CN106589195B - A method of preparing polyisoprene - Google Patents
A method of preparing polyisoprene Download PDFInfo
- Publication number
- CN106589195B CN106589195B CN201510680000.5A CN201510680000A CN106589195B CN 106589195 B CN106589195 B CN 106589195B CN 201510680000 A CN201510680000 A CN 201510680000A CN 106589195 B CN106589195 B CN 106589195B
- Authority
- CN
- China
- Prior art keywords
- aluminium
- rare
- alkyl
- method described
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
Abstract
The present invention relates to catalytic polymerization fields, disclose a kind of method preparing polyisoprene, including：Under the polymerization conditions, isoprene monomer and rare earth catalyst composition are subjected to haptoreaction, compound and halogen source in the rare earth catalyst composition containing Rare-earth chemicals, containing aluminium element, the compound containing aluminium element is alkyl aluminum and/or alkyl aluminium hydride, and the Rare-earth chemicals have structure shown in formula (I).Cis- Isosorbide-5-Nitrae linkage content is higher in the polyisoprene that the above method through the invention is prepared and narrow molecular weight distribution, moreover, the quality of the product obtained by the method for the present invention is small by the influence of fluctuations of polymeric reaction condition, is conducive to industrial production.
Description
Technical field
The present invention relates to catalytic polymerization fields, and in particular, to a method of preparing polyisoprene.
Background technology
With the development of auto industry, the demand of tire tread glue is also gradually increasing.Since China is subtropical countries,
It is not easy estate rubber tree come natural rubber of receiving, so needing to develop artificial synthesized isoprene rubber to substitute.Isoprene
High cis- 1,4 linkage content of polymer and narrow molecular weight distribution can improve the performance of the isoprene rubber synthesized.
CN102464745A describes a kind of rare earth catalyst composition for conjugate diene polymerization, the composition packet
It includes：
As the neodymium caprate or neodymium naphthenate of rare earth catalyst,
Diethyl aluminium hydride, triethyl aluminum be one such or two kinds or more of mixture,
- one chloro-di-isobutyl aluminum or aluminium diethyl monochloride.
In this carbon monoxide-olefin polymeric, cis--Isosorbide-5-Nitrae linkage content of obtained polyisoprene is 96.6 weight % to 97.2
Weight %.
CN1479754A describes a kind of method preparing high-cis-Isosorbide-5-Nitrae linkage content isoprene copolymer, the method
It is included in the presence of isoprene and is reacted with carbon monoxide-olefin polymeric, which includes：
A kind of diene monomers of conjugation
As the organic phosphoric acid neodymium of rare earth catalyst,
Including molecular formula is AlR3Or HAlR2Alkyl aluminum alkylating reagent,
Include the halogen donor of alkyl aluminum chloride.
In this preparation method, the preparation method of carbon monoxide-olefin polymeric is relatively complicated, and polymerize all in subzero, it has not been convenient to
Large-scale industrial application.
Document Macromol.Chem.Phys.200,1163-1166 (1999) describes one kind, and to be used to prepare butadiene poly-
The preparation method for closing object, wherein the carbon monoxide-olefin polymeric used includes：
A kind of conjugated diene monomer,
Rare earth compound,
General formula is AlR3Alkyl aluminum,
The halogen donor being made of alkyl aluminium halide.
In this carbon monoxide-olefin polymeric, the Nd { N (SiMe of nitrogen coordination have been used3)2}3As Rare-earth chemicals, but
Be the carbon monoxide-olefin polymeric preparation method it is too simple, be only simply mixed.This carbon monoxide-olefin polymeric is only used for butadiene
Polymerization reaction condition is required harsh when the polymerization for isoprene, and be affected by condition, the product of acquisition
Cis-content it is not high and molecular weight distribution is wider.
Invention content
The purpose of the present invention is overcoming the deficiencies of existing technologies, a kind of the poly- different of the high cis- Isosorbide-5-Nitrae linkage content of preparation newly is provided
The method of pentadiene.
To achieve the goals above, the present invention provides a kind of method preparing polyisoprene, and this method includes：It is polymerizeing
Under reaction condition, isoprene monomer and rare earth catalyst composition are subjected to haptoreaction, the rare earth catalyst composition
In compound and halogen source containing Rare-earth chemicals, containing aluminium element, the compound containing aluminium element is alkyl
Aluminium and/or alkyl aluminium hydride, the Rare-earth chemicals have structure shown in formula (I)：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl, C6-12Aryl, and institute
State R1、R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；
L is-OR7Or-NR8, wherein the R7With the heterocycle containing 2-10 carbon atom, the R are formed together with oxygen atom8
With the heterocycle containing 2-10 carbon atom or the R are formed together with nitrogen-atoms8For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
Cis- 1,4 linkage content is higher in the polyisoprene that the above method through the invention is prepared and molecular weight divides
Cloth is narrow, moreover, small by the influence of fluctuations of polymeric reaction condition by the quality of the product of the method acquisition of the present invention, that is to say, that
The method of the present invention can avoid carrying out under severe conditions, be conducive to industrial production.
