CN112409520B - Preparation of polybutadiene and catalyst thereof by homogeneous rare earth catalyst - Google Patents
Preparation of polybutadiene and catalyst thereof by homogeneous rare earth catalyst Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- 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 rare earth catalysts, in particular to a method for preparing polybutadiene and a catalyst thereof by adopting a homogeneous phase rare earth catalyst. 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 compound; third material: a halogenated compound; fourth material: conjugated dienes; and (3) a 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 fifth material content, and the homogeneous rare earth catalyst is a homogeneous system, has better stability, and is convenient for large-scale industrial production and use for preparing polybutene.
Description
Technical Field
The invention relates to the field of rare earth catalysts, in particular to a method for preparing polybutadiene and a catalyst thereof by adopting a homogeneous phase rare earth catalyst.
Background
Among synthetic rubbers, polybutadiene rubber (PBR) is the second largest rubber species next to styrene-butadiene rubber. The prior polybutadiene rubber can be prepared from titanium system, lithium system, cobalt system, nickel system and rare earth system, wherein the rare earth butadiene rubber has higher cis structure and lowest vinyl unit, and has very small branching degree, so that a macromolecular chain has very high regularity and perfect linear structure and has 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 abrasion resistance and fatigue resistance, and meeting the requirements of developing high-performance tires in the aspects of high speed, energy conservation, safety, environmental protection and the like.
The existing rare earth catalyst has a great problem that the activity of the catalyst is low and the consumption of the catalyst is high although the existing rare earth catalyst is all made of the available polybutadiene rubber material. This makes the material cost prohibitive, limiting the wide range of developments and uses.
Disclosure of Invention
The invention aims to provide a homogeneous rare earth catalyst with high activity and a homogeneous system, a preparation method thereof, polybutadiene and a preparation method thereof.
In order to achieve the above object, an aspect of the present invention provides a method for producing 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: neodymium phosphonate compounds shown in a formula (1);
a second material: an alkylaluminum compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
third material: halogenated compounds selected from one or more of halosilanes, sesquihaloalkylaluminum and haloalkylaluminum;
fourth material: conjugated dienes;
and (3) a fifth material: a compound represented by the formula (2);
(1)(2)/(S)>
Wherein R is a1 、R a2 、R b1 、R b2 、R c1 、R c2 、R d1 、R d2 And R is d3 Each independently is hydrogen, hydroxy, C 1 -C 20 Alkyl or C of (2) 1 -C 20 Alkoxy groups 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; and introducing the fourth material and the second material for second mixing, and then introducing the third material for ageing treatment.
In a second aspect, the present invention provides polybutadiene obtained by the above-mentioned preparation method.
The third aspect of the invention provides a preparation method of a homogeneous rare earth catalyst, which is prepared from a first material, a second material, a third material, a fourth material and a fifth material, wherein the mole ratio of the first material to the second material to the fifth material is 1:12-30:0.2-0.4;
a first material: neodymium phosphonate compounds shown in a formula (1);
a second material: an alkylaluminum compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
third material: halogenated compounds selected from one or more of halosilanes, sesquihaloalkylaluminum and haloalkylaluminum;
fourth material: conjugated dienes;
and (3) a fifth material: a compound represented by the formula (2);
(1)(2)/(S)>
Wherein R is a1 、R a2 、R b1 、R b2 、R c1 、R c2 、R d1 、R d2 And R is d3 Each independently is hydrogen, hydroxy, C 1 -C 20 Alkyl or C of (2) 1 -C 20 Alkoxy groups 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; and introducing the fourth material and the second material for second mixing, and then introducing the third material for ageing treatment.
In a fourth aspect the present invention provides a homogeneous rare earth catalyst obtainable by the process of the third aspect.
The homogeneous rare earth catalyst can still show higher activity under the condition of adopting lower fifth material content, and is in a homogeneous system, has better stability and is convenient for large-scale industrial production and use.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the present invention provides a process for the preparation of 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: neodymium phosphonate compounds shown in a formula (1);
a second material: an alkylaluminum compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
third material: halogenated compounds selected from one or more of halosilanes, sesquihaloalkylaluminum and haloalkylaluminum;
fourth material: conjugated dienes;
and (3) a fifth material: a compound represented by the formula (2);
(1)(2)/(S)>
Wherein R is a1 、R a2 、R b1 、R b2 、R c1 、R c2 、R d1 、R d2 And R is d3 Each independently is hydrogen, hydroxy, C 1 -C 20 Alkyl or C of (2) 1 -C 20 Alkoxy groups 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; and introducing the fourth material and the second material for second mixing, and then introducing the third material for ageing treatment.
