CN117567687B - High-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber and preparation method thereof - Google Patents
High-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber and preparation method thereof Download PDFInfo
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 156
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 43
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 42
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims description 20
- 150000001924 cycloalkanes Chemical class 0.000 claims description 6
- 150000002900 organolithium compounds Chemical class 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 37
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 239000005060 rubber Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000005303 weighing Methods 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- -1 epoxide compound Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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 application relates to high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber and a preparation method thereof, belonging to the technical field of rubber synthesis; the method comprises the following steps: mixing butadiene and styrene in a solvent to obtain a first solution; carrying out a first mixing reaction on an initiator and an epoxy compound to obtain a second solution; performing a second mixing reaction on the first solution and the second solution to obtain solution polymerized styrene-butadiene rubber; the method initiates the polymerization of butadiene and styrene by the product of the epoxy compound and the initiator, and can prepare purer solution polymerized styrene-butadiene rubber with high styrene content (30-40 percent) and low vinyl content (8-15 percent) and complete random sequence structure.
Description
Technical Field
The application relates to the technical field of rubber synthesis, in particular to high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber and a preparation method thereof.
Background
The solution polymerized styrene butadiene rubber (SSBR) has excellent comprehensive performance, and is an ideal tread rubber for preparing high-speed, safe, energy-saving and wear-resistant high-performance tires. The SSBR rubber performance is determined by the molecular structure of the rubber, and when a styrene micro-block exists in a molecular chain, the hysteresis loss of the rubber molecule in movement is increased, and the rolling resistance is improved, so that the preparation of the high-randomness SSBR without the styrene micro-block has important significance for improving the energy conservation of the tire.
Methods commonly employed for preparing random SSBR include: continuous/fed-batch, high temperature copolymerization and randomizing agent addition with control of monomer ratio or constant monomer concentration. The fed-batch method of controlling the monomer ratio has high control accuracy for the plant and process, requires highly automated means, and is difficult to synthesize random SSBR with high styrene content. The high-temperature copolymerization is generally carried out at a high temperature ranging from 130 ℃ to 160 ℃ and is easy to form gel. The method for adding the randomizing agent is simple and convenient, and the microstructure of the copolymer can be regulated by changing the type and the dosage of the randomizing agent, so that the rubber performance can meet different requirements.
Randomizers are classified into two types, one type is sigma type, and most of randomizers are polar compounds containing nitrogen and oxygen heteroatoms, such as ethers, amines and the like, which can improve the relative reactivity of styrene, reduce the reactivity ratio difference between styrene and butadiene, and realize uniform random copolymerization. But at the same time, the 1, 2-structure (i.e., vinyl) content of butadiene is increased, and it is difficult to prepare random SSBR with low vinyl content. The other is mu type, mainly various alkoxides and sulfonates, and metal ions of the mu type are sodium, potassium, barium and the like, which can reduce the relative reactivity of butadiene, reduce the reactivity difference between the butadiene and styrene and realize uniform random copolymerization. The compounds are complex to prepare, high purity is difficult to obtain, and impurities are contained to seriously interfere with the polymerization process.
Disclosure of Invention
In view of the above, the present application provides a high-styrene low-vinyl content randomization solution polymerized styrene-butadiene rubber and a preparation method thereof, so as to reduce the content of a styrene micro-block structure in a solution polymerized styrene-butadiene rubber product, improve randomization of the structure of the solution polymerized styrene-butadiene rubber, and simultaneously reduce the vinyl content in the solution polymerized styrene-butadiene rubber, thereby obtaining the solution polymerized styrene-butadiene rubber with high purity.
In a first aspect, the present application provides a method for preparing a high styrene low vinyl content randomizing solution polymerized styrene-butadiene rubber, the method comprising:
mixing butadiene and styrene in a solvent to obtain a first solution;
carrying out a first mixing reaction on an initiator and an epoxy compound to obtain a second solution;
and carrying out a second mixing reaction on the first solution and the second solution to obtain the solution polymerized styrene-butadiene rubber.
As an alternative embodiment, the molar ratio of the product of the reaction of the initiator and the epoxide compound to the remaining initiator is from 0.1 to 5:1.
