CN103788236A - Rare earth catalyst and preparation method thereof, and polyisoprene and preparation method thereof - Google Patents
Rare earth catalyst and preparation method thereof, and polyisoprene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a rare earth catalyst preparation method. The rare earth catalyst preparation method is characterized in that a component A neodymium carboxylate compound, a component B alkyl aluminum compound, a component C conjugated diene, a component D halide and a component E alkyl zinc with the general formula of ZnR' contact with each other in a first organic solvent, wherein R' is a C1-C4 alkyl group; and the above contact mode comprises the following steps: 1, adding the component D into a mixture comprising the component A and the component C to obtain a component A-C-D mixture; 2, adding the component B into the component A-C-D mixture to obtain a component A-C-D-B mixture; and adding the component E to the component A-C-D-B mixture. The invention also provides a rare earth catalyst obtained through the rare earth catalyst preparation method, and polyisoprene and a preparation method thereof. Polyisoprene with the molecular weight distribution of below 1.7, the cis-1,4-configuration content of above 98% and high molecular weight can be obtained in the invention, and the conversion rate of an isoprene monomer is above 90%.
Description
Technical field
The present invention relates to rare earth catalyst and preparation method thereof and polyisoprene and preparation method thereof.
Background technology
High-cis polyisoprene rubber (IR) (also referred to as polyisoprene) due to natural rubber structural similitude, be mainly used to replace natural rubber and be applied to tyre industry.Polyisoprene rubber has compared with natural rubber that purity is high, quality homogeneous, the time of plasticating are short, mixing easy, transparent color and luster, expansion and the advantage such as specific absorption is little, good fluidity.Improve the molecular weight of polyisoprene rubber and reduce molecular weight distribution simultaneously, be conducive to reduce when polyisoprene rubber is applied to tire rolling resistance.And in raising polyisoprene rubber, the content of cis Isosorbide-5-Nitrae-structure is also conducive to improve the mechanical property of polyisoprene rubber.Therefore, suitability for industrialized production obtains high molecular, cis Isosorbide-5-Nitrae-structural content is large, molecular weight distribution is little product becomes the development trend of synthetic polyisoprene rubber from now on.
The existing method of controlling polyisoprene rubber molecular weight and molecualr weight distribution has a lot, as regulated catalyst levels, adjust the reaction times, add chain-transfer agent and adding aluminum alkyls etc.
CN1342718A discloses a kind of polymerization process of rare earth catalyst diolefin, it is characterized in that catalyzer is formed by following several component hybrid reactions: (1) is containing the rare earth compound-L of phosphonate group or carboxyl
3ln, wherein L representative (2-ethylhexyl) phosphinidene, (2-ethylhexyl) phosphino-, new decyl, cycloalkyl and acetylacetone based; Rare earth Ln represents neodymium, praseodymium, pr-nd enriched product; (2) alkylaluminium cpd-R
na1H
3-n, R represent methylidene, ethyl, isobutyl-; N=2,3, or their mixture; (3) halogen-containing organic compound or organometallic compound; Halogen-containing organic compound is, trimethylammonium chloro silicon Anhui alkane, tertiary butyl chloride, chlorallylene; Halogen-containing organometallic compound is, di-isobutyl aluminum chloride, sesquialter aluminium triethyl; (4) organic compound-X of 3d group 4 transition metal
mmY
n, wherein M is cobalt, nickel, iron, titanium; X and Y represent phosphonate group and carboxyl, and they can be identical or different, when m=3-n, and n=0,1,2; When m=2-n, n=0,1; Phosphonate group compound is (2-ethylhexyl) phosphonous acid and (2-ethylhexyl) phosphonic acids, and carboxylic compound is selected 2 ethyl hexanoic acid, neodecanoic acid and naphthenic acid; Method for preparing catalyst is that mole ratio of components of each component is rare earth compound: alkylaluminium cpd: halogen-containing organic compound or organometallic compound: the organic compound of transition metal: monomer=1:10-60:1.5-5:0.02-0.5:3-20; Monomer is selected divinyl and isoprene, implements butadiene homopolymerization, isoprene homopolymerization and divinyl and isoprene copolymer, and monomer concentration is 10-16%, and in copolymerization, isoprene and divinylic monomer weight ratio are 20-50:80-50; Solvent adopts normal hexane, normal heptane, toluene and 1,2,4-tri-chlorination benzene; Catalyzer ageing concentration is 0.3-5 × 10-4 mole/milliliter, Aging Temperature 0-50 ℃, and digestion time is 5 minutes-48 hours.This invention is used for controlling polymericular weight and distribution thereof.When synthetic polyisoprenes, the limiting viscosity of the polymkeric substance of acquisition is 8.43-8.83dl/g, and cis Isosorbide-5-Nitrae-structural content is 95.6-96.7%, and molecular weight distributing index MWD is 1.43.
CN1295087A discloses the improved double-olefine polymerizing rare earth catalyst of a kind of aromatic hydrocarbons, it is characterized in that its composition has LnA
3-AlR
3-X-Ar is catalysis of rare-earth compound agent system and the LnC1 of representative
33L'-AlR
3-Ar is the Lanthanide Chloride Catalysts For Butadiene Polymerization system of representative: Ln is the rare earth element that represents La ~ Lu, selects wherein the highest active two kinds of elements of neodymium, praseodymium; A is carboxylate radical, and these carboxylate radicals are cycloalkanes acid group, 2 ethyl hexanoic acid root, neodecanoic acid root; AlR
3for organo-aluminium compound, they are triethyl aluminum, triisobutyl aluminium, diisobutylaluminium hydride; X is chloride compound, and they are aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, tertiary butyl chloride, trimethylchlorosilane; L is supplied for electronic compound, and they are Virahols, tributyl phosphate; Ar is aromatic hydrocarbons, and they are benzene, toluene, ethylbenzene, isopropyl benzene, dimethylbenzene, ortho-xylene, m-dimethylbenzene, p-dimethylbenzene, trimethylbenzene, mellitene, vinyl benzene, Vinylstyrene, naphthalene, dihydronaphthalene, naphthane, anthracene, phenanthrene.This invention is high along Isosorbide-5-Nitrae-structural content for keeping making, the polymkeric substance of high linearity gel-free, and can, by regulating aromatic hydrocarbon type and consumption effectively regulate the molecular weight of polymerisate, particularly reduce the molecular weight of polymerisate.Cis Isosorbide-5-Nitrae-structural content in the polyisoprene obtaining is 94.8-95.6%.
US2005/0137338A discloses a kind of method of preparing neodymium catalyst system, the method comprises that (1) neodymium carboxylate salt reacts generation neodymium-Al catalysts composition in the second organic solvent with organo-aluminium compound, and (2) react described neodymium-Al catalysts composition the described neodymium catalyst system that generates subsequently with halogen.This invention, can crystallization under stretching for obtaining the polyisoprene rubber of high-cis structural content and high three-dimensional regularity.In the polyisoprene obtaining, cis Isosorbide-5-Nitrae-structural content is 95.6-98.1%, and molecular weight distribution is M
w/ M
n=1.7-2.48 and weight-average molecular weight are in 3.32-24.2 × 10
5.In this inventive embodiment 21, openly having obtained weight-average molecular weight is 23.58 × 10
5, molecular weight distribution is 1.75 and cis Isosorbide-5-Nitrae-structural content polyisoprene that is 98.1%.
CN101045768A discloses a kind of rare earth catalyst of preparing polyisoprene, it is characterized in that, this rare earth catalyst component and proportioning are: A. rare earth organic compounds, select rare earth carboxylate or rare earth acidic phosphor/phosphine hydrochlorate; B. trialkylaluminium or alkyl aluminium hydride; C. muriate is: a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter aluminium triethyl, tertiary butyl chloride, benzyl chloride, chlorallylene, silicon tetrachloride or Me
4-nsiCl
nwherein n is 1,2 or 3; D. conjugated diolefin; The mol ratio of each component is B:A=5-30:1, C:A=1.0-4.0:1, D:A=5-20:1.This invention is used for the polyisoprene that obtains high-cis-Isosorbide-5-Nitrae structural content and narrow distribution and have stretch crystallization performance characteristics.Can obtain the polyisoprene that cis-Isosorbide-5-Nitrae structural content is 2.02-2.88 in 96.0-97.2% and molecular weight distribution.
Therefore,, in order to improve the performance of polyisoprene, the polyisoprene that obtains narrow molecular weight distribution remains technical issues that need to address.
Summary of the invention
The object of the invention is to obtain the polyisoprene of narrow molecular weight distribution, rare earth catalyst and preparation method thereof and polyisoprene and preparation method thereof are provided.
To achieve these goals, the invention provides a kind of preparation method of rare earth catalyst, the method comprises following each component is in contact with one another in the first organic solvent, and described component is:
A-carboxylic acid neodymium compound;
B-general formula is AlR
3and/or AlHR
2alkylaluminium cpd, wherein, R is C
1-C
6alkyl;
C-conjugated diene;
D-halogenide, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and there are one or more in the halohydrocarbon of general formula R X, wherein, R is C
1-C
4alkyl, X is bromine or chlorine; And
E-general formula is ZnR '
2zinc alkyl(s), wherein R ' is C
1-C
4alkyl;
The mode of described contact is:
(1) component D is joined in the mixture of component A and component C, obtain mixture ACD;
(2) B component is joined in described mixture ACD, obtain mixture ACDB;
(3) component E is joined in described mixture ACDB.
The rare earth catalyst that the present invention also provides a kind of preparation method who is provided by the invention described above to obtain.
The present invention also provides a kind of preparation method of polyisoprene, and the method is included under the second organic solvent and polymerizing catalyst existence, makes isoprene monomer carry out polyreaction; Wherein, the rare earth catalyst that described polymerizing catalyst provides for the invention described above.
The polyisoprene that the present invention also provides a kind of method being provided by the invention described above to prepare.
The technical scheme providing by the invention described above, the zinc alkyl(s) component comprising in rare earth catalyst provides rare earth catalyst with better catalytic performance, can obtain the polyisoprene of narrow molecular weight distribution.For example, in embodiment 1, contain zinc ethyl in rare earth catalyst, the weight-average molecular weight of the polyisoprene that polymerization obtains is 1,400,000, and molecular weight distribution is 1.5, and the cis Isosorbide-5-Nitrae-structural content of polyisoprene still reaches 98.7% simultaneously.And the catalyzer that does not comprise zinc alkyl(s) component is while carrying out isoprene polymerization, in comparative example 1, the molecular weight distribution of the polyisoprene of acquisition is 3.2, and in polymer architecture, the content of cis Isosorbide-5-Nitrae-structure is 98.2%.Visible, in the undiminished situation of content of technical scheme provided by the invention cis Isosorbide-5-Nitrae-structure in polyisoprene, obviously reduce the molecular weight distribution of polyisoprene.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of rare earth catalyst, the method comprises following each component is in contact with one another in the first organic solvent, and described component is:
A-carboxylic acid neodymium compound;
B-general formula is AlR
3and/or AlHR
2alkylaluminium cpd, wherein, R is C
1-C
6alkyl;
C-conjugated diene;
D-halogenide, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and there are one or more in the halohydrocarbon of general formula R X, wherein, R is C
1-C
4alkyl, X is bromine or chlorine; And
E-general formula is ZnR '
2zinc alkyl(s), wherein R ' is C
1-C
4alkyl;
The mode of described contact is:
(1) component D is joined in the mixture of component A and component C, obtain mixture ACD;
(2) B component is joined in described mixture ACD, obtain mixture ACDB;
(3) component E is joined in described mixture ACDB.
According to the present invention, the content of described component can be selected in relative broad range, and there is no particular limitation, and under preferable case, the molar ratio between described component is A:B:C:D:E=1:5-30:1-50:1-3:1-20.Further the molar ratio between preferred described component A and E is A:E=1:1-5.
According to the present invention, described zinc alkyl(s) can improve the catalytic performance of described rare earth catalyst, and the polymkeric substance that polymerization isoprene is obtained has the characteristic of narrow molecular weight distribution, does not reduce the content of cis Isosorbide-5-Nitrae-structure in polymkeric substance simultaneously.Two R ' in described zinc alkyl(s) can be identical, also can be different.Described C
1-C
4alkyl can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl.Under preferable case, described zinc alkyl(s) is one or more in zinc methide, zinc ethyl, di-isopropyl zinc and di-n-butyl zinc.
According to the present invention, described carboxylic acid neodymium compound is Primary Catalysts, and in described carboxylic acid neodymium, element neodymium is central metal atom, coordinates performance katalysis with Carboxylic Acid Ions.Carboxylic Acid Ions changes bond polarity and intensity etc. by the empty ligancy and the cloud density distribution that change element neodymium, thereby affects activity and the directional property of described rare earth catalyst.Under preferable case, described carboxylic acid neodymium compound is C
7-C
14carboxylic acid neodymium, preferred described carboxylic acid neodymium compound is one or more in neodymium naphthenate, n-caprylic acid neodymium, isocaprylic acid neodymium, neodymium caprate and n-capric acid neodymium.
According to the present invention, described alkylaluminium cpd is promotor, mainly plays alkylating, generates rare earth carbon active centre, also has removal of contamination, stabilizing active center and chain transfer simultaneously.In the present invention, under preferable case, described alkylaluminium cpd is one or more in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diisobutylaluminium hydride.
According to the present invention, described halogenide makes described master, promotor have high reactivity and can make monomer carry out high-cis polymerization.In the present invention, under preferable case, described halogenide is one or more in aluminium diethyl monochloride, sesquialter ethyl aluminum chloride and a chloro-di-isobutyl aluminum.
According to the present invention, described conjugated diene plays the effect of stablizing described master, promotor active centre, and in the present invention, under preferable case, described conjugated diene is C
4-C
6conjugated diene, preferred described conjugated diene is divinyl and/or isoprene.
According to the present invention, the first organic solvent using in the preparation method of described rare earth catalyst is not particularly limited, and is the varsol to described rare earth catalyst inertia, under preferable case, described the first organic solvent is aliphatic saturated hydrocarbon or alicyclic hydrocarbon, is preferably C
5-C
10alkane or naphthenic hydrocarbon, more preferably one or more in Skellysolve A, iso-pentane, normal hexane, hexanaphthene, normal heptane and octane.
In the present invention, in described preparation method, can component A, B component, component C, component D and component E be joined in the first organic solvent according to the mode of above-mentioned contact; Also can be that component A, B component, component D and component E are first dissolved in respectively in the first organic solvent, form multiple organic solution that contains different components, and then contact by the mode of above-mentioned contact.Preferably component A, B component, component D and component E are first dissolved in respectively in described the first organic solvent, form multiple organic solution that contains different components; Multiple organic solution that contains different components can be used different described the first organic solvents, also can all use identical described the first organic solvent, preferably uses the first identical organic solvent; Then contact according to the mode of above-mentioned contact.
In the present invention, to the concentration of the multiple organic solutions that contain different components that form, there is no particular limitation, obtain described rare earth catalyst as long as can meet, for example the concentration of component A solution is in neodymium element, can be 0.1-0.6mol/L, the concentration of B component solution can be 0.05-2mol/L, and the concentration of component D solution can be 0.05-2mol/L, and the concentration of component E solution can be 0.05-2mol/L.
According to the present invention, the mode of described contact can be carried out under inert atmosphere.Described inert atmosphere can be, for example nitrogen.
According to the present invention, there is no particular limitation for the each step in the mode of described contact, and under preferable case, the temperature that described component D joins in the mixture of component A and component C is 0 ℃-50 ℃, and at 0 ℃-50 ℃ ageing 1-30 minute, obtain mixture ACD; Described B component joins after described mixture ACD, and ageing 1-10 hour at 0 ℃-50 ℃, obtains mixture ACDB.The temperature that adds of described B component is preferably the temperature of mixture ACD after ageing, is 0-50 ℃.
In the present invention, after described component E joins in described mixture ACDB, supply the first organic solvent to the concentration of described rare earth catalyst in neodymium element, be 0.1 × 10
-5-2 × 10
-5mol/ml.
According to the present invention, in the method for described contact, in the described rare earth catalyst that the add-on of each component makes to obtain, the mol ratio of each component meets the requirement of described rare earth catalyst, under preferable case, in the described rare earth catalyst that the add-on of component A, B component, component C, component D and component E makes to obtain, the mol ratio of each component is A:B:C:D:E=1:5-30:1-50:1-3:1-20.Further the molar ratio between preferred described component A and E is A:E=1:1-5.
The rare earth catalyst that the present invention also provides a kind of preparation method who is provided by the invention described above to obtain.
According to the present invention, the described rare earth catalyst obtaining is homogeneous catalyst, is conducive to the operation of isoprene polymerization reaction.Component and proportion of composing that described rare earth catalyst contains are same as above, do not repeat them here.
The present invention also provides a kind of preparation method of polyisoprene, and the method is included under the second organic solvent and polymerizing catalyst existence, makes isoprene monomer carry out polyreaction; Wherein, the described rare earth catalyst that described polymerizing catalyst provides for the invention described above.
According to the present invention, the second organic solvent that described polyreaction is used is not particularly limited, and is the varsol to polyreaction inertia, and for example described the second organic solvent can be aliphatic saturated hydrocarbon and/or saturated alicyclic hydrocarbon; Preferably described the second organic solvent is C
5-C
10alkane and/or naphthenic hydrocarbon; More preferably described the second organic solvent is one or more in Skellysolve A, iso-pentane, normal hexane, hexanaphthene, normal heptane and octane.Described the second organic solvent and described the first organic solvent can be selected identical or different, and preferably described the second organic solvent and described the first organic solvent are identical.
According to the present invention, there is no particular limitation for the consumption of the second organic solvent that described polyreaction is used, and can guarantee described polyreaction, for example, can be that the concentration of isoprene monomer in described the second organic solvent is 8-20 % by weight.
According to the present invention, while carrying out polyreaction, the amount of the described rare earth catalyst of use is not particularly limited, can suitably select according to the molecular weight of the polymkeric substance of expection, for example, the consumption of described rare earth catalyst is that to make component A in described rare earth catalyst and the mol ratio of the isoprene monomer that carries out polyreaction be 0.8-3.0 × 10
-4: 1.
According to the present invention, the condition of carrying out described polyreaction can comprise temperature of reaction and reaction times, and for example, described temperature of reaction can be-30 ℃-80 ℃, and the described reaction times can be 0.1-5 hour; Preferably, described temperature of reaction is-20 ℃-50 ℃, and the described reaction times is 0.5-2 hour.
According to the present invention, in order to overcome oxygen inhibition, described polyreaction can be carried out in inert atmosphere.The method of maintenance inert atmosphere can be for to pass into rare gas element in polymerization reaction system.Described inert atmosphere can be for example nitrogen.
According to the present invention, after described polyreaction completes, can adopt the method for adding terminator that living polymer chains is lost activity, reach the object that stops described polyreaction.Kind and the consumption of described terminator are not particularly limited, as long as described terminator can make polymer active chain inactivation.Usually, described terminator can be water, C
1-C
6fatty alcohol, C
4-C
12aliphatic carboxylic acid and aryl polyol in one or more, described aryl polyol refers to that the hydrogen atom on phenyl ring has at least two to be replaced the compound being generated by hydroxyl.Preferably, described terminator is one or more in water, methyl alcohol, ethanol, Virahol and 2,6-di-tert-butyl hydroquinone.
The present invention is not particularly limited for the consumption of described terminator, as long as the consumption of described terminator can, by the active specy inactivation in polymerisate, repeat no more herein.
The polyisoprene that the present invention also provides a kind of preparation method of the polyisoprene being provided by the invention described above to obtain.
According to the present invention, this polyisoprene is greater than 98% with the content that carbon-13 magnetic resonance method is measured the cis Isosorbide-5-Nitrae-structure containing, and molecular weight distribution is less than 1.7, and weight-average molecular weight is not more than 2,500,000; The content of cis Isosorbide-5-Nitrae-structure that preferred described polyisoprene contains is 98.2-98.7%, and molecular weight distribution is for being more than or equal to 1.5 and be less than 1.7, and weight-average molecular weight is 100-250 ten thousand.
In the present invention, measure the structure of polyisoprene by carbon-13 magnetic resonance method.Use German Bruker 400MHz nuclear magnetic resonance analyser, solvent is deuterochloroform.
Below will describe the present invention by embodiment.In following examples, describe the present invention in detail by embodiment and comparative example below, but scope of the present invention is not limited to these embodiment.
In the present invention, the molecular weight and molecualr weight distribution of synthetic polyisoprene adopts Shimadzu LC-10AT type gel permeation chromatograph (GPC) to measure, and THF is moving phase, and probe temperature is 25 ℃, and Narrow distribution polystyrene is standard specimen.
Cis Isosorbide-5-Nitrae-structural content adopts German Bruker 400MHz nmr determination, and solvent is deuterochloroform; Or German Bruker Tensor 27 mid-infrared light spectrometers are measured.
Monomer conversion is defined as the weight and the percentage ratio of ratio of weight of participating in the isoprene that reacts of the polyisoprene of generation.
Embodiment 1
The present embodiment is for illustrating the preparation method of rare earth catalyst of the present invention and the polymerization of polyisoprene.
(1) rare earth catalyst preparation.Under nitrogen protection; in 20L catalyzer aging reactor, add 200ml isoprene (at 20 ℃; density is 0.68g/ml), 185ml concentration be 0.36mol/L neodymium caprate hexane solution and 10L hexane solution; adding 200ml concentration 0 ℃ of stirring is again 1mol/L aluminium diethyl monochloride hexane solution, continues ageing 30 minutes at 0 ℃.Then adding 890ml concentration is the triisobutyl aluminium hexane solution of 0.74mol/L, continue ageing 10 hours at 0 ℃, after ageing completes, adding 200ml concentration is the zinc ethyl hexane solution of 1mol/L, and add residue normal hexane to cumulative volume be 13.32L, rare earth catalyst agent concentration is 0.5 × 10
-5mol/ml.Obtain rare earth catalyst C1, each component mol ratio is neodymium caprate: triisobutyl aluminium: isoprene: aluminium diethyl monochloride: zinc ethyl=1:10:30:3:3.
(2) polyreaction.Under nitrogen protection, in 5L polymeric kettle, add successively 350g isoprene, 2000g normal hexane and 180ml rare earth catalyst C1, the concentration of isoprene monomer in normal hexane is 14 % by weight.Under 0 ℃ of condition, react after 120 minutes, polymer product solution is emitted and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction in still.Obtain polyisoprene 322g, monomer conversion is 92%.Polymerization result is in table 1.
Embodiment 2
The present embodiment is for illustrating the preparation method of rare earth catalyst of the present invention and the polymerization of polyisoprene.
(1) rare earth catalyst preparation.Under nitrogen protection; in 20L catalyzer aging reactor, add neodymium caprate hexane solution and the 10L hexane solution that 200ml isoprene, 185ml concentration are 0.36mol/L; adding 200ml concentration 0 ℃ of stirring is again 1mol/L aluminium diethyl monochloride hexane solution, continues contact reacts 30 minutes at 0 ℃.Then adding 1335ml concentration is the triisobutyl aluminium hexane solution of 0.74mol/L, continue ageing 10 hours at 0 ℃, after ageing completes, adding 134ml concentration is the dibutyl zinc hexane solution of 1mol/L, and add residue normal hexane to cumulative volume be 13.32L, rare earth catalyst agent concentration is 0.5 × 10
-5mol/ml.Obtain rare earth catalyst C2, each component mol ratio is neodymium caprate: triisobutyl aluminium: isoprene: aluminium diethyl monochloride: dibutyl zinc=1:15:30:3:2.
(2) polyreaction.Under nitrogen protection, in 5L polymeric kettle, add successively 350g isoprene, 2000g normal hexane and 180ml rare earth catalyst C2, the concentration of isoprene monomer in normal hexane is 14 % by weight.Under 0 ℃ of condition, react after 90 minutes, polymer product solution is emitted and added 2,6-di-tert-butyl hydroquinone methanol solution termination reaction in still.Obtain polyisoprene 315g, monomer conversion is 90%.Polymerization result is in table 1.
Embodiment 3
The present embodiment is for illustrating the preparation method of rare earth catalyst of the present invention and the polymerization of polyisoprene.
(1) rare earth catalyst preparation.Under nitrogen protection; in 20L catalyzer aging reactor, add neodymium caprate hexane solution and the 10L hexane solution that 200ml isoprene, 185ml concentration are 0.36mol/L; adding 200ml concentration 0 ℃ of stirring is again 1mol/L aluminium diethyl monochloride hexane solution, continues contact reacts 30 minutes at 0 ℃.Then adding 890ml concentration is the triisobutyl aluminium hexane solution of 0.74mol/L, continue ageing 10 hours at 0 ℃, after ageing completes, adding 200ml concentration is the di-isopropyl zinc hexane solution of 1mol/L, and add residue normal hexane to cumulative volume be 13.32L, rare earth catalyst agent concentration is 0.5 × 10
-5mol/ml.Obtain rare earth catalyst C3, each component mol ratio is neodymium caprate: triisobutyl aluminium: isoprene: aluminium diethyl monochloride: di-isopropyl zinc=1:10:30:3:3.
(2) polyreaction.Under nitrogen protection, in 5L polymeric kettle, add successively 350g isoprene, 2000g normal hexane and 180ml catalyzer C3, the concentration of isoprene monomer in normal hexane is 14 % by weight.Under 0 ℃ of condition, react after 60 minutes, polymers soln is emitted in still and add 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Obtain polyisoprene 322g, monomer conversion is 92%.Polymerization result is in table 1.
Embodiment 4
Prepare rare earth catalyst polymerization isoprene according to the method for embodiment 1, different is, the zinc ethyl hexane solution that is 1mol/L by 333ml concentration substitutes the zinc ethyl hexane solution that 200ml concentration is 1mol/L, obtain rare earth catalyst C4, each component mol ratio is neodymium caprate: triisobutyl aluminium: isoprene: aluminium diethyl monochloride: zinc ethyl=1:10:30:3:5.Obtain polyisoprene 332.5g, monomer conversion is 95%.Polymerization result is in table 1.
Comparative example 1
According to the method for embodiment 1, different, in rare earth catalyst, do not contain zinc ethyl.Polymerization result is in table 1.
Comparative example 2
According to the method for embodiment 2, different, in rare earth catalyst, do not contain dibutyl zinc.Polymerization result is in table 1.
Table 1
| Numbering | Cis Isosorbide-5-Nitrae-structural content (%) | Weight-average molecular weight (ten thousand) | Molecular weight distribution |
| Embodiment 1 | 98.7 | 140 | 1.5 |
| Embodiment 2 | 98.5 | 165 | 1.65 |
| Embodiment 3 | 98.2 | 145 | 1.65 |
| Embodiment 4 | 98.2 | 138 | 1.69 |
| Comparative example 1 | 98.2 | 173 | 3.2 |
| Comparative example 2 | 98.0 | 180 | 3.3 |
Polymer architecture analytical results by table 1 can be found out, the zinc alkyl(s) component containing in the rare earth catalyst composition of embodiment 1-3, improve the katalysis effect of polymerization isoprene, in obtaining high molecular, molecular weight distribution is less than 1.7, and cis Isosorbide-5-Nitrae-structural content in polyisoprene does not reduce.For example, in embodiment 1, contain zinc ethyl in rare earth catalyst, and while being 3:1 with the mol ratio of neodymium caprate, the weight-average molecular weight of the polyisoprene that polymerization obtains is 1,400,000, molecular weight distribution is 1.5, and wherein cis Isosorbide-5-Nitrae-structural content reaches 98.7%.But in comparative example 1, there is no zinc ethyl component in the catalyzer of polymerization, the weight-average molecular weight of the polyisoprene that polymerization obtains is 1,730,000, and wherein cis Isosorbide-5-Nitrae-structural content reaches 98.2%, but molecular weight distribution obviously broadens, and has reached 3.2.
In addition, by method polymerization isoprene of the present invention, the transformation efficiency of monomer reaches more than 90%.
Claims (10)
1. a preparation method for rare earth catalyst, the method comprises following each component is in contact with one another in the first organic solvent, described component is:
A-carboxylic acid neodymium compound;
B-general formula is AlR
3and/or AlHR
2alkylaluminium cpd, wherein, R is C
1-C
6alkyl;
C-conjugated diene;
D-halogenide, described halogenide is for having general formula AlR
2the aikyl aluminum halide of X, there is general formula Al
2r
3x
3sesquialkyl aluminium and there are one or more in the halohydrocarbon of general formula R X, wherein, R is C
1-C
4alkyl, X is bromine or chlorine; And
E-general formula is ZnR '
2zinc alkyl(s), wherein R ' is C
1-C
4alkyl;
The mode of described contact is:
(1) component D is joined in the mixture of component A and component C, obtain mixture ACD;
(2) B component is joined in described mixture ACD, obtain mixture ACDB;
(3) component E is joined in described mixture ACDB.
2. preparation method according to claim 1, wherein, the mol ratio between described component is A:B:C:D:E=1:5-30:1-50:1-3:1-20.
3. preparation method according to claim 1, wherein, described zinc alkyl(s) is one or more in zinc methide, zinc ethyl, di-isopropyl zinc and dibutyl zinc.
4. preparation method according to claim 1, wherein, the temperature that described component D adds is 0 ℃-50 ℃, and at 0 ℃-50 ℃ ageing 1-30 minute; After described B component adds at 0 ℃-50 ℃ ageing 1-10 hour.
5. according to the preparation method described in any one in claim 1-4, wherein, described carboxylic acid neodymium compound is C
7-C
14carboxylic acid neodymium, preferred described carboxylic acid neodymium compound is one or more in neodymium naphthenate, n-caprylic acid neodymium, isocaprylic acid neodymium, neodymium caprate and n-capric acid neodymium; Described alkylaluminium cpd is one or more in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diisobutylaluminium hydride; Described halogenide is one or more in aluminium diethyl monochloride, sesquialter ethyl aluminum chloride and a chloro-di-isobutyl aluminum; Described conjugated diene is C
4-C
6conjugated diene, preferred described conjugated diene is divinyl and/or isoprene.
6. the rare earth catalyst being obtained by the preparation method described in any one in claim 1-5.
7. a preparation method for polyisoprene, the method is included under the second organic solvent and polymerizing catalyst existence, makes isoprene monomer carry out polyreaction; Wherein, described polymerizing catalyst is rare earth catalyst claimed in claim 6.
8. the polyisoprene being prepared by method claimed in claim 7.
9. polyisoprene according to claim 8, wherein, in described polyisoprene, the content of cis Isosorbide-5-Nitrae-structure is greater than 98%, molecular weight distribution for be less than 1.7 and weight-average molecular weight be not more than 2,500,000.
10. polyisoprene according to claim 9, wherein, in described polyisoprene, the content of cis Isosorbide-5-Nitrae-structure is 98.2-98.7%, molecular weight distribution for be more than or equal to 1.5 and be less than 1.7 and weight-average molecular weight be 100-250 ten thousand.
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| CN107207654A (en) * | 2014-11-17 | 2017-09-26 | 株式会社普利司通 | The polymerisation in bulk of polyisoprene with preform catalyst |
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| US20020016423A1 (en) * | 2000-06-07 | 2002-02-07 | Young-Chan Jang | Process for controlling degree of branch of high 1,4-cis polybutadiene |
| CN1342719A (en) * | 2001-10-12 | 2002-04-03 | 中国科学院长春应用化学研究所 | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene |
| CN101927186A (en) * | 2009-06-22 | 2010-12-29 | 北京化工大学 | Rare earth catalyst system and method for preparing high cis-1,4-polyisoprene |
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| US20020016423A1 (en) * | 2000-06-07 | 2002-02-07 | Young-Chan Jang | Process for controlling degree of branch of high 1,4-cis polybutadiene |
| CN1342719A (en) * | 2001-10-12 | 2002-04-03 | 中国科学院长春应用化学研究所 | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene |
| CN101927186A (en) * | 2009-06-22 | 2010-12-29 | 北京化工大学 | Rare earth catalyst system and method for preparing high cis-1,4-polyisoprene |
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| CN107207654A (en) * | 2014-11-17 | 2017-09-26 | 株式会社普利司通 | The polymerisation in bulk of polyisoprene with preform catalyst |
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