CN112142915A - Preparation method of integrated rubber - Google Patents
Preparation method of integrated rubber Download PDFInfo
- Publication number
- CN112142915A CN112142915A CN202011022246.0A CN202011022246A CN112142915A CN 112142915 A CN112142915 A CN 112142915A CN 202011022246 A CN202011022246 A CN 202011022246A CN 112142915 A CN112142915 A CN 112142915A
- Authority
- CN
- China
- Prior art keywords
- polymerization
- kettle
- cyclohexane
- polymerization kettle
- butyllithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
Abstract
The invention discloses a preparation method of integrated rubber, which comprises the following steps: adding isoprene, styrene, butadiene, cyclohexane and a structure regulator into a No. 1 polymerization kettle respectively, stirring uniformly, and heating to 40-70 ℃; adding isoprene, styrene, butadiene, cyclohexane and a structure regulator into a polymerization kettle respectively, stirring uniformly, and heating to 40-70 ℃; respectively adding catalyst diluent of n-butyllithium into a No. 1 polymerization kettle and a No. 2 polymerization kettle, and respectively adding isopropanol into the No. 1 polymerization kettle and the No. 2 polymerization kettle after reaction time is reached to terminate the reaction; respectively obtaining a low molecular weight glue solution and a high molecular weight glue solution by a No. 1 polymerization kettle and a No. 2 polymerization kettle; transferring the glue solution in the No. 1 polymerization kettle and the No. 2 polymerization kettle to a mixing kettle according to the mass ratio of 0.05-0.2: 1, heating to 40 ℃, and stirring for 20 min; and pouring the glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and then drying to obtain the liquid glue filled type integrated rubber. The integrated rubber prepared by the method has lower Mooney viscosity.
Description
Technical Field
The invention relates to the technical field of rubber preparation, in particular to a preparation method of integrated rubber.
Background
The integrated rubber (SIBR) is a novel rubber for a tire tread, and is remarkably characterized in that a molecular chain is composed of chain segments with various structures, the chain segments have better flexibility and similar flexibility to butadiene rubber, the chain segments have weaker flexibility and similar flexibility to butadiene styrene rubber, the chain segments with different structures provide different performances of the rubber, and the chain segments with strong flexibility can enable the rubber to have excellent low-temperature performance, and meanwhile, the rolling friction resistance can be reduced, and the wear resistance of the tire is improved. The more rigid chain segment increases the wet grip of the rubber and improves the safety of the tire in running on wet and slippery road surfaces.
Since Nordsiek et al proposed the concept of integrated rubber, a great deal of work has been done in more than ten countries, such as the united states, germany, china, japan, korea, russia, france, etc., to improve the performance of integrated rubber. Since anionic polymerization has the characteristics of adjustable molecular weight and molecular structure, anionic solution polymerization is mostly adopted in the method for synthesizing the integrated rubber. In practical commercial applications, the most common method is to manipulate the copolymerization rate of styrene, butadiene and isoprene, and the 1, 2-structure of butadiene units and the 3, 4-structure of isoprene units in the polymer by adding a molecular structure modifier with polarity in combination with the adjustment of polymerization process conditions, thereby obtaining an SIBR having a certain regular distribution of multi-layered polymer chain structure.
The integrated rubber obtained by the traditional anionic solution polymerization method is a rigid structure polymer, and has single molecular weight, higher molecular weight and narrower molecular weight distribution, so that the integrated rubber has the defects of high Mooney viscosity, poor processability and the like in the actual industrial production. In addition, the filled oil is easy to separate out in the vulcanization process of the rubber, so that the use of later-stage vulcanized products is influenced, and the environment is also adversely affected. There is also a report in the literature that the star-structured integrated rubber is prepared by coupling reaction, so as to broaden the molecular weight distribution of the polymer and improve the processability thereof, but the effect is not obvious. There are also patents which disclose the use of emulsion polymerization to prepare integral rubbers, although free radical initiated emulsion polymerization systems can achieve broad molecular weight distributions, they have great limitations in the adjustment of rubber molecular weight and microstructure.
Disclosure of Invention
The object of the present invention is to provide a process for the preparation of an integrated rubber having a lower Mooney viscosity.
In order to achieve the purpose, the invention provides the following technical scheme: an integrated rubber preparation method comprises the following steps: step S1, replacing the polymerization kettle No. 1 with high-purity nitrogen and cleaning with cyclohexane, adding isoprene, styrene, butadiene, cyclohexane and a structure regulator into the polymerization kettle No. 1 respectively according to a proportion, uniformly stirring, and heating the polymerization kettle No. 1 to 40-70 ℃; step S2, replacing the polymerization kettle No. 2 with high-purity nitrogen and cleaning with cyclohexane, adding isoprene, styrene, butadiene, cyclohexane and a structure regulator into the polymerization kettle respectively in proportion, stirring uniformly, and heating the polymerization kettle No. 2 to 40-70 ℃; step S3, adding the catalyst diluent of n-butyllithium into a No. 1 polymerization kettle and a No. 2 polymerization kettle respectively to initiate monomer polymerization reaction for 4 hours; after the reaction time is reached, respectively adding isopropanol into No. 1 and No. 2 polymerization kettles to terminate the reaction; respectively obtaining a low molecular weight glue solution and a high molecular weight glue solution by a No. 1 polymerization kettle and a No. 2 polymerization kettle; step S4, transferring the glue solution in the polymerization kettle No. 1 and the polymerization kettle No. 2 to a mixing kettle according to the mass ratio of 0.05-0.2: 1, heating the mixing kettle to 40 ℃, and stirring at a high speed for 20 min; step S5, pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and then drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber; wherein the feeding molar ratio of isoprene, butadiene, styrene and cyclohexane in the polymerization kettle No. 1 and the polymerization kettle No. 2 is 3-5: 1-3: 30-50; wherein the feeding molar ratio of the catalyst diluent of isoprene to n-butyllithium in the polymerization kettle No. 1 is 250-350: 1; feeding mole ratio of catalyst diluent of isoprene and n-butyllithium in a No. 2 polymerization kettle is 2500-3500: 1; wherein the molar ratio of the catalyst diluent of the n-butyllithium to the structure regulator is 1: 0.01-0.1.
Further, before step 1, the preparation method further comprises: the preparation of the catalyst diluent of n-butyllithium is carried out by first replacing with high-purity nitrogen gas and washing the catalyst dilution kettle with cyclohexane, then injecting cyclohexane and hexane solution of n-butyllithium into the dilution kettle, wherein the mass ratio of the hexane solution of n-butyllithium to the cyclohexane is 1:49, stirring and mixing for 15 minutes to form the catalyst diluent of n-butyllithium.
Further, the n-butyllithium hexane solution has a concentration of 0.8M to 2.5M.
Further, the structure regulator is one or more of potassium tert-butoxide, potassium tert-amylate, tetrahydrofuran, sodium dodecyl benzene sulfonate, dimethoxyethane, diethylene glycol dimethyl ether, tetramethyl vinyl diamine, triethylamine and pentamethyl divinyl triamine.
Further, the structure regulator is potassium tert-butoxide.
Further, the feeding molar ratio of isoprene, butadiene, styrene and cyclohexane in the polymerization reactor No. 1 and the polymerization reactor No. 2 is 4:4:2: 40.
Further, the molar ratio of the catalyst diluent of the n-butyllithium to the structure regulator is 1: 0.05-0.1.
Further, the charging mass ratio of the isopropyl alcohol added for terminating the reaction in step S3 to the isoprene was 0.5: 1.
Further, the mass ratio of the glue solution in the No. 1 polymerization kettle to the glue solution in the No. 2 polymerization kettle fed into the mixing kettle is 0.1: 1.
The invention provides a method for preparing liquid rubber filled type integrated rubber by anion living polymerization. The method realizes low molecular weight liquid integrated rubber and high molecular weight solid integrated rubber with specific structures through active polymerization and introduction of a structure regulator, the solid integrated rubber is plasticized through the liquid integrated rubber, and the liquid integrated rubber can participate in co-vulcanization reaction in the vulcanization process and has small influence on the mechanical property of the solid rubber, so that the balance of the processing property and the mechanical property of the integrated rubber is realized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0468g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 40 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was heated to 40 ℃.
81.3ml of catalyst diluent was added to polymerization kettle No. 1 for 4 hours.
8.1ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
Transferring 10g of glue solution in the No. 1 polymerization kettle to a mixing kettle, transferring 190g of glue solution in the No. 2 polymerization kettle to the mixing kettle, heating the mixing kettle to 40 ℃, and stirring at high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Example 2
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0468g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 40 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was heated to 40 ℃.
81.3ml of catalyst diluent was added to polymerization kettle No. 1 for 4 hours.
8.1ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
Transferring 20g of glue solution in the polymerization kettle No. 1 to a mixing kettle, transferring 180g of glue solution in the polymerization kettle No. 2 to the mixing kettle, heating the mixing kettle to 40 ℃, and stirring at high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Example 3
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0468g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 40 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was heated to 40 ℃.
81.3ml of catalyst diluent was added to polymerization kettle No. 1 for 4 hours.
8.1ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
30g of glue solution in the polymerization kettle No. 1 is transferred to a mixing kettle, 170g of glue solution in the polymerization kettle No. 2 is transferred to the mixing kettle, the temperature of the mixing kettle is raised to 40 ℃, and the mixture is stirred at a high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Example 4
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0468g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 40 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was heated to 40 ℃.
68ml of catalyst diluent was added to polymerization kettle No. 1, and the reaction time was 4 hours.
6.8ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
Transferring 10g of glue solution in the No. 1 polymerization kettle to a mixing kettle, transferring 190g of glue solution in the No. 2 polymerization kettle to the mixing kettle, heating the mixing kettle to 40 ℃, and stirring at high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Example 5
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.117g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 40 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane, and 0.0117g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was heated to 40 ℃.
81.3ml of catalyst diluent was added to polymerization kettle No. 1 for 4 hours.
8.1ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
Transferring 10g of glue solution in the No. 1 polymerization kettle to a mixing kettle, transferring 190g of glue solution in the No. 2 polymerization kettle to the mixing kettle, heating the mixing kettle to 40 ℃, and stirring at high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Example 6
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 1.6M hexane solution of n-butyllithium were charged into the dilution vessel, and stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0468g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 40 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was heated to 40 ℃.
81.3ml of catalyst diluent was added to polymerization kettle No. 1 for 4 hours.
8.1ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
Transferring 10g of glue solution in the No. 1 polymerization kettle to a mixing kettle, transferring 190g of glue solution in the No. 2 polymerization kettle to the mixing kettle, heating the mixing kettle to 40 ℃, and stirring at high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Example 7
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 2M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0468g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 40 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was heated to 40 ℃.
81.3ml of catalyst diluent was added to polymerization kettle No. 1 for 4 hours.
8.1ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
Transferring 10g of glue solution in the No. 1 polymerization kettle to a mixing kettle, transferring 190g of glue solution in the No. 2 polymerization kettle to the mixing kettle, heating the mixing kettle to 40 ℃, and stirring at high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Example 8
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0468g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 50 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was warmed to 50 ℃.
81.3ml of catalyst diluent was added to polymerization kettle No. 1 for 4 hours.
8.1ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
Transferring 10g of glue solution in the No. 1 polymerization kettle to a mixing kettle, transferring 190g of glue solution in the No. 2 polymerization kettle to the mixing kettle, heating the mixing kettle to 40 ℃, and stirring at high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Example 9
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel No. 1 was purged with high-purity nitrogen and washed with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0468g of potassium tert-butoxide were added to the polymerization vessel No. 1, respectively, and stirred uniformly, and the polymerization vessel No. 1 was heated to 70 ℃.
Polymerization vessel No. 2 was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium tert-butoxide were added to polymerization vessel No. 2, respectively, and stirred. The polymerization kettle No. 2 was warmed to 70 ℃.
81.3ml of catalyst diluent was added to polymerization kettle No. 1 for 4 hours.
8.1ml of catalyst diluent was added to polymerization kettle No. 2, and the reaction time was 4 hours.
After the reaction time is reached, 13.6g of isopropanol are respectively added into the polymerization kettles No. 1 and No. 2 to terminate the reaction.
Transferring 10g of glue solution in the polymerization kettle No. 1 to a mixing kettle, transferring 190g of glue solution in the polymerization kettle No. 2 to the mixing kettle, heating the mixing kettle to 70 ℃, and stirring at high speed for 20 min.
And pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber.
Comparative example 1
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium t-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 40 ℃.
8.1ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 190g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Comparative example 2
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium t-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 40 ℃.
8.1ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 180g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Comparative example 3
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium t-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 40 ℃.
8.1ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 170g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Comparative example 4
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium t-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 40 ℃.
6.8ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 180g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Comparative example 5
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0117g of potassium tert-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 40 ℃.
8.1ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 180g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Comparative example 6
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 1.6M hexane solution of n-butyllithium were charged into the dilution vessel, and stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium t-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 40 ℃.
8.1ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 180g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Comparative example 7
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 2.0M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium t-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 40 ℃.
8.1ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 180g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Comparative example 8
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium t-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 50 ℃.
8.1ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 180g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Comparative example 9
The catalyst dilution vessel was purged with cyclohexane while purging with high-purity nitrogen, and then 490g of cyclohexane and 10g of a 0.8M hexane solution of n-butyllithium were poured into the dilution vessel, stirred and mixed for 15 minutes to obtain a diluted solution of n-butyllithium as a catalyst.
The polymerization vessel was purged with high-purity nitrogen and purged with cyclohexane, and 27.2g of isoprene, 20.8g of styrene, 21.6g of butadiene, 336g of cyclohexane and 0.0047g of potassium t-butoxide were added to the polymerization vessel, respectively, and stirred. The polymerization kettle was warmed to 70 ℃.
8.1ml of catalyst diluent was added to the polymerization kettle and the reaction time was 4 hours.
After the reaction time was reached, 13.6g of isopropyl alcohol was added to the polymerization vessel to terminate the reaction.
Pouring 180g of glue solution in the polymerization kettle into absolute ethyl alcohol for flocculation, and drying rubber obtained by flocculation to finally obtain the unfilled liquid glue type integrated rubber.
Note: number average molecular weight and polydispersity measurements were characterized by GPC
The 1,4 structure content was characterized by 1H NMR
Mooney viscosity test the Mooney viscosity test was carried out with reference to GB/T1232.1-2000
Table 1 examples 1-9 integrated rubber property table
TABLE 2 COMPARATIVE EXAMPLES 1-9 INTEGRATED RUBBER PROPERTIES
| Mooney viscosity | |
| Comparative example 1 | 60 |
| Comparative example 2 | 58 |
| Comparative example 3 | 60 |
| Comparative example 4 | 67 |
| Comparative example 5 | 60 |
| Comparative example 6 | 38 |
| Comparative example 7 | 34 |
| Comparative example 8 | 60 |
| Comparative example 9 | 61 |
As can be seen from the comparison of the Mooney viscosity data of the examples and comparative examples, the introduction of the low molecular weight liquid gum improves the processability of the integral rubber, so that the liquid gum filled type integral rubber has a lower Mooney viscosity than the unfilled type integral rubber. And because the liquid rubber contains double bonds and can be co-vulcanized with solid rubber, the liquid rubber has the advantages of no migration, no precipitation, small influence on mechanical properties and the like, and has obvious advancement compared with the disclosed oil-extended method.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of integrated rubber is characterized by comprising the following steps:
step S1, replacing the polymerization kettle No. 1 with high-purity nitrogen and cleaning with cyclohexane, adding isoprene, styrene, butadiene, cyclohexane and a structure regulator into the polymerization kettle No. 1 respectively according to a proportion, uniformly stirring, and heating the polymerization kettle No. 1 to 40-70 ℃;
step S2, replacing the polymerization kettle No. 2 with high-purity nitrogen and cleaning with cyclohexane, adding isoprene, styrene, butadiene, cyclohexane and a structure regulator into the polymerization kettle respectively in proportion, stirring uniformly, and heating the polymerization kettle No. 2 to 40-70 ℃;
step S3, adding the catalyst diluent of n-butyllithium into a No. 1 polymerization kettle and a No. 2 polymerization kettle respectively to initiate monomer polymerization reaction for 4 hours; after the reaction time is reached, respectively adding isopropanol into No. 1 and No. 2 polymerization kettles to terminate the reaction; respectively obtaining a low molecular weight glue solution and a high molecular weight glue solution by a No. 1 polymerization kettle and a No. 2 polymerization kettle;
step S4, transferring the glue solution in the polymerization kettle No. 1 and the polymerization kettle No. 2 to a mixing kettle according to the mass ratio of 0.05-0.2: 1, heating the mixing kettle to 40 ℃, and stirring at a high speed for 20 min;
step S5, pouring the mixed glue solution in the mixing kettle into absolute ethyl alcohol for flocculation, and then drying the rubber obtained by flocculation to finally obtain the liquid-filled glue type integrated rubber;
wherein the feeding molar ratio of isoprene, butadiene, styrene and cyclohexane in the polymerization kettle No. 1 and the polymerization kettle No. 2 is 3-5: 1-3: 30-50;
wherein the feeding molar ratio of the catalyst diluent of isoprene to n-butyllithium in the polymerization kettle No. 1 is 250-350: 1; feeding mole ratio of catalyst diluent of isoprene and n-butyllithium in a No. 2 polymerization kettle is 2500-3500: 1;
wherein the molar ratio of the catalyst diluent of the n-butyllithium to the structure regulator is 1: 0.01-0.1.
2. The method of preparing an integrated rubber according to claim 1, wherein the method of preparing further comprises, prior to step 1: the preparation of the catalyst diluent of n-butyllithium is carried out by first replacing with high-purity nitrogen gas and washing the catalyst dilution kettle with cyclohexane, then injecting cyclohexane and hexane solution of n-butyllithium into the dilution kettle, wherein the mass ratio of the hexane solution of n-butyllithium to the cyclohexane is 1:49, stirring and mixing for 15 minutes to form the catalyst diluent of n-butyllithium.
3. The method of claim 1, wherein the n-butyllithium is present in a hexane solution at a concentration of 0.8M to 2.5M.
4. The method of claim 1, wherein the structural regulator is one or more of potassium tert-butoxide, potassium tert-amylate, tetrahydrofuran, sodium dodecylbenzenesulfonate, dimethoxyethane, diglyme, tetramethylethylenediamine, triethylamine, and pentamethyldiethylenetriamine.
5. The method of claim 4, wherein the structural regulator is potassium tert-butoxide.
6. The integrated rubber preparation method of claim 1, wherein the feeding molar ratio of isoprene, butadiene, styrene and cyclohexane in the polymerization tank No. 1 and the polymerization tank No. 2 is 4:4:2: 40.
7. The method of claim 1, wherein the molar ratio of the n-butyllithium catalyst diluent to the structure modifier is 1:0.05 to 0.1.
8. The method for preparing integrated rubber according to claim 1, wherein the charging mass ratio of the isopropanol and the isoprene added in the step S3 for terminating the reaction is 0.5: 1.
9. The preparation method of the integrated rubber according to claim 1, wherein the mass ratio of the glue solution in the No. 1 polymerization kettle to the glue solution in the No. two polymerization kettles to be fed into the mixing kettle is 0.1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011022246.0A CN112142915A (en) | 2020-09-25 | 2020-09-25 | Preparation method of integrated rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011022246.0A CN112142915A (en) | 2020-09-25 | 2020-09-25 | Preparation method of integrated rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112142915A true CN112142915A (en) | 2020-12-29 |
Family
ID=73897088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011022246.0A Pending CN112142915A (en) | 2020-09-25 | 2020-09-25 | Preparation method of integrated rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112142915A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153255A (en) * | 1989-06-26 | 1992-10-06 | Japan Synthetic Rubber Co., Ltd. | Process for preparing a rubber composition having two different molecular weights |
| CN1653096A (en) * | 2002-03-15 | 2005-08-10 | 日本瑞翁株式会社 | Diene rubber, process for production thereof, rubber compositions, process for producing the same, and crosslinked rubbers |
| CN103467798A (en) * | 2012-06-06 | 2013-12-25 | 中国石油化工股份有限公司 | Elastomer composition and oil-extended rubber |
-
2020
- 2020-09-25 CN CN202011022246.0A patent/CN112142915A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153255A (en) * | 1989-06-26 | 1992-10-06 | Japan Synthetic Rubber Co., Ltd. | Process for preparing a rubber composition having two different molecular weights |
| CN1653096A (en) * | 2002-03-15 | 2005-08-10 | 日本瑞翁株式会社 | Diene rubber, process for production thereof, rubber compositions, process for producing the same, and crosslinked rubbers |
| CN103467798A (en) * | 2012-06-06 | 2013-12-25 | 中国石油化工股份有限公司 | Elastomer composition and oil-extended rubber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104350075B (en) | Copolymer, its rubber composition and tire is used | |
| US9133293B2 (en) | Copolymer rubber having a star-shaped block structure, the preparation process and use thereof | |
| CN105777946B (en) | Both-end is modified star-like solution polymerized butadiene styrene rubber and preparation method thereof and vulcanization rubber and its application | |
| CN108864434B (en) | Epoxy polysiloxane modified solution polymerized styrene-butadiene rubber, preparation and application thereof | |
| CN109251264B (en) | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof | |
| CN110746539A (en) | Molecular chain middle-end functionalized SSBR, synthesis method thereof and application thereof in tire tread rubber | |
| US20170114172A9 (en) | Branched Broad MWD Conjugated Diene Polymer | |
| CN107207632B (en) | Process for producing modified conjugated diene rubber | |
| JP2003531256A (en) | Process for preparing SBR rubber with improved processability and reduced rolling resistance | |
| CN112142915A (en) | Preparation method of integrated rubber | |
| CN102120798B (en) | Method for synthesizing star-shaped solution polymerized butadiene-styrene rubber by using modified initiator | |
| KR102155685B1 (en) | A composition for seeded polymerization, a conjugated diene copolymer, an molded body, and a method for preparing the same | |
| CN110256631A (en) | Ternary atactic copolymer and its preparation method and application containing beta-myrcene | |
| CN107286296B (en) | Application of butadiene-b-isoprene polymer | |
| CN108239225B (en) | Styrene butadiene rubber and preparation method thereof | |
| KR20150056312A (en) | A Method for Improving Coupling of Anion Conjugated Polymerization | |
| CN109575189B (en) | Monovinylarene-conjugated diene polymer and preparation method and application thereof | |
| CN108219067B (en) | Functionalized butadiene polymer and preparation method thereof | |
| CN112521554B (en) | Synthesis method of solution polymerized styrene-butadiene rubber, low-heat-generation solution polymerized styrene-butadiene rubber and automobile tire | |
| CN112694566B (en) | Method for synthesizing solution polymerized butadiene-isoprene rubber | |
| CN112409540B (en) | Method for synthesizing random solution polymerized styrene butadiene rubber | |
| CN106977656B (en) | Dendritic polydiene rubber and preparation method thereof | |
| KR101614985B1 (en) | Modified conjugated-diene polymers and process for their preparation | |
| Adams et al. | The Impact of Lithium Initiators on the Preparation of Synthetic Rubbers | |
| CN103848948B (en) | Partially hydrogenated terpolymer, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201229 |