As an alternative embodiment, the product of the reaction of the initiator and the epoxide is RCH (R') CH 2 OLi, wherein R' is-CH 3 or-H; r is an initiator residue, including any one of n-butyl, sec-butyl, tert-butyl, propyl and hexyl.
As an alternative embodiment, the ratio of the styrene to the butadiene is 3:7 to 4:6.
As an alternative embodiment, the temperature of the first mixing reaction is from 10 ℃ to 40 ℃; and/or the time of the first mixing reaction is 10min to 30min.
As an alternative embodiment, the epoxy compound comprises ethylene oxide and/or propylene oxide.
As an alternative embodiment, the temperature of the second mixing reaction is from 70 ℃ to 110 ℃; and/or the time of the second mixing reaction is 1h to 5h.
As an alternative embodiment, the initiator comprises an organolithium compound.
As an alternative embodiment, the organolithium compound includes at least one of n-butyllithium, sec-butyllithium, tert-butyllithium, propyllithium, and hexyllithium.
As an alternative embodiment, the solvent includes at least one solvent of aromatic hydrocarbons, aliphatic hydrocarbons, and cycloalkanes.
As an alternative embodiment, the solvent includes at least one of a C5 to C8 alkane and a C5 to C8 cycloalkane.
In a second aspect, the present application provides a high styrene low vinyl content randomized solution polymerized styrene-butadiene rubber made by the method of the first aspect.
As an alternative embodiment, the solution polymerized styrene-butadiene rubber has a molecular weight of 50000g/mol to 300000g/mol; and/or, the degree of randomness of the solution polymerized styrene-butadiene rubber is 100%; and/or, the vinyl content of the solution polymerized styrene-butadiene rubber is 8% to 15%; and/or, the solution polymerized styrene-butadiene rubber has a molecular weight distribution of 1.1 to 1.3.
As an alternative embodiment, the styrene content of the solution polymerized styrene-butadiene rubber is 30% to 40%.
Compared with the prior art, the technical scheme provided by the application has the following advantages:
(1) According to the method, polymerization of butadiene and styrene is initiated through a product obtained after an epoxy compound reacts with an initiator, so that relatively pure solution polymerized styrene-butadiene rubber with high styrene content (30-40%) and low vinyl content (8-15%) and a completely random sequence structure can be prepared;
(2) The preparation method is simple to operate, has low control requirement on the polymerization process, can complete polymerization at a lower temperature, and reduces gel generation in the polymerization process;
(3) According to the preparation method, the required raw materials are easy to obtain, and the prepared solution polymerized styrene-butadiene rubber product has high purity.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic flow chart of a method provided in an embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods. In addition, unless otherwise specifically indicated, the butadiene employed in the present invention is 1, 3-butadiene.
Fig. 1 is a schematic flow chart of a method provided in an embodiment of the present application, and as shown in fig. 1, the embodiment of the present application provides a method for preparing a high styrene low vinyl content randomizing solution polymerized styrene butadiene rubber, where the method includes:
s1, mixing butadiene and styrene in a solvent to obtain a first solution;
in some embodiments, the ratio of the styrene to the butadiene is 3:7 to 4:6.
In some embodiments, the initiator comprises an organolithium compound. Further, the organolithium compound includes at least one of n-butyllithium, sec-butyllithium, tert-butyllithium, propyllithium, and hexyllithium.
In some embodiments, the solvent is selected from at least one of the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, and cycloalkanes. Further, the solvent is at least one selected from the group consisting of benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, and cyclohexane.
S2, carrying out a first mixing reaction on the initiator and the epoxy compound to obtain a second solution;
in some embodiments, the molar ratio of the product after reaction of the initiator and the epoxy compound to the remaining initiator is from 0.1 to 5:1.
In some embodiments, the product after the reaction of the initiator and the epoxy compound is RCH (R') CH 2 OLi, wherein R' is-CH 3 or-H; r is an initiator residue, including any one of n-butyl, sec-butyl, tert-butyl, propyl and hexyl.