In addition, the present inventor is found that the novel rare-earth catalyst combination based on rare earth metal salt under study for action
Object, the novel rare-earth carbon monoxide-olefin polymeric include the Rare-earth chemicals as catalyst, which organises
Object is closed based on No. 57 elements in the periodic table of elements to the element between No. 71 elements, the novel rare-earth carbon monoxide-olefin polymeric by nitrogen with
Rare earth element forms coordinate bond, carries out the polymerization of isoprene polymerization, realizes cis- Isosorbide-5-Nitrae linkage content in resulting polymers
99 weight % are all higher than or are equal to, molecular weight distribution is less than or equal to 2.1.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of method preparing polyisoprene, this method includes：It under the polymerization conditions, will be different
Pentadiene monomer carries out haptoreaction with rare earth catalyst composition, has containing rare earth metal in the rare earth catalyst composition
Machine compound, compound and halogen source containing aluminium element, the compound containing aluminium element are alkyl aluminum and/or alkyl hydrides
Aluminium, the Rare-earth chemicals have structure shown in formula (I)：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl, C6-12Aryl, and institute
State R1、R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；
L is-OR7Or-NR8, wherein the R7With the heterocycle containing 2-10 carbon atom, the R are formed together with oxygen atom8
With the heterocycle containing 2-10 carbon atom or the R are formed together with nitrogen-atoms8For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
Under preferable case, in the structure shown in formula (I), M is neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or different,
It is each independently selected from hydrogen, C1-6Alkyl, C6-10Aryl, and the R1、R2、R3、R4、R5And R6Be asynchronously selected from hydrogen and
At least one of methyl；L is-OR7Or-NR8, wherein the R7It is miscellaneous containing 2-7 carbon atom with being formed together with oxygen atom
Ring, the R8With the heterocycle containing 2-7 carbon atom or the R are formed together with nitrogen-atoms8For C1-4Alkyl；X is 1,2 or 3,
And y=3-x.
In the case of more preferably, in the structure shown in formula (I), M is neodymium or cerium；R1、R2、R3、R4、R5And R6It is identical or not
Together, hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, isoamyl are each independently selected from
Base, n-hexyl, cyclopropyl, methylcyclopropyl groups, ethyl cyclopropyl, cyclopenta, methylcyclopentyl, cyclohexyl, phenyl, methylbenzene
Base, ethylphenyl, 3,5-dimethylphenyl, trimethylphenyl, Methylethyl phenyl, diethyl phenyl and triethyl group phenyl, and it is described
R1、R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；L is-OR7Or-NR8, wherein the R7With oxygen
Atom forms the heterocycle containing 2-4 carbon atom, the R together8With the heterocycle containing 2-5 carbon atom is formed together with nitrogen-atoms
Or the R8For C1-4Alkyl；X is 1,2 or 3, and y=3-x.
Under preferable case, in the structure shown in formula (I), the L and M is keyed by being coordinated.
According to a kind of preferred embodiment, in the structure shown in the formula (I) of the present invention, M is neodymium or cerium；R1、
R2、R3、R4、R5And R6It is identical or different, be each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, phenyl,
Aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethyl group phenyl,
And the R1、R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；L is selected from tetrahydrofuran, pyridine and second
Nitrile；X is 1,2 or 3, and y=3-x.
According to another preferred embodiment, in the structure shown in the formula (I) of the present invention, M is neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, benzene
Base, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, Methylethyl phenyl, ethylphenyl, diethyl phenyl and triethylbenzene
Base, and the R1、R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；X is 3, and y is 0.
According to the third preferred embodiment, in the structure shown in the formula (I) of the present invention, M is neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from methyl, n-propyl, normal-butyl, phenyl and cyclohexyl, and institute
State R1、R2、R3、R4、R5And R6It is asynchronously methyl；L is selected from tetrahydrofuran, pyridine and acetonitrile；X is 1 or 2, and y=3-x.
According to the 4th kind of preferred embodiment, in the structure shown in the formula (I) of the present invention, M is neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from methyl, normal-butyl and phenyl, and the R1、R2、R3、R4、R5
And R6It is asynchronously methyl；X is 3, and y is 0.
There is no particular limitation for method of the present invention to the Rare-earth chemicals of structure shown in preparation formula (I).
The method that those skilled in the art can take the synthesis complex of routine in the art according to structural formula is prepared.
Under preferable case, the present invention provides a kind of method preparing Rare-earth chemicals, which has
Machine compound has structure shown in formula (I), and this method includes：In the presence of protective gas and organic solvent, by rare earth gold
Category source is contacted with the compound of structure shown in formula (II), and the rare earth metal source is the compound containing element shown in M,
The organic solvent is selected from halogenated hydrocarbons, alcohols, aromatic hydrocarbons, halogenated aryl hydrocarbon, formula OR7Shown in Oxygenic heterocyclic compounds and formula NR8It is shown
At least one of compound,
Wherein, M, R1、R2、R3、R4、R5、R6、L、R7、R8, the definition such as present invention of x and y are aforementioned defines.
