CN105085720A - Composition for rare earth catalyst, rare earth catalyst, preparation method and application of rare earth catalyst and isoprene polymerization method - Google Patents
Composition for rare earth catalyst, rare earth catalyst, preparation method and application of rare earth catalyst and isoprene polymerization method Download PDFInfo
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- CN105085720A CN105085720A CN201410205771.4A CN201410205771A CN105085720A CN 105085720 A CN105085720 A CN 105085720A CN 201410205771 A CN201410205771 A CN 201410205771A CN 105085720 A CN105085720 A CN 105085720A
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Abstract
The invention provides a composition for a rare earth catalyst. The composition comprises a single amidinate lanthanide complex, aluminium alkyl and organic boron salt. Molar ratio of the single amidinate lanthanide complex to aluminium alkyl to organic boron salt is 1: (5-50): (0.5-2). The invention provides a rare earth catalyst and its preparation method and application. The catalyst contains a composition and an inert organic solvent, wherein the composition is the composition for a rare earth catalyst. The invention provides an isoprene polymerization method. The method comprises the step of contacting isoprene with the catalyst provided by the invention under the olefin polymerization condition. The catalyst provided by the invention has advantages of simple formula, economy and high polymerization activity and efficiency. By the use of the rare earth catalyst, polyisoprene with cis-structure content being greater than 96%, weight-average molecular weight being adjustable within the range of 0.5-1.5 millions and molecular weight distribution being 1.5-2.5 can be synthesized at room temperature.
Description
Technical field
The present invention relates to a kind of rare earth catalyst composition, and a kind of method of a kind of rare earth catalyst and its preparation method and application and isoprene polymerization.
Background technology
High-cis polyisoprene rubber (IR) due to natural rubber structural similitude, be mainly used to replace natural gum be applied to tyre industry.Polyisoprene rubber has compared with natural rubber that purity is high, quality is homogeneous, and the time of plasticating is short, mixing easy, transparent color and luster, expand and specific absorption little, the advantages such as good fluidity.When IR is applied to tire, molecular weight distribution can be reduced at the molecular weight improving polymkeric substance simultaneously and be conducive to reducing rolling resistance, wherein molecular weight distribution is one of chief reason, suitability for industrialized production obtains cis-content and is greater than 96%, and the product that molecular weight distribution is less than 3.0 is also the development trend of synthesizing polyisoprene rubber from now on.Cis-1,4-polyisoprene is polyisoprene rubber (cis-1, full name 4-polyisoprenerubber), it is the high-cis (cis-1 obtained by isoprene, 4 content are 92% ~ 97%) synthetic rubber, because its Structure and Properties and natural rubber are similar to, therefore also known as natural synthetic rubber, being the glue kind that in synthetic rubber (SR), over-all properties is best, is the third-largest glue kind being only second to styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber in world's synthetic rubber.
From Wllliams in 1860 by natural rubber resolvent isolates isoprene, many scientists are just devoted to the research with isoprene natural synthetic rubber.In research process, though make some progress in polymerization starter, the polyisoprene rubber of synthesis and the performance of natural rubber still have a certain distance.
Supply falls short of demand for natural rubber, facilitates the development of polyisoprene rubber.Within 1954, synthesized titanium system polyisoprene rubber and lithium system cis-1 with nineteen fifty-five, 4 content reach the polyisoprene (i.e. lithium system polyisoprene) of 92%.Nineteen sixty Shell chemical company achieves the suitability for industrialized production with lithium system polyisoprene rubber, and after this, countries in the world such as Holland, USSR (Union of Soviet Socialist Republics), Italy, France, Japan, Romania, South Africa and Brazil etc. achieve the suitability for industrialized production of polyisoprene all in succession.And China starts to develop polyisoprene rubber the sixties, within 2010, build up the rare-earth isoprene rubber device of first cover annual output 1.5 ten thousand tons by Maoming Luhua Chemical Industrial Co., Ltd., current polyisoprene rubber has welcome the gold period of development, and the units such as Qingdao Harold Ickes, Sinopec have device to go into operation in succession.
Compared with natural rubber, polyisoprene rubber also has that quality is homogeneous, and purity is high, and the time of plasticating is short, and mixed refining process is easy, of light color, expands and shrinks the advantages such as little, good fluidity.Polyisoprene rubber can be used alone, also can with natural rubber, cis-1,4-polybutadiene rubber etc. with the use of; Be mainly used in the tread rubber of tire, carcass glue and sidewall rubber, and rubber overshoes, adhesive tape, sizing agent, technique rubber item, dipped rubber goods and medical treatment, foodstuff rubber products etc.