In the invention, the initiation activity of the initiator is controlled by controlling the molar ratio of the product after the reaction of the initiator and the epoxy compound to the rest of the initiator. Excessive initiator and epoxy compound are reacted to give a product having a content which tends to decrease the activity of the initiator. In addition, the product of the reaction of the initiator and the epoxy compound is used as a mu-type compatibility body to be complexed with active species, so that the reactivity ratio of styrene monomer can be improved, the copolymerization activity of styrene and butadiene can be improved, and the random copolymerization of styrene can be promoted. In the present invention, the remaining initiator is at RCH (R') CH 2 The monomers polymerize under the action of OLi.
In some embodiments, the temperature of the first mixing reaction is from 10 ℃ to 40 ℃ (e.g., 15 ℃,20 ℃,25 ℃, 30 ℃, or 35 ℃); the first mixing reaction time is 10min to 30min (e.g., 15min, 20min, or 25 min). The epoxy compound includes ethylene oxide and/or propylene oxide.
In the present invention, the carbanion in the alkyllithium (i.e., organolithium compound) attacks a carbon atom on the ternary heterocycle, breaking the carbon-oxygen bond, the initiator residue being attached to the carbon atom, and the oxygen atom forming an oxygen lithium bond with lithium.
S3, carrying out a second mixing reaction on the first solution and the second solution to obtain the solution polymerized styrene-butadiene rubber.
In the present application, the product RCH (R') CH after reaction of the epoxy compound with the initiator 2 OLi is complexed with the residual initiator, the activity of the active center is regulated and controlled, the reactivity ratio of styrene monomer is improved, the copolymerization activity of styrene and butadiene is improved, and the styrene is promoted to be random, so that the styrene micro-block structure is eliminated. RCH (R') CH is different from sigma-allyl structure with mainly localized active center after complexation with sigma-type compatible body 2 OLi is a mu-type of compatible entity, so butadiene forms mainly a 1, 4-structure after addition with the active chain, with a low vinyl content. Thus, the random styrene-butadiene copolymer with low vinyl content is synthesized by the method.
In some embodiments, the temperature of the second mixing reaction is 70 ℃ to 110 ℃ (e.g., 75 ℃,80 ℃, 85 ℃, 90 ℃, 95 ℃,100 ℃, or 105 ℃); the second mixing reaction is for a time of 1h to 5h (e.g., 2h, 3h, 4h, or 4.5 h).
In the prior art, a method for preparing random SSBR generally adopts high-temperature copolymerization, and specifically comprises the following steps: continuous/fed-batch, high temperature copolymerization and randomizing agent addition with control of monomer ratio or constant monomer concentration. The high-temperature copolymerization is generally carried out at a high temperature ranging from 130 ℃ to 160 ℃ and is easy to form gel.
According to the preparation method, the polymerization of butadiene and styrene is initiated by a product obtained by reacting an epoxy compound with an initiator, and the polymerization reaction can be completed at a lower temperature (the polymerization can be performed at 70-110 ℃), so that the pure solution polymerized styrene-butadiene rubber with the content of high styrene (30-40%) and low vinyl (8-15%) and a completely random sequence structure is prepared. Since the polymerization reaction is carried out at 70 to 110 ℃, the reaction temperature is low, and thus the generation of gel during the polymerization can be reduced.
In the invention, the reaction temperature is too low to meet the index requirement of low vinyl, and too high temperature can generate a large amount of gel to influence the normal operation of the reaction. The reaction temperature is thus controlled to be 70℃to 110 ℃.
In addition, the preparation method provided by the invention is simple to operate, low in control requirement on the polymerization process, easy to obtain raw materials and high in purity of the prepared random SSBR.
Based on one general inventive concept, the embodiments of the present application also provide a high styrene low vinyl content randomized solution polymerized styrene-butadiene rubber prepared by the method provided above.
The solution polymerized styrene-butadiene rubber is prepared based on the method, specific steps of the method can refer to the embodiment, and as the solution polymerized styrene-butadiene rubber adopts part or all of the technical schemes of the embodiment, the solution polymerized styrene-butadiene rubber has at least all the beneficial effects brought by the technical schemes of the embodiment, and the detailed description is omitted.
In some embodiments, the solution polymerized styrene-butadiene rubber has a molecular weight of 50000g/mol to 300000g/mol (e.g., 80000g/mol, 100000g/mol, 150000g/mol, 200000g/mol, 250000g/mol, or 280000 g/mol); the randomness of the solution polymerized styrene-butadiene rubber is 100%; the vinyl content of the solution polymerized styrene-butadiene rubber is 8 to 15 percent; the solution polymerized styrene-butadiene rubber has a molecular weight distribution of 1.1 to 1.3 (e.g., 1.15, 1.2, or 1.25).
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
60g of butadiene, 40g of styrene and 1000ml of cyclohexane are added into a 2L polymerization kettle under the protection of nitrogen after purification treatment, and the mixture is stirred uniformly to obtain a first solution. To a 50mL bottom-inserted tube polymerization flask having a double branch tube was added 0.55mL of a t-butyllithium solution (1M), 20mL of cyclohexane, and ethylene oxide (0.05 mmol) was introduced thereinto, and the reaction was stirred at 25℃for 30 minutes to obtain a second solution. The first solution was heated to 90℃and the second solution in the polymerization flask was added to the first solution and reacted at 90℃for 2 hours. Finally, the flocculation was terminated with ethanol and the product was dried in a vacuum oven, and the conversion was measured to be 100% by weighing.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 201000g/mol and the molecular weight distribution was 1.15 as measured by Gel Permeation Chromatography (GPC) of model 515-2410 of Waters company. By BRUKER AV-600 nuclear magnetic resonance 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 13.1% and a styrene content of 39.5% by H-NMR calculation.
Example 2
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the conditions in example 1 were unchanged except that the ethylene oxide amount was changed to 0.25mmol. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 203000g/mol and the molecular weight distribution was 1.21 as measured by GPC. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 13.7% and a styrene content of 39.7% as measured by H-NMR spectrum calculation.
Example 3
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the conditions in example 1 were unchanged except that the amount of ethylene oxide was changed to 0.5mmol and the polymerization time was changed to 3 hours. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 208000g/mol and the molecular weight distribution was 1.27 as measured by GPC. 1 The styrene randomness of the solution polymerized styrene-butadiene rubber product of this example was 100%, the 1, 2-structure (i.e., vinyl) content was 14.1%, and the styrene content was 39.8% as measured by H-NMR spectrum calculation.
Example 4
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the conditions in example 1 were unchanged except that the amount of ethylene oxide was changed to 2.5mmol, the polymerization time was changed to 5 hours, and cyclohexane was changed to cyclopentane. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 212000g/mol as measured by GPC, and the molecular weight distribution was 1.3. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 14.9% and a styrene content of 38.9% as measured by H-NMR spectrum calculation.
Example 5
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the relevant conditions in example 1 were unchanged except that the polymerization temperature was changed to 70 ℃. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 196000g/mol and the molecular weight distribution was 1.18 as measured by GPC. 1 The styrene randomness of the solution polymerized styrene-butadiene rubber product of this example was 100%, the 1, 2-structure (i.e., vinyl) content was 14.1%, and the styrene content was 38.9% as measured by H-NMR spectrum calculation.
Example 6
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the relevant conditions in example 1 were unchanged except that the polymerization temperature was changed to 110℃and the polymerization time was changed to 1 hour, and cyclohexane was changed to n-hexane. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 206000g/mol and the molecular weight distribution was 1.25 as measured by GPC. 1 The styrene randomness of the solution polymerized styrene-butadiene rubber product of this example was 100%, the 1, 2-structure (i.e., vinyl) content was 10.1%, and the styrene content was 39.6% as measured by H-NMR spectrum calculation.
Example 7
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the relevant conditions in example 1 were unchanged except that the styrene amount was changed to 35g and the butadiene amount was changed to 65g. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 201000g/mol and the molecular weight distribution was 1.12 as measured by GPC. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 12.8% and a styrene content of 39.6% as measured by H-NMR spectrum calculation.
Example 8
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the conditions in example 1 were unchanged except that the styrene amount was changed to 30g, the butadiene amount was changed to 70g, and cyclohexane was changed to a toluene solution. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 200000g/mol and the molecular weight distribution was 1.10 as measured by GPC. 1 The styrene randomness of the solution polymerized styrene-butadiene rubber product of this example was 100%, the 1, 2-structure (i.e., vinyl) content was 12.2%, and the styrene content was 30.7% as measured by H-NMR spectrum calculation.
Example 9
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the conditions in example 1 were unchanged except that the amount of t-butyllithium was changed to 2.2mL and the amount of ethylene oxide was changed to 0.22mmol. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 51000g/mol as measured by GPC, and the molecular weight distribution was 1.18. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 14.9% and a styrene content of 39.7% as measured by H-NMR spectrum calculation.
Example 10
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the conditions were unchanged in example 1 except that the amount of t-butyllithium was changed to 0.33mL and the amount of ethylene oxide was changed to 0.033mmol. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 310000g/mol and the molecular weight distribution was 1.28 as measured by GPC. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 11.9% and a styrene content of 39.7% as measured by H-NMR spectrum calculation.
Example 11
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the relevant conditions in example 1 were unchanged except that ethylene oxide was changed to propylene oxide. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 195000g/mol and the molecular weight distribution was 1.22 as measured by GPC. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 9.8% and a styrene content of 39.7% as measured by H-NMR spectrum calculation.
Example 12
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the conditions in example 1 were unchanged except that ethylene oxide was changed to propylene oxide, and the amount thereof was changed to 0.5mmol. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 198000g/mol and the molecular weight distribution was 1.26 as measured by GPC. 1 The styrene randomness of the solution polymerized styrene-butadiene rubber product of this example was 100%, the 1, 2-structure (i.e., vinyl) content was 13.8%, and the styrene content was 39.5%, as measured by H-NMR spectrum calculation.
Example 13
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the relevant conditions in example 1 were unchanged, except that tert-butyllithium was changed to sec-butyllithium. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 205000g/mol and the molecular weight distribution was 1.18 as measured by GPC. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 8.8% and a styrene content of 39.8% as measured by H-NMR spectrum calculation.
Example 14
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the relevant conditions in example 1 were unchanged except that tert-butyllithium was changed to n-butyllithium. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 205000g/mol and the molecular weight distribution was 1.25 as measured by GPC. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 11.8% and a styrene content of 39.1% as measured by H-NMR spectrum calculation.
Example 15
A preparation method of high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber comprises the following steps:
the relevant conditions in example 1 were unchanged except that tert-butyllithium was changed to hexyllithium. The polymerization conversion was measured by weighing to be 100%.
The number average molecular weight of the solution polymerized styrene-butadiene rubber product of this example was 200000g/mol and the molecular weight distribution was 1.15 as measured by GPC. 1 The solution polymerized styrene-butadiene rubber product of this example was found to have a styrene randomness of 100%, a 1, 2-structure (i.e., vinyl) content of 10.8% and a styrene content of 39.3% as measured by H-NMR spectrum calculation.
Comparative example 1
A preparation method of solution polymerized styrene-butadiene rubber comprises the following steps:
60g of butadiene, 40g of styrene and 1000ml of cyclohexane are added into a 2L polymerization kettle under the protection of nitrogen after purification treatment, and the mixture is stirred uniformly and heated to 90 ℃. 0.5mL of t-butyllithium solution (1M) was added and the reaction was allowed to proceed for 2 hours. Finally, the flocculation was terminated with ethanol and the product was dried in a vacuum oven, and the conversion was measured to be 100% by weighing.
The solution polymerized styrene-butadiene rubber product of comparative example 1 had a number average molecular weight of 206000g/mol and a molecular weight distribution of 1.38 as measured by GPC. 1 The degree of styrene randomness in the solution polymerized styrene-butadiene rubber product of comparative example 1 was 29% and the 1, 2-structure (i.e., vinyl) content was 8.9% as measured by H-NMR spectrum calculation.
Comparative example 2
A preparation method of solution polymerized styrene-butadiene rubber comprises the following steps:
60g of butadiene, 40g of styrene and 1000ml of cyclohexane are added into a 2L polymerization kettle under the protection of nitrogen after purification treatment, and the mixture is stirred uniformly and heated to 110 ℃. 0.5mL sec-butyllithium solution (1M) was added and the reaction was allowed to proceed for 2 hours. Finally, the flocculation was terminated with ethanol and the product was dried in a vacuum oven, and the conversion was measured to be 100% by weighing.
The solution polymerized styrene-butadiene rubber product of comparative example 2 had a number average molecular weight of 202000g/mol and a molecular weight distribution of 1.18 as measured by GPC. 1 The degree of styrene randomness in the solution polymerized styrene-butadiene rubber product of comparative example 2 was 36% and the 1, 2-structure (i.e., vinyl) content was 7.8% as measured by H-NMR spectrum calculation.
As can be seen from the comparison of example 1 with comparative example 1 and example 13 with comparative example 2, the styrene units in the solution polymerized styrene-butadiene rubber with high styrene content and low vinyl content prepared by the method provided by the application example are distributed in random sequence, and the randomness reaches 100% and is far superior to the technical scheme of the comparative example without ethylene oxide. The invention can realize the uniform distribution of the styrene units in the copolymer within a selected range by changing the addition amount of the epoxy compound, the polymerization temperature and the organolithium type, eliminate the styrene micro-block structure and ensure that the vinyl content is controlled at a level below 15 percent.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1,2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the terms "include", "comprise", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber, which is characterized by comprising the following steps:
mixing butadiene and styrene in a solvent to obtain a first solution;
carrying out a first mixing reaction on an initiator and an epoxy compound to obtain a second solution;
performing a second mixing reaction on the first solution and the second solution to obtain solution polymerized styrene-butadiene rubber;
wherein the temperature of the second mixing reaction is 70 ℃ to 110 ℃;
the product after the reaction of the initiator and the epoxy compound is RCH (R') CH 2 OLi, wherein R' is-CH 3 or-H; r is an initiator residue, including any one of n-butyl, sec-butyl, tert-butyl, propyl and hexyl;
the molar ratio of the product of the reaction of the initiator and the epoxy compound to the rest of the initiator is 0.1 to 5:1;
the initiator includes an organolithium compound.
2. The method for preparing high-styrene low-vinyl-content randomization solution polymerized styrene-butadiene rubber according to claim 1, wherein the ratio of the styrene to the butadiene is 3:7 to 4:6.
3. The method for preparing high-styrene low-vinyl-content randomized solution polymerized styrene-butadiene rubber according to claim 1 or 2, wherein the temperature of the first mixing reaction is 10 ℃ to 40 ℃; and/or the time of the first mixing reaction is 10min to 30min.
4. The method for preparing high styrene low vinyl content randomization solution polymerized styrene-butadiene rubber according to claim 1 or 2, wherein the second mixing reaction time is 1h to 5h.
5. The method for preparing high styrene low vinyl content randomization solution polymerized styrene-butadiene rubber according to claim 3, wherein the second mixing reaction time is 1h to 5h.
6. The method for preparing a high styrene low vinyl content random solution polymerized styrene-butadiene rubber according to claim 1,2 or 5, wherein the solvent comprises at least one solvent selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons and cycloalkanes.
7. The method for preparing a high styrene low vinyl content random solution polymerized styrene-butadiene rubber according to claim 3, wherein the solvent comprises at least one solvent selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons and cycloalkanes.
8. The method for preparing a high styrene low vinyl content random solution polymerized styrene-butadiene rubber according to claim 4, wherein the solvent comprises at least one solvent selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, and cycloalkanes.
9. A high styrene low vinyl content randomized solution polymerized styrene-butadiene rubber, characterized in that said solution polymerized styrene-butadiene rubber is produced by the process of any one of claims 1 to 8.
10. The high styrene low vinyl content randomized solution polymerized styrene-butadiene rubber according to claim 9, wherein the molecular weight of the solution polymerized styrene-butadiene rubber is 50000g/mol to 300000g/mol; and/or, the degree of randomness of the solution polymerized styrene-butadiene rubber is 100%; and/or, the vinyl content of the solution polymerized styrene-butadiene rubber is 8% to 15%; and/or, the solution polymerized styrene-butadiene rubber has a molecular weight distribution of 1.1 to 1.3; and/or, the styrene content of the solution polymerized styrene-butadiene rubber is 30% to 40%.
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