CN108192002B - Method for preparing polyisoprene - Google Patents
Method for preparing polyisoprene Download PDFInfo
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- CN108192002B CN108192002B CN201611121813.1A CN201611121813A CN108192002B CN 108192002 B CN108192002 B CN 108192002B CN 201611121813 A CN201611121813 A CN 201611121813A CN 108192002 B CN108192002 B CN 108192002B
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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
- 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
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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
- C08F236/08—Isoprene
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
- C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
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Abstract
The invention relates to the field of polymers, and discloses a method for preparing polyisoprene, which comprises the following steps: under polymerization reaction conditions, sequentially contacting isoprene monomer serving as a main polymerization body with a first alkylating agent and a rare earth catalyst composition, wherein the rare earth catalyst composition contains a rare earth metal organic compound, a second alkylating agent and a halogen-containing compound, the rare earth metal organic compound has a structure shown in a formula (I), and the first alkylating agent and the second alkylating agent are respectively and independently selected from at least one of alkyl aluminum and alkyl aluminum hydride. The method provided by the invention can flexibly adjust the Mooney viscosity of the polymer product and can obtain a polyisoprene product with high content of cis-1, 4-structure and narrow molecular weight distribution.
Description
Technical Field
The invention relates to the field of polymers, in particular to a method for preparing polyisoprene.
Background
Rare earth catalyst compositions for the catalytic polymerization of conjugated diolefins generally comprise a rare earth catalyst, a cocatalyst, and a halogen source. Can catalyze conjugated diene monomer to become polymer with high cis structure. In particular, these polymer products can be used extensively in the manufacture of automobile tires, and the good polymer properties make the polymers have better physical properties and easier to process.
CN101193925A describes a rare earth catalyst composition for the polymerization of conjugated diolefins, which comprises:
neodymium [ tris (2-ethylhexyl) phosphate ] as rare earth catalyst,
-a diisobutylaluminum hydride, which is,
diethylaluminum chloride.
This prior art technique, in which an alkylaluminum compound is added before the introduction of the catalyst system, controls the polymer Mooney viscosity M L (1+4) between 40 and 50, and the resulting polyisoprene has a cis 1, 4-structure content between 96% and 97% by weight and a molecular weight distribution of less than 2.2.
CN1484657A describes a rare earth catalyst composition for the polymerization of conjugated diolefins, which comprises:
-an isoprene monomer having a molecular weight,
-a rare earth metal salt of an organic phosphoric acid,
-a general formula of AlR3Or HAlR2The aluminum alkyl(s) of (a),
-a halogen donor consisting of an alkylaluminum halide.
By means of the catalyst composition, polyisoprene products are obtained having a cis 1, 4-structure content of from 95.7 to 98.7% by weight, a broad Mooney viscosity M L (1+4) of from 60 to 90 and a molecular weight distribution of less than 2.5.
Commonly used neodymium-based catalysts include neodymium alkylcarboxylates, neodymium alkoxides, and neodymium phosphates, all of which are coordinately bonded to oxygen and neodymium. Hitherto, there have been few studies on a metal-organic compound catalyst for polymerization in which nitrogen and neodymium form a coordinate bond.
Disclosure of Invention
It is an object of the present invention to provide a process for producing a polyisoprene product which allows flexible adjustment of the Mooney viscosity of the polymer product.
It is another object of the present invention to provide a process which enables to obtain a polyisoprene product having a high cis-1, 4-structure content and a narrow molecular weight distribution.
The inventors have found in their studies that when a rare earth catalyst composition formed by using a rare earth metal organic compound having a structure represented by formula (I) is compounded with isoprene monomer as a main polymerization component, and the mixture is first contacted with a first alkylating agent and then contacted with the rare earth catalyst composition, the polymer product prepared therefrom has a high cis-1, 4-structure content and a narrow molecular weight distribution. And the required polymer products with various Mooney viscosities can be flexibly obtained by controlling the adding amount of the first alkylating agent, and particularly, the Mooney viscosity of the polymer products can be centralized between 60 and 90, and particularly between 60 and 70.
In order to achieve the above object, the present invention provides a method for preparing polyisoprene, which comprises: under polymerization reaction conditions, sequentially contacting isoprene monomer serving as a main polymerization body with a first alkylating agent and a rare earth catalyst composition, wherein the rare earth catalyst composition contains a rare earth metal organic compound, a second alkylating agent and a halogen-containing compound, the rare earth metal organic compound has a structure shown in a formula (I), and the first alkylating agent and the second alkylating agent are respectively and independently selected from at least one of alkyl aluminum and alkyl aluminum hydride,
wherein M is any one of lanthanide rare earth elements;
R1、R2、R3、R4、R5and R6Each independently selected from hydrogen and C1-8Alkyl of (C)6-12And said R is1、R2、R3、R4、R5And R6Not at least one selected from hydrogen and methyl.
The method provided by the invention can flexibly adjust the Mooney viscosity of the polymer product by controlling the adding amount of the first alkylating agent.
The method provided by the invention can obtain a polyisoprene product with high cis-1, 4-structure and narrow molecular weight distribution.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing polyisoprene, which comprises the following steps: under polymerization reaction conditions, sequentially contacting isoprene monomer serving as a main polymerization body with a first alkylating agent and a rare earth catalyst composition, wherein the rare earth catalyst composition contains a rare earth metal organic compound, a second alkylating agent and a halogen-containing compound, the rare earth metal organic compound has a structure shown in a formula (I), and the first alkylating agent and the second alkylating agent are respectively and independently selected from at least one of alkyl aluminum and alkyl aluminum hydride,
wherein M is any one of lanthanide rare earth elements;
R1、R2、R3、R4、R5and R6Each independently selected from hydrogen and C1-8Alkyl of (C)6-12And said R is1、R2、R3、R4、R5And R6Not at least one selected from hydrogen and methyl.
The first alkylating agent and the second alkylating agent may be the same or different. The terms "first" and "second" are used herein only for the purpose of distinguishing the alkylating agents added at different times, and those skilled in the art should not be construed as limiting the present invention.
“C1-8The "alkyl group" of (1) represents an alkyl group having 1 to 8 carbon atoms.
“C6-12The "aryl group" of (a) represents an aryl group having 6 to 12 carbon atoms.
Preferably, in formula (I), M is neodymium or cerium.
Preferably, in formula (I), R1、R2、R3、R4、R5And R6Each independently selected from hydrogen and C1-6Alkyl of (C)6-10And said R is1、R2、R3、R4、R5And R6Not at least one selected from hydrogen and methyl. More preferably, R1、R2、R3、R4、R5And R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, methylethylphenyl, ethylphenyl, diethylphenyl and triethylphenyl, and said R1、R2、R3、R4、R5And R6Not at the same time being at least one selected from hydrogen and methyl;
“C1-6the "alkyl group" of (1) represents an alkyl group having 1 to 6 carbon atoms.
“C6-10The "aryl group" of (a) represents an aryl group having 6 to 10 carbon atoms.
Two preferred embodiments are provided below to illustrate the rare earth metal organic compound in the rare earth catalyst composition involved in the foregoing method of the present invention.
Embodiment mode 1: in formula (I), M is neodymium or cerium; r1、R2、R3、R4、R5And R6Each independently selected from hydrogen and C1-6Alkyl of (C)6-10And said R is1、R2、R3、R4、R5And R6Not at least one selected from hydrogen and methyl.
Embodiment mode 2: in formula (I), M is neodymium or cerium; r1、R2、R3、R4、R5And R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, methylethylphenyl, ethylphenyl, diethylphenyl and triethylphenyl, and said R1、R2、R3、R4、R5And R6Not at least one selected from hydrogen and methyl.
In the present invention, the rare earth metal organic compound can be prepared by, for example, the following synthesis method:
contacting a rare earth metal source with a compound with a structure shown as a formula (II) in the presence of a protective gas and an organic solvent, wherein the rare earth metal source is a compound containing an element shown as M, the organic solvent is at least one selected from halogenated hydrocarbon, alcohols, aromatic hydrocarbon, halogenated aromatic hydrocarbon, oxygen-containing heterocyclic compound and nitrogen-containing heterocyclic compound, and R in the compound with the structure shown as the formula (II)1、R2、R3、R4、R5、R6The definitions of (A) are the same as those in the structure represented by formula (I) of the present invention.
Preferably, the rare earth metal source may be a salt containing an element represented by M, and may be, for example, any one of a chloride, a nitrate, and a sulfate containing an element represented by M.
Preferably, the molar ratio of the compound with the structure shown in the formula (II) to the rare earth metal source is 0.5-10: 1; preferably 1 to 4: 1.
the kind of the organic solvent is not particularly limited as long as the rare earth metal source and the compound having the structure represented by formula (II) can be dissolved therein, and it is preferable that the organic solvent is a polar organic solvent. For example, the organic solvent may be at least one of Tetrahydrofuran (THF), acetonitrile, and pyridine.
The amount of the organic solvent is not particularly limited and may be selected by those skilled in the art according to the amount conventionally used in the art.
The protective gas may be an inert gas that does not participate in the reaction, and may be, for example, nitrogen, argon, or the like.
Preferably, the conditions for contacting the rare earth metal source with the compound of the structure represented by formula (II) include: the temperature is 0-80 deg.C, and the time is 5-500 min.
The present invention can also concentrate the product obtained after the above-mentioned contact, and preferably, by adding an appropriate amount of a nonpolar solvent such as diethyl ether to the concentrated product to obtain crystals with higher purity.
Preferably, the conditions under which the isoprene monomer as the main polymerization body is contacted with the first alkylating agent include: the temperature is 0-120 deg.C, and the time is 0.1-100 min.
Preferably, the aluminum alkyl has the formula Al (R)1)3The structure shown, and the alkyl aluminum hydride has the formula HAl (R)2)2The structure shown; and R is1And R2Each independently selected from C1-12Alkyl group of (1).
Preferably, the aluminum alkyl has the formula Al (R)1)3Structure shown, and R1And R2Each independently selected from C1-8Alkyl groups of (a); more preferably, R1And R2Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and n-hexyl.
Preferably, the aluminum alkyl hydride has the formula HAl (R)2)2Structure shown, and R1And R2Each independently selected from C1-8Alkyl groups of (a); more preferably, R1And R2Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and n-hexyl.
Particularly preferably, the aluminum alkyl is triisobutylaluminum and/or triethylaluminum.
Particularly preferably, the alkylaluminum hydride is diisobutylaluminum hydride.
For the purposes of the present invention, the halogen-containing compound is preferably an alkyl halide, preferably of the general formula Al (R)2Alkyl aluminum halides of X, of the formula Al2(R)3(X)3Wherein R is ethyl, propyl, isopropyl, n-butyl, isobutyl or tert-butyl, X is a halogen element, preferably X is bromine or chlorine; more preferably, the halogen-containing compound is at least one of diethylaluminum chloride, sesquiethylaluminum chloride, diisobutylaluminum chloride, benzylchloride, benzylbromide, tert-butylchloride, methylsilane chloride and silicon tetrachloride; diethyl aluminum chloride and/or diisobutyl aluminum chloride are particularly preferred.
In the present invention, when the halogen-containing compound is an alkylaluminum halide, the alkylating agent is mainly distinguished from the halogen-containing compound by: the alkylating agent does not contain a halogen element, and the halogen-containing compound necessarily contains a halogen element.
The halogen elements of the present invention include fluorine, chlorine, bromine and iodine.
Preferably, in the rare earth catalyst composition, the content molar ratio of the rare earth metal organic compound to the second alkylating agent and the halogen-containing compound, calculated on the rare earth element, is 1: (2-10): (1-30); more preferably 1: (3-8): (1-15).
Preferably, the rare earth catalyst composition further comprises a conjugated diene monomer as a catalytic component. Preferably, the conjugated diene monomer is C4-6Conjugated diene monomer (b); more preferably one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene, and still more preferably isoprene monomer and/or butadieneAn alkene monomer.
Preferably, the content molar ratio of the conjugated diene monomer to the rare earth metal organic compound calculated by the rare earth element in the rare earth catalyst composition is (1-120): 1; more preferably (10-80): 1.
preferably, the rare earth catalyst composition is obtained by mixing a rare earth metal organic compound, a second alkylating agent, and a halogen-containing compound, optionally together with a conjugated diene monomer, in the presence of a solvent.