The performance cis-with it 1 of polyisoprene, 4 structural contents, molecular weight and distribution thereof are closely related, cis-Isosorbide-5-Nitrae content is greater than 98%, the polyisoprene of molecular weight more than 1,000,000 just can substitute natural rubber, the catalyst system adopted when this depends primarily on polymerization.Obtain synthesizing simple, stable, homogeneous phase, efficiently catalyzer, high cis-1 is kept under realizing 40-100 DEG C of polymerizing condition, since the problems such as 4 selectivity, polymericular weight and distribution thereof are controlled are half a century, academia, company and enterprise carry out the difficult problem of unremitting effort to solving.
Summary of the invention:
The object of the present invention is to provide a kind of novel rare earth catalyst of polymkeric substance preparing high-cis, narrow ditribution being different from prior art.
To achieve these goals, according to a first aspect of the invention, the invention provides a kind of rare earth catalyst composition, said composition comprises: single amidino groups rare earth compounding, aluminum alkyls and organic boron salt, wherein, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(5-50): (0.5-2).
According to a second aspect of the invention, the invention provides a kind of rare earth catalyst, this catalyzer contains composition and inert organic solvents, and described composition is rare earth catalyst composition of the present invention.
According to a third aspect of the invention we; the invention provides a kind of method preparing rare earth catalyst; wherein; the method comprises: under protection of inert gas; single amidino groups rare earth compounding, aluminum alkyls are contacted in inert organic solvents with organic boron salt; wherein, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(5-50): (0.5-2).
According to a forth aspect of the invention, the invention provides the application of catalyzer of the present invention in conjugate diene polymerization.
According to a fifth aspect of the invention, the invention provides a kind of method of isoprene polymerization, it is characterized in that, the method comprises: under olefin polymerization conditions, by isoprene and catalyst exposure of the present invention.
Catalyzer of the present invention has simple, the economic and polymerization activity of formula and the high advantage of efficiency, use that rare earth catalyst of the present invention can at room temperature synthesizing cis structural content be greater than 96%, weight-average molecular weight is adjustable in 50-150 ten thousand scope, molecular weight distribution is the polyisoprene of 1.5-2.5.
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.
As previously mentioned, the invention provides a kind of rare earth catalyst composition, said composition comprises: single amidino groups rare earth compounding, aluminum alkyls and organic boron salt, and wherein, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(5-50): (0.5-2).
According to composition of the present invention, the mol ratio of preferred single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(20-30): (0.8-1.2).
According to composition of the present invention, described single amidino groups rare earth compounding refers to only containing the rare earth compounding of an amidino groups group, and the range of choices of described single amidino groups rare earth compounding is wider, for the present invention, preferred described single amidino groups rare earth compounding is selected from [CyC (N-2,6-iPr
2c
6h
3)
2] Ln (CH
2siMe
3)
2(THF)
2, PhC (N-2,6-Me
2c
6h
3)
2] Ln (CH
2siMe
3)
2(THF)
2[CyC (N-2,6-Me
2c
6h
3)
2] Ln (CH
2siMe
3)
2(THF)
2in one or more, wherein, Ln is Y, Lu or Nd.
According to composition of the present invention, the range of choices of the kind of described aluminum alkyls is wider, it can be the routine selection of this area, for the present invention, preferred described aluminum alkyls be selected from aluminium trimethide, aluminium triethyl, triisobutyl aluminium, diisobutylaluminium hydride, three hexyl aluminium and aluminium diethyl monochloride one or more.What use in a particular embodiment of the present invention is triisobutyl aluminium.
According to composition of the present invention, the range of choices of the kind of described organic boron salt is wider, and for the present invention, preferred described organic boron salt is [PhNMe
2h] [B (C
6f
5)]
4or [Ph
3c] [B (C
6f
5)]
4.
As previously mentioned, according to a second aspect of the invention, the invention provides a kind of rare earth catalyst, this catalyzer contains composition and inert organic solvents, and described composition is rare earth catalyst composition of the present invention.
According to rare earth catalyst of the present invention, described inert organic solvents can be the inert organic solvents that this area routine uses, and for the present invention, preferred described inert organic solvents is toluene.
As previously mentioned; according to a third aspect of the invention we; the invention provides a kind of method preparing rare earth catalyst; wherein; the method comprises: under protection of inert gas; single amidino groups rare earth compounding, aluminum alkyls are contacted in inert organic solvents with organic boron salt, wherein, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(5-50): (0.5-2).
In the present invention, the substance classes of described single amidino groups rare earth compounding, aluminum alkyls and organic boron salt describes aforementioned, and the present invention does not repeat them here.
As previously mentioned, described inert organic solvents can be the inert organic solvents that this area routine uses, and for the present invention, preferred described inert organic solvents is toluene.
In the present invention, the temperature of preferably contact is room temperature (-10 DEG C to 40 °, preferred 10-30 DEG C).
In the present invention, the time of preferably contact is 1-10min.
According to one of the present invention preferred embodiment; method of the present invention comprises: under protection of inert gas; under toluene solvant exists; single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is added successively in the reactor of drying; in room temperature (-10 DEG C to 40 ° after adding completely; preferred 10-30 DEG C) under contact 1-10min, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(20-30): (0.8-1.2).
The invention provides the application of catalyzer of the present invention in conjugate diene polymerization.
Catalyzer of the present invention is used for conjugate diene polymerization, cis-structure content can be obtained high, the polymkeric substance of narrow molecular weight distribution.Catalyzer of the present invention is particularly suitable for the polymerization of isoprene, use it for the polymerization of isoprene, isoprene monomer transformation efficiency is more than 75%, and can obtain that cis-structure content is greater than 96%, weight-average molecular weight is adjustable in 50-150 ten thousand scope, molecular weight distribution is the polyisoprene of 1.5-2.5.
According to one of the present invention preferred embodiment, the invention provides a kind of method of isoprene polymerization, the method comprises: under olefin polymerization conditions, by isoprene and catalyst exposure of the present invention.
According to method of the present invention, the kind of the solvent that polymerization uses can be the routine selection of this area, and for the present invention, the solvent phase in the catalyzer of preferred described polymerization is same, such as, be toluene.
According to method of the present invention, the temperature of polymerization is preferably subzero 20 DEG C to 50 DEG C above freezing, is preferably 20-30 DEG C.
According to method of the present invention, the preferred polymeric time is 20-120min, is preferably 30-80min, is 60min in an embodiment of the present invention.
According to one of the present invention preferred embodiment, preferred described olefin polymerization conditions comprises: solvent is toluene, and polymerization temperature is subzero 20 DEG C to 50 DEG C above freezing, and polymerization time is 20-120min.
Carry out the polymerization of isoprene according to polymerization process of the present invention, isoprene monomer transformation efficiency is high, and can obtain cis-content and be greater than 96%, and weight-average molecular weight is 500,000-150 ten thousand, and molecular weight distribution is the polyisoprene of Mw/Mn=1.5-2.5.
In the present invention, rare gas element can be that the routine of this area is selected, and the rare gas element used in a particular embodiment of the present invention is nitrogen.
Describe the present invention in detail by embodiment and comparative example below, but scope of the present invention is not limited to these embodiments.
If not otherwise specified, the chemical reagent used in embodiment is chemically pure reagent.
In the present invention, the microtexture of the conjugated diene polymer of synthesis adopts German Bruker400MHz nmr determination, and solvent is deuterochloroform; Molecular weight and molecualr weight distribution adopts Shimadzu LC-10AT type gel permeation chromatograph (GPC) to measure, and THF is moving phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.
In the present invention, the solvent used in Kaolinite Preparation of Catalyst process, and polymerization use conjugated diene all through the process of nitrogen deoxygenation, and in solvent water-content lower than 10ppm.
In the present invention, monomer conversion is concept well known to those skilled in the art, in the present invention, monomer conversion refers to monomer is converted into polymkeric substance per-cent by polyreaction, and it is generally the weight of straight polymer and the ratio entering the monomer weight being polymerized workshop section.In the present invention, the weight of straight polymer is the weight of polymers soln and the product of polymer concentration, wherein, the weight of polymers soln refers to the weight of the polymers soln not adding terminator, and polymer concentration refers to straight polymer weight percent shared in a polymer solution.
Embodiment 1
The present embodiment is for illustration of the preparation method of catalyzer provided by the invention and the application in isoprene polymerization thereof.
Under nitrogen protection, at room temperature 10 DEG C, add successively in 1L reactor and be dissolved with 0.1mmol title complex [CyC (N-2,6-Me
2c
6h
3)
2] Nd (CH
2siMe
3)
2(THF)
2toluene solution 500ml, 2mmol triisobutyl aluminium, is dissolved with 0.08mol [Ph
3c] [B (C
6f
5)]
4toluene solution 100ml, contact 3min after obtain catalyzer; Add 1.6mol isoprene, react after 1 hour under 20 DEG C of conditions, polymers soln is released in still and adds the ethanolic soln termination reaction of 2,6-di-tert-butyl hydroquinone.Obtaining monomer conversion is as calculated 88%, and the cis-Isosorbide-5-Nitrae structural content of the polymkeric substance obtained is 97.5%, Mn=64 × 10
4, Mw/Mn=1.81.
Embodiment 2
The present embodiment is for illustration of the preparation method of catalyzer provided by the invention and the application in isoprene polymerization thereof.
Under nitrogen protection, at room temperature 20 DEG C, add successively in 1L reactor and be dissolved with 0.1mmol title complex [CyC (N-2,6-Me
2c
6h
3)
2] Y (CH
2siMe
3)
2(THF)
2toluene solution 500ml, 2mmol triisobutyl aluminium, is dissolved with 0.1mol [PhNMe
2h] [B (C
6f
5)]
4toluene solution 100ml, contact 5min after after obtain catalyzer; Add 1.6mol isoprene, react after 1 hour under 30 DEG C of conditions, polymers soln is released in still and adds the ethanolic soln termination reaction of 2,6-di-tert-butyl hydroquinone.Obtaining monomer conversion is as calculated 75%, and the cis-Isosorbide-5-Nitrae structural content of the polymkeric substance obtained is 97.1%, Mn=55 × 10
4, Mw/Mn=1.76.
Embodiment 3
The present embodiment is for illustration of the preparation method of catalyzer provided by the invention and the application in isoprene polymerization thereof.
Under nitrogen protection, at room temperature 30 DEG C, add successively in 1L reactor and be dissolved with 0.1mmol title complex [CyC (N-2,6-
ipr
2c
6h
3)
2] Lu (CH
2siMe
3)
2(THF)
2toluene solution 500ml, 3mmol triisobutyl aluminium, is dissolved with 0.1mol [Ph
3c] [B (C
6f
5)]
4toluene solution 100ml contact after 10min and obtain catalyzer; Add 1.6mol isoprene, react after 1 hour under 20 DEG C of conditions, polymers soln is released in still and adds the ethanolic soln termination reaction of 2,6-di-tert-butyl hydroquinone.Obtaining monomer conversion is as calculated 89%, and the cis-Isosorbide-5-Nitrae structural content of the polymkeric substance obtained is 98.6%, Mn=68 × 10
4, Mw/Mn=1.92.
Embodiment 4
The present embodiment is for illustration of the preparation method of catalyzer provided by the invention and the application in isoprene polymerization thereof.
Under nitrogen protection, at room temperature 20 DEG C, add successively in 1L reactor and dissolve 0.1mmol title complex [CyC (N-2,6-
ipr
2c
6h
3)
2] Nd (CH
2siMe
3)
2(THF)
2toluene solution 500ml, 2mmol triisobutyl aluminium, dissolves 0.12mol [Ph
3c] [B (C
6f
5)]
4toluene solution 100ml contact after 5min and obtain catalyzer; Add 1.6mol isoprene, react after 1 hour under 20 DEG C of conditions, polymers soln is released in still and adds the ethanolic soln termination reaction of 2,6-di-tert-butyl hydroquinone.Obtaining monomer conversion is as calculated 81%, and the cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 97.9%, Mn=63 × 10
4, Mw/Mn=2.16.
Embodiment 5
The present embodiment is for illustration of the preparation method of catalyzer provided by the invention and the application in isoprene polymerization thereof.
Under nitrogen protection, at room temperature 20 DEG C, add successively in 1L reactor and be dissolved with 0.1mmol title complex [CyC (N-2,6-
ipr
2c
6h
3)
2] Y (CH
2siMe
3)
2(THF)
2toluene solution 500ml, 3mmol triisobutyl aluminium, is dissolved with 0.1mol [Ph
3c] [B (C
6f
5)]
4toluene solution 100ml, contact 5min after obtain catalyzer; Add 1.6mol isoprene, react after 1 hour under 30 DEG C of conditions, polymers soln is released in still and adds the ethanolic soln termination reaction of 2,6-di-tert-butyl hydroquinone.Obtaining monomer conversion is as calculated 81%, and the cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 98.1%, Mn=62 × 10
4, Mw/Mn=2.14.
Embodiment 6
The present embodiment is for illustration of the preparation method of catalyzer provided by the invention and the application in isoprene polymerization thereof.
Under nitrogen protection, at room temperature 20 DEG C, add successively in 1L reactor and be dissolved with 0.1mmol title complex [PhC (N-2,6-Me
2c
6h
3)
2] Y (CH
2siMe
3)
2(THF)
2toluene solution 500ml, 3mmol triisobutyl aluminium, is dissolved with 0.1mol [Ph
3c] [B (C
6f
5)]
4toluene solution 100ml, contact 5min after obtain catalyzer; Add 1.6mol isoprene, react after 1 hour under 30 DEG C of conditions, polymers soln is released in still and adds the ethanolic soln termination reaction of 2,6-di-tert-butyl hydroquinone.Obtaining monomer conversion is as calculated 87%, and the cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 98.8%, Mn=65 × 10
4, Mw/Mn=2.08.
Embodiment 7
According to method Kaolinite Preparation of Catalyst and the polymerization of embodiment 6, unlike, triisobutyl aluminium is 5mmol, [Ph
3c] [B (C
6f
5)]
4for 0.05mmol, all the other conditions are all identical, and obtaining monomer conversion is as calculated 80%, and the cis-Isosorbide-5-Nitrae structural content of polymkeric substance is 96.8%, Mn=65 × 10
4, Mw/Mn=2.06.
More than describe the preferred embodiment of the present invention in detail, but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a rare earth catalyst composition, it is characterized in that, said composition comprises: single amidino groups rare earth compounding, aluminum alkyls and organic boron salt, and wherein, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(5-50): (0.5-2).
2. composition according to claim 1, wherein, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(20-30): (0.8-1.2).
3. composition according to claim 1, wherein, described single amidino groups rare earth compounding is selected from [CyC (N-2,6-iPr
2c
6h
3)
2] Ln (CH
2siMe
3)
2(THF)
2, PhC (N-2,6-Me
2c
6h
3)
2] Ln (CH
2siMe
3)
2(THF)
2[CyC (N-2,6-Me
2c
6h
3)
2] Ln (CH
2siMe
3)
2(THF)
2in one or more, wherein, Ln is Y, Lu or Nd.
4. composition according to claim 1, wherein, described aluminum alkyls be selected from aluminium trimethide, aluminium triethyl, triisobutyl aluminium, diisobutylaluminium hydride, three hexyl aluminium and aluminium diethyl monochloride one or more.
5. composition according to claim 1, wherein, described organic boron salt is [PhNMe
2h] [B (C
6f
5)]
4and/or [Ph
3c] [B (C
6f
5)]
4.
6. a rare earth catalyst, this catalyzer contains composition and inert organic solvents, it is characterized in that, described composition is the rare earth catalyst composition in claim 1-5 described in any one.
7. rare earth catalyst according to claim 6, wherein, described inert organic solvents is toluene.
8. prepare the method for rare earth catalyst for one kind; wherein; the method comprises: under protection of inert gas; single amidino groups rare earth compounding, aluminum alkyls are contacted in inert organic solvents with organic boron salt; wherein, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(5-50): (0.5-2).
9. method according to claim 8; wherein; the method comprises: under protection of inert gas; under toluene solvant exists; single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is added successively in the reactor of drying; under room temperature, contact 1-10min after adding completely, the mol ratio of single amidino groups rare earth compounding, aluminum alkyls and organic boron salt is 1:(20-30): (0.8-1.2).
10. the application of catalyzer in conjugate diene polymerization prepared by the method in the catalyzer in claim 6-7 described in any one or claim 8 or 9 described in any one.
The method of 11. 1 kinds of isoprene polymerizations, it is characterized in that, the method comprises: under olefin polymerization conditions, by catalyst exposure prepared by the method in the catalyzer in isoprene and claim 6-7 described in any one or claim 8 or 9 described in any one.
12. methods according to claim 11, wherein, described olefin polymerization conditions comprises: solvent is toluene, and polymerization temperature is subzero 20 DEG C to 50 DEG C above freezing, and polymerization time is 20-120min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837717A (en) * | 2016-06-14 | 2016-08-10 | 郭云琴 | Method for preparing polyethylene from rare earth compound |
| CN106084108A (en) * | 2016-06-14 | 2016-11-09 | 郭云琴 | A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber |
-
2014
- 2014-05-15 CN CN201410205771.4A patent/CN105085720B/en active Active
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| Title |
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| LIXIN ZHANG, ET AL.: "Isoprene Polymerization with Yttrium Amidinate Catalysts: Switching the Regio- and Stereoselectivity by Addition of AlMe3", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| 范士敏: "单（脒基）稀土二胺基配合物的合成、反应及其催化异戊二烯的聚合性能", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837717A (en) * | 2016-06-14 | 2016-08-10 | 郭云琴 | Method for preparing polyethylene from rare earth compound |
| CN106084108A (en) * | 2016-06-14 | 2016-11-09 | 郭云琴 | A kind of method that amidino groups rare earth alkyl compound prepares isoprene rubber |
| CN105837717B (en) * | 2016-06-14 | 2018-05-18 | 东莞市健鑫塑胶制品有限公司 | A kind of method that rare earth compounding prepares polyethylene |
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