CN112194758B - Isoprene-styrene copolymer and preparation method thereof - Google Patents
Isoprene-styrene copolymer and preparation method thereof Download PDFInfo
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- CN112194758B CN112194758B CN202010952451.0A CN202010952451A CN112194758B CN 112194758 B CN112194758 B CN 112194758B CN 202010952451 A CN202010952451 A CN 202010952451A CN 112194758 B CN112194758 B CN 112194758B
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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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
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- 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
Abstract
The invention discloses a high trans-polyisoprene/isotactic polystyrene copolymer and a preparation method thereof. The copolymer consists of 2 to 70 weight percent of isotactic polystyrene with the isotactic content of more than 75mol percent and 30 to 98 weight percent of trans-1, 4-structure content of more than 90mol percent of high trans-polyisoprene. The copolymer is prepared by copolymerizing isoprene and styrene by using a magnesium chloride supported titanium catalyst as a main catalyst and alkyl aluminum as a cocatalyst. The copolymer of the invention consists of isoprene monomer chain segments and styrene monomer chain segments with different sequence contents and distributions in a multilayer way. The thermal property and the physical and mechanical properties of the copolymer can be adjusted by adjusting the content of two chain links in the copolymer.
Description
Technical Field
The invention belongs to the field of synthetic rubber materials, and particularly relates to a preparation method of a trans-1, 4-structure polyisoprene and high isotactic structure polystyrene copolymer and a high trans-polyisoprene/isotactic polystyrene copolymer prepared by the method.
Background
The trans-1, 4-structure diene polymer is applicable to high-performance tire compounds due to excellent flex fatigue resistance, low rolling resistance, low compression heat generation and abrasion. Patents (CN103387641A, CN 105601814A, US 5,100,965, wo. Pat. No. 97,23521, US 4,020.115, US 5,844,044, UK Pat. appl.2,029,426, Journal Applied Polymer Science 2004,92:2941) report that butadiene (Bd) -isoprene (Ip) copolymer TBIR of high trans structure has excellent physical and mechanical properties, in particular excellent fatigue resistance and crack growth resistance, and is an ideal compound for developing high performance tires. Butadiene is copolymerized with styrene to obtain thermoplastic elastomer SBS or copolymer rubber SBR with excellent performance. Butadiene and styrene in SBS and SBR are both non-stereoregular copolymers.
Isoprene and styrene copolymerization can be achieved using free radical, anionic, cationic and coordination polymerization mechanisms. There are reports of obtaining high molecular weight styrene-isoprene comb graft copolymers by free radical emulsion polymerization. The radial polystyrene-polyisoprene-radial polystyrene triblock copolymer is prepared by taking n-BuLi as an initiator and cyclohexane as a solvent through an anion stepwise polymerization method, and the arm number of the terminal block can be accurately controlled. However, the block copolymer of styrene and isoprene is not suitable for a rubber for a tire because of its high glass transition temperature (Tg) and low abrasion resistance. At present, the coordination polymerization is mainly used for synthesizing a cis-1, 4-polyisoprene and styrene copolymer, mainly takes a rare earth catalyst and a metallocene catalyst system as main components, and reports on the synthesis of a stereoregular copolymer of isoprene and styrene under the catalysis of a traditional supported titanium catalyst are not found. Most of the styrene-isoprene copolymers reported so far have a block structure. And styrene in the copolymer appears on the main chain of the polyisoprene in a random distribution manner, so that the strength and the traction performance of the polymer are greatly improved, and the copolymer is more favorable for being used in rubber for rubber tires.
In order to develop a novel rubber material for high-performance tires and prepare trans-1, 4-structure polyisoprene and high isotactic structure polystyrene copolymer rubber, MgCl is adopted in the invention2The supported titanium catalyst is used for synthesizing isoprene rubber with a trans-1, 4-structure and polystyrene copolymer rubber with an identical structure (TPI-iPS copolymer rubber for short) by adopting a bulk copolymerization method. MgCl2The loaded titanium catalyst has the characteristics of high catalytic efficiency, controllable and adjustable spatial three-dimensional structure and the like. Meanwhile, by controlling the polymerization process, a high trans-polyisoprene/isotactic polystyrene copolymer with gradient composition or a high trans-polyisoprene/isotactic polystyrene copolymer with uniform composition is synthesized.
Disclosure of Invention
One of the objectives of the present invention is to synthesize a high trans polyisoprene/isotactic polystyrene copolymer with a gradient composition or a more uniform composition.
The invention also aims to provide a synthetic method for synthesizing the high-trans polyisoprene/isotactic polystyrene copolymer.
The invention also aims to provide a novel isoprene-styrene copolymer rubber with high tensile strength, excellent wear resistance and fatigue resistance, high wet skid resistance and low rolling resistance.
The isoprene-styrene copolymer is composed of styrene monomer units with the mole fraction of 2% -70% and isoprene monomer units with the mole fraction of 30% -98%; wherein the styrene monomer unit is of a high isotactic structure, and the isoprene monomer unit is of a high trans-1, 4-structure.
The trans-1, 4-structure content of the isoprene monomer unit in the isoprene-styrene copolymer of the present invention>90mol%, isotactic content of styrene monomer units>75 mol%, the weight-average molecular weight of the copolymer being 1X 104～150×104The molecular weight distribution is 1.4-15.8. The isotactic content of styrene monomer units is 75-94 mol%.
In the isoprene-styrene copolymer, styrene is distributed in an isoprene chain segment in a sequence structure of less than 10 monomer units; the glass transition temperature of the isoprene second-line chain segment is-69 ℃ to-62 ℃, and the melting temperature is 44 ℃ to 50 ℃; the glass transition temperature of the styrene chain segment is 99-112 ℃, and the melting temperature is 219.4-219.7 ℃.
The isoprene-styrene copolymer is synthesized by adopting a Ziegler-Natta catalytic system consisting of a supported titanium catalyst, an organic aluminum compound and an external electron donor; wherein the supported titanium catalyst is a spherical or non-spherical catalyst which takes magnesium dichloride as a carrier and contains a titanium compound, and titanium element accounts for 1 to 5 percent of the total mass of the magnesium dichloride supported titanium catalyst; the titanium compound is selected from TiCl4、TiBr4Or TiI4One of (1); the external electron donor is selected from one or more of silane compounds, ether compounds or ester compounds. The organic aluminum compound is one or more of triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, dihexyl aluminum monochloride and dioctyl aluminum monochloride; the external electron donor is one or two of organic compounds containing silicon or nitrogen or oxygen.
The preparation method of the isoprene-styrene copolymer comprises the following steps: adding a certain amount of organic solvent, isoprene, styrene, an organic aluminum compound and a magnesium dichloride supported titanium catalyst into a polymerization device for copolymerization, wherein the styrene and the isoprene areThe initial feeding molar ratio of 5: 100-90: 100, and the molar ratio of the titanium element to the monomer in the supported titanium catalyst is 1 x 10-8:1～1×10-41, the molar ratio of aluminum element in an organic aluminum compound to titanium element in a supported titanium catalyst is 20: 1-200: 1, the molar ratio of an external electron donor to titanium element in the supported titanium catalyst is 0: 1-20: 1, the molar ratio of an organic solvent to a monomer is 0: 100-300: 100, the polymerization temperature is 10-100 ℃, the molar ratio of hydrogen to the monomer is 0.0001: 1-1: 1, the polymerization time is 1-72 hours, the solvent and unreacted monomer are removed after the preset polymerization time is reached, and the isoprene-styrene copolymer of claim 1 is obtained by drying.
The preparation method of the isoprene-styrene copolymer comprises the following steps: adding a certain amount of organic solvent, isoprene, styrene, an organic aluminum compound and a magnesium dichloride supported titanium catalyst into a polymerization device for copolymerization, wherein the initial feeding molar ratio of the styrene to the isoprene is 5: 100-90: 100, and the molar ratio of a titanium element to a monomer in the supported titanium catalyst is 1 x 10-8:1～1×10-41, the molar ratio of an aluminum element in an organic aluminum compound to a titanium element in a supported titanium catalyst is 20: 1-200: 1, the molar ratio of an external electron donor to the titanium element in the supported titanium catalyst is 0: 1-20: 1, the molar ratio of an organic solvent to a monomer is 0: 100-300: 100, a styrene monomer is continuously or intermittently supplemented in the reaction process to keep the molar ratio of styrene to isoprene in the reaction system at an initial feeding molar ratio, the polymerization reaction temperature is 10-100 ℃, the molar ratio of hydrogen to the monomer is 0.0001: 1-1: 1, the polymerization time is 1-72 hours, the solvent and unreacted monomers are removed after the preset polymerization time is reached, and the isoprene-styrene copolymer of claim 1 is obtained by drying.
The preparation method of the isoprene-styrene copolymer comprises the following step of mixing an organic solvent and a solvent, wherein the organic solvent is one or more of pentane, isopentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, p-xylene, m-xylene, cumene, hydrogenated gasoline and raffinate oil.
The high-trans polyisoprene/isotactic polystyrene copolymer prepared by the method has high tensile strength and higher glass transition temperature, and vulcanized rubber of the copolymer is comprehensively balanced in the aspects of wear resistance, fatigue resistance, high wet skid resistance and low rolling resistance, so that the copolymer is an ideal material for developing high-performance rubber products.
The high-trans polyisoprene/isotactic polystyrene copolymer prepared by the method is applied to tread rubber of truck tires, car tires and giant tires, can obviously improve the wear resistance and fatigue resistance of the tires, obviously improve the wet skid resistance of the tires, reduce the rolling resistance and prepare green high-performance tires.
Detailed Description
Examples 1 to 4
To a 500ml one-neck flask which had been subjected to an anhydrous oxygen-free treatment, isoprene and styrene monomers, an alkylaluminum and a magnesium dichloride-supported titanium catalyst (supported titanium amount: 2.45 wt%) were sequentially charged under the conditions shown in Table 1, and hydrogen gas was simultaneously charged. And (3) raising the temperature to the set polymerization reaction temperature for copolymerization. After the polymerization is carried out for a corresponding time, 50ml of 2 vol% acidified ethanol containing 1 wt% of antioxidant 264 is used for terminating the reaction, unreacted monomers are removed, and the copolymer rubber is obtained by drying. The properties are shown in Table 1.
TABLE 1 examples 1 to 4
Example 5
171g of isoprene monomer, 48g of styrene monomer, 0.02mol of triisobutylaluminum and 0.08g of magnesium dichloride-supported titanium catalyst were sequentially added to a 500ml single-neck flask which had been subjected to anhydrous oxygen-free treatment, and simultaneously 6.5g of hydrogen gas was added. The temperature is raised to the set polymerization reaction temperature of 60 ℃ for copolymerization. During the reaction, styrene monomer was continuously supplemented to maintain the monomer molar ratio of isoprene to styrene in the reaction system at 5.44: 1. After 24 hours of polymerization, the reaction was terminated with 50ml of 2 vol% acidified ethanol containing 1 wt% of antioxidant 264, unreacted monomers were removed, and the copolymer rubber was obtained by drying. Tests show that the styrene content in the copolymer is 23.5 wt%, the trans-1, 4-structure content of isoprene is 97 mol%, styrene units are uniformly and randomly distributed in the copolymer, and the styrene isotacticity is 76%.
Claims (7)
1. The isoprene-styrene copolymer is characterized by consisting of 2-70% of styrene monomer units and 30-98% of isoprene monomer units in mole fraction; wherein the styrene monomer unit is of a high isotactic structure, and the isotactic content is 75-94 mol%; the isoprene monomer unit has high trans-1, 4-structure and trans-1, 4-structure content>90mol percent; the weight average molecular weight of the copolymer was 1X 104~150×104The molecular weight distribution is 1.4-15.8; the styrene in the copolymer is distributed in an isoprene chain segment in a sequence structure of less than 10 monomer units; the glass transition temperature of the isoprene chain segment is minus 69 ℃ to minus 62 ℃, and the melting temperature is 44 ℃ to 50 ℃; the glass transition temperature of the styrene chain segment is 99-112 ℃, and the melting temperature is 219.4-219.7 ℃.
2. The isoprene-styrene copolymer according to claim 1, wherein said copolymer is catalytically synthesized by a ziegler-natta catalyst system comprising a supported titanium catalyst, an organoaluminum compound, and an external electron donor; the supported titanium catalyst is a spherical or non-spherical catalyst which takes magnesium dichloride as a carrier and contains a titanium compound, and titanium element accounts for 1-5% of the total mass of the magnesium dichloride supported titanium catalyst; the organic aluminum compound is one or more of triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, dihexyl aluminum monochloride and dioctyl aluminum monochloride; the external electron donor is one or two of organic compounds containing silicon or nitrogen or oxygen.
3. The isoprene-styrene copolymer according to claim 2, wherein said titanium compound is selected from TiCl4、TiBr4Or TiI4One of (1); the external electron donor is selected from one or more of silane compounds, ether compounds or ester compounds.
4. The method for preparing an isoprene-styrene copolymer according to claim 1, wherein the isoprene-styrene copolymer is synthesized by the following steps: adding a certain amount of organic solvent, isoprene, styrene, an organic aluminum compound, a magnesium dichloride supported titanium catalyst and an external electron donor into a polymerization device, and simultaneously adding hydrogen to perform copolymerization reaction, wherein the initial feeding molar ratio of the styrene to the isoprene is 5: 100-90: 100, and the molar ratio of a titanium element in the magnesium dichloride supported titanium catalyst to a monomer is 1 x 10-8:1~1×10-41, the molar ratio of an aluminum element in an organic aluminum compound to a titanium element in a magnesium dichloride supported titanium catalyst is 20: 1-200: 1, the molar ratio of an external electron donor to the titanium element in the magnesium dichloride supported titanium catalyst is 0: 1-20: 1, the molar ratio of an organic solvent to a monomer is 0: 100-300: 100, the polymerization temperature is 10-100 ℃, the molar ratio of hydrogen to the monomer is 0.0001: 1-1: 1, the polymerization time is 1-72 hours, the solvent and unreacted monomers are removed after the preset polymerization time is reached, and the isoprene-styrene copolymer is obtained by drying.
5. The method for preparing an isoprene-styrene copolymer according to claim 1, wherein the isoprene-styrene copolymer is synthesized by the following steps: adding a certain amount of organic solvent, isoprene, styrene, an organic aluminum compound, a magnesium dichloride supported titanium catalyst and an external electron donor into a polymerization device, and simultaneously adding hydrogen to perform copolymerization reaction, wherein the initial feeding molar ratio of the styrene to the isoprene is 5: 100-90: 100, and the molar ratio of a titanium element in the magnesium dichloride supported titanium catalyst to a monomer is 1 x 10-8:1~1×10-41, the molar ratio of an aluminum element in an organic aluminum compound to a titanium element in a magnesium dichloride supported titanium catalyst is 20: 1-200: 1, the molar ratio of an external electron donor to the titanium element in the magnesium dichloride supported titanium catalyst is 0: 1-20: 1, the molar ratio of an organic solvent to a monomer is 0: 100-300: 100, and the aluminum element and the titanium element are continuously or intermittently reacted in the reaction processStyrene monomers are supplemented intermittently to keep the molar ratio of styrene to isoprene in a reaction system to be maintained at the initial feeding molar ratio, the polymerization reaction temperature is 10-100 ℃, the molar ratio of hydrogen to the monomers is 0.0001: 1-1: 1, the polymerization time is 1-72 hours, the solvent and unreacted monomers are removed after the preset polymerization time is reached, and the isoprene-styrene copolymer is obtained by drying.
6. The process according to claim 4 or 5, wherein the organic solvent is one or more selected from the group consisting of pentane, hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, benzene, toluene, p-xylene, m-xylene, cumene, hydrogenated gasoline and raffinate oil.
7. The use of the isoprene-styrene copolymer according to claim 1, wherein said copolymer is used in a tread rubber for truck tires, passenger tires and giant tires.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0505973A2 (en) * | 1991-03-28 | 1992-09-30 | Idemitsu Kosan Company Limited | Process for producing styrenic copolymer |
| US5306780A (en) * | 1990-01-16 | 1994-04-26 | Mobil Oil Corporation | Solid block elastomeric copolymers |
| CN107646046A (en) * | 2015-04-24 | 2018-01-30 | 倍耐力轮胎股份公司 | High-performance tire |
| CN107921817A (en) * | 2015-07-31 | 2018-04-17 | 倍耐力轮胎股份公司 | High-performance tire |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306780A (en) * | 1990-01-16 | 1994-04-26 | Mobil Oil Corporation | Solid block elastomeric copolymers |
| EP0505973A2 (en) * | 1991-03-28 | 1992-09-30 | Idemitsu Kosan Company Limited | Process for producing styrenic copolymer |
| CN107646046A (en) * | 2015-04-24 | 2018-01-30 | 倍耐力轮胎股份公司 | High-performance tire |
| CN107921817A (en) * | 2015-07-31 | 2018-04-17 | 倍耐力轮胎股份公司 | High-performance tire |
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