The definition of each group wherein in the compound of structure shown in structure and formula (II) shown in involved formula (I)
Identical as the foregoing teachings of the present invention, details are not described herein by the present invention, and those skilled in the art should not be construed as to the present invention
Limitation.
Preferably, the rare earth metal source can be the salt containing element shown in M, such as can be containing shown in M
Any one in the chloride of element, nitrate, sulfate.
Preferably, the compound of structure shown in the formula (II) and the dosage molar ratio in the rare earth metal source are 0.5-
10：1；Preferably 1-4：1.
The type of the organic solvent is not particularly limited, as long as enabling to the rare earth metal source and formula
(II) wherein just, the preferably described organic solvent is polar organic solvent, more preferred institute for the compound dissolving of structure shown in
It is the compound that coordinate bond can be formed with the M element to state organic solvent.
The dosage of the organic solvent is not particularly limited, those skilled in the art can be according to the routine of this field
Dosage is selected.Preferably, x and y in the target compound that those skilled in the art can also be prepared as needed
Ratio determine the dosage of organic solvent.
The protective gas can be to be not involved in the inert gas of reaction, such as can be nitrogen, argon gas etc..
Preferably, the condition contacted includes：Temperature is 0-80 DEG C, and the time is 5-500 minutes.
The present invention can also concentrate the product that above-mentioned contact obtains, and preferably, pass through the product to concentration
It is middle that suitable nonpolar solvent such as ether is added to obtain the higher crystal of purity.
The halogen source refers to being capable of providing the compound of halogen element, and the halogen element includes fluorine, chlorine, bromine, iodine.
In the rare earth catalyst composition, the Rare-earth chemicals, the compound containing aluminium element and
The content molar ratio of halogen source is 1：2-10：1-30；More preferably 1：4-8：1-15.
It should be strongly noted that can also contain aluminium element in the halogen source, the present invention is particularly defined containing halogen member
The compound of element and aluminium element also belongs to halogen source of the present invention；And the compound category containing aluminium element and without containing halogen element
In the compound of the present invention containing aluminium element.
Alkyl in the alkyl aluminum can be C2-C8Alkyl, specifically, the alkyl aluminum can be trimethyl aluminium, three
It is one or more in aluminium ethide, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium and three amyl aluminium；Preferably triethyl aluminum, three
At least one of aluminium isobutyl and triethyl aluminum；More preferably triisobutyl aluminium or triethyl aluminum.
Alkyl in the alkyl aluminium hydride can be C2-C4Alkyl, specifically, the alkyl aluminium hydride can be hydrogen
Change diethyl aluminum and/or hydrogenation dibutyl aluminium；Preferably hydrogenate dibutyl aluminium.
Preferably, when the M in Rare-earth chemicals is neodymium, the alkyl aluminum is preferably diisobutylaluminium hydride
Or triisobutyl aluminium.
The halogen source can be aikyl aluminum halide；It is preferred that the aikyl aluminum halide is diethyl aluminum chloride and/or two isobutyls
Base aluminium chloride.
The haptoreaction can carry out in the presence of an organic；It is preferred that the organic solvent be selected from n-hexane, pentane,
At least one of hexane, heptane, hexamethylene, toluene, dimethylbenzene and chlorobenzene；More preferably n-hexane.
The catalytic condition may include：Temperature is 0-100 DEG C, time 0.1-24h；Preferably, described to connect
Touching the condition reacted includes：Temperature is 5-80 DEG C, time 0.2-12h.Particularly, the catalytic time zero is ginseng
When existing in the same system with catalytic whole elements.
Preferably, the isoprene monomer and the dosage of the rare earth catalyst composition in terms of rare earth metal are rubbed
You are than being 1000-10000：1；More preferably 2000-9000：1；Particularly preferably 3500-9000：1.
It can also contain in the rare earth catalyst composition and be ready to use in monomer (the as isoprene for carrying out polymerisation
Monomer).In the rare earth catalyst composition, the monomer for being ready to use in progress polymerisation and the rare earth metal are organic
The molar ratio of compound is 1-120：1；Preferably 10-80：1.Under this condition, better catalytic activity can be obtained.
The rare earth catalyst composition can in the reaction process of polymerisation in-situ preparation, can also use in advance
The method of preparation produces.Specifically, the preparation method of the carbon monoxide-olefin polymeric may include：
Rare-earth chemicals, the compound containing aluminium element and halogen source and optional being ready to use in polymerize anti-
The monomer answered is mixed in inert hydrocarbon solvent.
In the present invention, described " by Rare-earth chemicals, the compound containing aluminium element and halogen source and optionally
Be ready to use in carry out polymerisation monomer mixed in inert hydrocarbon solvent " refer to, the mixing can exist or not
There are it is described be ready to use in the monomer for carrying out polymerisation in the case of carry out, that is to say, that it is above-mentioned described to carry out mixing needs
Or the monomer for being ready to use in and carrying out polymerisation is not needed.
