CN117567686A - Solution polymerized styrene-butadiene rubber with fixed block styrene content, and preparation method and application thereof - Google Patents
Solution polymerized styrene-butadiene rubber with fixed block styrene content, and preparation method and application thereof Download PDFInfo
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- CN117567686A CN117567686A CN202410062036.6A CN202410062036A CN117567686A CN 117567686 A CN117567686 A CN 117567686A CN 202410062036 A CN202410062036 A CN 202410062036A CN 117567686 A CN117567686 A CN 117567686A
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- styrene
- butadiene
- fixed block
- butadiene rubber
- solution polymerized
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 390
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title abstract description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 58
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 230000000977 initiatory effect Effects 0.000 claims description 16
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920005604 random copolymer Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 5
- 239000005060 rubber Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000001052 heteronuclear multiple bond coherence spectrum Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- -1 ESBR Substances 0.000 description 6
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000005100 correlation spectroscopy Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 241000028631 Microstomus pacificus Species 0.000 description 2
- 229920006978 SSBR Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000269978 Pleuronectiformes Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to solution polymerized styrene-butadiene rubber with fixed block styrene content, and a preparation method and application thereof, belonging to the technical field of rubber synthesis, wherein the method comprises the following steps: the structure regulator is tetrahydrofuran and ethylene glycol dimethyl ether, and the structure regulator, styrene, butadiene and initiator are mixed in solvent to perform polymerization reaction to obtain solution polymerized styrene-butadiene rubber with fixed block styrene content.
Description
Technical Field
The invention relates to the technical field of rubber synthesis, in particular to solution polymerized styrene-butadiene rubber with fixed block styrene content, and a preparation method and application thereof.
Background
With the rapid development of social economy and the continuous improvement of the living standard of people, the comfort and the functional demands of people on shoes are continuously improved, and higher demands are put on the weight, the slip resistance, the wear resistance, the rebound resilience, the shock absorption and the like of the shoes, so that the shoes are changed into attractive, safe, comfortable and heavy shoes only by paying attention to the appearance.
The solution polymerized styrene-butadiene rubber for shoes is mainly butadiene-styrene block copolymer, which can be plasticized and molded at high temperature and has the elastic characteristic of rubber at normal temperature. The solution polymerized styrene-butadiene rubber has the processing characteristics of good roller operability, calendaring performance, wear resistance, high filling performance and the like, has good compatibility with common sole materials such as TPR, ESBR, butadiene rubber and the like, and can be blended (or vulcanized) with the common sole materials, thereby preparing the shoe material with more excellent product performance. The shoe material manufactured by the method is mainly used for high-grade leather shoes, sport shoes, outdoor shoes and the like, and has the advantages of good appearance and touch, bright color, smooth surface, difficult shape and moderate hardness; when used for manufacturing the sports soles, the sole has the characteristics of clear patterns, no cross color, smooth surface and the like, and is well welcomed by shoemaking manufacturers.
Research on solution polymerized styrene-butadiene rubber at home and abroad is focused on random copolymerization solution polymerized styrene-butadiene rubber on one hand and on the other hand, on the production of SBS block copolymer by adopting a coupling method or a three-step method. At present, the control of the styrene block content in SBS block copolymers is poor.
The chinese patent publication No. CN102558465B discloses a method for synthesizing solution polymerized styrene-butadiene rubber, which comprises copolymerizing butadiene and styrene in hydrocarbon solvent by stepwise adding monomers and structure regulator at 0 to 130 ℃ with organolithium as initiator, and adding coupling agent with 2 to 4 functionalities after polymerization is basically completed for coupling reaction. The patent relates to sectional feeding, which increases the complexity of process operation and affects the production efficiency.
The Chinese patent publication No. CN116836335A discloses a functionalized solution polymerized styrene-butadiene rubber and a preparation method thereof, wherein secondary amine compounds and organic lithium are subjected to contact reaction in a nonpolar solvent to obtain a functionalized lithium amide initiator, and then styrene and butadiene are added to cause in-situ initiation of anion copolymerization reaction. However, the solution polymerized styrene-butadiene rubber prepared in this patent does not contain block styrene, and the rubber is used for manufacturing tires and cannot be applied to shoe materials.
Disclosure of Invention
In view of the above, the present invention provides a solution polymerized styrene-butadiene rubber with a fixed block styrene content, and a preparation method and application thereof, wherein styrene and butadiene are added into a reaction kettle together, so that most of styrene is randomly polymerized, and a small portion of styrene is self-polymerized to form block styrene, thereby improving control of styrene block content in the solution polymerized styrene-butadiene rubber.
In order to achieve the purpose, the invention adopts the following technical scheme.
In a first aspect of the present invention, there is provided a solution polymerized styrene-butadiene rubber having a fixed block styrene content, the structural units of the solution polymerized styrene-butadiene rubber comprising atactic co-polystyrene, block styrene, 1, 2-butadiene, cis-butadiene and trans-butadiene, wherein,
the content of total styrene (random copolymer styrene and block styrene) in the solution polymerized styrene-butadiene rubber with fixed block styrene content is 40% -50%;
the content of block styrene in the solution polymerized styrene-butadiene rubber with fixed block styrene content is 10 to 20 percent;
the content of 1, 2-butadiene in the solution polymerized styrene-butadiene rubber with the fixed block styrene content is 20 to 40 percent;
the content of cis-butadiene in the solution polymerized styrene-butadiene rubber with the fixed block styrene content is 25 to 30 percent;
the content of trans-butadiene in the solution polymerized styrene-butadiene rubber of the fixed block styrene content is 40% to 45%.
The distribution form of the block styrene in the solution polymerized styrene-butadiene rubber with the fixed block styrene content comprises four forms A, B, C and D, wherein the A, B, C and D forms of the block styrene respectively account for 25 to 35 percent, 15 to 25 percent, 5 to 20 percent and 40 to 50 percent of the total block styrene;
the block styrene in the solution polymerized styrene-butadiene rubber with fixed block styrene content is connected with trans-butadiene groups.
In a second aspect of the present invention, there is provided a method for preparing a solution polymerized styrene-butadiene rubber having a fixed block styrene content, the method comprising:
s1, a structure regulator is tetrahydrofuran and ethylene glycol dimethyl ether;
s2, mixing a structure regulator, styrene, butadiene and an initiator in a solvent for polymerization reaction to obtain the solution polymerized styrene-butadiene rubber with fixed block styrene content.
The preparation method of the solution polymerized styrene-butadiene rubber with fixed block styrene content comprises the following specific steps: under the protection of inert gas, adding a solvent into a reaction kettle, heating to 40-60 ℃, then adding a structure regulator, starting stirring to uniformly disperse the structure regulator in the solvent, then adding styrene and butadiene, finally adding an initiator to perform polymerization reaction, wherein the polymerization reaction temperature is continuously increased within 10-30 min, then is reduced for 1-2 min, then is continuously increased until the highest reaction temperature is reached, waiting for 10-30 min, and adding a terminator to terminate the reaction to obtain solution polymerized styrene-butadiene rubber with fixed block styrene content, wherein the initiator comprises n-butyllithium, and the solvent is one of cycloalkanes with carbon chain length of 5-8; tetrahydrofuran is present in an amount of from 0.15% to 0.5% by weight based on the total weight of styrene and butadiene.
As an alternative embodiment, the solvent is 5 to 10 times by weight of the total weight of styrene and butadiene, the initiator is 0.03 to 0.1% by weight of the total weight of styrene and butadiene, and the ethylene glycol dimethyl ether is 0.03 to 0.1% by weight of the total weight of styrene and butadiene.
The invention controls the content of the block styrene in a certain range by controlling the adding amount of the structure regulator and the superposition of the polymerization reaction temperature. The structure regulator is added to raise the reactivity ratio of styrene during copolymerization of styrene and butadiene. The excess addition of the structure modifier can cause the styrene and butadiene in the product to exhibit a random distribution when no block styrene is present.
The invention can realize the control of the content of the block styrene in the polymer by selecting different structure regulators, adjusting the addition amount of the structure regulators and the reaction temperature.
As an alternative embodiment, the polymerization reaction is initiated at a temperature of 40 ℃ to 60 ℃; and/or the polymerization reaction has a maximum reaction temperature of 70 ℃ to 110 ℃.
