CN112707985B - Homogeneous catalyst for preparing trans-1, 4-polyisoprene polymer, preparation method and application thereof - Google Patents
Homogeneous catalyst for preparing trans-1, 4-polyisoprene polymer, preparation method and application thereof Download PDFInfo
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- CN112707985B CN112707985B CN202011537259.1A CN202011537259A CN112707985B CN 112707985 B CN112707985 B CN 112707985B CN 202011537259 A CN202011537259 A CN 202011537259A CN 112707985 B CN112707985 B CN 112707985B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/08—Isoprene
Abstract
The invention belongs to the technical field of catalysts for synthesizing trans-1, 4-polyisoprene polymers, and discloses a homogeneous catalyst for preparing trans-1, 4-polyisoprene polymers, and a preparation method and application thereof. The homogeneous catalyst comprises a supported titanium catalyst and AlR3An alkylaluminum cocatalyst and a polyisoprene polymer; wherein, the AlR3R in the alkylaluminum cocatalyst is C1‑C6The number average molecular weight of the polyisoprene polymer is 1000-10000, and the mass fraction of cis-1, 4-polyisoprene in the polyisoprene polymer is not less than 30%. The homogeneous catalyst is a liquid phase catalyst, so that the problems of nonuniform polymerization, difficult control of polymerization reaction, large difference of product technical indexes and the like caused by difficult dispersion of solids in industrial production and polymerization processes are solved.
Description
Technical Field
The invention relates to a catalyst for synthesizing trans-1, 4-polyisoprene polymer, in particular to a homogeneous catalyst for preparing the trans-1, 4-polyisoprene polymer, a preparation method and application thereof.
Background
Trans-1, 4-polyisoprene is a crystalline material, shows the performance of high modulus and high tensile strength, the polymerization mode of trans-1, 4-polyisoprene usually has solution polymerization and bulk polymerization at present, solution polymerization is convenient for heat transfer and production process regulation and control, but the solvent content in the reaction system is as high as 90%, directly leads to long post-treatment process, more devices, high energy consumption, and brings about many environmental protection and pressure in the aspect of safety. Although the bulk polymerization can perfectly make up for the defects of long flow, multiple devices, high energy consumption and the like of solution polymerization, the polymerization reaction is generally carried out under the anaerobic condition, a supported titanium catalyst and aluminum alkyl are sequentially added into isoprene, constant-temperature stirring polymerization is carried out, methanol or ethanol is used as a terminator, the catalyst is a commonly used supported solid catalyst, the phase state of the supported catalyst is solid, the polymerization reaction process is solid-liquid two-phase polymerization, the dispersion is difficult in industrial production, the reaction progress is difficult to control, and the performance and the uniformity of a polymer are directly influenced. In view of the above, the invention provides a homogeneous catalyst for preparing trans-1, 4-polyisoprene polymer, a preparation method and an application thereof, wherein the catalyst is a titanium homogeneous catalyst, and a homogeneous bulk polymerization method is adopted at the early stage of polymerization reaction, so that the technical problems of uneven polymerization and difficult regulation and control of the production process in the existing polymerization reaction are solved.
Disclosure of Invention
In order to solve the technical problems of uneven polymerization and difficult regulation and control of the production process of the polymerization reaction in the prior art, the invention provides a homogeneous catalyst for preparing trans-1, 4-polyisoprene polymer.
The traditional Ti series catalyst is powder, and during the polymerization use process, the powder Ti and the alkyl aluminum are directly added into the isoprene for polymerization, or the powder Ti and the alkyl aluminum are mixed for reaction and then added into the isoprene for polymerization. The powder Ti is mixed with the alkyl aluminum to obtain the liquid catalyst containing the precipitate, and the liquid catalyst is still solid powder when directly used, so that the polymerization reaction process is solid-liquid two-phase polymerization.
In order to solve the technical problems, the invention adopts the following technical scheme:
the homogeneous catalyst for preparing trans-1, 4-polyisoprene polymer includes supported titanium catalyst, AlR3An alkylaluminum cocatalyst and a polyisoprene polymer; wherein, the AlR3R in the alkylaluminum cocatalyst is C1-C6The number average molecular weight of the polyisoprene polymer is 1000-10000, and the mass fraction of cis-1, 4-polyisoprene in the polyisoprene polymer is not less than 30%.
