CN1189784A - Ruthenium-based catalyst system for olefin metathesis - Google Patents
Ruthenium-based catalyst system for olefin metathesis Download PDFInfo
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- CN1189784A CN1189784A CN97190460A CN97190460A CN1189784A CN 1189784 A CN1189784 A CN 1189784A CN 97190460 A CN97190460 A CN 97190460A CN 97190460 A CN97190460 A CN 97190460A CN 1189784 A CN1189784 A CN 1189784A
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Abstract
A ruthenium-containing metathesis catalyst system which contains a ruthenium compound (A), a phosphorus compound (B), and a compound (C) containing one carbon-to-carbon triple bond. The mole ratio of compounds A:B:C is typically in the range of about 1.0:0.01-100:0.01-100. The ruthenium compound (A) is a Ru(II), Ru(III), or Ru(IV) compound containing an anionic ligand (X) and optionally an arene ligand and optionally a phosphorus compound ligand. The compound (B) is optional if the ruthenium compound (A) contains a phosphorus-containing ligand.
Description
The present invention relates to a kind of olefin metathesis (metathesis) antigravity system and olefin catalytic metathesis method.Disclose a kind of ruthenium base metathesis catalyst system, it comprises ruthenium compound (A), phosphorus compound (B) and contain the compound (C) of carbon-to-carbon triple bond.The molar ratio A of compound: B: C is usually 1: 0.01-100: in the scope of 0.01-100.Ruthenium compound (A) is Ru (II), the Ru (III) that contains anion ligand (X) and optional aromatic hydrocarbons ligand and optional phosphorus ligand, or Ru (IV) compound.If ruthenium compound (A) contains phosphorus ligand, phosphorus compound (B) is chosen wantonly.The present invention does not use diazonium compound as catalytic component or precursor.The present invention describes in detail
The invention provides a kind of simple ruthenium-based catalyst that is used for high strain, less strain and low strain cyclic olefin and acyclic olefin transposition, and diazonium compound need not be expensive or potential danger is as catalytic component or precursor.The present invention relates to a kind of olefin metathesis reactions that is used for, transposition depolymerization as intersection (cross) transposition, closed loop transposition and/or the unsaturated polymer of metathesis polymerization, ring-type and the acyclic olefin of the ring-opening metathesis polymerization of the transposition of the olefin metathesis of the metathesis polymerization of cycloolefin, acyclic olefin, functional olefines, cyclic olefin, acyclic dienes, ruthenium-based catalyst system, and the olefin metathesis method that so obtains.Antigravity system comprises ruthenium compound (A), phosphorus compound (B) and contain the compound (C) of carbon-to-carbon triple bond, and wherein, if ruthenium compound (A) contains phosphorus ligand, then phosphorus compound (B) is chosen wantonly.
Being used for ruthenium compound of the present invention (A) comprising: for example, contain Ru (II), the Ru (III) of anion ligand (X) and optional aromatic hydrocarbons ligand and optional phosphorus ligand (as phosphine or phosphite ester), or Ru (IV) compound.Usually, ruthenium compound can be represented with following general formula:
[RuX
n(PR '
3)
q(aromatic hydrocarbons)
p]
z
N=2 wherein, 3 or 4; Q=0,1,2,3 or 4; P=0 or 1; And z=1 or 2.
X is an anion ligand (an electronegative group), and X can be the aromatics anion ligand that contains the aliphatic anion ligand of about 20 carbon atoms of as many as or contain about 20 carbon atoms of as many as.X also can be selected from electronegative group, and as halogen, hydroxide, alkoxide, or X can also be nitrate anion (NO
3), nitrite anions (NO
2), acetate (CH
3CO
2), trifluoroacetic acid root (CF
3CO
2), acetylacetonate compound (CH
3COCHCOCH
3), hexafluoroacetylacetone compound (CF
3COCHCOCF
3), or its mixture.
The phosphorus compound ligand (PR '
3) can be phosphine or phosphite ester.R ' is selected from R and (OR), and wherein each R in phosphine or the phosphite ester group is identical or different, can be selected from hydrogen, alkyl, cycloalkyl aryl and aralkyl, replacement or unsubstituted, each has about 20 carbon atoms of as many as; But the substituting group halogen or the alkyl or aryl part of 20 carbon atoms at the most.If R ' is OR, then R ' and R are not hydrogen, if R ' is R, then at least one R is not a hydrogen.
The aromatic hydrocarbons ligand can be that replace or unsubstituted aromatic hydrocarbons ligand with about 30 carbon atoms of as many as; The substituting group of substituted arene ligand can be selected from halogen, have the alkyl and the aryl of about 25 carbon atoms of as many as, has about 25 carbon atom trialkylsilkls of as many as and diarye silyl, or its mixture.The aryl ligand can be selected from alkylbenzene, polyalkylbenzene, aryl benzene, polyaryl benzene, halogeno-benzene, haloalkyl benzene, halogenated aryl benzene, Fluhyzon, arylnaphthalene, many Fluhyzons, polyaryl naphthalene, naphthalene halide, haloalkyl naphthalene and halogenated aryl naphthalene.The aryl ligand can be benzene,toluene,xylene, cumene, cymol, to cymol, durene, trimethyl silyl benzene, 1, two (trimethyl silyl) benzene of 4-, or naphthalene.
Useful in the present invention ruthenium compound (A) comprising: [RuX
2(aromatic hydrocarbons)]
2, RuX
2(aromatic hydrocarbons) (PRR
1R
2), RuX
2(aromatic hydrocarbons) (PHRR
1), RuX
2(aromatic hydrocarbons) (PH
2R), RuX
2(aromatic hydrocarbons) [P (OR) (OR
1) (OR
2), RuX
3, RuX
3-hydrate, RuX
2(PRR
1R
2)
3, RuX
2(PHRR
1)
3, RuX
2(PH
2R)
3, RuX
2[P (OR) (OR
1) (OR
2)]
3, RuX
2(PRR
1R
2)
4, RuX
2(PHRR
1)
4, RuX
2(PH
2R)
4, or RuX
2[P (OR) (OR
1) (OR
2)]
4, wherein P is a phosphorus.
Radicals R in the phosphorus compound ligand of ruthenium compound (A), for example, above-mentioned R, R
1And R
2, can be identical or different, be selected from alkyl, cycloalkyl, aryl and alkaryl, that replace or unsubstituted, each group has about 20 carbon atoms of as many as (preferred about 12 carbon atoms of as many as, further preferred about 8 carbon atoms of as many as, preferred especially about 6 carbon atoms of as many as); Substituting group can be halogen (F, Cl, Br and I), the alkyl or aryl part of many about 20 carbon atoms (preferred about 12 carbon atoms of as many as, further preferred about 8 carbon atoms of as many as, preferred especially about 6 carbon atoms of as many as).
X be selected from the aliphatic ligand (as, about 20 carbon atoms of as many as, preferred about 12 carbon atoms of as many as, further preferred about 8 carbon atoms of as many as, the electronegative aliphatic group of preferred especially about 6 carbon atoms of as many as, as methyl, ethyl, propyl group, isopropyl, butyl, hexyl), the aromatics anion ligand (as, about 20 carbon atoms of as many as, preferred about 12 carbon atoms of as many as, the electronegative aromatic group part of further preferred about 8 carbon atoms of as many as, as phenyl, benzyl).X can be selected from electronegative group, as halogen (F, Cl, Br and I), hydroxide (OH), alkoxide (OR
3, R wherein
3Be selected from alkyl, cycloalkyl, aryl and aralkyl, each all has about 20 carbon atoms of as many as, preferred about 12 carbon atoms of as many as, further preferred about 8 carbon atoms of as many as, preferred especially about 6 carbon atoms of as many as)).X can be selected from nitrate anion (NO
3), nitrite anions (NO
2), acetate (CH
3CO
2), trifluoroacetic acid root (CF
3CO
2), acetylacetonate compound (CH
3COCHCOCH
3), hexafluoroacetylacetone compound (CF
3COCHCOCF
3), or its mixture.
Ruthenium compound (A), as: [RuX
2(aromatic hydrocarbons)]
2, RuX
2(aromatic hydrocarbons) (PRR
1R
2), RuX
2(aromatic hydrocarbons) (PH
2R), RuX
2(aromatic hydrocarbons) (PHRR
1) and RuX
2(aromatic hydrocarbons) [P (OR) (OR
1) (OR
2) in aromatic hydrocarbon group normally based on the arene derivatives of benzene or naphthalene.Aromatic hydrocarbon group includes the aromatics ligand (preferred about 20 carbon atoms of as many as, about 15 of further preferred as many as) of about 30 carbon atoms of as many as, can be that replace or unsubstituted, or its mixture.The substituting group number of aromatics ligand depends on virtue nuclear; For example, benzene nucleus can have about six substituting groups of as many as, and naphthalene is endorsed to have about 8 substituting groups of as many as.The substituting group that replaces the aromatics ligand can be selected from halogen (F, Cl, Br and I, preferred Cl), have about 25 carbon atoms of as many as (preferred about 20 carbon atoms of as many as, further preferred about 12 carbon atoms of as many as, preferred especially about 8 carbon atoms of as many as) alkyl and aryl, have about 25 carbon atoms of as many as (preferably about at the most 20 carbon atoms, more preferably about at the most 15 carbon atoms, most preferably from about 8 former 20 trialkylsilkls of carbon and diarye silyl) and its mixture.The aromatics ligand can be selected from alkylbenzene, polyalkylbenzene, aryl benzene, polyaryl benzene, halogeno-benzene, haloalkyl benzene, halogenated aryl benzene, Fluhyzon, many Fluhyzons, arylnaphthalene, polyaryl naphthalene, naphthalene halide, haloalkyl naphthalene, halogenated aryl naphthalene.The aromatics ligand can be benzene,toluene,xylene, cumene, cymol, to cymol, durene, trimethyl silyl benzene, 1, two (TMS) benzene of 4-, or naphthalene.
Phosphorus compound (B) can be selected from general formula PR usually
3, P (OR)
3, PH
2R, PHRR
1, PRR
1R
2And P (OR) (OR
1) (OR
2) phosphine and phosphite ester.Wherein R, R
1And R
2Identical or inequality, being selected from alkyl, cycloalkyl, aryl and alkaryl, can be that replace or unsubstituted, and each has about 20 carbon atoms of as many as (preferred about 12 carbon atoms of as many as, further preferred about 8 carbon atoms of as many as, preferred especially about 6 carbon atoms of as many as); Substituting group can be halogen (F, Cl, Br and I), the alkyl or aryl of about 20 carbon atoms of as many as (preferred about 12 carbon atoms of as many as, further preferred about 8 carbon atoms of as many as, preferred especially about 6 carbon atoms of as many as).Phosphorus compound (B) is phosphine compound preferably, further preferred C
3-C
8Trialkyl or tricyclic alkyl phosphine are selected from tricyclohexyl phosphine, tri isopropyl phosphine and three cyclopenta phosphines usually.If ruthenium compound (A) has the phosphorus ligand of containing, then phosphorus compound (B) is chosen wantonly.Have the ruthenium compound (A) that contains phosphorus ligand and comprise RuX
2(aromatic hydrocarbons) (PRR
1R
2), RuX
2(aromatic hydrocarbons) (PHRR
1), RuX
2(aromatic hydrocarbons) (PH
2R), RuX
2(aromatic hydrocarbons) [P (OR) (OR
1) (OR
2), RuX
2(PRR
1R
2)
3, RuX
2(PHRR
1)
3, RuX
2(PH
2R)
3, RuX
2[P (OR) (OR
1) (OR
2)]
3, RuX
2(PRR
1R
2)
4, RuX
2(PHRR
1)
4, RuX
2(PH
2R)
4, or RuX
2[P (OR) (OR
1) (OR
2)]
4, wherein P is a phosphorus; These compounds were described in detail in the above.
Catalyst compounds (C) contains the compound of carbon-to-carbon triple bond, can be to replace or unsubstituted C
2-C
20(preferred about 16 carbon atoms of as many as, further preferred about 12 carbon atoms of as many as, preferred especially about 8 carbon atoms of as many as) alkynes, as terminal alkynes, interior alkynes (internalalkyne), or have one or more (as 1 or 2) aliphatic or aromatic functional group substituting group (preferred about 20 carbon atoms of as many as, further preferred about 12 carbon atoms of as many as, preferred especially about 8 carbon atoms of as many as), halogen (F, Cl, Br and I), ester, hydroxyl, ketone, aldehyde, ether, carboxyl, acid amides, acid anhydride, nitrile, silicyl or amine functional group substituting group, or its mixture.Catalyst compounds (C) can be selected from acetylene (C
2H
2), propine, the 1-butine, the 2-butine, the 1-pentyne, valerylene, the 1-hexin, the 2-hexin, the 3-hexin, the 1-heptyne, the 1-octyne, the 1-decine, the 1-dodecyne, trimethyl silyl acetylene, phenylacetylene, dibenzenyl, 2-butine-1, the 4-glycol, 2-butine-1, the ester derivant of 4-glycol, as 1,4-acetoxyl group-2-butine, 2-butine-1,4-diol monoacetate, 2-butine-1, the 4-glycol diacetate, 2-butine-1,4-glycol mono-propionate, 2-butine-1,4-glycol dipropionate, 2-butine-1,4-glycol mono benzoate, 2-butine-1,4-glycol dibenzoate.