According to a kind of preferred embodiment, by Rare-earth chemicals, the compound containing aluminium element and halogen
The step of monomer that source and optional being ready to use in carry out polymerisation is mixed in inert hydrocarbon solvent include：
(1) by the Rare-earth chemicals and compound containing aluminium element and optionally described in be ready to use in progress
The conjugated diene of polymerisation carries out hybrid reaction in inert hydrocarbon solvent；
(2) halogen source is introduced into mixture system to be aged.
Under preferable case, in the present invention, in step (1), the condition of the hybrid reaction includes：Temperature is 5-40
℃；Time is 0.01-2h.
Under preferable case, in the present invention, in step (2), the condition of the ageing includes：Temperature is 45-85 DEG C；When
Between be 0.02-5h.
The inert hydrocarbon solvent includes but not limited to arsol (such as toluene) or aliphatic series or alicyclic solvents (such as penta
Alkane, pentane, isopentane, hexanes mixtures, n-hexane, hexamethylene, hexahydrotoluene, heptane mixture or normal heptane).
The dosage of the inert hydrocarbon solvent so that in the rare earth catalyst composition, the preferably described rare earth metal has
Concentration >=0.0002mol/L of machine compound.
The entire polymerization process of the present invention is steadily easily controllable, is very suitable for serialization industrial production, obtained poly-
Cis- Isosorbide-5-Nitrae linkage content is high in composition powder, and molecular weight distribution is less than or equal to 2.1.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
The present invention will be described in detail by way of examples below.
In following embodiment, the cis- Isosorbide-5-Nitrae linkage content in the polymeric articles uses C13 nuclear magnetic resonance methods or near-infrared
Analytic approach measures；The molecular weight distribution of the polyisoprene product is by gpc measurement；Prepare metal-organic raw material by
Commercial sources obtain, and particularly, are bought in Sigma-Aldrich medicaments company.
Preparation example 1-9 is used to prepare Rare-earth chemicals.
Embodiment 1-9 is used to illustrate the method for preparing polyisoprene of the present invention.
Preparation example 1
The preparation of three (1,3- diphenyl -1,1,3,3- tetramethyl, two silicon substrate amine) neodymiums, structural formula are as follows：
In the presence of nitrogen, NdCl is introduced into flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3- tetramethyls
Two silicon substrate amine (6.5 mMs), and 25 milliliters of THF is added thereto, it is stirred 30 minutes at 25 DEG C, then at 50 DEG C
It is evaporated under reduced pressure to solution and is condensed into 1-2 milliliters, 0.5 milliliter of ether is then added.Clear crystal is obtained in the solution.
Preparation example 2
The preparation of three (1,3- dibutyl -1,1,3,3- tetramethyl, two silicon substrate amine) neodymiums, structural formula are as follows：
In the presence of nitrogen, NdCl is introduced into flask3(2.0 mMs) and 1,3- dibutyl -1,1,3,3- tetramethyls
Two silicon substrate amine (7.5 mMs)；And be added thereto 25 milliliters of pyridine, it is stirred 60 minutes at 20 DEG C, then at 50 DEG C
Under be evaporated under reduced pressure to solution and be condensed into 1-2 milliliters, 0.5 milliliter of ether is then added.Clear crystal is obtained in the solution.
Preparation example 3
The preparation of three (1,3- diphenyl -1,1,3,3- tetramethyl, two silicon substrate amine) ceriums, structural formula are as follows：
In the presence of nitrogen, CeCl is introduced into flask3(2.0 mMs) and 1,3- diphenyl -1,1,3,3- tetramethyls
Two silicon substrate amine (7.0 mMs)；And be added thereto 25 milliliters of acetonitrile, it is stirred 20 minutes at 40 DEG C, then at 50 DEG C
Under be evaporated under reduced pressure to solution and be condensed into 1-2 milliliters, 0.5 milliliter of ether is then added.Clear crystal is obtained in the solution.
Preparation example 4
The preparation of two (1,3- diphenyl -1,1,3,3- tetramethyl, two silicon substrate amine) tetrahydrofuran neodymiums, structural formula are as follows：
In the presence of nitrogen, NdCl is introduced into flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3- tetramethyls
Two silicon substrate amine (4.0 mMs)；And be added thereto 25 milliliters of THF, it is stirred 30 minutes at 30 DEG C, then at 50 DEG C
It is evaporated under reduced pressure to solution and is condensed into 1-2 milliliters, 0.5 milliliter of ether is then added.Clear crystal is obtained in the solution.
Preparation example 5
The preparation of two (1,3- diphenyl -1,1,3,3- tetramethyl, two silicon substrate amine) pyridine neodymiums, structural formula are as follows：
In the presence of nitrogen, NdCl is introduced into flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3- tetramethyls
Two silicon substrate amine (4.0 mMs)；And be added thereto 25 milliliters of pyridine, it is stirred 20 minutes at 40 DEG C, then at 50 DEG C
Under be evaporated under reduced pressure to solution and be condensed into 1-2 milliliters, 0.5 milliliter of ether is then added.Clear crystal is obtained in the solution.
Preparation example 6
The preparation of two (1,3- diphenyl -1,1,3,3- tetrapropyl, two silicon substrate amine) tetrahydrofuran ceriums, structural formula are as follows：
In the presence of nitrogen, CeCl is introduced into flask3(2.1 mMs) and 1,3- diphenyl -1,1,3,3- tetrapropyls
Two silicon substrate amine (4.0 mMs)；And be added thereto 25 milliliters of THF, it is stirred 20 minutes at 45 DEG C, then at 50 DEG C
It is evaporated under reduced pressure to solution and is condensed into 1-2 milliliters, 0.5 milliliter of ether is then added.Clear crystal is obtained in the solution.
Preparation example 7
The preparation of (1,3- dipropyl -1,1,3, the 3- tetrabutyl, two silicon substrate amine)-two tetrahydrofuran ceriums, the following institute of structural formula
Show：
In the presence of nitrogen, CeCl is introduced into flask3(2.1 mMs) and the 1,3- dipropyl -1,1,3,3- tetrabutyls
Two silicon substrate amine (2.0 mMs)；And be added thereto 25 milliliters of THF, it is stirred 25 minutes at 30 DEG C, then at 50 DEG C
It is evaporated under reduced pressure to solution and is condensed into 1-2 milliliters, 0.5 milliliter of ether is then added.Clear crystal is obtained in the solution.
Preparation example 8
The preparation of (1,3- dicyclohexyl -1,1,3,3- tetramethyl, two silicon substrate amine)-two pyridine neodymiums, structural formula are as follows：
In the presence of nitrogen, NdCl is introduced into flask3(2.1 mMs) and 1,3- dicyclohexyl -1,1,3,3- tetramethyls
Two silicon substrate amine of base (2.0 mMs)；And be added thereto 25 milliliters of pyridine, it is stirred 20 minutes at 50 DEG C, then 50
It is evaporated under reduced pressure at DEG C to solution and is condensed into 1-2 milliliters, 0.5 milliliter of ether is then added.Colourless crystalline substance is obtained in the solution
Body.
Preparation example 9
The preparation of two (1,3- Hexaethyl, two silicon nitrogen amine) acetonitrile neodymiums, structural formula are as follows：
Under a nitrogen, NdCl is introduced into flask3(1.1 mMs) and hexaethyl disilazine (2.1 mMs)；And
25 milliliters of acetonitrile is added thereto, is stirred 30 minutes at 35 DEG C, is then evaporated under reduced pressure to solution and is concentrated at 50 DEG C
At 1-2 milliliters, 0.5 milliliter of ether is then added.Clear crystal is obtained in the solution.
Embodiment 1
In the presence of nitrogen, the n-hexane of 50mL is introduced into flask, the rare earth metal that 0.24mmol preparation examples 1 obtain has
Machine compound and 4.1mmol isoprene contact 5 minutes at being 30 DEG C in temperature；1.0mmol triisobutyl aluminiums are subsequently introduced,
It is contacted 30 minutes at being 30 DEG C in temperature；0.72mmol diethyl aluminum chlorides are subsequently introduced, 2h is aged at being 60 DEG C in temperature；With
0.96mol isoprene is introduced afterwards to be polymerize, and is reacted 3h at being 30 DEG C in temperature, is then kept reaction whole by the way that methanol is added
Only, polymeric articles are obtained.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 99.7 weight %, molecular weight distribution 1.8 in polymeric articles.
Embodiment 2
In the presence of nitrogen, the n-hexane of 50mL is introduced into flask, the rare earth metal that 0.24mmol preparation examples 2 obtain has
Machine compound and 7.2mmol isoprene contact 7 minutes at being 35 DEG C in temperature；It is subsequently introduced 1.44mmol and hydrogenates two isobutyls
Base aluminium contacts 20 minutes at being 35 DEG C in temperature；Be subsequently introduced 0.72mmol diisobutyl aluminum chlorides, temperature be 60 DEG C at it is old
Change 2.5h；It is subsequently introduced 1mol isoprene to be polymerize, reacts 4h at being 35 DEG C in temperature, then made instead by the way that methanol is added
It should terminate, obtain polymeric articles.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 99.5 weight %, molecular weight distribution 1.8 in polymeric articles.
Embodiment 3
In the presence of nitrogen, the n-hexane of 50mL is introduced into flask, the rare earth metal that 0.24mmol preparation examples 3 obtain has
Machine compound and 7.2mmol isoprene contact 15 minutes at being 20 DEG C in temperature；1.44mmol triethyl aluminums are subsequently introduced,
It is contacted 30 minutes at being 20 DEG C in temperature；0.72mmol diisobutyl aluminum chlorides are subsequently introduced, 3h is aged at being 50 DEG C in temperature；
It is subsequently introduced 1.2mol isoprene to be polymerize, reacts 3h at being 60 DEG C in temperature, then keep reaction whole by the way that methanol is added
Only, polymeric articles are obtained.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 99.5 weight %, molecular weight distribution 1.9 in polymeric articles.
Embodiment 4-5
Embodiment 4-5 is carried out using method similar to Example 1, the difference is that using preparation example 4 in embodiment 4
The rare earth metal organic compound that preparation example 1 in the Rare-earth chemicals alternative embodiment 1 being prepared is prepared
Object；It is prepared by the preparation example 1 in the Rare-earth chemicals alternative embodiment 1 being prepared using preparation example 5 in embodiment 5
Obtained Rare-earth chemicals.
Remaining is in the same manner as in Example 1.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 99.6 weight % in the polymeric articles that embodiment 4 obtains, and molecular weight distribution is
1.7；
Cis- Isosorbide-5-Nitrae linkage content is 99.6 weight %, molecular weight distribution 1.8 in the polymeric articles that embodiment 5 obtains.
Embodiment 6-7
Embodiment 6-7 is carried out using method similar to Example 3, the difference is that using preparation example 6 in embodiment 6
The rare earth metal organic compound that preparation example 3 in the Rare-earth chemicals alternative embodiment 3 being prepared is prepared
Object；It is prepared by the preparation example 3 in the Rare-earth chemicals alternative embodiment 3 being prepared using preparation example 7 in embodiment 7
Obtained Rare-earth chemicals.
Remaining is in the same manner as in Example 3.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 99.4 weight % in the polymeric articles that embodiment 6 obtains, and molecular weight distribution is
1.8；
Cis- Isosorbide-5-Nitrae linkage content is 99.5 weight %, molecular weight distribution 1.9 in the polymeric articles that embodiment 7 obtains.
Embodiment 8-9
Embodiment 8-9 is carried out using method similar to Example 2, the difference is that using preparation example 8 in embodiment 8
The rare earth metal organic compound that preparation example 2 in the Rare-earth chemicals alternative embodiment 2 being prepared is prepared
Object；It is prepared by the preparation example 2 in the Rare-earth chemicals alternative embodiment 2 being prepared using preparation example 9 in embodiment 9
Obtained Rare-earth chemicals.
Remaining is in the same manner as in Example 2.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 99.5 weight % in the polymeric articles that embodiment 8 obtains, and molecular weight distribution is
1.9；
Cis- Isosorbide-5-Nitrae linkage content is 99.3 weight %, molecular weight distribution 1.7 in the polymeric articles that embodiment 9 obtains.
Comparative example 1
Polymeric articles are prepared according to method described in embodiment 1, the difference is that being replaced using neodymium chloride in this comparative example
The Rare-earth chemicals that the preparation example 1 changed in embodiment 1 is prepared.
Remaining is in the same manner as in Example 1.
As a result：It can not detect polymeric articles.
Comparative example 2
Polymeric articles are prepared according to the method described in embodiment 2, the difference is that being replaced using neodymium oxalate in this comparative example
The Rare-earth chemicals that the preparation example 2 changed in embodiment 2 is prepared.
Remaining is in the same manner as in Example 2.
As a result：It can not detect polymeric articles.
Comparative example 3
Polymeric articles are prepared according to method described in embodiment 3, the difference is that being used in this comparative example
Macro.Chem.Phys. Nd (N (the SiMe in (200,1163)3)2)3Preparation example 3 in alternative embodiment 3 is prepared dilute
Earth metal organic compound.
Remaining is in the same manner as in Example 3, obtains polymeric articles.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 93.6 weight %, molecular weight distribution 2.7 in polymeric articles.
Comparative example 4
Polymeric articles are prepared according to the method described in embodiment 2, the difference is that being used in this comparative example
Macro.Chem.Phys. Nd (N (the SiMe in (200,1163)3)2)3Preparation example 2 in alternative embodiment 2 is prepared dilute
Earth metal organic compound.
Remaining is in the same manner as in Example 2, obtains polymeric articles.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 87.6 weight %, molecular weight distribution 3.4 in polymeric articles.
Comparative example 5
Polymeric articles are prepared according to method described in embodiment 1, the difference is that being used in this comparative example
Macro.Chem.Phys. Nd (N (the SiMe in (200,1163)3)2)3Preparation example 1 in alternative embodiment 1 is prepared dilute
Earth metal organic compound.
Remaining is in the same manner as in Example 1, obtains polymeric articles.
As a result：Cis- Isosorbide-5-Nitrae linkage content is 80.7 weight %, molecular weight distribution 3.2 in polymeric articles.
By the result of embodiment 1-9 and comparative example 1-5 it is recognised that the poly- isoamyl that method using the present invention is prepared
The cis- Isosorbide-5-Nitrae linkage content of diene is higher, and the product molecular weight distribution obtained is relatively narrow, is suitble to industrialized production.
Moreover, can also be seen that from the result of embodiment 1-9：The cis- of polymeric articles that the method for the present invention obtains contains
Amount is small with the variation fluctuation of reaction condition, and molecular weight distribution is also relatively narrow.However, comparative example 3-5's the results show that using Nd is contained
(N(SiMe3)2)3Catalyst polymerisation when, in the polymeric articles of acquisition cis-content with reaction condition variation
Fluctuation is big, and the molecular weight distribution of the product obtained is also wider.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (17)
1. a kind of method preparing polyisoprene, this method include：Under the polymerization conditions, by isoprene monomer with it is dilute
Native carbon monoxide-olefin polymeric carries out haptoreaction, and Rare-earth chemicals are contained in the rare earth catalyst composition, contain aluminium
The compound and halogen source of element, the compound containing aluminium element are alkyl aluminum and/or alkyl aluminium hydride, which is characterized in that
The Rare-earth chemicals have structure shown in formula (I)：
Wherein, M is any one in lanthanide rare metallic element；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-8Alkyl, C6-12Aryl, and the R1、
R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；
L is-OR7Or-NR8, wherein the R7With the heterocycle containing 2-10 carbon atom, the R are formed together with oxygen atom8With nitrogen
Atom forms the heterocycle containing 2-10 carbon atom or the R together8For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
2. according to the method described in claim 1, wherein, in the structure shown in formula (I), M is neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, C1-6Alkyl, C6-10Aryl, and the R1、
R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；
L is-OR7Or-NR8, wherein the R7With the heterocycle containing 2-7 carbon atom, the R are formed together with oxygen atom8With nitrogen original
Son forms the heterocycle containing 2-7 carbon atom or the R together8For C1-4Alkyl；
X is 1,2 or 3, and y=3-x.
3. according to the method described in claim 2, wherein, in the structure shown in formula (I), M is neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, Methylethyl phenyl, ethylphenyl, diethyl phenyl and three second
Base phenyl, and the R1、R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；
L is selected from tetrahydrofuran, pyridine and acetonitrile；
X is 1 or 2, and y=3-x.
4. according to the method described in claim 2, wherein, in the structure shown in formula (I), M is neodymium or cerium；
R1、R2、R3、R4、R5And R6It is identical or different, it is each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, Methylethyl phenyl, ethylphenyl, diethyl phenyl and three second
Base phenyl, and the R1、R2、R3、R4、R5And R6It is asynchronously selected from least one of hydrogen and methyl；
X is 3, and y is 0.
5. according to the method described in any one of claim 1-4, wherein described in the rare earth catalyst composition
The content molar ratio of Rare-earth chemicals, the compound containing aluminium element and halogen source is 1：2-10：1-30.
6. according to the method described in claim 5, wherein, in the rare earth catalyst composition, the rare earth metal is organic
The content molar ratio of compound, the compound containing aluminium element and halogen source is 1：4-8：1-15.
7. according to the method described in any one of claim 1-4, wherein the alkyl aluminum be trimethyl aluminium, triethyl aluminum,
It is one or more in tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium and three amyl aluminium；The alkyl aluminium hydride is hydrogenation diethyl
Base aluminium and/or hydrogenation dibutyl aluminium.
8. according to the method described in claim 7, wherein, the alkyl aluminum is triisobutyl aluminium and/or triethyl aluminum.
9. according to the method described in claim 7, wherein, the alkyl aluminium hydride is hydrogenation dibutyl aluminium.
10. according to the method described in any one of claim 1-4, wherein the halogen source is aikyl aluminum halide.
11. according to the method described in claim 10, wherein, the aikyl aluminum halide is diethyl aluminum chloride and/or two isobutyls
Base aluminium chloride.
12. described organic according to the method described in claim 1, wherein, the haptoreaction carries out in the presence of an organic
Solvent is selected from least one of pentane, hexane, heptane, hexamethylene, toluene, dimethylbenzene and chlorobenzene.
13. according to the method for claim 12, wherein the organic solvent is n-hexane.
14. according to the method described in claim 1, wherein, the catalytic condition includes：Temperature is 0-100 DEG C, the time
For 0.1-24h.
15. the method according to claim 1 or 14, wherein the isoprene monomer in terms of rare earth metal described in
The molar ratio of the dosage of rare earth catalyst composition is 1000-10000：1.
16. being gathered according to the method described in claim 1, wherein, in the rare earth catalyst composition also containing to be ready to use in
Close the isoprene monomer of reaction.
17. according to the method for claim 16, wherein described to be ready to use in the isoprene monomer for carrying out polymerisation and institute
The content molar ratio for stating Rare-earth chemicals is 1-120：1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510680000.5A CN106589195B (en) | 2015-10-19 | 2015-10-19 | A method of preparing polyisoprene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510680000.5A CN106589195B (en) | 2015-10-19 | 2015-10-19 | A method of preparing polyisoprene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589195A CN106589195A (en) | 2017-04-26 |
| CN106589195B true CN106589195B (en) | 2018-11-02 |
Family
ID=58554920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510680000.5A Active CN106589195B (en) | 2015-10-19 | 2015-10-19 | A method of preparing polyisoprene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589195B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1479754A (en) * | 2000-11-13 | 2004-03-03 | �����ּ�����˾ | Synthetic polyisoprenes and their preparation method |
| CN1484657A (en) * | 2000-11-09 | 2004-03-24 | �����ּ�����˾ | Catalytic system and method for preparing elastomers using same |
| CN1568332A (en) * | 2001-10-12 | 2005-01-19 | 陶氏环球技术公司 | Metal complex compositions and their use as catalysts to produce polydienes |
| CN101475652A (en) * | 2008-12-25 | 2009-07-08 | 中国科学院长春应用化学研究所 | Rare earth catalyst for isoprene high cis 1,4-polymerization and preparation |
| CN102532355A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
| CN102558400A (en) * | 2010-12-09 | 2012-07-11 | 中国石油化工股份有限公司 | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof |
| CN103450373A (en) * | 2012-05-28 | 2013-12-18 | 中国石油化工股份有限公司 | Composition used for rare earth catalyst, rare earth catalyst and its application |
-
2015
- 2015-10-19 CN CN201510680000.5A patent/CN106589195B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1484657A (en) * | 2000-11-09 | 2004-03-24 | �����ּ�����˾ | Catalytic system and method for preparing elastomers using same |
| CN1479754A (en) * | 2000-11-13 | 2004-03-03 | �����ּ�����˾ | Synthetic polyisoprenes and their preparation method |
| CN1568332A (en) * | 2001-10-12 | 2005-01-19 | 陶氏环球技术公司 | Metal complex compositions and their use as catalysts to produce polydienes |
| CN101475652A (en) * | 2008-12-25 | 2009-07-08 | 中国科学院长春应用化学研究所 | Rare earth catalyst for isoprene high cis 1,4-polymerization and preparation |
| CN102532355A (en) * | 2010-12-09 | 2012-07-04 | 中国石油化工股份有限公司 | Homogenous neodymium-based rare earth catalyst, and its preparation method and application |
| CN102558400A (en) * | 2010-12-09 | 2012-07-11 | 中国石油化工股份有限公司 | Neodymium-based homogeneous phase rare earth catalyst and preparation method and application thereof |
| CN103450373A (en) * | 2012-05-28 | 2013-12-18 | 中国石油化工股份有限公司 | Composition used for rare earth catalyst, rare earth catalyst and its application |
Non-Patent Citations (1)
| Title |
|---|
| Polymerization of butadiene with a new catalyst based on a neodymium amide precursor;Christophe Boisson et al;《Macromol. Chem. Phys》;19990421;第200卷(第5期);第1163-1166 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589195A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10280243B2 (en) | Copolymer of ethylene and a conjugated diene, and process for its production | |
| BR112013019812B1 (en) | METALLIC COMPLEX CATALYST AND POLYMERIZATION METHODS APPLYING THE SAME | |
| US9416205B2 (en) | Organometallic complex catalyst and polymerization method employing same | |
| CN109912732B (en) | Bond-forming pyridylamine iron-based catalyst and preparation method and application thereof | |
| EP3738927A1 (en) | Metallic complex catalyst, polymerization methods employing same and polymer products thereof | |
| EP2900702A1 (en) | Organometallic catalyst complex and polymerization method employing same | |
| CN103360516A (en) | Neodymium homogeneous phase rare earth catalyst composition and neodymium homogeneous phase rare earth catalyst as well as preparation method and application of neodymium homogeneous phase rare earth catalyst | |
| KR20140109393A (en) | Bulk Polymerization Process for Producing Polydienes | |
| CN112409539B (en) | Butadiene-isoprene copolymer and preparation method thereof | |
| CN106589195B (en) | A method of preparing polyisoprene | |
| CN105330773B (en) | Rare earth catalyst composition and a kind of rare earth catalyst and its preparation method and application | |
| US8604143B2 (en) | Catalysts for polymerization of isoprene and preparations and uses thereof | |
| BR112013019814B1 (en) | LANTHANIDE COMPLEX CATALYST AND POLYMERIZATION METHOD USING THE SAME | |
| CN112409520B (en) | Preparation of polybutadiene and catalyst thereof by homogeneous rare earth catalyst | |
| CN112194748B (en) | Polyisoprene and preparation method thereof | |
| CN112142893B (en) | Polyisoprene and preparation method thereof | |
| CN106589239B (en) | A method of preparing butadiene/isoprene copolymer | |
| Moinet et al. | Triisobutylaluminium-promoted formation of lanthanide hydrides | |
| CN112442148B (en) | Homogeneous rare earth catalyst and preparation method thereof, polybutadiene and preparation method thereof | |
| CN108192002A (en) | A kind of method for preparing polyisoprene | |
| CN115246899B (en) | Stereoblock polybutadiene and preparation method thereof | |
| CN106588962A (en) | Rare-earth metal organic compound, rare-earth catalyst composition, and their preparation methods and application | |
| CN112442151B (en) | Catalytic copolymerization for preparing poly (butadiene-isoprene) | |
| CN106916240A (en) | A kind of method for preparing rare-earth isoprene rubber catalyst | |
| CN108456272B (en) | Catalyst composition for olefin polymerization, application thereof and method for polymerizing conjugated diene monomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |