CN103788236B - 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 kind of preparation method of rare earth catalyst, it is ZnR ' that the method comprises component A-carboxylic acid neodymium compound, B-alkylaluminium cpd, C-conjugated diene, D-halogenide and E-general formula
2zinc alkyl(s), wherein R ' is C
1-C
4alkyl, contact with each other in the first organic solvent; The mode of described contact is: component D joins in the mixture of component A and component C by (1), obtains mixture ACD; (2) B component is joined in described mixture ACD, obtain mixture ACDB; (3) component E is joined in described mixture ACDB.Present invention also offers rare earth catalyst and polyisoprene and preparation method thereof that a kind of preparation method thus obtains.The present invention can obtain molecular weight distribution and be less than 1.7, and cis Isosorbide-5-Nitrae-structural content is greater than 98%, the polyisoprene that molecular weight is high, and the transformation efficiency of isoprene monomer is more than 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 be applied to tyre industry.Polyisoprene rubber has compared with natural rubber that purity is high, quality is homogeneous, the time of plasticating is short, mixing easy, the advantage such as transparent color and luster, expansion and specific absorption is little, good fluidity.The molecular weight improving polyisoprene rubber reduces molecular weight distribution simultaneously, is conducive to reducing rolling resistance when polyisoprene rubber is applied to tire.And the content improving cis Isosorbide-5-Nitrae-structure in polyisoprene rubber is also conducive to the mechanical property improving 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 synthesizing polyisoprene rubber from now on.
The existing method controlling polyisoprene rubber molecular weight and molecualr weight distribution has a lot, as regulated catalyst levels, adjustment reaction times, adding chain-transfer agent and add 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 reaction: (1) is containing the rare earth compound-L of phosphonate group or carboxyl
3ln, wherein L represents (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 represents methyl, 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 represents phosphonate group and carboxyl, and they can be identical or different, during m=3-n, and n=0,1,2; During m=2-n, n=0,1; Phosphonate group compound is (2-ethylhexyl) phosphonous acid and (2-ethylhexyl) phosphonic acids, and carboxylic compound selects 2 ethyl hexanoic acid, neodecanoic acid and naphthenic acid; Method for preparing catalyst is, the molar composition ratio 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 selects divinyl and isoprene, and implement butadiene homopolymerization, isoprene homopolymerization and divinyl and isoprene copolymer, monomer concentration is 10-16%, and in copolymerization, isoprene and divinylic monomer weight ratio are 20-50:80-50; Solvent adopt normal hexane, normal heptane, toluene and 1,2,4-tri-chlorination benzene; Catalyst aging concentration is 0.3-5 × 10-4 mole/milliliter, Aging Temperature 0-50 DEG C, and digestion time is 5 minutes-48 hours.This invention is for controlling polymericular weight and distribution thereof.During 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 double-olefine polymerizing rare earth catalyst that a kind of aromatic hydrocarbons improves, and 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 representing La ~ Lu, selects wherein active the highest neodymium, praseodymium two kinds of elements; 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 for keeping obtained high along Isosorbide-5-Nitrae-structural content, and the polymkeric substance of high linearity gel-free, and the molecular weight by regulating aromatic hydrocarbon type and consumption effectively to regulate polymerisate, particularly reduce the molecular weight of polymerisate.Cis Isosorbide-5-Nitrae-structural content in the polyisoprene obtained is 94.8-95.6%.
US2005/0137338A discloses a kind of method preparing neodymium catalyst system, the method comprises (1) neodymium carboxylate salt and organo-aluminium compound react generation neodymium-Al catalysts composition in a second organic solvent, and described neodymium-Al catalysts composition and halogen react and generate described neodymium catalyst system by (2) subsequently.This invention, can crystallization under stretch for obtaining the polyisoprene rubber of high-cis structural content and high three-dimensional regularity.In the polyisoprene obtained, 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 obtain weight-average molecular weight is 23.58 × 10
5, molecular weight distribution be 1.75 and cis Isosorbide-5-Nitrae-structural content be the polyisoprene of 98.1%.
CN101045768A discloses a kind of rare earth catalyst preparing polyisoprene, it is characterized in that, this rare earth catalyst component and proportioning are: A. rare earth organic compounds, selects 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 for obtaining high-cis-Isosorbide-5-Nitrae structural content and narrow ditribution and having the polyisoprene of stretch crystallization performance characteristics.Can obtain cis-Isosorbide-5-Nitrae structural content at 96.0-97.2% and molecular weight distribution is the polyisoprene of 2.02-2.88.
Therefore, in order to improve the performance of polyisoprene, the polyisoprene obtaining narrow molecular weight distribution remains technical issues that need to address.
Summary of the invention
The object of the invention is the polyisoprene obtaining narrow molecular weight distribution, provide rare earth catalyst and preparation method thereof and polyisoprene and preparation method thereof.
To achieve these goals, the invention provides a kind of preparation method of rare earth catalyst, the method comprises and following each component being contacted with each other 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 have in the halohydrocarbon of general formula R X one or more, 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.
Present invention also offers the rare earth catalyst that a kind of preparation method provided by the invention described above obtains.
Present invention also offers a kind of preparation method of polyisoprene, the method makes isoprene monomer carry out polyreaction under being included in the second organic solvent and polymerizing catalyst existence; Wherein, the rare earth catalyst that provides for the invention described above of described polymerizing catalyst.
Present invention also offers the polyisoprene that a kind of method provided by the invention described above prepares.
By the technical scheme that the invention described above provides, the zinc alkyl(s) component comprised in rare earth catalyst provides rare earth catalyst with better catalytic performance, can obtain the polyisoprene of narrow molecular weight distribution.Such as, in embodiment 1, containing zinc ethyl in rare earth catalyst, the weight-average molecular weight of being polymerized the polyisoprene obtained 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 not comprising zinc alkyl(s) component is when carrying out isoprene polymerization, as 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, significantly reduce the molecular weight distribution of polyisoprene in the undiminished situation of content of technical scheme provided by the invention cis Isosorbide-5-Nitrae-structure in polyisoprene.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of 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 and following each component being contacted with each other 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 have in the halohydrocarbon of general formula R X one or more, 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.Molar ratio between further 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 polymerized 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 play katalysis with Carboxylic Acid Ions.Carboxylic Acid Ions is distributed by the empty ligancy and cloud density changing element neodymium and is changed bond polarity and intensity etc., thus 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, neodymium iso-octanate, 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 has high reactivity also 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 ethylmercury chloride aluminium 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 used 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 first organic solvent is aliphatic saturated hydrocarbon or alicyclic hydrocarbon, is preferably C
5-C
10alkane or naphthenic hydrocarbon, be more preferably in Skellysolve A, iso-pentane, normal hexane, hexanaphthene, normal heptane and octane one or more.
In the present invention, in described preparation method, component A, B component, component C, component D and component E can 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 the first organic solvent respectively, form multiple organic solution containing 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 described first organic solvent respectively, form multiple organic solution containing different components; Multiple organic solution containing different components can use different described first organic solvents, also all can use identical described 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 containing different components formed, there is no particular limitation, described rare earth catalyst is obtained as long as can meet, such as the concentration of component solution A 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 solution D 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 an inert atmosphere.Described inert atmosphere can be, such as nitrogen.
According to the present invention, there is no particular limitation for each step in the mode of described contact, and under preferable case, the described component D temperature joined in the mixture of component A and component C is 0 DEG C-50 DEG C, and at 0 DEG C-50 DEG C ageing 1-30 minute, obtain mixture ACD; After described B component joins described mixture ACD, ageing 1-10 hour at 0 DEG C-50 DEG C, obtains mixture ACDB.Described B component add the temperature that temperature is preferably mixture ACD after ageing, be 0-50 DEG C.
In the present invention, after described component E joins in described mixture ACDB, supplying the concentration of the first organic solvent to described rare earth catalyst in neodymium element, is 0.1 × 10
-5-2 × 10
-5mol/ml.
According to the present invention, in the method for described contact, the add-on of each component makes the mol ratio of each component in the described rare earth catalyst obtained meet the requirement of described rare earth catalyst, under preferable case, the add-on of component A, B component, component C, component D and component E makes the mol ratio of each component in the described rare earth catalyst obtained be A:B:C:D:E=1:5-30:1-50:1-3:1-20.Molar ratio between further preferred described component A and E is A:E=1:1-5.
Present invention also offers the rare earth catalyst that a kind of preparation method provided by the invention described above obtains.
According to the present invention, the described rare earth catalyst obtained is homogeneous catalyst, is conducive to the operation of isoprene polymerization reaction.The component that described rare earth catalyst contains and proportion of composing same as above, do not repeat them here.
The present invention also provides a kind of preparation method of polyisoprene, and the method makes isoprene monomer carry out polyreaction under being included in the second organic solvent and polymerizing catalyst existence; Wherein, the described rare earth catalyst that provides for the invention described above of described polymerizing catalyst.