By "obtained by mixing a rare earth metal organic compound, an alkylating agent, and a halogen-containing compound, optionally with conjugated diene monomer", it is meant that the mixing can be carried out in the presence or absence of the conjugated diene monomer.
Further preferably, the rare earth catalyst composition is obtained by first mixing a rare earth metal organic compound and a second alkylating agent, optionally together with a conjugated diene monomer, in the presence of a solvent, and then second mixing the product obtained after the first mixing with a halogen-containing compound.
Preferably, the conditions of the first mixing include: the temperature is 5-60 ℃; the time is 0.01-4 h.
Preferably, the conditions of the second mixing include: the temperature is 30-85 ℃; the time is 0.02-5 h.
Preferably, the solvent in the process of preparing the rare earth catalyst composition includes, but is not limited to, an aromatic solvent (e.g., toluene) or an aliphatic or alicyclic solvent (e.g., pentane, n-pentane, isopentane, a hexane mixture, n-hexane, cyclohexane, methylcyclohexane, a heptane mixture, or n-heptane).
Preferably, the molar ratio of the first alkylating agent to the rare earth catalyst composition on a rare earth element basis is (1-15): 1; more preferably (1-10): 1.
preferably, the polymerization conditions include: the temperature is 0-100 ℃, and more preferably 5-80 ℃; the time is 0.1 to 24 hours, more preferably 0.2 to 12 hours.
Preferably, the molar ratio of the isoprene monomer as the main polymerization body to the rare earth catalyst composition calculated by the rare earth metal element is (1000-: 1, more preferably (5000-: 1.
preferably, the polymerization reaction is carried out in the presence of an inert solvent selected from at least one of pentane, hexane, heptane, cyclohexane, toluene, xylene, and chlorobenzene.
In the present invention, the living polymer may be directly terminated or aged by using a terminating agent commonly used in the art, for example, at least one of water, an alcohol solvent and a phenol solvent, preferably at least one of water, methanol, ethanol, n-propanol, isopropanol and 2, 6-di-t-butyl-p-cresol, which will be known to those skilled in the art and will not be described in detail herein.
The polymer product prepared by the method has the cis-1, 4 structure content of more than 99 weight percent, the molecular weight distribution of less than 2.1, the Mooney viscosity M L (1+4) measured according to ASTM D1646 at 100 ℃ of between 60 and 70, and the whole polymerization process is stable and easy to control, thus being very suitable for continuous industrial production.
The present invention will be described in detail below by way of examples.
The chemical reagents used in the examples were all chemically pure reagents, unless otherwise specified.
In the present invention, the cis 1, 4-structure content of the conjugated diene polymer synthesized was measured by a German Bruker Tensor 27 infrared spectrometer, the molecular weight and the molecular weight distribution were measured by an Shimadzu L C-10AT Gel Permeation Chromatograph (GPC), THF was used as a mobile phase, narrow distribution polystyrene was used as a standard, the temperature was 25 ℃ and the Mooney viscosity M L (1+4) was measured by ASTMD1646 AT 100 ℃.
The starting materials for the preparation of the metal organic compounds are commercially available, in particular, from Sigma-Aldrich pharmaceutical company.
Preparation example 1: this preparation was used to prepare neodymium tris (1, 3-diphenyl-1, 1,3, 3-tetramethyldisilylamine), of the formula:
NdCl was introduced into a flask in the presence of nitrogen3(2.1mmol) and 1, 3-diphenyl-1, 1,3, 3-tetramethyldisilylamine (6.5mmol) and 25m L of THF were added thereto, stirred at 25 ℃ for 30min, then distilled at 50 ℃ under reduced pressure until the solution was concentrated to about 2m L, then 0.5m L of diethyl ether was added to give colorless crystals in 92% yield.
Preparation example 2: this preparation was used to prepare neodymium tris (1, 3-dibutyl-1, 1,3, 3-tetramethyldisilylamine), of the formula:
NdCl was introduced into a flask in the presence of nitrogen3(2.0mmol) and 1, 3-dibutyl-1, 1,3, 3-tetramethyldisilylamine (7.5mmol) and 25m L of pyridine was added thereto and stirred at 20 ℃ for 60min, followed by distillation under reduced pressure at 50 ℃ until the solution was concentrated to about 2m L, followed by addition of 0.5m L of diethyl ether to give colorless crystals in 88% yield.
Preparation example 3: this preparation example was used to prepare cerium tris (1, 3-diphenyl-1, 1,3, 3-tetraethyldisilane) having the following structural formula:
in the presence of nitrogen, CeCl was introduced into the flask3(2.0mmol) and 1, 3-diphenyl-1, 1,3, 3-tetraethyldisilazane (7.0mmol) and 25m of L acetonitrile was added thereto, stirred at 40 ℃ for 20min, then distilled at 50 ℃ under reduced pressure until the solution was concentrated to about 2m L, and then 0.5m L of diethyl ether was added to give colorless crystals in a yield of 96%.
Example 1: for preparing polyisoprene products
Into a flask, 50m L of n-hexane, 0.3mmol of the rare earth metal organic compound obtained in preparation example 1 and 15mmol of isoprene monomer were introduced in the presence of nitrogen, and contacted at a temperature of 30 ℃ for 5min, followed by introduction of 1.2mmol of triisobutylaluminum (second alkylating agent) and contact at a temperature of 30 ℃ for 30min, followed by introduction of 1.2mmol of diethylaluminum chloride and aging at a temperature of 60 ℃ for 2h, to obtain a rare earth catalyst composition Z1.
3L of n-hexane and 2.4mol of isoprene monomer as a main polymerization were introduced into a 10L reactor, followed by 0.9mmol of triisobutylaluminum (first alkylating agent) and stirring at 25 ℃ for 5min, then the foregoing rare earth catalyst composition Z1 was added and reacted at a temperature of 50 ℃ for 3h, and then the reaction was terminated by adding methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 99.3% by weight, the Mooney viscosity M L (1+4) was 85, and the molecular weight distribution was 2.0.
Comparative example 1
This comparative example was carried out in a similar manner to example 1, except that: in this comparative example, 0.9mmol of triisobutylaluminum (first alkylating agent) was not added. Specifically, the method comprises the following steps:
3L of n-hexane and 2.4mol of isoprene monomer as a main polymerization were introduced into a 10L reactor, and then the rare earth catalyst composition Z1 prepared in example 1 was added to react at a temperature of 50 ℃ for 3 hours, followed by terminating the reaction by adding methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 99.2% by weight, the Mooney viscosity M L (1+4) was 96, and the molecular weight distribution was 1.9.
Example 2: for preparing polyisoprene products
Into a flask, 50m of L n-hexane, 0.3mmol of the rare earth metal organic compound obtained in preparation example 2 and 12mmol of 1, 3-butadiene monomer were introduced in the presence of nitrogen, and contacted at a temperature of 25 ℃ for 10min, followed by introduction of 1.5mmol of diisobutylaluminum hydride (second alkylating agent) at a temperature of 25 ℃ for 20min, followed by introduction of 1.2mmol of diisobutylaluminum chloride, and aged at a temperature of 70 ℃ for 1.8h, to obtain rare earth catalyst composition Z2.
In a 10L reactor, 3L of n-hexane and 2.7mol of isoprene monomer as a main polymerization were introduced, followed by 1.2mmol of triethylaluminum (first alkylating agent) and stirring at 20 ℃ for 10min, followed by addition of the foregoing rare earth catalyst composition Z2 and reaction at 45 ℃ for 3.5h, followed by termination of the reaction by addition of methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content of the polymer product was 99.3% by weight, the Mooney viscosity M L (1+4) was 77, and the molecular weight distribution was 1.9.
Comparative example 2
This comparative example was carried out in a similar manner to example 2, except that: in this comparative example, 1.2mmol of triethylaluminum (first alkylating agent) was not added. Specifically, the method comprises the following steps:
3L of n-hexane and 2.7mol of isoprene monomer as a main polymerization were introduced into a 10L reactor, and then the rare earth catalyst composition Z2 prepared in example 2 was added to react at a temperature of 45 ℃ for 3.5 hours, followed by terminating the reaction by adding methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 99.3% by weight, the Mooney viscosity M L (1+4) was 95, and the molecular weight distribution was 2.0.
Example 3: for preparing polyisoprene products
Into a flask, 50m of L n-hexane, 0.3mmol of the rare earth metal organic compound prepared in preparation example 3 and 21mmol of isoprene monomer were introduced in the presence of nitrogen, and contacted at a temperature of 35 ℃ for 15min, followed by introduction of 2.4mmol of triethylaluminum (second alkylating agent) and contact at a temperature of 35 ℃ for 50min, followed by introduction of 3mmol of diisobutylaluminum chloride and aging at a temperature of 85 ℃ for 2.5h, to obtain a rare earth catalyst composition Z3.
3L of n-hexane and 2.1mol of isoprene monomer as a main polymerization were introduced into a 10L reactor, followed by 1.5mmol of triisobutylaluminum (first alkylating agent) and stirring at 30 ℃ for 5min, then the foregoing rare earth catalyst composition Z3 was added and reacted at a temperature of 50 ℃ for 4h, and then the reaction was terminated by adding methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 99.4% by weight, the Mooney viscosity M L (1+4) was 66, and the molecular weight distribution was 2.0.
Comparative example 3
This comparative example was carried out in a similar manner to example 3, except that: the rare earth metal organic compound in this comparative example was neodymium chloride, that is, 0.3mmol of neodymium chloride was substituted for 0.3mmol of the rare earth metal organic compound prepared in preparation example 3 in this comparative example.
In the presence of nitrogen, 50m of L n-hexane, 0.3mmol of neodymium chloride and 21mmol of isoprene monomer were introduced into a flask and contacted at a temperature of 35 ℃ for 15min, followed by 2.4mmol of triethylaluminum (second alkylating agent) and at a temperature of 35 ℃ for 50min, followed by 3mmol of diisobutylaluminum chloride and aged at a temperature of 85 ℃ for 2.5h to obtain a rare earth catalyst composition DZ 1.
3L of n-hexane and 2.1mol of isoprene monomer as a main polymerization were introduced into a 10L reactor, followed by 1.5mmol of triisobutylaluminum (first alkylating agent) and stirring at 30 ℃ for 5min, followed by addition of the foregoing rare earth catalyst composition DZ1 and reaction at a temperature of 50 ℃ for 4h, followed by termination of the reaction by addition of methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 97.0% by weight, the Mooney viscosity M L (1+4) was 90, and the molecular weight distribution was 2.3.
Example 4: for preparing polyisoprene products
This example was carried out using the same rare earth catalyst composition Z1 as in example 1, except that the first alkylating agent was 1.2mmol of triisobutylaluminum.
Specifically, 3L of n-hexane and 2.4mol of isoprene monomer as a main polymerization body were introduced into a 10L reactor, followed by 1.2mmol of triisobutylaluminum (first alkylating agent) and stirring at 25 ℃ for 5min, then the foregoing rare earth catalyst composition Z1 was added and reacted at 50 ℃ for 3h, and then the reaction was terminated by adding methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 99.5% by weight, the Mooney viscosity M L (1+4) was 76, and the molecular weight distribution was 2.0.
Example 5: for preparing polyisoprene products
This example was carried out using the same rare earth catalyst composition Z1 as in example 1, except that the first alkylating agent was 1.5mmol of triisobutylaluminum.
Specifically, 3L of n-hexane and 2.4mol of isoprene monomer as a main polymerization body were introduced into a 10L reactor, followed by 1.5mmol of triisobutylaluminum (first alkylating agent) and stirring at 25 ℃ for 5min, followed by addition of the foregoing rare earth catalyst composition Z1, reaction at 50 ℃ for 3h, followed by termination of the reaction by addition of methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 99.5% by weight, the Mooney viscosity M L (1+4) was 67, and the molecular weight distribution was 2.0.
Example 6: for preparing polyisoprene products
This example was carried out using the same rare earth catalyst composition Z1 as in example 1, except that the first alkylating agent was 1.8mmol of triisobutylaluminum.
Specifically, 3L of n-hexane and 2.4mol of isoprene monomer as a main polymerization body were introduced into a 10L reactor, followed by 1.8mmol of triisobutylaluminum (first alkylating agent) and stirring at 25 ℃ for 5min, followed by addition of the foregoing rare earth catalyst composition Z1, reaction at 50 ℃ for 3h, followed by termination of the reaction by addition of methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 99.6% by weight, the Mooney viscosity M L (1+4) was 65, and the molecular weight distribution was 2.0.
Example 7: for preparing polyisoprene products
This example was carried out using the same rare earth catalyst composition Z1 as in example 1, except that the first alkylating agent was 2.1mmol of triisobutylaluminum.
Specifically, 3L of n-hexane and 2.4mol of isoprene monomer as a main polymerization body were introduced into a 10L reactor, followed by 2.1mmol of triisobutylaluminum (first alkylating agent) and stirring at 25 ℃ for 5min, then the foregoing rare earth catalyst composition Z1 was added and reacted at 50 ℃ for 3h, and then the reaction was terminated by adding methanol to obtain a polymer product.
As a result, the cis 1, 4-structure content in the polymer product was 99.6% by weight, the Mooney viscosity M L (1+4) was 65, and the molecular weight distribution was 2.0.
From the results of the above examples and comparative examples, it can be seen that: the method provided by the invention can flexibly adjust the Mooney viscosity of the polymer product by controlling the adding amount of the first alkylating agent. The method provided by the invention can obtain a polyisoprene product with high cis-1, 4-structure and narrow molecular weight distribution.
In particular, the results of comparative examples 1,4 to 7 show that: the more the amount of alkylating agent added before the addition of the catalyst composition, the more the Mooney viscosity of the polymer product obtained according to the invention decreases, and the more the amount of aluminum alkyl added before the addition reaches a certain value, the more the Mooney viscosity reaches a stable value, i.e. between 60 and 70. That is, the present invention allows flexibility in obtaining desired polymer products of different Mooney viscosities by controlling the amount of alkylating agent added prior to the addition of the catalyst composition. The polymer products obtained by the process of the present invention have a cis 1, 4-structure content of 99.0 wt% or more and a molecular weight distribution of 2.1 or less.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (24)
1. A method of making polyisoprene, the method comprising: under polymerization reaction conditions, sequentially contacting isoprene monomer serving as a main polymerization body with a first alkylating agent and a rare earth catalyst composition, wherein the rare earth catalyst composition contains a rare earth metal organic compound, a second alkylating agent and a halogen-containing compound, the rare earth metal organic compound has a structure shown in a formula (I), and the first alkylating agent and the second alkylating agent are respectively and independently selected from at least one of alkyl aluminum and alkyl aluminum hydride,
wherein M is any one of lanthanide rare earth elements;
R1、R2、R3、R4、R5and R6Each independently selected from hydrogen and C1-8Alkyl of (C)6-12And said R is1、R2、R3、R4、R5And R6Not simultaneously selected from at least one of hydrogen and methyl.
2. The process according to claim 1, wherein, in formula (I), M is neodymium or cerium; r1、R2、R3、R4、R5And R6Each independently selected from hydrogen and C1-6Alkyl of (C)6-10Aryl group of (1).
3. The process according to claim 1, wherein, in formula (I), M is neodymium or cerium; r1、R2、R3、R4、R5And R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, methylethylphenyl, ethylphenyl, diethylphenyl and triethylphenyl.
4. The method of any one of claims 1-3, wherein the aluminum alkyl has the formula Al (R)1)3The structure shown, and the alkyl aluminum hydride has the formula HAl (R)2)2The structure shown; and R is1And R2Each independently selected from C1-12Alkyl group of (1).
5. The method of claim 4, wherein R1And R2Each independently selected from C1-8Alkyl group of (1).
6. The method of claim 4, wherein R1And R2Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and n-hexyl.
7. The process according to any one of claims 1-3, wherein the aluminum alkyl is triisobutylaluminum and/or triethylaluminum.
8. The process according to any one of claims 1 to 3, wherein the alkylaluminum hydride is diisobutylaluminum hydride.
9. A method according to any one of claims 1 to 3, wherein the halogen-containing compound is an alkyl halide.
10. The method of claim 9, wherein the alkyl halide is selected from at least one of diethylaluminum chloride, sesquiethylaluminum chloride, diisobutylaluminum chloride, benzylchloride, benzylbromide, tert-butylchloride, methylsilane chloride, and silicon tetrachloride.
11. The process according to any one of claims 1 to 3, wherein the rare earth catalyst composition comprises the rare earth metal organic compound and the second alkylating agent and the halogen-containing compound in a molar ratio, calculated as rare earth element, of 1: (2-10): (1-30).
12. The process of claim 11, wherein the rare earth catalyst composition has a content molar ratio of the rare earth metal organic compound to the second alkylating agent and the halogen-containing compound, calculated as the rare earth element, of 1: (3-8): (1-15).
13. The process of any of claims 1-3, wherein the rare earth catalyst composition further comprises a conjugated diene monomer as a catalytic component.
14. The process of claim 13 wherein the conjugated diene monomer is C4-6The conjugated diene monomer of (1).
15. The process of claim 13, wherein the conjugated diene monomer is one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene, and 2, 3-dimethylbutadiene.
16. The method of claim 13, wherein the conjugated diene monomer is an isoprene monomer and/or a butadiene monomer.
17. The process of claim 13 wherein the content molar ratio of conjugated diene monomer to rare earth metal organic compound, calculated as rare earth element, in the rare earth catalyst composition is (1-120): 1.
18. the process of any of claims 1-3, wherein the rare earth catalyst composition is obtained by mixing a rare earth metal organic compound, a second alkylating agent, and a halogen-containing compound in the presence of a solvent; or the rare earth catalyst composition is obtained by mixing a rare earth metal organic compound, a second alkylating agent, a halogen-containing compound and a conjugated diene monomer in the presence of a solvent.
19. The process of claim 18, wherein the rare earth catalyst composition is prepared by first mixing a rare earth metal organic compound and a second alkylating agent in the presence of a solvent; or the rare earth catalyst composition is prepared by firstly mixing a rare earth metal organic compound, a second alkylating agent and a conjugated diene monomer in the presence of a solvent;
and then carrying out second mixing on the product obtained after the first mixing and a halogen-containing compound to obtain the halogen-free.
20. The method of claim 19, wherein the conditions of the first mixing comprise: the temperature is 5-60 ℃; the time is 0.01 to 4 hours;
the conditions of the second mixing include: the temperature is 30-85 ℃; the time is 0.02-5 h.
21. The process of any one of claims 1 to 3, wherein the molar ratio of the first alkylating agent to the rare earth catalyst composition, calculated as rare earth element, is (1-15): 1.
22. the process of claim 21, wherein the molar ratio of the first alkylating agent to the rare earth catalyst composition on a rare earth element basis is (1-10): 1.
23. the method of any of claims 1-3, wherein the polymerization reaction conditions comprise: the temperature is 0-100 ℃ and the time is 0.1-24 h.
24. The process of claim 1, wherein the polymerization reaction is carried out in the presence of an inert solvent selected from at least one of pentane, hexane, heptane, cyclohexane, toluene, xylene, and chlorobenzene.
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|---|---|---|---|---|
| EP1095952A1 (en) * | 1999-10-28 | 2001-05-02 | Bayer Ag | Catalyst based on rare earth metals |
| CN1484657A (en) * | 2000-11-09 | 2004-03-24 | �����ּ�����˾ | Catalytic system and method for preparing elastomers using same |
| CN102190832A (en) * | 2010-03-12 | 2011-09-21 | 青岛科技大学 | Poly-1-butene elastomer material and preparation method thereof |
| CN103450373A (en) * | 2012-05-28 | 2013-12-18 | 中国石油化工股份有限公司 | Composition used for rare earth catalyst, rare earth catalyst and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1095952A1 (en) * | 1999-10-28 | 2001-05-02 | Bayer Ag | Catalyst based on rare earth metals |
| CN1484657A (en) * | 2000-11-09 | 2004-03-24 | �����ּ�����˾ | Catalytic system and method for preparing elastomers using same |
| CN102190832A (en) * | 2010-03-12 | 2011-09-21 | 青岛科技大学 | Poly-1-butene elastomer material and preparation method thereof |
| CN103450373A (en) * | 2012-05-28 | 2013-12-18 | 中国石油化工股份有限公司 | Composition used for rare earth catalyst, rare earth catalyst and its application |
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