According to the invention, through introducing the polymer of the key component isoprene, the mass fraction of cis-1, 4-polyisoprene in the polymer is not less than 30%, the prepared catalyst can be ensured to be fully dissolved in polyisoprene, and the polymer of isoprene with low molecular weight and low viscosity can perform coordination reaction on the supported titanium catalyst, so that the phase state of the supported titanium catalyst is changed from a solid phase to a liquid phase, and the liquid phase homogeneous catalyst with low viscosity and capable of being dissolved in isoprene is obtained.
Preferably, the supported titanium catalyst and AlR3The molar ratio of the alkylaluminum cocatalyst to the polyisoprene polymer is 1:1-10: 1-50. Meanwhile, the dosage of the low-molecular-weight and low-viscosity isoprene polymer is strictly controlled, when the dosage is too low, the isoprene polymer cannot be coordinated with all Ti to generate a new catalyst, when the dosage is too high, the increase of the amount of the polymer coordinated with the Ti influences the viscosity of the catalyst, and when the viscosity of the catalyst is too high, the dispersion of the catalyst in the later polymerization process is influenced, so that the purposes of controlling polymerization and product stability cannot be achieved.
More preferably, the AlR3The alkyl aluminum cocatalyst is triisobutyl aluminum; the supported titanium catalyst is TiCl4/MgCl2。
The invention also provides a preparation method of the homogeneous catalyst, and the supported titanium catalyst and the AlR are proportionally mixed under the protection of nitrogen gas3And (3) sequentially adding the alkyl aluminum cocatalyst and the polyisoprene polymer into a reaction vessel, and reacting at 0-60 ℃ for 10-240min to obtain the homogeneous catalyst.
Another object of the present invention is to provide a method for preparing trans-1, 4-polyisoprene polymer using the above homogeneous catalyst, which comprises adding isoprene and AlR under nitrogen protection3The alkyl aluminum cocatalyst reacts for 0.5 to 2 hours at the temperature of between 10 ℃ below zero and 25 ℃, then the homogeneous catalyst of claim 1 is added to react for 0.5 to 72 hours at the temperature of between 10 ℃ below zero and 25 ℃, and the reaction is stopped to obtain the trans-1, 4-polyisoprene polymer.
At the beginning of the reaction, isoprene was added first, and AlR3The alkyl aluminum cocatalyst is reacted for a time sufficient to allow AlR3Can be completely completed with micro-water, micro-oxygen and other impurities in isoprene, ensures the cleanliness of a system, and further ensures the catalytic effect after the homogeneous catalyst is addedThe control of product indexes such as rate, product molecular weight, distribution, Mooney and the like is also aimed at obtaining a product with narrower and more controllable molecular weight distribution.
Preferably, ethanol is used for terminating the polymerization reaction, and after standing and settling, the trans-1, 4-polyisoprene polymer is obtained by vacuum drying.
Firstly, the homogeneous catalyst provided by the invention is used for polymerization reaction, and can improve the catalytic effect of the catalyst and the polymerization efficiency of the polymerization reaction. The solid catalyst or the two-phase catalyst containing the precipitate cannot be uniformly distributed in the polymerization production process, so that the active center of the catalyst is partially agglomerated and cannot exert the maximum effect of the catalyst. The solid catalyst or the two-phase catalyst containing the precipitate is easy to adhere and remain on the wall of a polymerization kettle in the polymerization production process, so that a large part of the catalyst cannot be uniformly dispersed in a polymerization solution, the efficiency of the catalyst is greatly reduced, and the production loss is increased.
Secondly, the homogeneous catalyst of the invention can reduce the difficulty of conveying and metering materials in production. The traditional catalyst is light solid powder or two-phase liquid containing precipitate, requires inert environment protection in the conveying and metering processes, and has high difficulty in actual conveying and metering of production. The light solid powder cannot be metered on line, and only can be metered and added manually, so that the production efficiency is greatly reduced, and meanwhile, because the catalyst reacts violently in water, air and oxygen, the manual operation brings great danger and inconvenience; although the two-phase liquid containing the precipitate can be conveyed and metered on line by using mechanical equipment, the uniformity of the conveyed and metered catalyst is difficult to ensure due to the precipitate, and the polymerization control, the product index and the stability control of the product are influenced. The homogeneous low-viscosity catalyst can realize accurate and stable online conveying, and ensures the stability of the catalyst, thereby ensuring the stable control of polymerization and the stable control of products. The traditional catalyst causes molecules to agglomerate on the kettle wall to form gel due to the attachment of the kettle wall, thereby bringing great instability to products. In the operation and maintenance of actual production equipment, the maintenance frequency of a polymerization kettle is reduced under the condition of using a homogeneous catalyst, so that the production efficiency is improved.
The invention provides a homogeneous catalyst for preparing trans-1, 4-polyisoprene polymer, a preparation method thereof and a homogeneous bulk polymerization method, wherein a polymer of isoprene with low molecular weight and low viscosity as a key component is introduced to perform coordination reaction on a supported titanium catalyst, so that the phase state of the supported titanium catalyst is changed from a solid phase to a liquid phase. According to the technical scheme, compared with solution polymerization, the polymerization reaction provided by the invention uses a bulk polymerization process, has no solvent, can avoid the problems of long post-treatment process, more devices, high energy consumption and the like, does not need post-treatment and monomer solvent recovery processes, and has the advantages of simple process flow, high production efficiency, low cost and no three-waste pollution; compared with the traditional titanium bulk polymerization, the catalyst prepared by the invention is liquid phase rather than solid, so that the problems of nonuniform polymerization, difficult control of polymerization reaction, large difference of product technical indexes and the like caused by difficult dispersion of solid in industrial production and polymerization processes are avoided.
Detailed Description
The invention discloses a homogeneous catalyst for preparing trans-1, 4-polyisoprene polymer, a preparation method and application thereof, and a person skilled in the art can use the content for reference and appropriately improve process parameters to realize the homogeneous catalyst. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
EXAMPLE 1 preparation of homogeneous catalyst
Under the protection of nitrogen, a supported titanium catalyst TiCl with the molar ratio of 1:1:1 is added4/MgCl2、AlR3Sequentially adding an alkyl aluminum cocatalyst tripropyl aluminum and a polyisoprene polymer into a reaction vessel, and reacting at 0 ℃ for 240min to obtain a homogeneous catalyst; the number average molecular weight of the polyisoprene polymer is 1000, the mass fraction of cis-1, 4-polyisoprene in the polyisoprene polymer is 35%, and the room temperature viscosity of the obtained homogeneous catalyst is 10 pa.s.
EXAMPLE 2 preparation of homogeneous catalyst
Under the protection of nitrogen, a supported titanium catalyst TiCl with the molar ratio of 1:10:50 is added4/MgCl2、AlR3Sequentially adding an alkyl aluminum cocatalyst, namely triethyl aluminum and a polyisoprene polymer into a reaction vessel, and reacting at 60 ℃ for 10min to obtain a homogeneous catalyst; the number average molecular weight of the polyisoprene polymer is 10000, the mass fraction of cis-1, 4-polyisoprene in the polyisoprene polymer is 60%, and the room temperature viscosity of the obtained homogeneous catalyst is 105pa.
EXAMPLE 3 preparation of homogeneous catalyst
Under the protection of nitrogen, a supported titanium catalyst TiCl with the molar ratio of 1:5:25 is added4/MgCl2、AlR3Sequentially adding an alkyl aluminum cocatalyst triisobutyl aluminum and a polyisoprene polymer into a reaction vessel, and reacting at 30 ℃ for 120min to obtain a homogeneous catalyst; the number average molecular weight of the polyisoprene polymer is 5000, the mass fraction of cis-1, 4-polyisoprene in the polyisoprene polymer is 80%, and the room temperature viscosity of the obtained homogeneous catalyst is 45 pa.s.
The homogeneous catalysts prepared in examples 1 to 3 had suitable viscosity, and in the preparation of the homogeneous catalysts, if the amount of polyisoprene polymer added was too low, only a pasty solid mixture containing a large amount of powder could be obtained, and since the amount of isoprene polymer was too low, a liquid phase catalyst could not be obtained at all. If the amount of polyisoprene polymer added is too high, the trans 1, 4 structure content in the product polymer may be less than 98%. If the mass fraction of cis-1, 4-polyisoprene in the polyisoprene polymer is less than 30%, a high-viscosity semisolid catalyst is obtained, and the mixing process is difficult to carry out; when the mass fraction of cis-1, 4-polyisoprene is less than 30%, the remaining structure may be either trans-1, 4 structure or 3, 4 structure, and neither structure can synthesize liquid-phase catalyst, so that the fluidity is not affected.
EXAMPLE 4 Synthesis of trans-1, 4-polyisoprene Polymer
Adding isoprene and adding AlR under the protection of nitrogen3Triisobutylaluminum as an alkylaluminum cocatalyst reacts for 1 hour at 15 ℃, then the homogeneous catalyst prepared in the example 3 is added to react for 36 hours at 10 ℃, ethanol is used for terminating the polymerization reaction, and the product polymer is obtained by standing, settling and vacuum drying, wherein the content of the trans-1, 4-polyisoprene polymer in the obtained product polymer is 99%, the molecular weight distribution of the product polymer is 3.5, and the catalytic efficiency is 50000g/1 gTi.
The homogeneous catalyst prepared in the embodiment 3 is in a liquid homogeneous state, no precipitation phenomenon occurs, the homogeneous catalyst can be rapidly and uniformly distributed in a polymerization solution in the polymerization process, no adhesion and agglomeration phenomenon is formed in the kettle wall, and the conveying and metering of materials in the process are easy to realize.
EXAMPLE 5 preparation of trans-1, 4-Polyisoprene Polymer
Adding isoprene and adding AlR under the protection of nitrogen3An alkyl aluminum cocatalyst, namely triethyl aluminum, reacts for 2 hours at the temperature of minus 10 ℃, then the homogeneous catalyst prepared in the embodiment 2 is added to react for 72 hours at the temperature of minus 10 ℃, ethanol is adopted to terminate the polymerization reaction, the mixture is kept stand and settled and then is dried in vacuum to obtain the trans-1, 4-polyisoprene polymer, and the trans-1, 4-polyisoprene polymer in the obtained product polymerThe content of the compound is 98 percent, the molecular weight distribution of the product polymer is 3.2, and the catalytic efficiency is 58000g/1 gTi.
The homogeneous catalyst prepared in the example 2 is in a liquid homogeneous state, no precipitation phenomenon occurs, the homogeneous catalyst can be rapidly and uniformly distributed in a polymerization liquid in the polymerization process, no adhesion and agglomeration phenomenon is formed in the kettle wall, and the conveying and metering of materials in the process are easy to realize.
EXAMPLE 6 preparation of trans-1, 4-Polyisoprene Polymer
Adding isoprene and adding AlR under the protection of nitrogen3An alkylaluminum cocatalyst tripropylaluminum is reacted for 0.5h at 25 ℃, then the homogeneous catalyst prepared in the example 2 is added to react for 0.5h at-10 ℃, ethanol is adopted to terminate the polymerization reaction, the mixture is stood for settling and then dried in vacuum to obtain the trans-1, 4-polyisoprene polymer, the content of the trans-1, 4-polyisoprene polymer in the obtained product polymer is 99 percent, the molecular weight distribution of the product polymer is 3.6, and the catalytic efficiency is 28000g/1 gTi.
The homogeneous catalyst prepared in the example 2 is in a liquid homogeneous state, no precipitation phenomenon occurs, the homogeneous catalyst can be rapidly and uniformly distributed in a polymerization liquid in the polymerization process, no adhesion and agglomeration phenomenon is formed in the kettle wall, and the conveying and metering of materials in the process are easy to realize.
Comparative example 1
Under the protection of nitrogen, adding isoprene, and adding supported titanium catalyst TiCl4/MgCl with the molar ratio of 1:52And AlR3And (2) reacting triisobutylaluminum serving as an alkyl aluminum cocatalyst for 36 hours at 10 ℃, terminating the polymerization reaction by using ethanol, standing for settling, and drying in vacuum to obtain the trans-1, 4-polyisoprene polymer. The content of trans-1, 4-polyisoprene polymer in the obtained product polymer is 98%, the molecular weight distribution of the product polymer is 5.7, and the catalytic efficiency is 3000g/1 gTi.
Supported titanium catalyst TiCl4/MgCl2Is solid powder, AlR3 alkyl aluminum cocatalyst is liquid, and the two can be mixed in turn to obtain two-phase state of supernatant and lower layer precipitate, and the catalyst is still in polymerization liquid during polymerizationThe precipitate particles are kept, the solution cannot be rapidly and uniformly distributed in the polymerization solution, the adhesion and agglomeration phenomena are formed in the kettle wall, even the gel phenomenon occurs, and the conveying and metering of the materials are difficult in the process.
Comparative example 2
Adding isoprene and adding AlR under the protection of nitrogen3Triisobutylaluminum as alkyl aluminum cocatalyst is reacted for 1h at 15 ℃, and then supported titanium catalyst TiCl with the molar ratio of 1:5 is added4/MgCl2And AlR3And (2) reacting triisobutylaluminum serving as an alkyl aluminum cocatalyst for 36 hours at 10 ℃, terminating the polymerization reaction by using ethanol, standing for settling, and drying in vacuum to obtain the trans-1, 4-polyisoprene polymer. The content of trans-1, 4-polyisoprene polymer in the obtained product polymer is 98%, the molecular weight distribution of the product polymer is 5.0, and the catalytic efficiency is 3600g/1 gTi.
Supported titanium catalyst TiCl4/MgCl2And AlR3The alkyl aluminum cocatalyst is in a two-phase liquid shape, precipitation occurs, the catalyst cannot be dissolved in polymerization liquid and cannot be rapidly and uniformly distributed in the polymerization process, adhesion and agglomeration phenomena are formed in the kettle wall, and the conveying and metering of materials are difficult in the process.
From the catalytic results of comparative examples 1 and 2, whether or not AlR was added prior to the reaction3The molecular weight distribution and the catalytic efficiency of the finally obtained polymer are not ideal when the alkyl aluminum cocatalyst is used for purification treatment.
Comparative example 3
Under the protection of nitrogen, the homogeneous catalyst prepared in example 3 was added, the reaction was carried out for 36 hours at 10 ℃, ethanol was used to terminate the polymerization reaction, and after standing and settling, the polymer was vacuum-dried to obtain a trans-1, 4-polyisoprene polymer, wherein the content of the trans-1, 4-polyisoprene polymer in the obtained polymer product was 98%, the molecular weight distribution of the polymer product was 4.6, and the catalytic efficiency was 49000g/1 gTi.
Comparative example 3 no AlR addition prior to reaction3The aluminum alkyl cocatalyst is used for purifying, has little influence on the catalytic efficiency of the catalyst, but can influence the molecules of the final product polymerAnd (4) quantity distribution.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A homogeneous catalyst for the preparation of trans-1, 4-polyisoprene polymer, characterized in that: comprises a supported titanium catalyst and AlR3An alkylaluminum cocatalyst and a polyisoprene polymer; wherein, the AlR3R in the alkyl aluminum cocatalyst is C1-C6The number average molecular weight of the polyisoprene polymer is 1000-10000, and the mass fraction of cis-1, 4-polyisoprene in the polyisoprene polymer is not less than 30 percent; the supported titanium catalyst and AlR3The molar ratio of the alkylaluminum cocatalyst to the polyisoprene polymer is 1:1-10: 1-50.
2. The homogeneous catalyst of claim 1, wherein: the AlR3The alkyl aluminum cocatalyst is triisobutyl aluminum; the supported titanium catalyst is TiCl4/MgCl2。
3. The homogeneous catalyst of claim 1, wherein: the preparation method of the homogeneous catalyst comprises the following steps of proportionally mixing the supported titanium catalyst and AlR under the protection of nitrogen3And sequentially adding an alkyl aluminum cocatalyst and a polyisoprene polymer into a reaction vessel, and reacting at 0-60 ℃ for 10-240min to obtain the homogeneous catalyst.
4. A process for preparing trans-1, 4-polyisoprene polymer using the homogeneous catalyst as claimed in any one of claims 1 to 3, wherein: adding isoprene under the protection of nitrogen, adding AlR according to any one of claims 1-33An alkylaluminum cocatalyst, reacting at-10-25 deg.C for 0.5-2h, then adding the catalyst of any of claims 1-3And (3) reacting the phase catalyst for 0.5 to 72 hours at the temperature of between 10 ℃ below zero and 25 ℃, and stopping the reaction to obtain the trans-1, 4-polyisoprene polymer.
5. Use of the method of claim 4; terminating the polymerization reaction by using ethanol, standing and settling, and drying in vacuum to obtain the trans-1, 4-polyisoprene polymer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117501A (en) * | 1995-02-17 | 1996-02-28 | 青岛化工学院 | Synthesis of homotrans-1,4-polyisoprene |
| CN103204973A (en) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | Trans-1,4-polydiene copolymer having low molecular weight, and preparation method and use thereof |
| CN105985472A (en) * | 2015-02-09 | 2016-10-05 | 中国石油化工股份有限公司 | Rare earth catalyst and preparation method thereof and polyisoprene preparation method |
| CN109651546A (en) * | 2018-12-13 | 2019-04-19 | 中国科学院长春应用化学研究所 | A kind of supported trans-1,4-iroprene polymer Titanium series catalyst of polymer support and its application method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117501A (en) * | 1995-02-17 | 1996-02-28 | 青岛化工学院 | Synthesis of homotrans-1,4-polyisoprene |
| CN103204973A (en) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | Trans-1,4-polydiene copolymer having low molecular weight, and preparation method and use thereof |
| CN105985472A (en) * | 2015-02-09 | 2016-10-05 | 中国石油化工股份有限公司 | Rare earth catalyst and preparation method thereof and polyisoprene preparation method |
| CN109651546A (en) * | 2018-12-13 | 2019-04-19 | 中国科学院长春应用化学研究所 | A kind of supported trans-1,4-iroprene polymer Titanium series catalyst of polymer support and its application method |
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