Represent that with compound molar ratio A: B: C is usually 1: 0.01-100: between the 0.01-100 (preferred 1.0: 0.1-40: 0.1-40, more preferably 1.0: 0.2-20: 0.2-20).Represent that with compound molar ratio A: B is usually 1: between the 0.01-100 (preferred 1.0: 0.1-40, more preferably 1.0: 0.2-20).
Have been found that hydrogen (H
2) existence can improve activity of such catalysts, the conversion ratio of reactant and productive rate.In the methods of the invention, (not strict although pressure requires, its dividing potential drop is from about 1 * 10 usually for hydrogen
-2The mmHg-200 atmospheric pressure, preferably from about 0.1mmHg-100 atmospheric pressure, more preferably 1mmHg is to about 20 atmospheric pressure) improved activity of such catalysts, the conversion ratio of reactant and productive rate as the existence of antigravity system activator.
Antigravity system is used for the transposition of alkene in the inventive method, comprises the ring-opening metathesis polymerization of cyclic olefin, the transposition of acyclic olefin, oligomeric or the polymerization of acyclic dienes transposition, the cross metathesis of ring-type or acyclic olefin, closed loop transposition, the transposition depolymerization of unsaturated polymer, the transposition of functional olefines.Antigravity system can successfully make high strain cyclic olefin (as the derivative of ENB and ENB, norbornadiene, cyclobutane and Cycloene derivate, bicyclopentadiene) and less strain cyclic diene hydrocarbon (as, cyclopentene, cycloheptene, cyclo-octene, or 1, the 5-cyclo-octadiene, cyclodecene, cyclododecene and 1,5, the 9-cyclodoecatriene) transposition.Containing also can transposition just like the alkene of ester, hydroxyl, ketone, aldehyde, ether, carboxyl, acid amides, acid anhydride, nitrile, halogen (F, Cl, Br and I) and/or amine functional group.
Preferably, activator exists as a component of antigravity system, to improve catalytic activity, improves the conversion ratio of reactant, improves output.Have now found that hydrogen (H
2), can be used as the activator of antigravity system.Can suppose the activity of the hydrogen dissolving in liquid phase the raising (liquid phase mainly is made up of olefin reactant pure or that be dissolved in solvent) antigravity system.Be known that, hydrogen is soluble in solvent, under the pressure that improves, big (A.Seidell, Solubilities of Inorganicand Metal OrganicCompounds of the solubility of hydrogen in medium, Vol.1, D.Van Nostrand Co., N.Y., N.Y., 1940, p.564-567).These solvents are included in to be enumerated below.
Antigravity system can selectively contain the catalytic component that makes the hydrogen-containing compound dehydrogenation, and hydrogen-containing compound is as the hydrogen source on the spot under this method reaction condition, and for example, when having ruthenium on the activated carbon, 1,2,3,4-tetrahydro-naphthalene is dehydrogenated to naphthalene and H
2, cyclohexanol dehydrogenation becomes H
2And cyclohexanone; These dehydrogenation reactions are known.
Used antigravity system dissolves or is suspended in the liquid phase, and liquid phase mainly is made up of olefin reactant pure or that be dissolved in solvent.Can use all kinds of solvents, comprise aliphatic solvent, as pentane, hexane, heptane, decane, naphthalane and carrene, arsol, as benzene,toluene,xylene, chlorobenzene and dichloro-benzenes, and other solvent, as ether and oxolane.Antigravity system can use under nitrogen, argon gas, helium, air, carbon dioxide or hydrogen atmosphere, is lower than an atmospheric pressure (under the vacuum) at you usually and uses to 200 atmospheric pressure.Hydrogen atmosphere is preferred.Usually can use wide temperature, pressure and reaction time range.The olefin metathesis method of use antigravity system of the present invention can be in the temperature, about 1 * 10 of about 0 ℃-250 ℃ (preferred about 0 ℃-200 ℃, further preferred ℃-150 ℃)
-2Carry out under mmHg-200 the atmospheric pressure (preferably about 0.1mmHg-100 atmospheric pressure, further preferred 1mmHg-20 atmospheric pressure).Use the reaction time (time of staying in flow reactor) of the olefin metathesis method of antigravity system of the present invention can be second to one day, preferred 5 minutes to 10 hours.
Have now found that, under the condition that has carbon monoxide-olefin polymeric of the present invention to exist, in the cross metathesis reaction of acyclic or the non-conjugated compound of ring-type, can prepare the straight chain official energy acyclic olefin compound that contains simple function insatiable hunger polymer, wherein said polymer has functional group.
Under the reaction condition that the olefin polymerization compound existence that comprises the non-conjugated compound of cyclic olefin and contain the sense olefin(e) compound is arranged, can prepare straight chain two sense telechelic unsaturated polymers with an inner carbon-to-carbon double bond and an end group.These straight chain non-crosslinked two sense telechelic unsaturated polymers that have the reactive terminal group are suitable for further functionalized, or are incorporated in other polymer with preparation block copolymer and other products.
Straight chain non-crosslinked two sense telechelic unsaturated polymers with the inventive method preparation are to have the real straight chain compound that strictness has the rule structure, have the rule structure to have the end group of accurate qualification.
As well known fact, in olefin metathesis reactions side reaction can take place.These side reactions comprise the addition of two keys in alkylation, isomerization, cyclisation and the molecular structure.Surprisingly, have been found that under condition of the present invention that these side reactions are minimum in the cross metathesis reaction.(well known in the prior art with NMR spectrum
13C NMR) measures discovery, the average functionality at least 0.7 (as 0.7-1.0) of the monofunctional polymer of the inventive method preparation.With NMR spectrum (
13C NMR) measures discovery, two functional polymers' of the inventive method preparation average functionality at least 1.7 (as 1.7-1.0).With the method for nuclear magnetic resonance spectrometry degree of functionality by Nubel, P.O. wait the people to be described in " Preparation of an ester-terminated telechelicpolybutadiene by a two-step olefin matathesis process ", (Joumal ofMolecular Catalysis A.:Chemical (1997), 115:43-50).
Monofunctional polymer and telechelic two functional polymers with the inventive method preparation prepare by metathesis reaction, and this reaction is cross metathesis reaction or the reaction of the cross metathesis between ring-type and the acyclic olefin compound between the acyclic olefin compound.The cross metathesis reaction can be divided three classes usually: atom exchange between (1) two kind of olefin(e) compound, produce two kinds of different olefin(e) compounds, and (2) cyclic olefin open loop produces acyclic polymers, and the degraded of (3) olefin polymer produces low-molecular-weight oligomer.Reaction of the present invention belongs to this three class.
The non-crosslinked straight chain simple function and the huge legendary turtle double functional copolymer far away that obtain with the inventive method are defined as: have the polymer that the straight chain hydrocarbon chain of the repeated monomer unit of 3-30 carbon atom is formed by strictness basically, described hydrocarbon chain maybe can cause crosslinked side group without any side chain.The monomer number of repetitive can be 3-10,000.
The non-crosslinked straight chain simple function telechelic polymer of the inventive method preparation is defined as: have the monofunctional polymer that a terminal active group and average functionality are at least 0.7 (being measured by NMR).The non-crosslinked straight chain two sense telechelic polymers of the inventive method preparation are defined as: have two functional polymers that terminal active end group and average functionality are at least 1.7 (being measured by NMR).
The invention provides a kind of transposition catalysis process for preparing non-crosslinked simple function and telechelic two functional polymers with the simple function olefin(e) compound, wherein, measure (nuclear magnetic resonance) with NMR, degree of functionality at least 0.7, two functional polymers' of monofunctional polymer average functionality is at least 1.7.The present invention also provides a kind of simple function and telechelic two functional polymers, and wherein, the functional group is the end group with reactivity, and end group is to be in position like this, can be further functionalized and/or be incorporated in other compound of reaction.The inventive method also can be used to prepare simple function and telechelic two functional polymers, and wherein, functional components comprises end group, particularly the ester group as acetoxyl group.Here, functional group is defined as ester, hydroxyl, ketone, aldehyde, ether, carboxyl, acid amides, acid anhydride, nitrile, halogen (F, Cl, Br and I) and/or amine functional group.
The following example only is an illustrative, should not be thought of as limitation of the scope of the invention.
Embodiment 1-5 has illustrated that this antigravity system is to low strain cyclic olefin, suitable, suitable-1, and the 5-cyclo-octadiene (1,5-COD), the ability of open loop olefin metathesis polymerisation thing, and the acyclic olefin that contains the ester functional group, suitable-1,4-diacetoxy-2-butylene (suitable-1,4-DAB), olefin metathesis ability.Antigravity system is used for 1,5-COD and suitable-1, and the cross metathesis of 4-DAB, producing acetic acid esters is 1 of end group, the 4-polybutadiene:
Embodiment 1
Present embodiment has been described the effect when having the carbon-to-carbon triple bond compound to exist, and wherein ruthenium compound (A) is 1.0: 4.0: 0.22 to the molar ratio of phosphorus compound (B) and carbon-to-carbon triple bond (C).Having 1,4-diacetoxy-2-butylene, 1 is under the condition that 4-DAB exists, in the nitrogen inert atmosphere, after reacting 3 hours under 90 ℃, 1, the 5-cyclo-octadiene (1, be 1 of end 5-COD) to ethyl ester, the conversion ratio of 4-polybutadiene is 35wt%, 1, and the corresponding conversion ratio of 4-DAB is 17wt%.At 90 ℃ after following 22 hours, acetic acid esters is terminal 1, and the conversion ratio of 4-polybutadiene is 39wt%, 1, and the corresponding conversion ratio of 4-DAB is 27wt%.
By 0.098g[(RuCl
2(p-cymol)]
2(0.16mmol, Strem Chemicals, Inc.), 0.18g tricyclohexyl phosphine (0.64mmol, Aldrich), 3.7ml is suitable-1,4-diacetoxy-2-butylene (" suitable-1,4-DAB ", 23mmol, 95+% purity, TCI America, lot number FCZ02), 15.0ml is suitable, suitable-1,5-cyclo-octadiene (" 1,5-COD ", 122mmol, GC analyzes, purity 99.9%) and the solution formed of 35ml chlorobenzene (Aldrich HPLC level, on the 4A molecular sieve dry cross), at the N of an atmospheric pressure (15psia)
2Down, at the bottom of the garden of the 100ml that packs in the glass flask.Flame ion detector (FID) gas-chromatography (GC) the analysis showed that it contains the alkynes 1 of 0.15wt%, 4-two acyloxy-2-butine; Therefore, above-mentioned solution contains 0.035mmol 1,4-diacetoxy-2-butine (therefore industry is suitable-1, and the 4-DAB product contains 1,4-diacetoxy-2-butine).The flask that fills solution is immersed in 90 ℃ the oil bath, and solution is used magnetic agitation under blanket of nitrogen.At 90 ℃ after following 3 hours, solution is carried out FIDGC the analysis showed that, the COD conversion ratio is 35wt%, the DAB conversion ratio is 17wt%.After (under 90 ℃) 22 hours, GC the analysis showed that the COD conversion ratio is 39wt%, and the DAB conversion ratio is 27wt%.The reaction solution cool to room temperature.Under vacuum (under 80-95 ℃ and 0.2-0.4mmHg pressure 1.5 hours),, obtain the brown low viscosity liquid form product of 5.2 grams by rotary evaporation chlorobenzene solvent, COD and DAB that some are residual.This product contains residual DAB (to be used
13C NMR the analysis showed that 6wt%).The GC analysis result of product is as follows: M
n=370, M
w=2590, M
w/ M
n=7 (solvents (THF); The polybutadiene calibration; The molecular weight that comprises residual DAB calculates).
Outturn sample is dissolved in CDCl
3In, and use Varian VXR-300 spectrometer, by
13C and
1H NMR spectrum is analyzed.(in solution, add the acetylacetonate compound conduct of chromium
13Loose dose of C NMR research).NMR the analysis showed that to have 1 in the product, 4-polybutadiene skeleton structure, and the ratio of suitable-anti-carbon-to-carbon double bond is 72: 28.By
13The observed chain end group of C NMR ratio is 97 moles of % acetic acid esters type end group (CH
2) C (O) CH
3) and 3 moles of % ethene end group (CH=CH
2).
The analysis showed that product is the low molecular weight polybutadiene material, have acetic acid esters type functional group as main chain end group.This is 1,5-COD and 1, the hope product of 4-DAB cross metathesis reaction.Details is listed in the table 1.Embodiment 2
Present embodiment is undertaken by the method for embodiment 1, exception be the hydrogen (H that is reflected at an atmospheric pressure (15psia)
2) carry out in the atmosphere, to confirm the beneficial effect of hydrogen to catalytic activity, reaction-ure conversion-age and productive rate.Hydrogen, H
2Existence make having 1, under the condition that 4-diacetoxy-2-butylene exists, 1, the 5-cyclo-octadiene is 1 of an end to acetic acid esters, the 35wt% of the conversion ratio of 4-polybutadiene from embodiment 1 brings up to 70wt%, and 1, the conversion ratio of 4-diacetoxy-2-butylene is correspondingly brought up to 34wt% from the 17wt% of embodiment 1.
By 0.098g[(RuCl
2(p-cymol)]
2(0.16mmol, Strem Chemicals, Inc.), 0.18g tricyclohexyl phosphine (0.64mmol, Aldrich), 3.7ml suitable-1,4-diacetoxy-2-butylene (" suitable-1,4-DAB ", 23mmol, 95+% purity, TCI America, lot number FCZ02), 15.0mml suitable, suitable-1, (GC analyzes the 5-cyclo-octadiene for " 1; 5-COD ", 122mmol, purity 99.9%) and another part solution of forming of 35ml chlorobenzene (AldrichHPLC level, on the 4A molecular sieve dry cross) at the N of an atmospheric pressure (15psia)
2Down, at the bottom of the garden of the 100ml that packs in the glass flask.It is suitable-1 that FID GC analyzes, and 4-DAB shows that it contains the alkynes 1 of 0.15wt%, 4-two acyloxy-2-butine; Therefore, above-mentioned solution contains 0.035mmol 1,4-diacetoxy-2-butine.Flask is immersed in 90 ℃ the oil bath.Then, under the pressure of an atmospheric pressure (15psia), with the flow of 100ml/min by hydrogen (H
2) bubbling is by the solution in the flask 10 minutes.(hydrogen enters solution from the stainless steel syringe needle point of submergence, discharges flask from the pipe that is connected with the flask ullage space, enters an oily diffuser (bubbler)).After 10 minutes, stop hydrogen and enter flask.Then, in 90 ℃ and static hydrogen (15psia) atmosphere, magnetic agitation solution.After (under 90 ℃) 3 hours, GC the analysis showed that the COD conversion ratio is 70wt%, and the DAB conversion ratio is 34wt%.After (under 90 ℃) 22 hours, GC the analysis showed that the COD conversion ratio is 76wt%, and the DAB conversion ratio is 44wt%.As can be seen, these conversion ratios are twices of the conversion ratio that obtains among the embodiment 1.Compare with embodiment 1, unique variation is to have hydrogen to exist.
The reaction solution cool to room temperature.Under vacuum (under 80 ℃ and 0.2mmHg pressure 1.5 hours),, obtain the brown low viscosity liquid form product of 10.75 grams by rotary evaporation chlorobenzene solvent, COD and DAB that some are residual.As can be seen, be the twice of the conversion ratio that obtains among the embodiment 1.This product contains residual DAB (to be used
13C NMR the analysis showed that 4wt%).The GC analysis result of product is as follows: M
n=410, M
w=2200, M
w/ M
n=5.4 (THF solvents; The polybutadiene calibration; The molecular weight that comprises residual DAB calculates).Outturn sample is dissolved in chloroform-d (CDCl
3) in, and use the VarianVXR-300 spectrometer, by
13C and
1H NMR spectrum is analyzed.(in solution, add the acetylacetonate compound conduct of chromium
13Loose dose of C NMR research).NMR the analysis showed that to have 1 in the product, 4-polybutadiene skeleton structure, and the ratio of suitable-anti-carbon-to-carbon double bond is 69: 31.By
13The observed chain end group of C NMR ratio is 98 moles of % acetic acid esters type end group (CH
2) C (O) CH
3) and 2 moles of % ethene end group (CH=CH
2).
The analysis showed that product is the low molecular weight polybutadiene material, have acetic acid esters type functional group as main chain end group.This is 1,5-COD and 1, the hope product of 4-DAB cross metathesis reaction.
This product is removed catalyst residue and DAB in order to following method.Product (～8.4 gram) is dissolved in the chlorobenzene (25ml) that contains 50mg butylation hydroxylating toluene (BHT).By diameter be 1 inch contain 20 the gram 200 order silica gel (Aldrich) the post filtering solution.(5 * 50ml) wash this post, and cleaning solution is added in the filtrate to use chlorobenzene then.Under vacuum, remove and desolvate, obtain 5.6 gram shallow brown oils by rotary evaporation.With every part is twice flushing oil of methyl alcohol of 70ml; Washing is strong agitation methyl alcohol/oil mixture at room temperature, and makes mixture leave standstill phase-splitting, shifts out then and discard that methyl alcohol carries out mutually.Vacuum (under 80 ℃ and the 0.4mmHg pressure 1 hour) under remove methyl alcohol by rotary evaporation, obtain 4.8 gram light browns, low viscosity oily fluid product (label 19303-155).Product after this processing is carried out gpc analysis, and the result is as follows: M
n=840, M
w=2490, M
w/ M
n=3.0 (THF solvents; The polybutadiene calibration).NMR analyzes (with top described identical) and shows that the product of handling contains the DAB of 0.5wt%, NMR analyzes and shows also that simultaneously the product of handling has 1,4-polybutadiene skeleton structure, the ratio of suitable-anti-carbon-to-carbon double bond is 69: 31, and chain end group ratio is 98 moles of % acetic acid esters type end groups and 2 moles of % ethene end groups.XRF analysis is measured, and ruthenium content is 0.047wt%.Details sees Table 1.Embodiment 3
Present embodiment has been described the molar ratio that changes catalytic component, A: B: C be 1.0: 2.0: 0.44 with the effect of the catalytic component ratio of embodiment 1 and 2 relatively.Temperature drops to 60 ℃ from 90 ℃.Reaction time was increased to 4 hours from 3 hours.Reaction pressure is brought up at H from the atmospheric pressure (15psia) of embodiment 1 and 2
2Under 17psia.1, the 4-COD conversion ratio is 57wt%, and with 1 among the embodiment 1,4-COD conversion ratio 35wt% comparison is to have improved, and the 70wt% comparison with embodiment 2 has then descended.
By 0.098g[(RuCl
2(p-cymol)]
2(0.16mmol, Strem Chemicals, Inc.), the 0.09g tricyclohexyl phosphine (0.32mmol, Aldrich), 7.4ml is suitable-1,4-DAB (47mmol), 30.0mml1, the solution that 5-COD (244mmol) and 10ml chlorobenzene are formed, N
2Under the atmosphere (15psia), in the 6-ounce glass Fisher-Porter bottle of packing into.Because suitable-1, have 0.15wt%t 1 among the 4-DAB, 4-diethoxy-2-butine contains 0.07mmol 1 in the solution, 4-diethoxy butine.The sealing bottle, and be immersed in 60 ℃ the oil bath, solution magnetic agitation 20 minutes is all dissolved all solids.Then, bottle hydrogen (H
2) be forced into 17psia.After the pressurization, bottle seal (is closed the valve of sources of hydrogen) under quiet Hydrogen Vapor Pressure, and solution stirs 4 hours (counting from pressurized with hydrogen) down at 60 ℃.These are after 4 hours, and the pressure in the bottle drops to 6psia.Bottle cool to room temperature and decompression are with FID GC analytical solution, to determine the conversion ratio of reactant.The conversion ratio that calculates COD is 57wt%; The conversion ratio of DAB is 27wt%.
Add 5 gram active carbon (100 order Darco G-60 brand) and 50mgBHT, at N
2Stirred 1/2 hour under atmosphere and the room temperature, the filter activity charcoal makes the solution decolouring.Under vacuum (under 90 ℃ and 0.1-1mmHg pressure 1 hour),, obtain the liquid thick product of 12.6 gram yellow oilies by rotary evaporation chlorobenzene solvent, COD and most of remaining DAB.Thick product is with the methyl alcohol continuous washing of every part of 150ml three times; Washing is strong agitation methyl alcohol/oil mixture at room temperature, and makes mixture leave standstill phase-splitting, shifts out then and discard that methyl alcohol carries out mutually.From the oil after the washing, remove methyl alcohol by rotary evaporation under the vacuum (at 90 ℃ and 0.1-1mmHg), obtaining 9.5 gram yellow oily liquid final products.
The gpc analysis result of final products is as follows: M
n=1400, M
w=2620, M
w/ M
n=1.9 (THF solvents); The polybutadiene calibration).NMR analyzes (except that using Varian Unity-500 spectrometer, with top described identical) show that final products have 1,4-polybutadiene skeleton structure, the ratio of suitable-anti-carbon-to-carbon double bond are 69: 31, and chain end group ratio is 99+ mole % acetic acid esters type end group and 1 mole of % ethene end group.In addition, NMR analyzes and to be further illustrated in the polybutadiene skeleton, about 1% or carbon-to-carbon double bond still less by hydrogenation (with respect to pure insatiable hunger 1,4-butadiene skeleton structure).XRF analysis is measured, and ruthenium content is 174ppm.Details sees Table 1.Embodiment 4
Present embodiment has been described the ratio of carbon-to-carbon triple bond component (C) in the raising catalytic component, and A: B: C is 1.0: 2.0: 3.0, and component (C) has increased about 7 times.All other reactions are undertaken by embodiment 3.1, the 4-COD conversion ratio is brought up to 86wt% from the 57wt% of embodiment 3.
Present embodiment is undertaken by the mode of embodiment 3, exception be add in the reaction solution extra 1,4-diacetoxy-2-butine.For accomplishing this point, preparation l, (0.82g is Aldrich) in the stock solution of chlorobenzene (total liquor capacity 10ml) for 4-diacetoxy-2-butine.The stock solution of a l0ml, corresponding to 0.48mmol (0.082g), 1,4-diacetoxy-2-butine is added in the reaction solution, this reaction solution is by 0.098g[(RuCl
2(p-cymol)]
2(0.16mmol), 0.09g tricyclohexyl phosphine (0.32mmol), 7.4ml be suitable-1,4-DAB (47mmol), 30.0ml, 1,5-COD (244mmol) and 10ml chlorobenzene are formed, the N that is placed on
2In the 6-ounce glass Fisher-Porter bottle of atmosphere (15psia).Be reflected under 60 ℃ and carry out, initial hydrogen pressure is 17-18psig.React after 4 hours, GC the analysis showed that the conversion ratio of COD is 86%, and the conversion ratio of DAB is 46%, the conversion ratio that obtains in the embodiment 3 (do not have in the reaction solution extra 1,4-diacetoxy-2-butine).In addition, GC analyzes and also shows, after reaction 4 hours, and 1,4-diacetoxy-2-butine has transformed substantially fully.
The method of embodiment 3 is decoloured, washs and is separated reactor product.Obtain the thick product of 20.4 grams; Obtain 15.7 gram light brown oily liquid final products.The gpc analysis result of final products is as follows: M
n=1150, M
w=2140, M
w/ M
n=1.9 (THF solvents; The polybutadiene calibration).NMR analyzes (with top described identical) and shows that final products have 1,4-polybutadiene skeleton structure, and the ratio of suitable-anti-carbon-to-carbon double bond is 63: 37, chain end group ratio is 99.5+ mole % acetic acid esters type end group and 0.5 mole of % ethene end group.In addition, NMR analyzes and is further illustrated in the polybutadiene skeleton, and the carbon-to-carbon double bond less than 1% is by hydrogenation (with respect to pure insatiable hunger 1,4-butadiene skeleton structure).XRF analysis is measured, and ruthenium content is 86ppm.Details sees Table 1.
Embodiment 3 and 4 acetic acid esters are that terminal polybutadiene product can pass through heat or catalyzing hydrolysis or alcoholysis reaction, as alkali or acid-catalyzed hydrolysis, are converted into the polybutadiene of hydroxyl for end.
Embodiment 5
Present embodiment has been described the beneficial effect of chlorine catalyst activator in improving olefin metathesis reactions speed and reaction conversion ratio.
Present embodiment is undertaken by the method for embodiment 4, exception be to be reflected under the condition that does not have hydrogen to exist to carry out; But at N
2Atmosphere (15psia) is carried out.(another unique difference is with the 10ml among the 9ml chlorobenzene replacement embodiment 4).After reacting 4 hours (60 ℃), GC the analysis showed that only have 5%COD to transform, and does not detect the conversion of DAB.Details sees Table 1.
Embodiment 6-9 has described this antigravity system to low strain cyclic olefin, and is suitable, suitable-1, and 5-cyclo-octadiene (" 1,5-COD ") ring-opening metathesis polymerization (ROMP) produces 1, the effect of 4-polybutadiene:
Embodiment 6
This embodiment has described under the condition that the catalyst existence that contains ruthenium compound (A), phosphorus compound (B) and carbon-to-carbon triple bond (C) is arranged, and the cyclic olefin ring-opening metathesis polymerization prepares high molecular polymer, wherein A: B: the molar ratio of C is 1.0: 2.0: 3.0.
Used alkynes is non-end-group alkyne, is the 3-hexin.The stock solution of preparation 3-hexin (Aldrich) in chlorobenzene, its concentration is 0.039g 3-hexin/ml.By 0.098g[(RuCl
2(p-cymol)]
2(0.16mmol), 0.09g tricyclohexyl phosphine (0.32mmol), 1.0ml 3-hexin stock solution (0.48mmol 3-hexin), 30.0ml 1, the reaction solution that 5-COD (224mmol) and 10ml chlorobenzene are formed is put into N
2In the 6-ounce glass Fisher-Porter bottle of atmosphere (15psia).Sealing bottle, and being immersed in 60 ℃ the oil bath, all dissolves all solids at solution magnetic agitation a few minutes.Then, bottle hydrogen (H
2) be forced into 20psig.After the pressurization, bottle seal (is closed the valve of sources of hydrogen) under quiet Hydrogen Vapor Pressure, and solution stirs 4 hours (counting from pressurized with hydrogen) down at 60 ℃.These are after 4 hours, and the pressure in the bottle drops to 2psig.Compare during with the reaction beginning, it is very sticking that reaction solution becomes, and is difficult to stir.Bottle cool to room temperature and decompression, with FID GC analytical solution, the conversion ratio that calculates COD is 8.5wt%.
With heptane diluting reaction solution.Add BHT (50mg) and active carbon (5.5g, 100 order Darco G-60 brand).Agitating solution at room temperature is by removing by filter active carbon.Under vacuum (95 ℃, 0.1-1mmHg) remove from filtrate by rotary evaporation and desolvate and volatilizable thing, obtain the solid product of 1.4 gram dirty-green, thickness.The gpc analysis result is as follows: M
n=134,000, M
w=280,000, M
w/ M
n=2.1 (THF solvents; The polystyrene calibration).
13C and
1H NMR analyzes (as embodiment 3) and shows that product has 1,4-polybutadiene skeleton structure, and the ratio of suitable-anti-carbon-to-carbon double bond is 75: 25.Analyze demonstration, product is a macromolecule 1, and the 4-polybutadiene is 1, the hope product of the ring opening metathesis polymerization of 5-cyclo-octadiene (ROMP).Detailed results sees Table 1.Embodiment 7
Present embodiment is described component (C), the effect of carbon-to-carbon triple bond component in the antigravity system, and wherein alkynes is Terminal Acetylenes.1, the conversion ratio of 4-COD is brought up to 56wt% from the 8.5wt% of embodiment 6, the terminal alkynes of alkynes right and wrong in embodiment 6.
Used alkynes is Terminal Acetylenes, the 1-decine.This embodiment is undertaken by the method for embodiment 6, exception be to use 1-decine (0.48mmol, Aldrich) the 3-hexin in the surrogate response solution.The stock solution of preparation 1-decine (Aldrich) in chlorobenzene, its concentration is 0.066g1-decine/ml.In reaction solution, use the stock solution of 1.0ml.The bottle that fills reaction solution arrives 15pisa with pressurized with hydrogen.At 60 ℃ after following 45 minutes, viscosity significantly rises, to such an extent as to magnetic agitation stops.Reaction is after 4 hours down at 60 ℃, and solution is solid-state near the quality homogeneous, and pressure of the inside of a bottle drops to 12pisg.Then, bottle cool to room temperature, and decompression.The COD conversion ratio that GC calculates is 56wt%.
Under vacuum, from filtrate, remove and desolvate and volatilizable thing, obtain the solid product of 11.5 gram dirty-green, thickness by rotary evaporation.The gpc analysis result is as follows: M
n=112,000, M
w=280,000, M
w/ M
n=2.5 (THF solvents; The polystyrene calibration).
13C and
1H NMR analyzes (as embodiment 3) and shows that product has non-hydrogenation 1,4-polybutadiene skeleton structure, and the ratio of suitable anti-carbon-to-carbon double bond is 68: 32.Analyze demonstration, product is a macromolecule 1, and the 4-polybutadiene is 1, the hope product of the ring opening metathesis polymerization of 5-cyclo-octadiene (ROMP).Detailed results sees Table 1.Embodiment 8
Present embodiment is described in the antigravity system to replace the effect of non-Terminal Acetylenes as (C), and wherein alkynes is 1,4-diacetoxy butine.1, the conversion ratio of 4-COD drops to 43wt% from the 56wt% of embodiment 7.
Used alkynes is 1,4-diacetoxy butine.This embodiment is undertaken by the method for embodiment 6, exception be to use 1,4-diacetoxy butine (0.48mmol, Aldrich) the 3-hexin in the surrogate response solution.Preparation 1, the stock solution of 4-diacetoxy butine (Aldrich) in chlorobenzene, its concentration is 0.082g 1,4-diacetoxy butine/ml.In reaction solution, use the stock solution of 1.0ml.The bottle that fills reaction solution arrives 16pisg with pressurized with hydrogen.At 60 ℃ after following 30 minutes, viscosity significantly rises, to such an extent as to magnetic agitation stops.Reaction is after 3 hours down at 60 ℃, and solution is near the rubber-like solid of quality homogeneous, and pressure of the inside of a bottle drops to 14-15pisg.Then, bottle cool to room temperature, and decompression.The COD conversion ratio that GC calculates is 43wt%.Polymeric articles is not separated, and detailed results sees Table 1.Embodiment 9
Present embodiment alkynes.This embodiment has described and has been the needed alkynes of catalyzed alkene metathesis reaction (component that contains carbon-to-carbon triple bond) effectively.
This embodiment is undertaken by the method for embodiment 8, exception be not use alkynes (1,4-diacetoxy butine).Reaction is after 4 hours down at 60 ℃, and bottle is depressed and dropped to 2pisg, and the viscosity of reaction solution is not seen rising, then, and bottle cool to room temperature and decompression.The COD conversion ratio that GC calculates is 0%, and detailed results sees Table 1.
Table 1
| Embodiment | Catalytic component (mmol) | Reactant (mmol) | Reaction condition | Conversion ratio (wt%) | |||||
| ??A | ??B | ????C | ?1，4- DAB | ??1，5- ??COD | ??℃ | Hour | ??COD | ??DAB | |
| ????1 | 0.16 | 0.64 | ?0.035 | ??23 | ??122 | ??90 | ????3 | ????35 | ????17 |
| ????2 | 0.16 | 0.64 | ?0.035 | ??23 | ??122 | ??90 | ????3 | ????70 | ????34 |
| ????3 | 0.16 | 0.32 | ??0.07 | ??47 | ??244 | ??60 | ????4 | ????57 | ????27 |
| ????4 | 0.16 | 0.32 | ??0.48 | ??47 | ??244 | ??60 | ????4 | ????86 | ????46 |
| ????5 | 0.16 | 0.32 | ??0.48 | ??47 | ??244 | ??60 | ????4 | ????5 | ????0 |
| ????6 | 0.16 | 0.32 | ??0.48 | ??0 | ?244 | ?60 | ????4 | ????8.5 | ????- |
| ????7 | 0.16 | 0.32 | ??0.48 | ??0 | ?244 | ?60 | ????4 | ????56 | ????- |
| ????8 | 0.16 | 0.32 | ??0.48 | ??0 | ?244 | ?60 | ????3 | ????43 | ????- |
| ????9 | 0.16 | 0.32 | ????0 | ??0 | ?244 | ?60 | ????4 | ????0 | ????- |
Annotate: catalytic component is represented with the mmol of compound
A=ruthenium component
The B=phosphorus component
C=carbon-to-carbon triple bond component embodiment 10-13
Embodiment 10-13 is undertaken by the method for embodiment 1, exception be the amount of catalytic component B, promptly phosphorus compound is represented with the molal quantity of compound, progressively increases, with the effect of explanation as the increase of the phosphorus compound of antigravity system component.Other reaction condition is as follows.
By O.049g[(RuCl
2(p-cymol)]
2(0.08mmol, Chemicals, Inc.), 0.022-0.09g tricyclohexyl phosphine (0.080-0.32mmol), 0.082g 1,4-diacetoxy-2-butine (0.48mmol, Narchem Corp., purity 98%), 30.0ml 1,5-COD (224mmol, GC purity assay 99.9%) and the reaction solution formed of 10ml chlorobenzene, be put in the 6-ounce glass Fisher-Porter bottle of nitrogen atmosphere (15psia).The sealing bottle, and be immersed in 60 ℃ the oil bath, the solution magnetic agitation is all dissolved up to solid.Then, bottle hydrogen (H
2) be forced into 15-20psig.After the pressurization, bottle seal (is closed the valve of sources of hydrogen) under quiet Hydrogen Vapor Pressure, and after pressurized with hydrogen, solution stirred 4 hours down at 60 ℃.Then, bottle cool to room temperature and decompression.To determine conversion ratio, the details of embodiment 10-13 sees Table 2 with FID GC analytical solution.
Table 2
Annotate: A=[(RuCl
2(p-cymol)]
2
| Embodiment | Catalytic component | Reaction condition | Conversion ratio (wt%) | |||||||
| ????A ??g?????mmol | ????B ??g??mmol | ????C ??g??mmol | ????H 2??℃ (pisg) | DAB??COD | ||||||
| ????10 | ?0.049 | ?0.080 | ?0.022 | ?0.08 | 0.082 | ?0.48 | ??20 | ??60 | ??3 | ??9 |
| ????11 | ?0.049 | ?0.080 | ?0.045 | ?0.16 | 0.082 | ?0.48 | ????15 | ??60 | ??31 | ??71 |
| ????12 | ?0.049 | ?0.080 | ?0.067 | ?0.24 | 0.082 | ?0.48 | ?18-16 | ??60 | ??36 | ??76 |
| ????13 | ?0.049 | ?0.080 | ?0.090 | ?0.32 | 0.082 | ?0.48 | ?18-16 | ??60 | ??16 | ??46 |
The B=tricyclohexyl phosphine
C=1,4-diacetoxy-2-butine embodiment 14-15
Carry out embodiment 14 and 15 and improve hydrogen (H with explanation
2) effect of pressure.
Preparation is by [(RuCl
2(p-cymol)]
2, tricyclohexyl phosphine, 1,4-diacetoxy-2-butine and reactant are along 1,4-diacetoxy butylene (suitable-1,4-DAB) (7.4ml, 47mmol) and suitable, suitable-1,5-cyclo-octadiene (1,5-COD) (30.0ml 224mmol) and the reaction solution formed of 10ml chlorobenzene, is put in the 6-ounce glass Fisher-Porter bottle of nitrogen atmosphere (15psia).The sealing bottle, and be immersed in 60 ℃ the oil bath.The solution magnetic agitation is all dissolved up to solid.Then, bottle hydrogen (H
2) be forced into required necessary pressure.After the pressurization, bottle seal and is closed the valve of sources of hydrogen under quiet Hydrogen Vapor Pressure, and after pressurized with hydrogen, solution stirred 4 hours down at 60 ℃.Then, bottle cool to room temperature and decompression.With FID GC analytical solution to determine conversion ratio.
Embodiment 14 and 15 detailed results see Table 3.
Table 3
Annotate: A=[(RuCl
2(p-cymol)]
2
| Embodiment | Catalytic component | Reaction condition | Conversion ratio (wt%) | |||||||
| ????A ??g??mmol | ????B ??g??mmol | ????C ??g??mmol | ??H 2??℃ (pisg) | DAB?COD | ||||||
| ????14 | ?0.049 | 0.080 | ?0.056 | ?0.20 | 0.082 | ?0.48 | ????16 | ?60 | ?33 | ??76 |
| ????15 | ?0.049 | 0.080 | ?0.056 | ?0.20 | 0.082 | ?0.48 | ??50 | ?60 | ?37 | ??76 |
The B=tricyclohexyl phosphine
C=1,4-diacetoxy-2-butine embodiment 16-17
Carry out embodiment 16 and 17 effects with explanation raising catalytic component (C).
Make with the following method.Preparation is by [(RuCl
2(p-cymol)]
2(0.098g, 0.16mmol,), tricyclohexyl phosphine (0.09g, 0.32mmol), 1,4-diacetoxy-2-butine (Aldrich), suitable-1, (7.4ml 47mmol) and the reaction solution formed of 10ml chlorobenzene, is put in the 6-ounce glass Fisher-Porter bottle of nitrogen atmosphere (15psia) 4-DAB.The sealing bottle, and be immersed in 60 ℃ the oil bath, the solution magnetic agitation is all dissolved up to solid.Then, bottle hydrogen (H
2) be forced into 15-20psig.After the pressurization, bottle seal (is closed the valve of sources of hydrogen) under quiet Hydrogen Vapor Pressure, and solution stirs 4 hours (after pressurized with hydrogen) down at 60 ℃.Then, bottle cool to room temperature and decompression.With FID GC analytical solution to determine conversion ratio.Response data and reaction-ure conversion-age see Table 4.
Table 4
Embodiment 18-21
| Embodiment | Catalytic component | Reaction condition | