CN112409520A - Polybutadiene prepared by homogeneous rare earth catalyst and catalyst thereof - Google Patents

Polybutadiene prepared by homogeneous rare earth catalyst and catalyst thereof Download PDF

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CN112409520A
CN112409520A CN201910773353.8A CN201910773353A CN112409520A CN 112409520 A CN112409520 A CN 112409520A CN 201910773353 A CN201910773353 A CN 201910773353A CN 112409520 A CN112409520 A CN 112409520A
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rare earth
catalyst
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earth catalyst
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CN112409520B (en
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唐正伟
赵姜维
徐林
邵明波
孙伟
李建成
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • C08F136/06—Butadiene
    • 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
    • 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
    • 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
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Abstract

The invention relates to the field of rare earth catalysts, in particular to polybutadiene prepared by adopting a homogeneous rare earth catalyst and a catalyst thereof. The preparation method of the polybutadiene comprises the following steps: (1) providing a homogeneous rare earth catalyst; (2) polymerizing butadiene in a second organic solvent in the presence of the homogeneous rare earth catalyst of step (1); the homogeneous rare earth catalyst is prepared from a first material, a second material, a third material, a fourth material and a fifth material. A first material: a compound represented by the formula (1); a second material: an alkylaluminum-based compound; a third material: a halogenated compound; and a fourth material: a conjugated diene; and (5) fifth material: a compound represented by the formula (2). The catalyst of the invention can still show higher activity under the condition of adopting lower content of the fifth material, and the homogeneous phase rare earth catalyst is a homogeneous phase system, has better stability and is convenient for large-scale industrial production and use to prepare polybutene.

Description

Polybutadiene prepared by homogeneous rare earth catalyst and catalyst thereof
Technical Field
The invention relates to the field of rare earth catalysts, in particular to polybutadiene prepared by adopting a homogeneous rare earth catalyst and a catalyst thereof.
Background
Among synthetic rubbers, polybutadiene rubber (PBR) is the second largest rubber species next to styrene-butadiene rubber. At present, polybutadiene rubber can be prepared from a titanium system, a lithium system, a cobalt system, a nickel system and a rare earth system, wherein the rare earth butadiene rubber has a higher cis-structure and a lowest vinyl unit, and the branching degree is very small, so that a macromolecular chain has very high regularity and a perfect linear structure, and has a strong crystallization tendency under stretching, thereby endowing the rare earth butadiene rubber with higher elasticity, better stretching property, lower heat generation and rolling resistance, excellent physical and mechanical properties such as wear resistance and fatigue resistance, and the like, and meeting the development requirements of high-performance tires on the aspects of high speed, energy conservation, safety, environmental protection and the like.
Although available polybutadiene rubber materials are obtained by the existing rare earth catalysts, the problems that the activity of the catalysts is low and the consumption of the catalysts is high exist. This makes the material cost high, has restricted extensive development and use.
Disclosure of Invention
The invention aims to provide a homogeneous rare earth catalyst which has high activity and is in a homogeneous system, a preparation method thereof, polybutadiene and a preparation method thereof.
In order to achieve the above object, one aspect of the present invention provides a method for preparing polybutadiene, the method comprising:
(1) providing a homogeneous rare earth catalyst;
(2) polymerizing butadiene in a second organic solvent in the presence of the homogeneous rare earth catalyst of step (1);
in the step (1), the homogeneous rare earth catalyst is prepared from a first material, a second material, a third material, a fourth material and a fifth material, wherein the molar ratio of the first material to the second material to the fifth material is 1: 12-30: 0.2-0.4;
a first material: a neodymium phosphonate compound represented by formula (1);
a second material: an alkylaluminum-based compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
a third material: a halogenated compound selected from one or more of a halosilane, an aluminum sesquihaloalkyi, and an aluminum haloalkyi;
and a fourth material: a conjugated diene;
and (5) fifth material: a compound represented by the formula (2);
formula (1)
Figure BDA0002174280970000021
Formula (2)
Figure BDA0002174280970000022
Wherein R isa1、Ra2、Rb1、Rb2、Rc1、Rc2、Rd1、Rd2And Rd3Each independently is hydrogen, hydroxy, C1-C20Alkyl or C1-C20Alkoxy group of (a);
the preparation method of the homogeneous rare earth catalyst comprises the following steps: in a first organic solvent, carrying out first mixing on a first material and a fifth material, and then carrying out standing treatment, wherein the standing treatment time is more than 1 h; then introducing a fourth material and a second material for second mixing, and then introducing a third material for aging treatment.
The second aspect of the present invention provides a polybutadiene obtained by the above-mentioned production process.
The third aspect of the invention provides a preparation method of a homogeneous rare earth catalyst, wherein the homogeneous rare earth catalyst is prepared from a first material, a second material, a third material, a fourth material and a fifth material, and the molar ratio of the first material to the second material to the fifth material is 1: 12-30: 0.2-0.4;
a first material: a neodymium phosphonate compound represented by formula (1);
a second material: an alkylaluminum-based compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
a third material: a halogenated compound selected from one or more of a halosilane, an aluminum sesquihaloalkyi, and an aluminum haloalkyi;
and a fourth material: a conjugated diene;
and (5) fifth material: a compound represented by the formula (2);
formula (1)
Figure BDA0002174280970000031
Formula (2)
Figure BDA0002174280970000032
Wherein R isa1、Ra2、Rb1、Rb2、Rc1、Rc2、Rd1、Rd2And Rd3Each independently is hydrogen, hydroxy, C1-C20Alkyl or C1-C20Alkoxy group of (a);
the preparation method of the homogeneous rare earth catalyst comprises the following steps: in a first organic solvent, carrying out first mixing on a first material and a fifth material, and then carrying out standing treatment, wherein the standing treatment time is more than 1 h; then introducing a fourth material and a second material for second mixing, and then introducing a third material for aging treatment.
In a fourth aspect, the invention provides a homogeneous rare earth catalyst prepared by the method of the third aspect.
The homogeneous phase rare earth catalyst can still show higher activity under the condition of adopting lower content of the fifth material, is a homogeneous phase system, has better stability and is convenient for large-scale industrial production and use.
Detailed Description
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.
In one aspect, the present invention provides a method for preparing polybutadiene, comprising:
(1) providing a homogeneous rare earth catalyst;
(2) polymerizing butadiene in a second organic solvent in the presence of the homogeneous rare earth catalyst of step (1);
in the step (1), the homogeneous rare earth catalyst is prepared from a first material, a second material, a third material, a fourth material and a fifth material, wherein the molar ratio of the first material to the second material to the fifth material is 1: 12-30: 0.2-0.4;
a first material: a neodymium phosphonate compound represented by formula (1);
a second material: an alkylaluminum-based compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
a third material: a halogenated compound selected from one or more of a halosilane, an aluminum sesquihaloalkyi, and an aluminum haloalkyi;
and a fourth material: a conjugated diene;
and (5) fifth material: a compound represented by the formula (2);
formula (1)
Figure BDA0002174280970000041
Formula (2)
Figure BDA0002174280970000042
Wherein R isa1、Ra2、Rb1、Rb2、Rc1、Rc2、Rd1、Rd2And Rd3Each independently is hydrogen, hydroxy, C1-C20Alkyl or C1-C20Alkoxy group of (a);
the preparation method of the homogeneous rare earth catalyst comprises the following steps: in a first organic solvent, carrying out first mixing on a first material and a fifth material, and then carrying out standing treatment, wherein the standing treatment time is more than 1 h; then introducing a fourth material and a second material for second mixing, and then introducing a third material for aging treatment.
According to the present invention, it is preferred that the process of the present invention is controlled so that the polybutadiene obtained has a weight average molecular weight of 2.5X 105-3.3×105g/mol, the content of cis-1, 4-polymeric structure is more than 97 mol%, the molecular weight distribution index is less than 2.5, and the Mooney viscosity ML of raw rubber(1+4)40-65 ℃ at 100 ℃. Preferably, the above process is such that the polybutadiene obtained has a weight average molecular weight of 2.5X 105-3.2×105g/mol, the content of cis-1, 4-polymeric structure is 97.5-100 mol%, the molecular weight distribution index is 1.7-2.5, and the Mooney viscosity ML of the raw rubber(1+4)40-65 ℃ at 100 ℃.
According to the invention, the amount of said homogeneous rare earth catalyst used may be suitably adjusted according to the polybutadiene required, in order to obtain a weight-average molecular weight of 2.5X 105-3.3×105g/mol, the content of cis-1, 4-polymeric structure is more than 97 mol%, the molecular weight distribution index is less than 2.5, and the Mooney viscosity ML of raw rubber(1+4)Polybutadiene having a temperature of 40 to 65 ℃ at 100 ℃, preferably, the homogeneous rare earth catalyst is used in an amount such that the first mass is used in an amount of 20 to 200. mu. mol, preferably 30 to 100. mu. mol, relative to 1mol of butadiene.
According to the invention, the second organic solvent may be any hydrocarbon solvent inert to the polymerization reaction, and may be, for example, C5-C10Alkane, C5-C10Cycloalkanes and C6-C12Preferably one or more of hexane, cyclohexane, heptane, pentane, isopentane, octane, methylcyclohexane, benzene, toluene, xylene and cumene. Wherein the amount of the second organic solvent may vary within a wide range, and preferably, the amount of the second organic solvent is 300-1000 parts by weight with respect to 100 parts by weight of butadiene.
According to the present invention, preferably, the polymerization conditions include: the temperature is 50-90 ℃ and the time is 1-5 h. More preferably, the polymerization conditions include: the temperature is 60-80 ℃ and the time is 1.5-3 h.
According to the invention, the polymerization can be carried out in an inert atmosphere in order to overcome the destruction of the active centers of the catalyst by oxygen. The inert atmosphere may be maintained by evacuating the reaction vessel and introducing a gas selected from nitrogen, argon, helium, and the like.
In the invention, the inventor of the invention researches and discovers that the dosage of the fifth material has great influence on the catalyst property, and when the dosage of the fifth material is too small, the composition can not be completely dissolved in a solvent and can not play a role in obviously improving the catalyst activity; when the amount of the fifth material added is too large, formation of active sites is hindered, which in turn results in a decrease in catalytic activity. The fifth material may promote the composition of the present invention to form a homogeneous solution and may also provide more catalytically active sites, thereby increasing the activity of the rare earth catalyst. When the first material and the fifth material are controlled to be subjected to standing treatment for a long time after first mixing, the rare earth homogeneous catalyst can be prepared from the fifth material in a relatively low dosage, and therefore, under the preparation method of the invention, the dosage of the fifth material can be reduced to a molar ratio of the first material to the fifth material of 1: 0.2-0.4. Preferably, the molar ratio of the first material to the fifth material is 0.25-0.35.
According to the invention, preferably, the molar ratio of the first material to the third material is 1: 2-5. Preferably, the molar ratio of the first material to the fourth material is 1: 10-80, preferably 1: 40-60. By adopting the proportion in the molar ratio range, the high-activity homogeneous rare earth catalyst which is more suitable for preparing polybutadiene of the invention can be obtained.
According to the invention, the standing treatment is preferably carried out for a period of time of from 1 to 60 hours, preferably from 5 to 50 hours, more preferably from 5 to 36 hours (for example from 5 to 10 hours or from 5 to 8 hours). Preferably, the temperature of the standing treatment is 10 to 40 ℃.
According to the present invention, preferably, the conditions of the first mixing include: the temperature is 10-40 deg.C, and the time is 10-200 min.
According to the present invention, preferably, the conditions of the second mixing include: the temperature is 10-50 deg.C, and the time is 10-200 min.
According to the present invention, preferably, the aging conditions include: the temperature is 40-80 deg.C, and the time is 30-300 min.
According to the invention, preferably, the dialkylaluminum hydride is of the formula AlH (R)2Said trialkyl aluminum is represented by the formula Al (R)3Each R is independently selected from C1-C6Alkyl group of (1). More preferably, the second material is one or more of diethylaluminum hydride, dipropylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum and triisobutylaluminum.
According to the invention, preferably, the halosilane is of the formula Si (R)1)4-nXnSaid sesquihaloalkylaluminum is represented by the formula Al2(R1)3X3Said haloalkylaluminum is represented by the formula Al (R)1)2X, wherein each R is1Each independently selected from C1-C6Each X is independently selected from halogen (e.g., F, Cl, Br), and n is an integer from 1 to 4. More preferably, the third material is one or more of monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, diethylaluminum chloride and diisobutylaluminum chloride.
According to the bookInvention, preferably, Ra1、Ra2、Rb1、Rb2、Rc1And Rc2Each independently is C1-C20Alkyl or C1-C20Alkoxy of (3), preferably C4-C12Alkyl or C4-C12More preferably n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethylhexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecyloxy or n-dodecoxy.
According to the invention, preferably Rd1、Rd2And Rd3Each independently is hydroxy, C4-C12Alkyl or C4-C12Alkoxy group of (a); more preferably, Rd1Is hydroxy, Rd2And Rd3Each independently is n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethylhexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecyloxy or n-dodecoxy.
The neodymium phosphonate compound can be obtained by a conventional method in the art, and for example, can be a commercially available product or can be prepared by a conventional method in the art, and the invention is not particularly limited thereto.
Specific examples of the neodymium phosphonate-based compound may be, for example, one or more compounds selected from the group consisting of compounds represented by the following formulae:
formula (1-1): in the formula (1), Ra1、Ra2、Rb1、Rb2、Rc1And Rc2Are all 2-ethylhexyloxy (i.e. di (2-ethylhexyl) phosphonate neodymium);
formula (1-2): in the formula (1), Ra1、Ra2、Rb1、Rb2、Rc1And Rc2Are both 2-methylhexyloxy (i.e. di (2-methylhexyl) phosphonate neodymium);
formula (1-3): in the formula (1), Ra1、Ra2、Rb1、Rb2、Rc1And Rc2Both are n-hexyloxy (i.e., neodymium di (n-hexyl) phosphonate).
The compound represented by formula (2) may be obtained by a method conventional in the art, and may be, for example, a commercially available product or a method conventional in the art.
Among them, specific examples of the compound represented by formula (2) may be, for example, one or more selected from compounds represented by the following formulae:
formula (2-1): in the formula (2), Rd1Is hydroxy, Rd2And Rd3Are all 2-ethylhexyloxy (i.e., di (2-ethylhexyl) phosphonate);
formula (2-2): in the formula (2), Rd1Is hydroxy, Rd2And Rd3Are all 2-methylhexyloxy (i.e. di (2-methylhexyl) phosphonate);
formula (2-3): in the formula (2), Rd1Is hydroxy, Rd2And Rd3Are both n-hexyloxy (i.e., di (n-hexyl) phosphonate).
According to the invention, the conjugated diene in the composition is capable of stabilizing the active center of the catalyst, generally the conjugated diene refers to an olefinic monomer having a conjugated double bond, preferably the conjugated diene is one or more of 1, 3-butadiene, isoprene, piperylene and 2, 4-hexadiene. It should be understood that the conjugated diene and the butadiene used hereinafter to form the polybutadiene should be metered separately.
According to the invention, by means of the catalyst of the inventionThe preparation method is to make the obtained rare earth catalyst in a homogeneous phase state, and the homogeneous rare earth catalyst is understood to be a homogeneous solution containing the first material, the second material, the third material, the fourth material and the fifth material. Wherein the amount of the first organic solvent may vary within wide limits, preferably the amount of the solvent in the homogeneous solution is such that the concentration of the first material is from 0.01 to 0.5mmol/mL, preferably from 0.01 to 0.1mmol/mL, more preferably from 0.01 to 0.02 mmol/mL. The first organic solvent may be any of a variety of solvents that can be suitably used to prepare a homogeneous solution of the homogeneous rare earth catalyst of the present invention, preferably C5-C10Alkane, C5-C10Cycloalkanes and C6-C12Preferably one or more of pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene, and cumene. The first solvent herein is understood to be a generic term for the solvents contained in the homogeneous rare earth catalyst produced, i.e., including the solvent added during the first mixing, and also including the solvent introduced during subsequent processing, including the solvent introduced in the form of a solution of the active component.
Wherein, the first material can be provided in the form of pure substance or solution, and when the first material is provided in the form of solution, the concentration of the solution of the first material can be 0.01-0.5 mol/L. The solvent may be selected from the first organic solvents employed in the homogeneous solutions described above.
Wherein, the second material can be provided in the form of its pure substance or in the form of a solution, and when the second material is provided in the form of a solution, the concentration of the solution of the second material can be, for example, 0.01-5 mol/L. The solvent may be selected from the first organic solvents employed in the homogeneous solutions described above.
The third material may be provided in the form of a pure substance or a solution, and when the third material is provided in the form of a solution, the concentration of the solution of the third material may be, for example, 0.01 to 5 mol/L. The solvent may be selected from the first organic solvents employed in the homogeneous solutions described above.
Wherein, the fourth material can be provided in the form of a pure substance or a solution, and when the fourth material is provided in the form of a solution, the concentration of the solution of the fourth material can be 0.01-5mol/L, for example. The solvent may be selected from the first organic solvents employed in the homogeneous solutions described above.
Wherein, the fifth material can be provided in the form of a pure substance or a solution, and when the fifth material is provided in the form of a solution, the concentration of the solution of the fifth material can be, for example, 0.01-0.5 mol/L. The solvent may be selected from the first organic solvents employed in the homogeneous solutions described above.
The preparation method of the polybutadiene still has the following advantages under the condition of less E component consumption:
(1) the catalyst consumption is low, and is below 110mgNd/kgBR (the amount of Nd required for producing 1kg of polybutadiene);
(2) the polybutadiene obtained has a suitable molecular weight, i.e. the polybutadiene obtained has a weight average molecular weight of 2.5X 105-3.3×105g/mol, Mooney viscosity ML of crude rubber(1+4)40-65 ℃ at 100 ℃;
(3) the obtained polybutadiene has a narrow molecular weight distribution, namely the molecular weight distribution index of the obtained polybutadiene is below 2.5;
(4) the polybutadiene thus obtained was a high-cis polybutadiene having a cis-1, 4-polymerized structure content of 97 mol% or more (based on the molar amount of the total structural units of the polybutadiene).
The second aspect of the present invention provides a polybutadiene obtained by the above-mentioned production process.
According to the invention, the polybutadiene preferably has a weight-average molecular weight of 2.5X 105-3.3×105g/mol, the content of cis-1, 4-polymeric structure is more than 97 mol%, the molecular weight distribution index is less than 2.5, and the Mooney viscosity ML of raw rubber(1+4)40-65 ℃ at 100 ℃.Preferably, the polybutadiene has a weight average molecular weight of 2.5X 105-3.2×105g/mol, the content of cis-1, 4-polymeric structure is 97.5-100 mol%, the molecular weight distribution index is 1.7-2.5, and the Mooney viscosity ML of the raw rubber(1+4)40-65 ℃ at 100 ℃.
The third aspect of the invention provides a preparation method of a homogeneous rare earth catalyst, wherein the homogeneous rare earth catalyst is prepared from a first material, a second material, a third material, a fourth material and a fifth material, and the molar ratio of the first material to the second material to the fifth material is 1: 12-30: 0.2-0.4;
a first material: a neodymium phosphonate compound represented by formula (1);
a second material: an alkylaluminum-based compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
a third material: a halogenated compound selected from one or more of a halosilane, an aluminum sesquihaloalkyi, and an aluminum haloalkyi;
and a fourth material: a conjugated diene;
and (5) fifth material: a compound represented by the formula (2);
formula (1)
Figure BDA0002174280970000111
Formula (2)
Figure BDA0002174280970000112
Wherein R isa1、Ra2、Rb1、Rb2、Rc1、Rc2、Rd1、Rd2And Rd3Each independently is hydrogen, hydroxy, C1-C20Alkyl or C1-C20Alkoxy group of (a);
the preparation method of the homogeneous rare earth catalyst comprises the following steps: in a first organic solvent, carrying out first mixing on a first material and a fifth material, and then carrying out standing treatment, wherein the standing treatment time is more than 1 h; then introducing a fourth material and a second material for second mixing, and then introducing a third material for aging treatment.
Preferred features of the process and associated descriptions are as hereinbefore described with reference to the first aspect.
In a fourth aspect, the invention provides a homogeneous rare earth catalyst prepared by the method of the third aspect.
According to the present invention, the homogeneous rare earth catalyst comprises the above first material, second material, third material, fourth material and fifth material of the present invention, and the molar ratio of the first material to the fifth material is 1: 0.2-0.4. Although the molar ratio of the first material to the fifth material is 1: 0.2-0.4, namely the dosage of the fifth material is lower, but the homogeneous phase rare earth catalyst prepared from the fifth material under the condition of lower dosage can be used for catalyzing the polymerization of butadiene by the method of the invention, and a polybutadiene product with higher cis-structure content and a molecular weight meeting the requirement of a certain range is obtained.
The present invention will be described in detail below by way of examples.
In the following examples, the Mooney viscosity was measured using a Mooney viscometer without a rotor, model SMV-201SK-160, manufactured by Shimadzu corporation, Japan, in which the preheating time was 1min, the rotation time was 4min, and the measuring temperature was 100 ℃.
The molecular weight and molecular weight distribution were determined by HLC-8320 Gel Permeation Chromatography (GPC) from Tosoh, Japan, and 2 TSKgelSuperMultipolypore HZ-M analytical columns were prepared, with THF as mobile phase, narrow-distribution polystyrene as standard sample, and temperature of 40 deg.C.
The cis 1, 4-polymeric structure content was determined by means of an infrared spectrometer in Bruker Tensor 27, Germany.
Preparation example 1
30mL of hydrochloric acid (concentration 12mol/L) was added to 0.05mol of Nd2O3Then heated to boiling and stirred for 30min to obtain NdCl3The aqueous solution was pale purple and transparent. 0.3mol of acetone solution of di (2-ethylhexyl) phosphonate (180mL of acetone) was added to 450mL of aqueous sodium hydroxide solution (sodium hydroxide content: 0.3mol), and mixed well to obtain a pale yellow solution, followed by addition of the above NdCl3Mixing the aqueous solution with stirring to obtain a mixture containing fine white particlesFiltering the suspension of the precipitate, washing the filter cake for 3 times by using proper amount of distilled water and acetone respectively, and then placing the filter cake in an oven at 60 ℃ for drying for 72 hours to obtain the di (2-ethylhexyl) phosphonate neodymium.
Catalyst preparation example 1
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
Under nitrogen protection, 250mL of hexane, 3.2mmol of neodymium di (2-ethylhexyl) phosphonate, and 1.05mmol of di (2-ethylhexyl) phosphonate were mixed at 20 ℃ and then allowed to stand for 24 hours. Then adding 51.2mL of hexane solution of diisobutylaluminum hydride with the concentration of 1mol/L and 160mmol of butadiene at the temperature of 30 ℃, stirring and mixing for 30min, then heating to 60 ℃, adding 9.6mL of hexane solution of diethylaluminum chloride with the concentration of 1mol/L, and aging for 2h to obtain a catalyst in a homogeneous solution state, namely a homogeneous rare earth catalyst C1, wherein the content of Nd element is 0.0099 mmol/mL; the molar ratio of neodymium di (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and di (2-ethylhexyl) phosphonate is 1: 16: 3: 50: 0.3.
catalyst preparation example 2
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
Under nitrogen protection, 250mL of hexane, 3.2mmol of neodymium di (2-ethylhexyl) phosphonate, and 1.12mmol of neodymium di (2-ethylhexyl) phosphonate were mixed at 20 ℃ and then allowed to stand for 5 hours. Then adding 51.2mL of hexane solution of diethyl aluminum hydride with the concentration of 1mol/L and 128mmol of butadiene at the temperature of 30 ℃, stirring and mixing for 30min, then heating to 80 ℃, adding 9.28mL of hexane solution of diisobutyl aluminum chloride with the concentration of 1mol/L, and aging for 2h to obtain a catalyst in a homogeneous solution state, namely a homogeneous rare earth catalyst C2, wherein the content of Nd element is 0.0099 mmol/mL; the molar ratio of neodymium di (2-ethylhexyl) phosphonate, diethylaluminum hydride, diisobutylaluminum chloride, butadiene and di (2-ethylhexyl) phosphonate is 1: 16: 2.9: 40: 0.35.
catalyst preparation example 3
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
Under the protection of nitrogen, 250mL of hexane, 3.2mmol of neodymium di (2-ethylhexyl) phosphonate and 0.80mmol of neodymium di (2-ethylhexyl) phosphonate were mixed at 20 ℃ and then allowed to stand for 36 hours. Then adding 51.2mL of hexane solution of diisobutylaluminum hydride with the concentration of 1mol/L and 160mmol of butadiene at the temperature of 30 ℃, stirring and mixing for 30min, then heating to 60 ℃, adding 9.6mL of hexane solution of diethylaluminum chloride with the concentration of 1mol/L, and aging for 2h to obtain a catalyst in a homogeneous solution state, namely a homogeneous rare earth catalyst C1, wherein the content of Nd element is 0.0099 mmol/mL; the molar ratio of neodymium di (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and di (2-ethylhexyl) phosphonate is 1: 16: 3: 50: 0.25.
catalyst preparation example 4
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
According to the method described in catalyst preparation example 1, except that the amount of butadiene was 256mmol, a homogeneous solution catalyst, i.e., a homogeneous rare earth catalyst C3, in which the content of Nd element was 0.0096mmol/mL, was obtained; the molar ratio of neodymium di (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and di (2-ethylhexyl) phosphonate is 1: 16: 3: 80: 0.3.
catalyst preparation example 5
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
According to the method described in catalyst preparation example 1, except that bis (2-ethylhexyl) phosphonate was used in an amount of 1.28mmol, thereby obtaining a catalyst in a homogeneous solution state, i.e., a homogeneous rare earth catalyst C4, in which the content of Nd element was 0.0099 mmol/mL; the molar ratio of neodymium di (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and di (2-ethylhexyl) phosphonate is 1: 16: 3: 50: 0.4.
catalyst preparation example 6
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
According to the method described in catalyst preparation example 1, except that bis (2-ethylhexyl) phosphonate was used in an amount of 0.80mmol, thereby obtaining a catalyst in a homogeneous solution state, i.e., a homogeneous rare earth catalyst C5, in which the content of Nd element was 0.0099 mmol/mL; the molar ratio of neodymium di (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and di (2-ethylhexyl) phosphonate is 1: 16: 3: 50: 0.25.
catalyst preparation example 7
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
According to the method described in catalyst preparation example 1, except that the amount of the hexane solution of diisobutylaluminum hydride at a concentration of 1mol/L was 96mL, the catalyst in the state of a homogeneous solution, i.e., homogeneous rare earth catalyst C6, in which the content of Nd element was 0.0087mmol/mL, was obtained; the molar ratio of neodymium di (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and di (2-ethylhexyl) phosphonate is 1: 30: 3: 50: 0.3.
catalytic preparation example 8
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
According to the method described in catalyst preparation example 1, except that 38mL of a hexane solution of diisobutylaluminum hydride having a concentration of 1mol/L was used, the catalyst in the state of a homogeneous solution, i.e., homogeneous rare earth catalyst C7, in which the content of Nd element was 0.0103mmol/mL, was obtained; the molar ratio of neodymium di (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and di (2-ethylhexyl) phosphonate is 1: 12: 3: 50: 0.3.
catalytic preparation example 9
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
According to the method of catalyst preparation example 1, except that hexane, neodymium bis (2-ethylhexyl) phosphonate and bis (2-ethylhexyl) phosphonate are mixed and then are allowed to stand for 2 hours, namely the homogeneous rare earth catalyst C9.
Catalytic preparation example 10
This preparation example is intended to illustrate the homogeneous rare earth catalyst and the preparation method thereof according to the present invention.
According to the method described in example 1, except that hexane, neodymium bis (2-ethylhexyl) phosphonate and neodymium bis (2-ethylhexyl) phosphonate were mixed and left to stand for 72 hours, catalyst C10 was obtained in the form of a homogeneous solution.
Comparative example 1
The process of example 1 was followed, except that neodymium phosphonate and di (2-ethylhexyl) phosphonate were not allowed to stand after mixing, to give catalyst DC1 in the form of a homogeneous solution.
Comparative example 2
According to the process described in example 1, except that di (2-ethylhexyl) phosphonate was not used, catalyst DC2 was obtained, which contained a large amount of suspended solids.
Comparative example 3
The procedure described in example 1 was followed, except that bis (2-ethylhexyl) phosphonate was replaced with an equimolar amount of triphenylphosphine, to give catalyst DC3, which contained a small amount of suspended solids.
Polymerization examples 1 to 10
Under the protection of nitrogen, 900g of hexane, 200g of butadiene and a certain amount of the catalyst C1-C10 (the amount and the type are shown in Table 1) are polymerized for 2 hours at 60 ℃ to obtain the corresponding polybutadiene, and the properties of the obtained polybutadiene are shown in Table 1.
Polymerization comparative example 1
The procedure described in polymerization example 1 was followed, except that catalyst DC1 was used instead of catalyst C1, to obtain the corresponding polybutadiene, the properties of which are shown in Table 1.
Polymerization comparative example 2
The procedure described in polymerization example 1 was followed, except that catalyst DC2 was used instead of catalyst C1, to obtain the corresponding polybutadiene, the properties of which are shown in Table 1.
Polymerization comparative example 3
The procedure described in polymerization example 1 was followed, except that catalyst DC3 was used instead of catalyst C1, to obtain the corresponding polybutadiene, the properties of which are shown in Table 1.
TABLE 1
Figure BDA0002174280970000171
Figure BDA0002174280970000181
As can be seen from the results in table 1, the composition of the present invention can be promoted to form a homogeneous solution by standing with a smaller amount of the fifth material, and can also provide more catalytic active sites, thereby increasing the activity of the rare earth catalyst.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (15)

1. A process for the preparation of polybutadiene, characterized in that it comprises:
(1) providing a homogeneous rare earth catalyst;
(2) polymerizing butadiene in a second organic solvent in the presence of the homogeneous rare earth catalyst of step (1);
in the step (1), the homogeneous rare earth catalyst is prepared from a first material, a second material, a third material, a fourth material and a fifth material, wherein the molar ratio of the first material to the second material to the fifth material is 1: 12-30: 0.2-0.4;
a first material: a neodymium phosphonate compound represented by formula (1);
a second material: an alkylaluminum-based compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
a third material: a halogenated compound selected from one or more of a halosilane, an aluminum sesquihaloalkyi, and an aluminum haloalkyi;
and a fourth material: a conjugated diene;
and (5) fifth material: a compound represented by the formula (2);
formula (1)
Figure FDA0002174280960000011
Formula (2)
Figure FDA0002174280960000012
Wherein R isa1、Ra2、Rb1、Rb2、Rc1、Rc2、Rd1、Rd2And Rd3Each independently is hydrogen, hydroxy, C1-C20Alkyl or C1-C20Alkoxy group of (a);
the preparation method of the homogeneous rare earth catalyst comprises the following steps: in a first organic solvent, carrying out first mixing on a first material and a fifth material, and then carrying out standing treatment, wherein the standing treatment time is more than 1 h; then introducing a fourth material and a second material for second mixing, and then introducing a third material for aging treatment.
2. The production method according to claim 1, wherein the homogeneous rare earth catalyst is used in an amount such that the first material is used in an amount of 20 to 200 μmol with respect to 1mol of butadiene;
preferably, the polymerization conditions include: the temperature is 50-90 ℃ and the time is 1-5 h.
3. The production method as claimed in claim 1 or 2, wherein the method is such that the polybutadiene obtained has a weight average molecular weight of 2.5 x 105-3.3×105The content of the g/mol, cis-1, 4-polymeric structure is more than 97mol percentMolecular weight distribution index of 2.5 or less, and Mooney viscosity ML of raw rubber(1+4)40-65 ℃ at 100 ℃.
4. The method of claim 1, wherein the molar ratio of the first material to the third material is 1: 2-5;
preferably, the molar ratio of the first material to the fourth material is 1: 10-80.
5. The method according to any one of claims 1 to 4, wherein the standing treatment is carried out for a period of time ranging from 1 to 60 hours, preferably from 5 to 50 hours, more preferably from 5 to 36 hours;
preferably, the conditions of the first mixing include: the temperature is 10-40 deg.C, and the time is 10-200 min;
preferably, the conditions of the second mixing include: the temperature is 10-50 deg.C, and the time is 10-200 min;
preferably, the aging conditions include: the temperature is 40-80 deg.C, and the time is 30-300 min.
6. A process according to any one of claims 1 to 5, wherein the dialkylaluminium hydride is of the formula AlH (R)2Said trialkyl aluminum is represented by the formula Al (R)3Each R is independently selected from C1-C6Alkyl groups of (a);
the halosilane has the formula Si (R)1)4-nXnSaid sesquihaloalkylaluminum is represented by the formula Al2(R1)3X3Said haloalkylaluminum is represented by the formula Al (R)1)2X, wherein each R is1Each independently selected from C1-C6Each X is independently selected from halogen and n is an integer from 1 to 4.
7. The process according to claim 1 or 6, wherein the second material is one or more of diethylaluminum hydride, dipropylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum and triisobutylaluminum;
the third material is one or more of monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, aluminum sesquiethylate, aluminum sesquiisobutylchloride, aluminum diethylchloride and aluminum diisobutylalchloride.
8. The method of any one of claims 1-7, wherein Ra1、Ra2、Rb1、Rb2、Rc1And Rc2Each independently is C1-C20Alkyl or C1-C20Alkoxy of (3), preferably C4-C12Alkyl or C4-C12More preferably n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethylhexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecyloxy or n-dodecoxy;
Rd1、Rd2and Rd3Each independently is hydroxy, C4-C12Alkyl or C4-C12Alkoxy group of (a); more preferably, Rd1Is hydroxy, Rd2And Rd3Each independently is n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethylhexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecyloxy or n-dodecoxy.
9. The process of any one of claims 1-8, wherein the conjugated diene is one or more of 1, 3-butadiene, isoprene, piperylene, and 2, 4-hexadiene.
10. Polybutadiene obtained by the production process according to any one of claims 1 to 9.
11. The preparation method of the homogeneous rare earth catalyst is characterized in that the homogeneous rare earth catalyst is prepared from a first material, a second material, a third material, a fourth material and a fifth material, wherein the molar ratio of the first material to the second material to the fifth material is 1: 12-30: 0.2-0.4;
a first material: a neodymium phosphonate compound represented by formula (1);
a second material: an alkylaluminum-based compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
a third material: a halogenated compound selected from one or more of a halosilane, an aluminum sesquihaloalkyi, and an aluminum haloalkyi;
and a fourth material: a conjugated diene;
and (5) fifth material: a compound represented by the formula (2);
formula (1)
Figure FDA0002174280960000041
Formula (2)
Figure FDA0002174280960000042
Wherein R isa1、Ra2、Rb1、Rb2、Rc1、Rc2、Rd1、Rd2And Rd3Each independently is hydrogen, hydroxy, C1-C20Alkyl or C1-C20Alkoxy group of (a);
the preparation method of the homogeneous rare earth catalyst comprises the following steps: in a first organic solvent, carrying out first mixing on a first material and a fifth material, and then carrying out standing treatment, wherein the standing treatment time is more than 1 h; then introducing a fourth material and a second material for second mixing, and then introducing a third material for aging treatment.
12. The method of claim 11, wherein the molar ratio of the first material to the third material is 1: 2-5;
preferably, the molar ratio of the first material to the fourth material is 1: 10-80 parts;
preferably, the standing treatment time is 1-60h, preferably 5-50h, more preferably 5-36 h;
preferably, the conditions of the first mixing include: the temperature is 10-40 deg.C, and the time is 10-200 min;
preferably, the conditions of the second mixing include: the temperature is 10-50 deg.C, and the time is 10-200 min;
preferably, the aging conditions include: the temperature is 40-80 deg.C, and the time is 30-300 min.
13. The process according to claim 11 or 12, wherein the dialkylaluminum hydride is represented by the formula AlH (R)2Said trialkyl aluminum is represented by the formula Al (R)3Each R is independently selected from C1-C6Alkyl groups of (a);
preferably, the second material is one or more of diethylaluminum hydride, dipropylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum and triisobutylaluminum;
preferably, the halosilane is of the formula Si (R)1)4-nXnSaid sesquihaloalkylaluminum is represented by the formula Al2(R1)3X3Said haloalkylaluminum is represented by the formula Al (R)1)2X, wherein each R is1Each independently selected from C1-C6Each X is independently selected from the group consisting of halogen,n is an integer of 1 to 4;
preferably, the third material is one or more of monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, diethylaluminum chloride and diisobutylaluminum chloride;
preferably, the conjugated diene is one or more of 1, 3-butadiene, isoprene, piperylene and 2, 4-hexadiene.
14. The method of any one of claims 11-13, wherein Ra1、Ra2、Rb1、Rb2、Rc1And Rc2Each independently is C1-C20Alkyl or C1-C20Alkoxy of (3), preferably C4-C12Alkyl or C4-C12More preferably n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethylhexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecyloxy or n-dodecoxy;
Rd1、Rd2and Rd3Each independently is hydroxy, C4-C12Alkyl or C4-C12Alkoxy group of (a); more preferably, Rd1Is hydroxy, Rd2And Rd3Each independently of the others is n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, 2-methylhexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethylhexoxyN-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy or n-dodecyloxy.
15. A homogeneous rare earth catalyst obtained by the production method according to any one of claims 11 to 14.
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