According to the present invention, the second organic solvent that described polyreaction uses is not particularly limited, and be the varsol to polyreaction inertia, such as described second organic solvent can be aliphatic saturated hydrocarbon and/or saturated alicyclic hydrocarbon; Preferably described second organic solvent is C
5-C
10alkane and/or naphthenic hydrocarbon; More preferably described second organic solvent is one or more in Skellysolve A, iso-pentane, normal hexane, hexanaphthene, normal heptane and octane.Described second organic solvent and described first organic solvent can be selected identical or different, and preferably described second organic solvent and described 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 uses, and can ensure that described polyreaction is carried out, such as, can be the concentration of isoprene monomer in described second organic solvent be 8-20 % by weight.
According to the present invention, the amount of carrying out the described rare earth catalyst of use during polyreaction is not particularly limited, suitably can select according to the molecular weight of the polymkeric substance of expection, such as, the consumption of described rare earth catalyst is make component A in described rare earth catalyst be 0.8-3.0 × 10 with the mol ratio of the isoprene monomer carrying out polyreaction
-4: 1.
According to the present invention, the condition of carrying out described polyreaction can comprise temperature of reaction and reaction times, and such as, described temperature of reaction can be-30 DEG C-80 DEG C, and the described reaction times can be 0.1-5 hour; Preferably, described temperature of reaction is-20 DEG C-50 DEG C, 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 an inert atmosphere.The method of maintenance inert atmosphere can for pass into rare gas element in polymerization reaction system.Described inert atmosphere can be such as 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 stopping 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 optionally substituted by a hydroxyl group generated compound.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 by the active specy inactivation in polymerisate, can repeat no more herein.
The polyisoprene that the preparation method that present invention also offers a kind of polyisoprene provided by the invention described above obtains.
According to the present invention, the content that this polyisoprene carbon-13 magnetic resonance method measures the cis Isosorbide-5-Nitrae-structure contained is greater than 98%, 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 being 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 Bruker400MHz nuclear magnetic resonance analyser, solvent is deuterochloroform.
Below will be described 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 embodiments.
In the present invention, the molecular weight and molecualr weight distribution of the polyisoprene of synthesis adopts Shimadzu LC-10AT type gel permeation chromatograph (GPC) to measure, and THF is moving phase, and probe temperature is 25 DEG C, and Narrow distribution polystyrene is standard specimen.
Cis Isosorbide-5-Nitrae-structural content adopts German Bruker400MHz nmr determination, and solvent is deuterochloroform; Or German BrukerTensor27 mid-infrared light spectrometer measures.
The percentage ratio of the ratio of the weight of the isoprene that the weight that monomer conversion is defined as the polyisoprene of generation is reacted with participation.
Embodiment 1
The preparation method of the present embodiment for illustration of rare earth catalyst of the present invention and the polymerization of polyisoprene.
(1) rare earth catalyst preparation.Under nitrogen protection; 200ml isoprene is added (at 20 DEG C in the catalyst aging still of 20L; density is 0.68g/ml), 185ml concentration is neodymium caprate hexane solution and the 10L hexane solution of 0.36mol/L; adding 200ml concentration 0 DEG C of stirring is again 1mol/L aluminium diethyl monochloride hexane solution, to continue at 0 DEG C ageing 30 minutes.Then the triisobutyl aluminium hexane solution that 890ml concentration is 0.74mol/L is added, continue ageing 10 hours at 0 DEG C, the zinc ethyl hexane solution that 200ml concentration is 1mol/L is added after ageing completes, 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 molar is than being 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 350g isoprene, 2000g normal hexane and 180ml rare earth catalyst C1 successively, the concentration of isoprene monomer in normal hexane is 14 % by weight.React after 120 minutes under 0 DEG C of condition, polymer product solution is released in still and adds 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Obtain polyisoprene 322g, monomer conversion is 92%.Polymerization result is in table 1.
Embodiment 2
The preparation method of the present embodiment for illustration of rare earth catalyst of the present invention and the polymerization of polyisoprene.
(1) rare earth catalyst preparation.Under nitrogen protection; in the catalyst aging still of 20L, add 200ml isoprene, neodymium caprate hexane solution that 185ml concentration is 0.36mol/L and 10L hexane solution; adding 200ml concentration 0 DEG C of stirring is again 1mol/L aluminium diethyl monochloride hexane solution, to continue at 0 DEG C contact reacts 30 minutes.Then the triisobutyl aluminium hexane solution that 1335ml concentration is 0.74mol/L is added, continue ageing 10 hours at 0 DEG C, the dibutyl zinc hexane solution that 134ml concentration is 1mol/L is added after ageing completes, 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 molar is than being 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 350g isoprene, 2000g normal hexane and 180ml rare earth catalyst C2 successively, the concentration of isoprene monomer in normal hexane is 14 % by weight.React after 90 minutes under 0 DEG C of condition, polymer product solution is released in still and adds 2,6-di-tert-butyl hydroquinone methanol solution termination reaction.Obtain polyisoprene 315g, monomer conversion is 90%.Polymerization result is in table 1.
Embodiment 3
The preparation method of the present embodiment for illustration of rare earth catalyst of the present invention and the polymerization of polyisoprene.
(1) rare earth catalyst preparation.Under nitrogen protection; in the catalyst aging still of 20L, add 200ml isoprene, neodymium caprate hexane solution that 185ml concentration is 0.36mol/L and 10L hexane solution; adding 200ml concentration 0 DEG C of stirring is again 1mol/L aluminium diethyl monochloride hexane solution, to continue at 0 DEG C contact reacts 30 minutes.Then the triisobutyl aluminium hexane solution that 890ml concentration is 0.74mol/L is added, continue ageing 10 hours at 0 DEG C, the di-isopropyl zinc hexane solution that 200ml concentration is 1mol/L is added after ageing completes, 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 molar is than being 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 350g isoprene, 2000g normal hexane and 180ml catalyzer C3 successively, the concentration of isoprene monomer in normal hexane is 14 % by weight.React after 60 minutes under 0 DEG C of condition, polymers soln is released in still and adds 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
Rare earth catalyst is prepared and polymerized isoprene according to the method for embodiment 1, unlike, the zinc ethyl hexane solution that 200ml concentration is 1mol/L is substituted with the zinc ethyl hexane solution that 333ml concentration is 1mol/L, obtain rare earth catalyst C4, each component molar is than being 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, unlike, not containing zinc ethyl in rare earth catalyst.Polymerization result is in table 1.
Comparative example 2
According to the method for embodiment 2, unlike, not containing dibutyl zinc in rare earth catalyst.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 |
Can be found out by the polymer architecture analytical results of table 1, the zinc alkyl(s) component contained in the rare earth catalyst composition of embodiment 1-3, improve the katalysis effect of polymerized isoprene, while acquisition high molecular, molecular weight distribution is less than 1.7, and the cis Isosorbide-5-Nitrae-structural content in polyisoprene does not reduce.Such as, in embodiment 1, containing zinc ethyl in rare earth catalyst, and when being 3:1 with the mol ratio of neodymium caprate, the weight-average molecular weight of being polymerized the polyisoprene obtained is 1,400,000, and molecular weight distribution is 1.5, and wherein cis Isosorbide-5-Nitrae-structural content reaches 98.7%.But in comparative example 1, do not have zinc ethyl component in the catalyzer of polymerization, the weight-average molecular weight of being polymerized the polyisoprene obtained is 1,730,000, and wherein cis Isosorbide-5-Nitrae-structural content reaches 98.2%, but molecular weight distribution obviously broadens, and reaches 3.2.
In addition, by method polymerized isoprene of the present invention, the transformation efficiency of monomer reaches more than 90%.
Claims (8)
1. a preparation method for rare earth catalyst, the method comprises and following each component being contacted with each other 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 have in the halohydrocarbon of general formula R X one or more, 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 DEG C-50 DEG C, and at 0 DEG C-50 DEG C ageing 1-30 minute; After described B component adds at 0 DEG C-50 DEG C ageing 1-10 hour.
5. according to the preparation method in claim 1-4 described in any one, wherein, described carboxylic acid neodymium compound is C
7-C
14carboxylic 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 ethylmercury chloride aluminium and a chloro-di-isobutyl aluminum; Described conjugated diene is C
4-C
6conjugated diene.
6. preparation method according to claim 5, wherein, described carboxylic acid neodymium compound is one or more in neodymium naphthenate, n-caprylic acid neodymium, neodymium iso-octanate, neodymium caprate and n-capric acid neodymium; Described conjugated diene is divinyl and/or isoprene.
7. the rare earth catalyst obtained by the preparation method in claim 1-6 described in any one.
8. a preparation method for polyisoprene, the method makes isoprene monomer carry out polyreaction under being included in the second organic solvent and polymerizing catalyst existence; Wherein, described polymerizing catalyst is rare earth catalyst according to claim 7.
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| 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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