As an alternative embodiment, the polymerization reaction is initiated at a temperature of 45 ℃ to 50 ℃; and/or the polymerization reaction has a maximum reaction temperature of 80 ℃ to 95 ℃.
In the present invention, the temperature of the polymerization reaction mainly affects the contents of 1, 2-butadiene and block styrene. As the reaction temperature increases, the 1, 2-butadiene content decreases and, at the same time, the block styrene content increases. Therefore, the polymerization temperature needs to be controlled within a certain interval to ensure that the content of the 1, 2-butadiene and the block styrene meets the index requirement.
As an alternative embodiment, the polymerization is a batch polymerization.
In a third aspect, the invention provides an application of solution polymerized styrene-butadiene rubber with fixed block styrene content in shoe materials.
Most of the existing solution polymerized styrene-butadiene rubber is applied to the field of tires, and in order to realize high anti-skid performance of the tires, it is expected that no block exists in the structureAnd (3) styrene. The presence of the partially blocked styrene in the rubber for shoes can increase the hardness of the product, improve the wear resistance, prolong the flex life, enhance the tear resistance, have good color and luster, have good in-mold flow property and other excellent properties. Therefore, the SSBR for shoes needs to have a certain block styrene, and the average molecular weight of the SSBR for shoes needs to be controlled to be (6-12) x 10 4 Dalton。
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the solution polymerized styrene-butadiene rubber with fixed block styrene content, a structural regulator compounded by tetrahydrofuran and ethylene glycol dimethyl ether is adopted, a certain amount of styrene units in the solution polymerized styrene-butadiene rubber with fixed block styrene content are uniformly and randomly distributed on a macromolecular chain, and a certain amount of styrene units exist in the form of blocks, namely styrene homopolymers, on the macromolecular chain, so that the better control of the styrene block content is realized;
(2) The solution polymerized styrene-butadiene rubber with fixed block styrene content prepared by the preparation method of the invention has the Mooney viscosity ML (1+4) of 40 to 50 at 100 ℃, the total styrene (random copolymer styrene and block styrene) content of 40 to 50%, the block styrene content of 10 to 20%, the 1, 2-butadiene content of 20 to 40%, the cis-butadiene content of 25 to 30% and the trans-butadiene content of 40 to 45%, and is especially suitable for shoe materials.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a flow chart showing a method for preparing a solution polymerized styrene-butadiene rubber with a fixed block styrene content according to example 4 of the present invention;
FIG. 2 is a block styrene-butadiene rubber solution having a styrene content of fixed block according to example 4 of the present invention 1 H-NMR spectrum;
FIG. 3 is a block styrene-butadiene rubber solution having a styrene content of fixed block according to example 4 of the present invention 13 C-NMR spectrum;
FIG. 4 is a partial enlarged view of a solution polymerized styrene-butadiene rubber with a fixed block styrene content according to example 4 of the present invention 13 C-NMR spectrum;
FIG. 5 is an infrared spectrum of a solution polymerized styrene-butadiene rubber with a fixed block styrene content according to example 4 of the present invention;
FIG. 6 is a chart showing the nuclear magnetic resonance COSY spectrum of the solution polymerized styrene-butadiene rubber with fixed block styrene content provided in example 4 of the present invention;
FIG. 7 is a nuclear magnetic resonance HMBC spectrum a of the solution polymerized styrene-butadiene rubber with fixed block styrene content provided in the embodiment 4 of the present invention;
FIG. 8 is a nuclear magnetic resonance HMBC spectrum b of the solution polymerized styrene-butadiene rubber with fixed block styrene content provided in example 4 of the present invention;
FIG. 9 is a nuclear magnetic resonance HMBC spectrum c of the solution polymerized styrene-butadiene rubber with fixed block styrene content provided in example 4 of the present invention;
FIG. 10 is a graph showing a partial fitting of hydrogen spectra of a solution polymerized styrene-butadiene rubber having a fixed block styrene content provided in example 4 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Some embodiments according to the first aspect of the present invention provide a solution polymerized styrene-butadiene rubber having a fixed block styrene content, the structural units of the solution polymerized styrene-butadiene rubber including atactic co-polystyrene, block styrene, 1, 2-butadiene, cis-butadiene and trans-butadiene, wherein,
the content of total styrene (random copolymer styrene and block styrene) in the solution polymerized styrene-butadiene rubber of fixed block styrene content is 40% to 50% (e.g., 42%, 45% or 48%);
the content of block styrene in the solution polymerized styrene-butadiene rubber of the fixed block styrene content is 10% to 20% (e.g., 12%, 15% or 18%);
the content of 1, 2-butadiene in the solution polymerized styrene-butadiene rubber of the fixed block styrene content is 20% to 40% (e.g., 25%, 30% or 35%);
the content of cis-butadiene in the fixed block styrene-containing solution polymerized styrene-butadiene rubber is 25% to 30% (e.g., 26%, 27%, 28% or 29%);
the content of trans-butadiene in the solution polymerized styrene-butadiene rubber of the fixed block styrene content is 40% to 45% (e.g., 41%, 42%, 43% or 44%).
The distribution forms of the block styrene in the solution polymerized styrene-butadiene rubber with fixed block styrene content include four forms A, B, C and D, wherein the four forms A, B, C and D of the block styrene respectively account for 25 to 35% (e.g., 26%, 30% or 33%), 15 to 25% (e.g., 18%, 20% or 23%), 5 to 20% (e.g., 7%, 10%, 12%, 15% or 18%) and 40 to 50% (e.g., 42%, 45% or 48%) of the total block styrene;
the block styrene in the solution polymerized styrene-butadiene rubber with fixed block styrene content is connected with trans-butadiene groups.
Fig. 1 is a flow chart of a method for preparing a solution polymerized styrene-butadiene rubber with a fixed block styrene content according to some embodiments of the second aspect of the present invention.
As shown in fig. 1, some embodiments of the present invention provide a method for preparing a solution polymerized styrene-butadiene rubber having a fixed block styrene content, comprising:
s1, a structure regulator is tetrahydrofuran and ethylene glycol dimethyl ether;
s2, mixing a structure regulator, styrene, butadiene and an initiator in a solvent for polymerization reaction to obtain the solution polymerized styrene-butadiene rubber with fixed block styrene content.
Specifically, the preparation method of the solution polymerized styrene-butadiene rubber with fixed block styrene content comprises the following steps: under the protection of inert gas, adding a certain amount of solvent into a reaction kettle, heating to 40-60 ℃, then adding a metered structure regulator, starting stirring to uniformly disperse the structure regulator in the solvent, then adding metered styrene and butadiene, finally, adding n-butyllithium to initiate polymerization, wherein the polymerization temperature is continuously increased within 10-30 min in the polymerization process, then reducing for 1-2 min, then continuously heating until the highest reaction temperature is reached, waiting for 10-30 min, and adding a terminator to terminate the reaction to obtain the solution polymerized styrene-butadiene rubber with the fixed block styrene content.
In some embodiments, the solvent is 5 to 10 times (e.g., 5, 10 times) the total weight of styrene and butadiene, the initiator is 0.03 to 0.1% of the total weight of styrene and butadiene (e.g., 0.03%, 0.05%, 0.10%), the tetrahydrofuran is 0.15 to 0.5% of the total weight of styrene and butadiene (e.g., 0.15%, 0.25%, 0.5%), and the ethylene glycol dimethyl ether is 0.03 to 0.1% of the total weight of styrene and butadiene (e.g., 0.03%, 0.05%, 0.10%).
In some embodiments, the polymerization reaction is initiated at a temperature of 40 ℃ to 60 ℃ (e.g., 45 ℃, 50 ℃, or 55 ℃); the highest reaction temperature of the polymerization reaction is 70℃to 110 ℃ (e.g., 80 ℃, 85 ℃, or 95 ℃); the polymerization reaction reaches the maximum reaction temperature for a period of 5min to 30min (e.g., 10min, 15min, or 20 min). Preferably, the polymerization reaction is initiated at a temperature of 45℃to 50 ℃ (e.g., 46 ℃, 48 ℃, or 49 ℃); the polymerization reaction has a maximum reaction temperature of 80℃to 95℃C (e.g., 82 ℃, 85℃or 90 ℃).
Based on one general inventive concept, the embodiment of the invention also provides a solution polymerized styrene-butadiene rubber with fixed block styrene content, which is prepared by adopting the preparation method of the solution polymerized styrene-butadiene rubber with fixed block styrene content.
The solution polymerized styrene-butadiene rubber with the fixed block styrene content is prepared based on a method, and specific steps of the method can refer to the embodiment, and as the solution polymerized styrene-butadiene rubber with the fixed block styrene content adopts part or all of the technical schemes of the embodiment, at least all the beneficial effects brought by the technical schemes of the embodiment are provided, and are not described in detail herein.
The structural index of the solution polymerized styrene-butadiene rubber with the fixed block styrene content is that the Mooney viscosity ML (1+4) is between 40 and 50 ℃ and the total styrene (random copolymer styrene and block styrene) content is between 40 and 50 percent, the block styrene content is between 10 and 20 percent, the 1, 2-butadiene content is between 20 and 40 percent, the cis-butadiene content is between 25 and 30 percent and the trans-butadiene content is between 40 and 45 percent.
Based on one general inventive concept, the embodiments of the present invention also provide an application of the solution polymerized styrene-butadiene rubber with a fixed block styrene content, including using the solution polymerized styrene-butadiene rubber as provided above for shoe materials. Specifically, the solution polymerized styrene-butadiene rubber can be used as a sole material.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. 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.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
a preparation method of solution polymerized styrene-butadiene rubber with fixed block styrene content comprises the following steps: under the protection of inert gas, 2000g of solvent (cyclopentane) is added into a 5L batch polymerization kettle, 0.8g of structure regulator (0.2 g of ethylene glycol dimethyl ether and 0.6g of tetrahydrofuran) is continuously added into the batch polymerization kettle, stirring is started, the structure regulator is uniformly dispersed into the solvent, the preheating is carried out to enable the initiation temperature to be 50.5 ℃, the preheating temperature is 50.5 ℃, 165g of styrene and 190g of butadiene are then added, after stirring for 5min, an initiator (0.2 g of n-butyllithium) is further added, the polymerization reaction temperature is continuously increased within 30min, then the reduction of 2min occurs, then the continuous heating is carried out until the highest reaction temperature is reached, the reaction is further waited for 15min, and finally, a terminator (trimethylchlorosilane) is added to terminate the reaction, so that the solution polymerized styrene-butadiene rubber with fixed block styrene content is obtained.
Example 2:
the difference from example 1 is that the addition amount of the structure regulator is changed to 0.17g of ethylene glycol dimethyl ether and 0.6g of tetrahydrofuran, the initiation temperature is shown in Table 3, and the rest steps are the same.
Example 3:
the difference from example 1 is that the addition amount of the structure regulator is changed to 0.14g of ethylene glycol dimethyl ether and 0.6g of tetrahydrofuran, the initiation temperature is shown in Table 3, and the rest steps are the same.
Example 4:
the difference from example 1 is that the addition amount of the structure regulator is changed to 0.11g of ethylene glycol dimethyl ether and 0.6g of tetrahydrofuran, the initiation temperature is shown in Table 3, and the rest steps are the same.
Example 5:
the difference from example 1 is that the addition amount of the structure regulator is changed to 0.11g of ethylene glycol dimethyl ether and 1.2g of tetrahydrofuran, the initiation temperature is shown in Table 3, and the rest steps are the same.
Example 6:
the difference from example 1 is that the addition amount of the structure regulator is changed to 0.11g of ethylene glycol dimethyl ether and 1.8g of tetrahydrofuran, the initiation temperature is shown in Table 3, and the rest steps are the same.
Comparative example 1:
the difference from example 1 is that the structure regulator is changed to 0.089g of tetrahydrofurfuryl ethyl ether, the initiation temperature is shown in Table 3, and the rest of the steps are the same.
Comparative example 2:
the difference from example 1 is that the structure regulator is changed to 6.0g of tetrahydrofuran and the initiation temperature is shown in Table 3, the rest of the steps being identical.
Comparative example 3:
the difference from example 1 is that the structure regulator is changed to 0.1g of 2, 2-bis (2-tetrahydrofuranyl) propane, the initiation temperature is shown in Table 3, and the rest of the steps are the same.
Comparative example 4:
the difference from example 1 is that the structure regulator is changed to 0.16g of 2, 2-bis (2-tetrahydrofuranyl) propane, the initiation temperature is shown in Table 3, and the rest of the steps are the same.
Comparative example 5:
the difference from example 1 is that the structure regulator is changed to 0.14g of ethylene glycol dimethyl ether, the initiation temperature is shown in Table 3, and the rest steps are the same.
Comparative example 6:
the difference from example 1 is that the structure regulator is changed to 0.28g of ethylene glycol dimethyl ether, the initiation temperature is shown in Table 3, and the rest steps are the same.
The microstructure and performance test of the solution polymerized styrene-butadiene rubber with fixed block styrene content of the present invention were carried out as follows.
Test 1: the microstructure test of the solution polymerized styrene-butadiene rubber with fixed block styrene content prepared in example 4 of the present invention is shown in FIGS. 2 to 5, wherein FIG. 2 is a view of the solution polymerized styrene-butadiene rubber provided in example 4 of the present invention 1 H-NMR spectrum; FIG. 3 is a block diagram of a solution polymerized styrene-butadiene rubber according to example 4 of the present invention 13 C-NMR spectrum; FIG. 4 is a partial enlarged view of a solution polymerized styrene-butadiene rubber according to example 4 of the present invention 13 C-NMR spectrum; fig. 5 is an infrared spectrum of the solution polymerized styrene-butadiene rubber provided in example 4 of the present invention.
As can be seen from fig. 2 and 5, the solution polymerized styrene-butadiene rubber of the present invention having a fixed block styrene content is composed of five structural units, which are respectively random copolymerized styrene, block styrene, 1, 2-butadiene, cis-butadiene and trans-butadiene; specifically, as can be seen from the infrared spectrogram in fig. 5, the total styrene (random copolymer styrene and block styrene) and cis-butadiene, trans-butadiene and 1, 2-butadiene related information in the solution polymerized styrene-butadiene rubber with a fixed block styrene content; information about random copolymer styrene, block styrene and 1, 2-butadiene can be seen from the H-spectrum of FIG. 2.
Test 2: the solution polymerized styrene-butadiene rubber with the fixed block styrene content prepared in the embodiment 4 of the invention is subjected to COSY and HMBC spectrograms, and the results are shown in figures 6 to 9, wherein figure 6 is a nuclear magnetic resonance COSY spectrogram of the solution polymerized styrene-butadiene rubber with the fixed block styrene content provided in the embodiment 4 of the invention; FIG. 7 is a nuclear magnetic resonance HMBC spectrum a of the solution polymerized styrene-butadiene rubber with fixed block styrene content provided in the embodiment 4 of the present invention; FIG. 8 is a nuclear magnetic resonance HMBC spectrum b of the solution polymerized styrene-butadiene rubber with fixed block styrene content provided in example 4 of the present invention; FIG. 9 is a nuclear magnetic resonance HMBC spectrum c of the solution polymerized styrene-butadiene rubber with fixed block styrene content provided in example 4 of the present invention; from the figure, the blocked styrene groups are mainly linked to trans-butadiene groups, and are analyzed as follows: 1) 1.82ppm of hydrogen atoms of the block styrene group and 1.95ppm of hydrogen atoms of the trans-butadiene group in the COSY spectrogram are 3J-coupled (shown by two arrows in FIG. 6), and the chemical bonds between the two are proved to be directly connected; 2) In the HMBC spectra, the carbon atom at 40.5ppm of the blocked styrene group is coupled to 1.95ppm of hydrogen atoms of the trans-butadiene group (as indicated by the arrow labeled b in FIG. 7), demonstrating a close chemical bond between them. Meanwhile, it was found that 32.6ppm of carbon atoms of the trans-butadiene group were also coupled with 1.82ppm of hydrogen atoms of the block styrene group (as indicated by the arrow labeled a in FIG. 7); 3) In the HMBC spectrogram, the carbon atom at 40.5ppm of the block styrene group is coupled with the hydrogen atom at 5.50ppm of the trans-butadiene group (shown by the arrow in FIG. 8), which proves that the chemical bonds are similar; 4) In the HMBC spectra, the carbon atom at 128.3ppm of the blocked styrene group is coupled to 1.95ppm of hydrogen atoms of the trans-butadiene group (as indicated by the arrow labeled b in FIG. 9), demonstrating a close chemical bond between them. Meanwhile, it was found that 130.0ppm of carbon atoms of the trans-butadiene group were also coupled with 1.82ppm of hydrogen atoms of the block styrene group (as indicated by the arrow labeled a in FIG. 9).
Test 3: the solution polymerized styrene-butadiene rubber with a fixed block styrene content prepared in example 4 of the present invention was subjected to partial fitting of hydrogen spectrum, with para (6.95 ppm) and meta (7.04 ppm) positions on the benzene ring in the block styrene 1 H atom chemical shift and non-block styrene 1 The H atoms have coincident chemical shifts, so that only the ortho positions on the benzene ring in the block styrene are fit 1 The fitting result is shown in fig. 10, fig. 10 is a graph of partial fitting of hydrogen spectrum of solution polymerized styrene-butadiene rubber with fixed block styrene content provided in example 4 of the present invention, in fig. 10, 3 represents an actual detection spectrum, 1 represents gaussian fitting, and 2 represents gaussian superposition of fitting.
Solution polymerized styrene-butadiene rubber according to fixed block styrene content 1 The H-NMR spectrum is partially fitted with chemical shift of curve and judgment of peak type, and four possible distribution forms of block styrene are shown in Table 1.
Solution polymerized styrene-butadiene rubber reverse gating according to fixed block styrene content 13 The C-NMR spectrum shows four possible distribution forms of block styrene, namely chemical shift, peak type and sectional integral area judgment at 125-126ppm, and the specific data are shown in Table 2.
From tables 1 to 2, the data are very good agreement, indicating that the block styrene does exist in four forms in the solution polymerized styrene-butadiene rubber of the invention with a fixed block styrene content.
As can be seen from fig. 6 to 10, the block styrene exists in four distribution forms in the solution polymerized styrene-butadiene rubber of the present invention with a fixed block styrene content, and the block styrene groups are mainly linked to trans-butadiene groups; in the solution polymerized styrene-butadiene rubber with fixed block styrene content, the total styrene (random copolymerized styrene and block styrene) content is 40-50%, the block styrene content is 10-20%, and the random copolymerized polystyrene content is 20-40%; in addition, 20% to 40% (based on 100% butadiene) of the butadiene in the copolymer after addition is present as a 1, 2-butadiene structure, and 60% to 80% (based on 100% butadiene) is present as a 1, 4-butadiene (cis-butadiene and trans-butadiene) structure.
Test 4: the solution polymerized styrene-butadiene rubber with the styrene content of the fixed block in the embodiments 1 to 6 of the present invention was subjected to a performance test including microstructure, mooney viscosity, etc. after being agglomerated and briquetted. As shown in Table 3, the test results show that the invention adopts tetrahydrofuran and ethylene glycol dimethyl ether as the structure regulator, and each example has the microstructure and Mooney viscosity of the solution polymerized styrene-butadiene rubber with fixed block styrene content in the designed range at the specified initiation temperature, and the invention can prepare the solution polymerized styrene-butadiene rubber with fixed block styrene content with low Mooney viscosity and high block styrene content by randomly copolymerizing the residual styrene and butadiene by taking tetrahydrofuran and ethylene glycol dimethyl ether as the structure regulator and adjusting the reactivity ratio of the styrene and adopting other structure regulators, although the total styrene (random copolymerized styrene and block styrene) content and vinyl content meet the index requirement, the block styrene content and Mooney viscosity can not meet the index requirement as shown by the comparative examples 1 to 6.
Test 5: the application of the solution polymerized styrene-butadiene rubber with the fixed block styrene content in shoe materials is characterized in that the solution polymerized styrene-butadiene rubber with the fixed block styrene content prepared in the embodiment 2, the embodiment 3, the embodiment 4, the comparative example 4 and the comparative example 6 is put into a mixing roll for mixing, then a special compounding agent for white smoke shoe materials is poured into the mixing roll for mixing until the set time, and then the materials are discharged, pressed into tablets and cooled for performance evaluation. As shown in Table 4, the performance evaluation results show that the 90 degree tearing and DIN abrasion performance of the solution polymerized styrene-butadiene rubber with fixed block styrene content prepared in examples 2 to 4 of the invention are obviously better than those of comparative examples 4 and 6, and the solution polymerized styrene-butadiene rubber with fixed block styrene content can meet the use requirement of high-end shoe materials.
The technical characteristics form the embodiment of the invention, have stronger adaptability and implementation effect, and can increase or decrease unnecessary technical characteristics according to actual needs so as to meet the requirements of different situations.
Claims (7)
1. The solution polymerized styrene-butadiene rubber with fixed block styrene content is characterized in that the structural units of the solution polymerized styrene-butadiene rubber with fixed block styrene content comprise atactic co-polystyrene, block styrene, 1, 2-butadiene, cis-butadiene and trans-butadiene; wherein,
the content of random copolymer styrene and block styrene in the solution polymerized styrene-butadiene rubber with fixed block styrene content is 40 to 50 percent;
the content of block styrene in the solution polymerized styrene-butadiene rubber with fixed block styrene content is 10 to 20 percent;
the content of 1, 2-butadiene in the solution polymerized styrene-butadiene rubber with the fixed block styrene content is 20 to 40 percent;
the content of cis-butadiene in the solution polymerized styrene-butadiene rubber with the fixed block styrene content is 25 to 30 percent;
the content of trans-butadiene in the solution polymerized styrene-butadiene rubber with the fixed block styrene content is 40 to 45 percent;
the distribution forms of the block styrene in the solution polymerized styrene-butadiene rubber with fixed block styrene content comprise A, B, C and D; wherein the A, B, C and D forms of block styrene comprise 25% to 35%, 15% to 25%, 5% to 20% and 40% to 50% of the total block styrene, respectively;
the block styrene in the solution polymerized styrene-butadiene rubber with fixed block styrene content is connected with a trans-butadiene structural unit.
2. A method for preparing the solution polymerized styrene-butadiene rubber with fixed block styrene content according to claim 1, comprising:
s1, a structure regulator is tetrahydrofuran and ethylene glycol dimethyl ether;
s2, mixing a structure regulator, styrene, butadiene and an initiator in a solvent for polymerization reaction to obtain solution polymerized styrene-butadiene rubber with fixed block styrene content;
the polymerization reaction is specifically carried out as follows: under the protection of inert gas, adding a solvent into a reaction kettle, heating to 40-60 ℃, then adding a structure regulator, starting stirring to uniformly disperse the structure regulator in the solvent, then adding styrene and butadiene, finally adding an initiator to perform polymerization reaction, wherein the polymerization reaction temperature is continuously increased within 10-30 min, then is reduced for 1-2 min, then is continuously increased until the highest reaction temperature is reached, waiting for 10-30 min, and adding a terminator to terminate the reaction to obtain solution polymerized styrene-butadiene rubber with fixed block styrene content, wherein the initiator comprises n-butyllithium, and the solvent is one of cycloalkanes with carbon chain length of 5-8; tetrahydrofuran is present in an amount of from 0.15% to 0.5% by weight based on the total weight of styrene and butadiene.
3. The method for preparing a solution polymerized styrene-butadiene rubber having a fixed block styrene content according to claim 2, wherein the weight of the solvent is 5 to 10 times the total weight of styrene and butadiene, the weight of the initiator is 0.03 to 0.1% of the total weight of styrene and butadiene, and the weight of ethylene glycol dimethyl ether is 0.03 to 0.1% of the total weight of styrene and butadiene.
4. The method for preparing a solution polymerized styrene-butadiene rubber with a fixed block styrene content according to claim 2 or 3, wherein the initiation temperature of the polymerization reaction is 40 ℃ to 60 ℃; and/or the polymerization reaction has a maximum reaction temperature of 70 ℃ to 110 ℃.
5. The method for preparing a solution polymerized styrene-butadiene rubber with fixed block styrene content according to claim 4, wherein the initiation temperature of the polymerization reaction is 45 ℃ to 50 ℃; and/or the polymerization reaction has a maximum reaction temperature of 80 ℃ to 95 ℃.
6. The method for preparing a solution polymerized styrene-butadiene rubber having a fixed block styrene content according to claim 2, 3 or 5, wherein the polymerization is a batch polymerization.
7. Use of the solution polymerized styrene-butadiene rubber of fixed block styrene content according to claim 1 in shoe materials.
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| CN116355152A (en) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | High-transparency block type solution polymerized styrene-butadiene rubber and preparation method thereof |
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