According to the present invention, it is preferable that the method of the present invention is controlled such that the weight average molecular weight of the obtained polybutadiene is2.5×10 5 -3.3×10 5 g/mol, cis 1, 4-polymeric structure content of 97mol% or more, molecular weight distribution index of 2.5 or less, raw rubber Mooney viscosity ML (1+4) The temperature of 100 ℃ is 40-65 ℃. Preferably, the above process is such that the weight average molecular weight of the polybutadiene obtained is 2.5X10 5 -3.2×10 5 g/mol, cis 1, 4-polymeric structure content of 97.5-100mol%, molecular weight distribution index of 1.7-2.5, raw rubber Mooney viscosity ML (1+4) The temperature of 100 ℃ is 40-65 ℃.
According to the present invention, the amount of the homogeneous rare earth catalyst may be appropriately adjusted according to the desired polybutadiene in order to obtain a weight average molecular weight of 2.5X10 5 -3.3×10 5 g/mol, cis 1, 4-polymeric structure content of 97mol% or more, molecular weight distribution index of 2.5 or less, raw rubber Mooney viscosity ML (1+4) Polybutadiene at 100℃of 40-65, preferably the homogeneous rare earth catalyst is used in such an amount that the first mass is used in an amount of 20-200. Mu. Mol, preferably 30-100. Mu. Mol, relative to 1mol of butadiene.
According to the present invention, the second organic solvent may be any hydrocarbon solvent inert to the polymerization reaction, and may be, for example, C 5 -C 10 Alkanes, C 5 -C 10 Cycloalkanes and C 6 -C 12 Preferably 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 to 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 1-5h. More preferably, the polymerization conditions include: the temperature is 60-80 ℃ and the time is 1.5-3h.
According to the present invention, the polymerization reaction may be performed in an inert atmosphere in order to overcome the damage of the catalyst active center by oxygen. The inert atmosphere may be maintained by evacuating the reaction vessel and then introducing a gas selected from the group consisting of nitrogen, argon, helium, and the like.
In the invention, the inventor of the invention 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 the solvent, and the effect of obviously improving the catalyst activity can not be achieved; when the amount of the fifth material added is too large, the formation of active sites is hindered, which in turn leads to a decrease in catalytic activity. The fifth material may promote the formation of a homogeneous solution of the composition of the present invention 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 the first mixing, the fifth material can be made to prepare the rare earth homogeneous catalyst with relatively low dosage, and therefore, under the preparation method of the invention, the dosage of the fifth material can be reduced to the 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 present 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 more suitable for preparing the polybutadiene of the invention can be obtained.
According to the present invention, the time of the standing treatment is preferably 1 to 60 hours, preferably 5 to 50 hours, more preferably 5 to 36 hours (e.g., 5 to 10 hours or 5 to 8 hours). Preferably, the temperature of the standing treatment is 10-40 ℃.
According to the present invention, preferably, the conditions of the first mixing include: the temperature is 10-40deg.C, and the time is 10-200min.
According to the present invention, preferably, the conditions of the second mixing include: the temperature is 10-50deg.C, and the time is 10-200min.
According to the invention, the aging conditions preferably include: the temperature is 40-80deg.C, and the time is 30-300min.
According to the invention, preferably, the dialkylaluminum hydride is of the formula AlH (R) 2 The trialkylaluminum is represented by formula Al (R) 3 Each R is independently selected from C 1 -C 6 Is a hydrocarbon group. More preferably, the second material is one or more of diethyl aluminum hydride, dipropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, tripentyl aluminum, trihexyl aluminum, and triisobutyl aluminum.
According to the invention, preferably, the halosilane is represented by the formula Si (R 1 ) 4-n X n The sesquihaloalkylaluminum is represented by Al 2 (R 1 ) 3 X 3 The haloalkylaluminum is represented by the formula Al (R 1 ) 2 X is represented by, wherein each R 1 Each independently selected from C 1 -C 6 Each X is independently selected from the group consisting of 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, aluminum sesquiethyl chloride, aluminum sesquiisobutyl chloride, aluminum diethyl chloride and aluminum diisobutyl chloride.
According to the invention, preferably R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Each independently is C 1 -C 20 Alkyl or C of (2) 1 -C 20 Alkoxy of (C) is preferred 4 -C 12 Alkyl or C of (2) 4 -C 12 More 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-pentyloxy, 2-methylpentyloxy, 2-ethylpentyloxy, n-hexyloxy, 2-methylhexyloxy, 2-ethylhexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy or n-dodecyloxyA base.
According to the invention, preferably R d1 、R d2 And R is d3 Each independently is hydroxy, C 4 -C 12 Alkyl or C of (2) 4 -C 12 Alkoxy groups of (a); more preferably, R d1 Is hydroxy, R d2 And R is d3 Each 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-pentyloxy, 2-methylpentyloxy, 2-ethylpentyloxy, n-hexyloxy, 2-methylhexyloxy, 2-ethylhexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy or n-dodecyloxy.
The neodymium phosphonate compound may be obtained in a conventional manner in the art, for example, commercially available, or may be prepared by a conventional method in the art, and the present invention is not limited thereto.
Wherein, specific examples of the neodymium phosphonate compound may be selected from, for example, one or more of the compounds shown in the following formulas:
formula (1-1): in the formula (1), R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Are all 2-ethylhexyl oxy groups (namely, neodymium di (2-ethylhexyl) phosphonate);
formula (1-2): in the formula (1), R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Are all 2-methylhexyloxy groups (namely, neodymium di (2-methylhexyl) phosphonate);
formula (1-3): in the formula (1), R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Are n-hexyloxy groups (namely, di (n-hexyl) neodymium phosphonate).
The compound represented by the formula (2) may be obtained in a manner conventional in the art, for example, commercially available, or may be obtained by a method conventional in the art, and the present invention is not particularly limited thereto.
Wherein, specific examples of the compound represented by the formula (2) may be selected from, for example, one or more of the compounds represented by the following formulas:
formula (2-1): in the formula (2), R d1 Is hydroxy, R d2 And R is d3 Are all 2-ethylhexyl oxy groups (namely, di (2-ethylhexyl) phosphonate);
formula (2-2): in the formula (2), R d1 Is hydroxy, R d2 And R is d3 Are all 2-methylhexyloxy (namely, di (2-methylhexyl) phosphonate);
formula (2-3): in the formula (2), R d1 Is hydroxy, R d2 And R is d3 Are n-hexyloxy (i.e., di (n-hexyl) phosphonate).
According to the present invention, the conjugated diene in the composition is capable of stabilizing the catalyst active center, and generally refers to an olefin 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 hereinafter used to form polybutadiene should be metered separately.
According to the invention, the obtained rare earth catalyst is in a homogeneous state by the preparation method of the catalyst, 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 a wide range, preferably the amount of the solvent in the homogeneous solution is such that the concentration of the first material is 0.01-0.5mmol/mL, preferably 0.01-0.1mmol/mL, more preferably 0.01-0.02mmol/mL. The first organic solvent may be various solvents that can be suitably used for preparing the homogeneous solution of the homogeneous rare earth catalyst of the present invention, preferably C 5 -C 10 Alkanes, C 5 -C 10 Cycloalkanes and C 6 -C 12 Preferably pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, octylOne or more of an alkane, benzene, toluene, xylene, and cumene. The first solvent is understood herein to be the generic term for the solvent contained in the homogeneous rare earth catalyst obtained, i.e. to include the solvent added during the first mixing, as well as the solvent introduced during the subsequent treatment, including the solvent introduced in the form of a solution of the active ingredient.
Wherein the first material may be provided in the form of a pure substance or in the form of a solution, and when the first material is provided in the form of a solution, the concentration of the solution of the first material may be, for example, 0.01 to 0.5mol/L. The solvent may be selected from the first organic solvents used in the homogeneous solutions described above.
Wherein the second material may 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 may be, for example, 0.01 to 5mol/L. The solvent may be selected from the first organic solvents used in the homogeneous solutions described above.
Wherein the third material may be provided in the form of a pure substance thereof or in the form of 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 5mol/L. The solvent may be selected from the first organic solvents used in the homogeneous solutions described above.
Wherein the fourth material may be provided in the form of its pure substance or in the form of a solution, and when the fourth material is provided in the form of a solution, the concentration of the solution of the fourth material may be, for example, 0.01 to 5mol/L. The solvent may be selected from the first organic solvents used in the homogeneous solutions described above.
Wherein the fifth material may be provided in the form of a pure material thereof or in the form of a solution, and when the fifth material is provided in the form of a solution, the concentration of the solution of the fifth material may be, for example, 0.01 to 0.5mol/L. The solvent may be selected from the first organic solvents used 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) At low catalyst consumption, the catalyst consumption is 110mgNd/kg BR or less (the amount of Nd required for producing 1kg of polybutadiene);
(2) The polybutadiene obtained has a suitable molecular weight, i.e.the weight-average molecular weight of the polybutadiene obtained is 2.5X10 5 -3.3×10 5 g/mol, raw rubber Mooney viscosity ML (1+4) The temperature of 100 ℃ is 40-65;
(3) The obtained polybutadiene has a narrower molecular weight distribution, i.e., the molecular weight distribution index of the obtained polybutadiene is below 2.5;
(4) The polybutadiene obtained is a high cis-polybutadiene having a cis-1, 4-polymeric structure content of 97mol% or more (based on the total molar amount of structural units of the polybutadiene).
In a second aspect, the present invention provides polybutadiene obtained by the above-mentioned preparation method.
According to the invention, the polybutadiene preferably has a weight average molecular weight of 2.5X10 5 -3.3×10 5 g/mol, cis 1, 4-polymeric structure content of 97mol% or more, molecular weight distribution index of 2.5 or less, raw rubber Mooney viscosity ML (1+4) The temperature of 100 ℃ is 40-65 ℃. Preferably, the polybutadiene has a weight average molecular weight of 2.5X10 5 -3.2×10 5 g/mol, cis 1, 4-polymeric structure content of 97.5-100mol%, molecular weight distribution index of 1.7-2.5, raw rubber Mooney viscosity ML (1+4) The temperature of 100 ℃ is 40-65 ℃.
The third aspect of the invention provides a preparation method of a homogeneous rare earth catalyst, which is prepared from a first material, a second material, a third material, a fourth material and a fifth material, wherein the mole ratio of the first material to the second material to the fifth material is 1:12-30:0.2-0.4;
a first material: neodymium phosphonate compounds shown in a formula (1);
a second material: an alkylaluminum compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
third material: halogenated compounds selected from one or more of halosilanes, sesquihaloalkylaluminum and haloalkylaluminum;
fourth material: conjugated dienes;
and (3) a fifth material: a compound represented by the formula (2);
(1)(2)/(S)>
Wherein R is a1 、R a2 、R b1 、R b2 、R c1 、R c2 、R d1 、R d2 And R is d3 Each independently is hydrogen, hydroxy, C 1 -C 20 Alkyl or C of (2) 1 -C 20 Alkoxy groups 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; and introducing the fourth material and the second material for second mixing, and then introducing the third material for ageing treatment.
Preferred features of the preparation process and the associated description are as described above for the first aspect.
In a fourth aspect the present invention provides a homogeneous rare earth catalyst obtainable by the process of the third aspect.
According to the invention, the homogeneous rare earth catalyst comprises the first material, the second material, the third material, the fourth material and the fifth material, and the molar ratio of the first material to the fifth material is 1: conditions of 0.2 to 0.4. Although the molar ratio of the first material to the fifth material is 1: the dosage of the fifth material is 0.2-0.4, namely the dosage of the fifth material is lower, but the homogeneous rare earth catalyst prepared by the fifth material under the lower dosage can be used for catalyzing the polymerization of butadiene by the method of the invention, and the polybutadiene product with higher cis-structure content and molecular weight meeting the requirements of a certain range is obtained.
The present invention will be described in detail by examples.
In the following examples, mooney viscosity was measured using a SMV-201SK-160 rotor-free Mooney viscometer manufactured by Shimadzu corporation, wherein the preheating time was 1min, the rotation time was 4min, and the test temperature was 100 ℃.
Molecular weight and molecular weight distribution were measured by using a Gel Permeation Chromatograph (GPC) of the type Cao Chan HLC-8320, 2 TSKgelSuperMultipore HZ-M analytical columns were arranged, THF was the mobile phase, and narrow-distribution polystyrene was the standard sample, at 40 ℃.
The cis 1, 4-polymeric structure content was determined using an infrared spectrometer in Bruker Tensor 27, germany.
Preparation example 1
30mL of hydrochloric acid (12 mol/L) was added to 0.05mol of Nd 2 O 3 Then heated to boiling and stirred for 30min to obtain NdCl 3 The aqueous solution was pale purple in transparency. 0.3mol of acetone solution of di (2-ethylhexyl) phosphonate (180 mL of acetone) was added to 450mL of sodium hydroxide aqueous solution (sodium hydroxide content 0.3 mol), and mixed uniformly to obtain pale yellow solution, and then the above NdCl was added 3 The aqueous solution is stirred and mixed to obtain suspension containing fine white granular precipitate, the suspension is filtered and a filter cake is respectively washed for 3 times by a proper amount of distilled water and acetone, and then the suspension is placed in a 60 ℃ oven to be dried for 72 hours, thus obtaining the bis (2-ethylhexyl) neodymium phosphonate.
Catalyst preparation example 1
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
250mL of hexane, 3.2mmol of neodymium di (2-ethylhexyl) phosphonate, and 1.05mmol of di (2-ethylhexyl) phosphonate were mixed at 20℃under nitrogen and allowed to stand for 24h. Then adding 51.2mL of 1mol/L diisobutyl aluminum hydride hexane solution and 160mmol of butadiene at 30 ℃ and stirring and mixing for 30min, then heating to 60 ℃, adding 9.6mL of 1mol/L diethyl aluminum chloride hexane solution, and aging for 2h to obtain a homogeneous phase solution state catalyst, namely a homogeneous phase rare earth catalyst C1, wherein the content of Nd element is 0.0099mmol/mL; the molar ratio of neodymium bis (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and bis (2-ethylhexyl) phosphonate is 1:16:3:50:0.3.
catalyst preparation example 2
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
250mL of hexane, 3.2mmol of neodymium di (2-ethylhexyl) phosphonate, and 1.12mmol of di (2-ethylhexyl) phosphonate were mixed at 20℃under nitrogen and allowed to stand for 5h. Then adding 51.2mL of 1mol/L hexane solution of diethyl aluminum hydride and 128mmol of butadiene at 30 ℃ and stirring and mixing for 30min, then heating to 80 ℃, adding 9.28mL of 1mol/L hexane solution of diisobutyl aluminum chloride, 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 0.0099mmol/mL; the molar ratio of neodymium bis (2-ethylhexyl) phosphonate, diethylaluminum hydride, diisobutylaluminum chloride, butadiene and bis (2-ethylhexyl) phosphonate is 1:16:2.9:40:0.35.
catalyst preparation example 3
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
250mL of hexane, 3.2mmol of neodymium di (2-ethylhexyl) phosphonate, and 0.80mmol of di (2-ethylhexyl) phosphonate were mixed at 20℃under nitrogen and allowed to stand for 36h. Then adding 51.2mL of 1mol/L diisobutyl aluminum hydride hexane solution and 160mmol of butadiene at 30 ℃ and stirring and mixing for 30min, then heating to 60 ℃, adding 9.6mL of 1mol/L diethyl aluminum chloride hexane solution, and aging for 2h to obtain a homogeneous phase solution state catalyst, namely a homogeneous phase rare earth catalyst C1, wherein the content of Nd element is 0.0099mmol/mL; the molar ratio of neodymium bis (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and bis (2-ethylhexyl) phosphonate is 1:16:3:50:0.25.
catalyst preparation example 4
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
According to the method described in catalyst preparation example 1, except that the amount of butadiene used was 256mmol, a catalyst in the form of a homogeneous solution, i.e., a homogeneous rare earth catalyst C3, was obtained, in which the content of Nd element was 0.0096mmol/mL; the molar ratio of neodymium bis (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and bis (2-ethylhexyl) phosphonate is 1:16:3:80:0.3.
catalyst preparation example 5
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
According to the method described in catalyst preparation example 1, except that the amount of di (2-ethylhexyl) phosphonate was 1.28mmol, a catalyst in the form of a homogeneous solution, i.e., homogeneous rare earth catalyst C4, was obtained, in which the content of Nd element was 0.0099mmol/mL; the molar ratio of neodymium bis (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and bis (2-ethylhexyl) phosphonate is 1:16:3:50:0.4.
catalyst preparation example 6
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
According to the method described in catalyst preparation example 1, except that the amount of di (2-ethylhexyl) phosphonate was 0.80mmol, a catalyst in the form of a homogeneous solution, i.e., homogeneous rare earth catalyst C5, was obtained, in which the content of Nd element was 0.0099mmol/mL; the molar ratio of neodymium bis (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and bis (2-ethylhexyl) phosphonate is 1:16:3:50:0.25.
catalyst preparation example 7
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
According to the method described in catalyst preparation example 1, except that the hexane solution of diisobutylaluminum hydride at a concentration of 1mol/L was used in an amount of 96mL, thereby obtaining a catalyst in a homogeneous solution state, i.e., homogeneous rare earth catalyst C6, in which the content of Nd element was 0.0087mmol/mL; the molar ratio of neodymium bis (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and bis (2-ethylhexyl) phosphonate is 1:30:3:50:0.3.
catalytic preparation example 8
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
According to the method described in catalyst preparation example 1, except that the hexane solution of diisobutylaluminum hydride at a concentration of 1mol/L was used in an amount of 38mL, thereby obtaining a catalyst in a homogeneous solution state, i.e., homogeneous rare earth catalyst C7, in which the content of Nd element was 0.0103mmol/mL; the molar ratio of neodymium bis (2-ethylhexyl) phosphonate, diisobutylaluminum hydride, diethylaluminum chloride, butadiene and bis (2-ethylhexyl) phosphonate is 1:12:3:50:0.3.
catalytic preparation example 9
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
The procedure described in catalyst preparation 1 was followed except that hexane, neodymium di (2-ethylhexyl) phosphonate, and di (2-ethylhexyl) phosphonate were mixed and then allowed to stand for 2 hours, i.e., homogeneous rare earth catalyst C9.
Catalytic preparation example 10
This preparation example is used to illustrate the homogeneous rare earth catalyst of the present invention and its preparation method.
According to the method of example 1, except that hexane, neodymium di (2-ethylhexyl) phosphonate, and di (2-ethylhexyl) phosphonate were mixed and then allowed to stand for 72 hours, catalyst C10 was obtained in the state of a homogeneous solution.
Comparative example 1
According to the method of example 1, except that neodymium phosphonate and di (2-ethylhexyl) phosphonate were not allowed to stand after mixing, catalyst DC1 was obtained in the state of a homogeneous solution.
Comparative example 2
According to the method of 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
According to the method of example 1, except that triphenylphosphine was used instead of di (2-ethylhexyl) phosphonate in equimolar amounts, catalyst DC3 was obtained, which contained a small amount of suspended solids.
Polymerization examples 1 to 10
900g of hexane, 200g of butadiene and a certain amount of the catalysts C1-C10 (the amount and the types are shown in Table 1) are polymerized for 2 hours at 60 ℃ under the protection of nitrogen to obtain the corresponding polybutadiene, and the properties of the obtained polybutadiene are shown in Table 1.
Polymerization comparative example 1
According to the method of polymerization example 1, except that catalyst DC1 was used instead of catalyst C1, the corresponding polybutadiene was obtained, and the properties of the obtained polybutadiene were shown in Table 1.
Polymerization comparative example 2
According to the method of polymerization example 1, except that catalyst DC2 was used instead of catalyst C1, the corresponding polybutadiene was obtained, and the properties of the obtained polybutadiene were as shown in Table 1.
Polymerization comparative example 3
According to the method of polymerization example 1, except that catalyst DC3 was used instead of catalyst C1, the corresponding polybutadiene was obtained, and the properties of the obtained polybutadiene were shown in Table 1.
TABLE 1
From the results of Table 1, it can be seen that the composition of the present invention can be caused to form a homogeneous solution at a smaller amount of the fifth material by standing, and can also provide more catalytically active sites, thereby improving the activity of the rare earth catalyst.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (40)
1. A process for the preparation of 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: neodymium phosphonate compounds shown in a formula (1);
a second material: an alkylaluminum compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
third material: halogenated compounds selected from one or more of halosilanes, sesquihaloalkylaluminum and haloalkylaluminum;
fourth material: conjugated dienes;
and (3) a fifth material: a compound represented by the formula (2);
(1)(2)/(S)>
Wherein R is a1 、R a2 、R b1 、R b2 、R c1 、R c2 、R d1 、R d2 And R is d3 Each independently is hydroxy or C 1 -C 20 Alkoxy groups 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; and introducing the fourth material and the second material for second mixing, and then introducing the third material for ageing treatment.
2. The preparation method according to claim 1, wherein the homogeneous rare earth catalyst is used in an amount such that the amount of the first material is 20 to 200. Mu. Mol with respect to 1mol of butadiene.
3. The production method according to claim 2, wherein the conditions of the polymerization reaction include: the temperature is 50-90 ℃ and the time is 1-5h.
4. The process according to any one of claims 1 to 3, wherein the process is such that the weight-average molecular weight of the polybutadiene obtained is 2.5X10 5 -3.3×10 5 g/mol, cis 1, 4-polymeric structure content of 97mol% or more, molecular weight distribution index of 2.5 or less, raw rubber Mooney viscosity ML (1+4) The temperature of 100 ℃ is 40-65 ℃.
5. The method of claim 1, wherein the molar ratio of the first material to the third material is 1:2-5.
6. The method according to claim 5, wherein the molar ratio of the first material to the fourth material is 1:10-80.
7. The production method according to any one of claims 1 to 3 and 5 to 6, wherein the time of the leaving treatment is 1 to 60 hours.
8. The production method according to claim 7, wherein the time of the leaving treatment is 5 to 50 hours.
9. The production method according to claim 8, wherein the time of the leaving treatment is 5 to 36 hours.
10. The method of preparing according to claim 7, wherein the conditions of the first mixing include: the temperature is 10-40deg.C, and the time is 10-200min.
11. The method of preparing according to claim 7, wherein the second mixing conditions include: the temperature is 10-50deg.C, and the time is 10-200min.
12. The method of claim 7, wherein the aging conditions comprise: the temperature is 40-80deg.C, and the time is 30-300min.
13. The process of any one of claims 1-3, 5-6, and 8-12, wherein the dialkylaluminum hydride is of the formula AlH (R) 2 The trialkylaluminum is represented by formula Al (R) 3 Each R is independently selected from C 1 -C 6 Alkyl of (a);
the halosilane is prepared from Si (R) 1 ) 4-n X n The sesquihaloalkylaluminum is represented by Al 2 (R 1 ) 3 X 3 The haloalkylaluminum is represented by the formula Al (R 1 ) 2 X is represented by, wherein each R 1 Each independently selected from C 1 -C 6 Each X is independently selected from the group consisting of halogen, and n is an integer of 1 to 4.
14. The process of claim 1, wherein the second material is one or more of diethyl aluminum hydride, dipropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, tripentyl aluminum, trihexyl aluminum, and triisobutyl aluminum;
the third material is one or more of monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, aluminum sesquiethoxide, aluminum sesquibutoxide, diethyl aluminum chloride and diisobutyl aluminum chloride.
15. The method of any one of claims 1-3, 5-6, 8-12, and 14, wherein R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Each independently is C 1 -C 20 Alkoxy groups of (a).
16. The method of claim 15, wherein R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Each independently is C 4 -C 12 Alkoxy groups of (a).
17. The method of claim 16, wherein R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Each independently is n-butoxy, iso-butoxy, 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-undecoxy or n-dodecoxy.
18. The method of claim 15, wherein R d1 、R d2 And R is d3 Each independently is hydroxy or C 4 -C 12 Alkoxy groups of (a).
19. The method of claim 18, wherein R d1 Is hydroxy, R d2 And R is d3 Each independently is n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-methylpentoxy, 2-ethylpentoxy, n-hexoxy, 2-methylhexoxy, 2-ethyloxyA hexyloxy group, a n-heptyloxy group, a n-octyloxy group, a n-nonyloxy group, a n-decyloxy group, a n-undecyloxy group or a n-dodecyloxy group.
20. The process of any of claims 1-3, 5-6, 8-12, 14, and 16-19, wherein the conjugated diene is one or more of 1, 3-butadiene, isoprene, piperylene, and 2, 4-hexadiene.
21. Polybutadiene produced by the production process according to any of claims 1 to 20.
22. 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 mole ratio of the first material to the second material to the fifth material is 1:12-30:0.2-0.4;
a first material: neodymium phosphonate compounds shown in a formula (1);
a second material: an alkylaluminum compound selected from one or more of dialkylaluminum hydride and trialkylaluminum;
third material: halogenated compounds selected from one or more of halosilanes, sesquihaloalkylaluminum and haloalkylaluminum;
fourth material: conjugated dienes;
and (3) a fifth material: a compound represented by the formula (2);
(1)(2)/(S)>
Wherein R is a1 、R a2 、R b1 、R b2 、R c1 、R c2 、R d1 、R d2 And R is d3 Each independently is hydroxy or C 1 -C 20 Is an alkane of (2)An oxy group;
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; and introducing the fourth material and the second material for second mixing, and then introducing the third material for ageing treatment.
23. The method of claim 22, wherein the molar ratio of the first material to the third material is 1:2-5.
24. The method of claim 23, wherein the first material and the fourth material are present in a molar ratio of 1:10-80.
25. The production method according to claim 23, wherein the time of the leaving treatment is 1 to 60 hours.
26. The production method according to claim 25, wherein the time of the leaving treatment is 5 to 50 hours.
27. The production method according to claim 26, wherein the time of the leaving treatment is 5 to 36 hours.
28. The method of preparing of claim 23, wherein the first mixing conditions comprise: the temperature is 10-40deg.C, and the time is 10-200min.
29. The method of preparing according to claim 23, wherein the second mixing conditions comprise: the temperature is 10-50deg.C, and the time is 10-200min.
30. The method of claim 23, wherein the aging conditions comprise: the temperature is 40-80deg.C, and the time is 30-300min.
31. According to any one of claims 22-30The preparation method, wherein the dialkyl aluminum hydride is represented by the formula AlH (R) 2 The trialkylaluminum is represented by formula Al (R) 3 Each R is independently selected from C 1 -C 6 Is a hydrocarbon group.
32. The process of claim 31, wherein the second material is one or more of diethyl aluminum hydride, dipropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, tripentyl aluminum, trihexyl aluminum, and triisobutyl aluminum.
33. The method of claim 31, wherein the halosilane is selected from the group consisting of the formula Si (R 1 ) 4-n X n The sesquihaloalkylaluminum is represented by Al 2 (R 1 ) 3 X 3 The haloalkylaluminum is represented by the formula Al (R 1 ) 2 X is represented by, wherein each R 1 Each independently selected from C 1 -C 6 Each X is independently selected from the group consisting of halogen, and n is an integer of 1 to 4.
34. The method of claim 31, wherein the third material is one or more of monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, aluminum sesquiethoxide, aluminum sesquibutoxide, diethyl aluminum chloride, and diisobutyl aluminum chloride.
35. The method of claim 31, wherein the conjugated diene is one or more of 1, 3-butadiene, isoprene, piperylene, and 2, 4-hexadiene.
36. The production method according to any one of claims 22 to 30 and 32 to 35, wherein R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Each independently is C 1 -C 20 Alkoxy groups of (a).
37. The method of claim 36, wherein R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Each independently is C 4 -C 12 Alkoxy groups of (a).
38. The method of claim 37, wherein R a1 、R a2 、R b1 、R b2 、R c1 And R is c2 Each independently is n-butoxy, iso-butoxy, 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-undecoxy or n-dodecoxy.
39. The method of claim 36, wherein R d1 Is hydroxy, R d2 And R is d3 Each independently is n-butoxy, iso-butoxy, 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-undecoxy or n-dodecoxy.
40. A homogeneous rare earth catalyst prepared by the preparation method of any one of claims 22 to 39.
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