorless transparent product, the initiator residue in the product is remarkably reduced (less than 100 ppm), and the glue solution still keeps a colorless transparent state after being aged at high temperature for a certain time without adding an antioxidant, thus showing high heat-resistant stability. Compared with the effect of the comparative example 1, the invention proves that the transparency and the aging-resistant thermal stability of the polymer glue solution can be effectively improved and the impurity residue in the product can be reduced by controlling a certain amount of the terminating agent and adding the organic solvent B and the activated carbon and then separating the solid. The comparison with the effect of the comparative example 2 proves that the invention can effectively improve the transparency and the aging-resistant thermal stability of the polymer glue solution and reduce the impurity residue in the product by adopting the specific terminator. Compared with the effect of the comparative example 3, the method proves that after the reaction is terminated, the organic solvent B and the activated carbon are added, and then the solid is separated, so that the transparency and the aging-resistant thermal stability of the polymer glue solution can be effectively improved, and the impurity residue in the product is reduced. Compared with the effect of the comparative example 4, the introduction of the terminating agent, the addition of the organic solvent B and the addition of the activated carbon, and the separation of the solid can effectively improve the transparency and the aging-resistant thermal stability of the polymer glue solution and reduce the impurity residue in the product. Compared with the effect of the comparative example 5, the invention proves that after the reaction is terminated, the organic solvent B and the activated carbon are added, and then the solid is separated, so that the transparency and the aging-resistant thermal stability of the polymer glue solution can be effectively improved, the impurity residue in the product is reduced, and the aging-resistant stability can be even better improved compared with the product added with the antioxidant.
The foregoing examples are included merely to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A preparation method of a colorless transparent liquid hydrocarbon polymer is characterized by comprising the following steps:
a) Under the conditions of protective atmosphere and initiator existence, carrying out anionic polymerization reaction on the monomer in an organic solvent A to obtain a polymer solution;
b) Mixing the polymer solution with a terminator to terminate the reaction, then adding an organic solvent B and activated carbon, then carrying out solid-liquid separation to remove solids, and drying the obtained separation liquid to obtain a colorless transparent liquid hydrocarbon polymer;
wherein:
the initiator is an organic lithium compound;
the monomer is a conjugated diene monomer and/or an alkenyl aromatic hydrocarbon monomer;
the organic solvent A is an aprotic polar solvent or a mixed solvent of the aprotic polar solvent and an aprotic polar solvent;
the terminator is water and/or alcohol;
the organic solvent B is a nonpolar organic solvent.
2. The method according to claim 1, wherein the concentration of the initiator in the organic solvent A is 0.005 to 4mol/L;
the mol ratio of the terminating agent to the initiator is (5.0-8.0) to 1.
3. The method according to claim 1, wherein the organic solvent B is one or more selected from cyclohexane, n-hexane, n-pentane, n-heptane, toluene, xylene, and raffinate oil;
the dosage of the organic solvent B is 10-50% of the volume of the polymer solution.
4. The process according to claim 1, wherein said conjugated diene monomer is butadiene and/or isoprene;
the alkenyl aromatic hydrocarbon monomer is styrene and/or alkyl substituted styrene.
5. The method according to claim 1, wherein in the organic solvent A:
the nonpolar solvent is selected from one or more of cyclohexane, n-hexane, n-pentane, n-heptane, toluene, xylene and raffinate oil;
the aprotic polar solvent is one or more selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and N, N, N, N-tetramethyl ethylenediamine;
the mass fraction of the monomer in the organic solvent A is 8-60%.
6. The preparation method according to claim 1, wherein the temperature of the anionic polymerization reaction is-40 ℃ to 70 ℃ and the time is 2min to 5h.
7. The preparation method according to claim 1, wherein the volume ratio of the nonpolar solvent to the aprotic polar solvent in the mixed solvent is (0.1-40) to 1;
the initiator is selected from one or more of methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, iso-butyllithium and naphthalene lithium.
8. The method according to claim 1, wherein step b) comprises in particular:
adding a terminator into the polymer solution, stirring to terminate the reaction, then adding an organic solvent B, fully stirring, then adding activated carbon, stirring, then carrying out solid-liquid separation to remove solids, and drying the obtained separation liquid to obtain the colorless transparent liquid hydrocarbon polymer.
9. The production method according to claim 1 or 8, characterized in that the solid-liquid separation is centrifugation or filtration;
the drying is vacuum drying;
the drying temperature is 50-120 ℃ and the drying time is 1-5 h.
10. The method according to claim 1 or 8, wherein the reaction is terminated at a temperature of-40 ℃ to 60 ℃ for 5 to 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211180230.1A CN115340618A (en) | 2022-09-27 | 2022-09-27 | Preparation method of colorless transparent liquid hydrocarbon polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211180230.1A CN115340618A (en) | 2022-09-27 | 2022-09-27 | Preparation method of colorless transparent liquid hydrocarbon polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115340618A true CN115340618A (en) | 2022-11-15 |
Family
ID=83956403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211180230.1A Pending CN115340618A (en) | 2022-09-27 | 2022-09-27 | Preparation method of colorless transparent liquid hydrocarbon polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115340618A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490105A (en) * | 2006-07-19 | 2009-07-22 | 埃克森美孚化学专利公司 | Process to produce polyolefins using metallocene catalysts |
| CN102702408A (en) * | 2012-06-04 | 2012-10-03 | 辽宁和运合成橡胶研究院有限公司 | Preparation method of diene-based liquid rubber |
| CN103087364A (en) * | 2011-11-04 | 2013-05-08 | 中国石油化工股份有限公司 | Liquid rubber and preparation method thereof |
| CN107805288A (en) * | 2017-11-06 | 2018-03-16 | 山东玉皇化工有限公司 | A kind of preparation method of low-molecular-weight liquid polydiene |
-
2022
- 2022-09-27 CN CN202211180230.1A patent/CN115340618A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490105A (en) * | 2006-07-19 | 2009-07-22 | 埃克森美孚化学专利公司 | Process to produce polyolefins using metallocene catalysts |
| CN103087364A (en) * | 2011-11-04 | 2013-05-08 | 中国石油化工股份有限公司 | Liquid rubber and preparation method thereof |
| CN102702408A (en) * | 2012-06-04 | 2012-10-03 | 辽宁和运合成橡胶研究院有限公司 | Preparation method of diene-based liquid rubber |
| CN107805288A (en) * | 2017-11-06 | 2018-03-16 | 山东玉皇化工有限公司 | A kind of preparation method of low-molecular-weight liquid polydiene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100279347B1 (en) | Manufacturing Method of Polydimethylsiloxane Block Copolymer | |
| CN102485762A (en) | Colourless butylbenzene segmented copolymer with low gel content and preparation method thereof | |
| Yu et al. | Efficiency of the sec-butyllithium/m-diisopropenylbenzene diadduct as an anionic polymerization initiator in apolar solvents | |
| CN101407564A (en) | Process for the preparation of a hydrogenated conjugated diene-based polymer | |
| CN109251264B (en) | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof | |
| JP4458683B2 (en) | Process for preparing hydrogenated polymers with improved color | |
| KR100411861B1 (en) | Process for the removal of metal catalysts from the selectively hydrogenated polymers by using organotitanium compound | |
| CN109181813B (en) | Star viscosity index improver for lubricating oil and preparation method thereof | |
| CN111085271B (en) | Hydrogenation catalyst for producing hydrogenated styrene-conjugated diene copolymer, method for producing hydrogenation catalyst, hydrogenation method, and hydrogenated copolymer | |
| CN106188356A (en) | A kind of Tetraheteropoly rare earth catalyst system and catalyzing and its preparation method and application | |
| CN107200797B (en) | Preparation method of polymer | |
| CN111087495B (en) | Hydrogenation catalyst for producing hydrogenated styrene-conjugated diene copolymer, method for producing hydrogenation catalyst, hydrogenation method, and hydrogenated copolymer | |
| CN115340618A (en) | Preparation method of colorless transparent liquid hydrocarbon polymer | |
| CN109251263B (en) | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof | |
| CN107915797B (en) | Liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation method thereof | |
| CN113817102B (en) | Preparation method of styrene thermoplastic elastomer | |
| CN1100064C (en) | Concurrent epoxidation and catalyst residue extraction | |
| EP0998502A1 (en) | Enhanced hydrogenation catalyst removal from block copolymers by reduction in polymer cement viscosity by increasing the vinyl content of the block copolymers | |
| US6177521B1 (en) | Hydrogenation of polymers | |
| CN117229431A (en) | Preparation method of selectively hydrogenated liquid polybutadiene rubber | |
| CN106977656B (en) | Dendritic polydiene rubber and preparation method thereof | |
| CN117327219A (en) | Preparation method of high-vinyl liquid polybutadiene rubber | |
| CN1358776A (en) | Process for polymerizing 1,3-butadiene | |
| CN106589170B (en) | Composite initiator and anionic polymerization method | |
| CN116715790A (en) | Preparation method of conjugated diene polymer with high side group content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240130 Address after: 266045 101, Building 2, No. 51-1, Wuyang Road, Shibei District, Qingdao, Shandong Applicant after: Qingdao Xuandao Technology Co.,Ltd. Country or region after: China Address before: 266045 101, Building 2, No. 51-1, Wuyang Road, Shibei District, Qingdao, Shandong Applicant before: Qingdao Xuandao Technology Co.,Ltd. Country or region before: China Applicant before: CHAMBROAD CHEMICAL INDUSTRY RESEARCH INSTITUTE Co.,Ltd. |
|
| TA01 | Transfer of patent application right |