CN112707994B - Preparation method of end-epoxy-terminated functionalized solution-polymerized styrene-butadiene rubber - Google Patents

Preparation method of end-epoxy-terminated functionalized solution-polymerized styrene-butadiene rubber Download PDF

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CN112707994B
CN112707994B CN202011458754.3A CN202011458754A CN112707994B CN 112707994 B CN112707994 B CN 112707994B CN 202011458754 A CN202011458754 A CN 202011458754A CN 112707994 B CN112707994 B CN 112707994B
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butadiene rubber
styrene
polymerized styrene
epoxy
solution
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CN112707994A (en
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冯岸超
孙连伟
高丙轮
王雪
徐林
张立群
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Beijing University of Chemical Technology
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    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
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    • 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
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    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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 

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Abstract

A preparation method of end-epoxy functionalized solution-polymerized styrene-butadiene rubber belongs to the technical field of rubber, and is characterized in that single-end or double-end epoxy group-terminated solution-polymerized styrene-butadiene rubber is obtained by controlling styrene butadiene to be copolymerized in a solution by using a RAFT reagent. Wherein, the solution polymerized styrene-butadiene rubber with the molecular weight of 1000-25000 can be obtained by changing the feeding ratio of the two monomers and the RAFT reagent, and the solution polymerized styrene-butadiene rubber with the mass fraction of styrene of 15-85 percent can be obtained by changing the feeding ratio of the styrene and the butadiene. By the method, the solution-polymerized styrene-butadiene rubber with different molecular weights and different chain segment structures can be obtained simply through RAFT polymerization, and the problem that chain end functionalization is difficult to realize in the preparation process of the solution-polymerized styrene-butadiene rubber is well solved.

Description

Preparation method of end-epoxy-terminated functionalized solution-polymerized styrene-butadiene rubber
Technical Field
The invention discloses a preparation method of single-end or double-end epoxy group-terminated solution-polymerized styrene-butadiene rubber, belonging to the technical field of rubber.
Background
The solution polymerized styrene-butadiene rubber has the advantages of low heat generation, low shrinkage, high vulcanization speed, small rolling resistance, excellent wet skid resistance and wear resistance and the like, and is widely applied to the tire industry, in particular to high-performance tires such as green tires, antiskid tires, ultra-light tires and the like. At present, the solution polymerized styrene-butadiene rubber is mainly obtained by anionic polymerization, but the disadvantages that an organic lithium compound has high risk, the price is increased year by year, the chain end functionalization of the solution polymerized styrene-butadiene rubber is difficult to realize and the like exist, and people turn the attention to low cost and low risk free radical polymerization to replace the traditional anionic polymerization method. RAFT polymerization is one kind of controllable active free radical polymerization, and has the advantages of mild reaction condition, controllable molecular weight, narrow molecular weight distribution, easy chain end functionalization, etc.
The invention content is as follows:
the invention provides a preparation method of end-epoxy functionalized solution polymerized styrene-butadiene rubber. The end-epoxy-terminated functional solution-polymerized styrene-butadiene rubber is obtained by controlling butadiene-styrene copolymerization through RAFT polymerization, and has the structural characteristics that styrene and butadiene are arranged in the middle of a molecular chain of the solution-polymerized styrene-butadiene rubber, the solution-polymerized styrene-butadiene rubber is of a linear random structure, and one side or two sides of the chain end of the molecular chain are terminated by epoxy groups.
The preparation method of the epoxy functionalized solution polymerized styrene-butadiene rubber comprises the following steps:
RAFT polymerization of styrene and butadiene was carried out in a 150mL stainless steel high temperature high pressure reactor. Adding a solvent, a styrene monomer, a butadiene monomer, an RAFT reagent and an initiator into a reactor, wherein the molar ratio of the styrene monomer to the RAFT reagent is 80-1000, the molar ratio of the RAFT reagent to the initiator is 5:1-1:1. Using reactor N 2 Rinse 3 times, then degas the solution and place the reactor at N 2 And (4) sealing the lower part. The reactor was heated at 95 ℃ for 30 hours with stirring. After the reaction is finished, precipitating the reaction solution in methanol with 50-300 times of volume, centrifugally separating the polymer, and drying in a vacuum oven to constant mass to obtain the chain-end epoxy functionalized solution polymerized styrene-butadiene rubber with the mass fraction of styrene being in the range of 15-85% and the molecular weight being in the range of 1000-25000.
The RAFT reagent in the preparation method is xanthate compound with single end or double ends as epoxy groups.
The solvent used in the above preparation method comprises dioxane, tetrahydrofuran, n-hexane, cyclohexane and other organic solvents.
The initiator in the preparation method also comprises Azodiisobutyronitrile (AIBN), azodiisoheptanonitrile (ABVN) azo initiator, benzoyl peroxide, acetophenone peroxide and di-tert-butyl peroxide organic peroxide initiator.
The invention provides a method for preparing chain end epoxy functionalized solution polymerized styrene-butadiene rubber by RAFT polymerization, which can obtain the solution polymerized styrene-butadiene rubber with the molecular weight of 1000-25000 and the molecular weight distribution of 1.1-1.5, and can simply realize the chain end epoxy functionalization of the solution polymerized styrene-butadiene rubber. The obtained chain-end epoxy functionalized solution polymerized styrene-butadiene rubber can directly react with hydroxyl on the surface of white carbon black, can be used as a rubber matrix or a rubber coupling agent, reduces the use amount of Si69 by more than 50% in the traditional processing process, and simultaneously reduces the gas emission of VOCs by more than half, thereby reducing the environmental hazard in the rubber processing process on the premise of uniformly dispersing the white carbon black in the rubber matrix.
Drawings
FIG. 1 is a schematic view of the rubber structure of the present invention
FIG. 2 shows the structure and NMR of the epoxide group-terminated RAFT reagent BODAAT
FIG. 3 is kinetic data of the polymerization process of the present invention
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the embodiment are all conventional commercial products, and the equipment used is conventional equipment.
Example 1
Dioxane (40.00 mL), styrene (7.00 g), butadiene (5.00 g), RAFT agent (BODAAT, 0.33 g), di-t-butyl peroxide (0.024 g) were charged to a 100mL stainless steel autoclave reactor, the reactor headspace was purged with N 2 Rinse 3 times, degas the solution three times, and place the reactor at N 2 And (4) sealing the lower part. The reactor was heated at 95 ℃ for 30 hours with stirring. After completion of the reaction, the reaction mixture was precipitated into methanol (600.00 mL). The polymer was separated using a 15000-revolution centrifuge and dried to constant mass in a vacuum oven (25 ℃,0.70 kPa) to give a double-ended epoxy functionalized solution-polymerized styrene-butadiene rubber with a molecular weight of 2300 with a styrene mass fraction of 23%.
Example 2
Tetrahydrofuran (40.00 mL), styrene (11.45 g), butadiene (5.00 g), RAFT reagent (BODAAT, 0.0975 g), azobisisobutyronitrile (0.027 g) was charged to the reactor and the reactor headspace was purged with N 2 Rinse 3 times, degas the solution three times, and place the reactor at N 2 And (4) sealing the lower part. The reactor was heated at 70 ℃ for 50 hours with stirring. After completion of the reaction, the reaction mixture was precipitated into methanol (600.00 mL). The polymer was separated using a 15000-revolution centrifuge and dried to constant mass in a vacuum oven (25 ℃,0.70 kPa) to give an epoxy functionalized solution polymerized styrene-butadiene rubber with a styrene mass fraction of 65% and a molecular weight of 2,0000.
Embodiment 3
Taking dioxane (40.00 mL), styrene (0.067 mol), butadiene (0.092 mol), RAFT reagent (0.836 mmol) and azobisisobutyronitrile (0.164 mmol) and adding the mixture into a 100mL stainless steel high-temperature high-pressure reactor, and using N to replace the head space of the reactor 2 Rinse 3 times, degas the solution three times, and place the reactor at N 2 And (4) sealing the lower part. The reactor was heated at 95 ℃ for 30 hours with stirring. After completion of the reaction, the reaction mixture was precipitated into methanol (600.00 mL). The polymer was separated using a 15000-revolution centrifuge and dried to constant mass in a vacuum oven (25 ℃,0.7 kpa) to give a single-ended epoxy functionalized solution-polymerized styrene-butadiene rubber with a styrene mass fraction of 23% and a molecular weight of 2100.
The preparation method adopts xanthate RAFT reagent with a single end as an epoxy group.
Example 4
Cyclohexane (40.00 mL), styrene (0.11 mol), butadiene (0.092 mol), RAFT reagent (0.836 mmol), and benzoyl peroxide (0.164 mmol) were charged to a 100mL stainless steel autoclave reactor, and the reactor headspace was replaced with N 2 Rinse 3 times, degas the solution three times, and place the reactor at N 2 And (4) sealing the lower part. The reactor was heated at 60 ℃ for 30 hours with stirring. After completion of the reaction, the reaction mixture was precipitated into methanol (600.00 mL). The polymer was separated using a 15000-revolution centrifuge and dried to constant mass in a vacuum oven (25 ℃,0.7 kPa) to give a styrene mass fraction of67% of single-end epoxy functionalized solution polymerized styrene-butadiene rubber with molecular weight of 2000.
The preparation method selects xanthate RAFT reagent with epoxy group at single end.
Example 5
The following formulation was used: the modified styrene-butadiene rubber comprises 96.3g of solution polymerized styrene-butadiene rubber SSBR, 30g of BR9000, 70g of VN3, 3g of silane coupling agent Si69, 23 mass percent of styrene, 7g of double-end epoxy functionalized solution polymerized styrene-butadiene rubber with the molecular weight of 2000, 2g of stearic acid, 3.5g of ZnO, 2g of accelerator NS, 2g of accelerator D, 1g of anti-aging agent 4020 and 1.7g of sulfur.
The method comprises the following specific processing steps: and (2) banburying the solution polymerized styrene butadiene rubber SSBR and BR9000 in an internal mixer for 2 minutes at the temperature of 50 ℃, then equally dividing the mixture of VN3, si69 and the double-end epoxy functionalized solution polymerized styrene butadiene rubber into the internal mixer for banburying four times, and adding ZnO, stearic acid and an antioxidant 4020 into the internal mixer for banburying for 7 minutes when the mixture is added for the last time. The temperature of the internal mixer is adjusted to 150 ℃ and the heat treatment is carried out for 5 minutes.
And (3) adding the mixture treated by the internal mixer, sulfur, an accelerator NS and an accelerator D into an open mill for milling for 10 minutes to obtain a rubber compound. And (3) placing the rubber compound in a flat vulcanizing instrument for vulcanizing for 35 minutes at the temperature of 150 ℃ and under the pressure of 15MPa to obtain the processed solution polymerized styrene-butadiene rubber. The difference between the maximum and minimum storage modulus of the compound (Δ G') was 360.75kPa as determined by the rubber processing rheometer, meaning that the white carbon filler was uniformly dispersed.

Claims (2)

1. An end-epoxy functionalized solution polymerized styrene-butadiene rubber is characterized in that: the middle of the molecular chain comprises a polystyrene segment and a polybutadiene segment, and the molecular chain is of a linear random structure; the molecular chain end is terminated by an epoxy group, the structural formula is one of the following formulas, wherein n is more than or equal to 3 and less than or equal to 150; m is more than or equal to 5 and less than or equal to 200:
Figure FDA0003716747920000012
2. a process for preparing the end-epoxidized functionalized solution-polymerized styrene-butadiene rubber according to claim 1, characterized in that: using a RAFT reagent with a single end or double ends as epoxy groups, and copolymerizing polystyrene and butadiene in a solution to obtain chain-end epoxy functional solution polymerized styrene-butadiene rubber; the method comprises the following specific operation steps: adding a magnetic stirrer, a solvent, styrene, butadiene, a RAFT reagent and an initiator into a high-pressure reaction kettle, wherein the molar ratio of styrene monomer to butadiene monomer is 100-1 2 Sealing, stirring and heating for 30 hours at 95 ℃, precipitating the reaction solution in methanol with 50-300 times of volume after the reaction is finished, and obtaining the end epoxy functionalized solution polymerized styrene-butadiene rubber with the mass fraction of styrene being within 15-85% and the molecular weight being within 1000-25000;
when the RAFT reagent adopts xanthate compounds with single-end epoxy, the obtained chain-end epoxy functionalized solution polymerized styrene-butadiene rubber is terminated by the single-end epoxy group; when the RAFT reagent selects a xanthate compound with epoxy at both ends, the obtained chain-end epoxy functionalized solution polymerized styrene-butadiene rubber is terminated with an epoxy group at both ends;
the solvent is selected from tetrahydrofuran, normal hexane, cyclohexane and dioxane organic solvent;
the initiator is azo initiator or organic peroxide initiator.
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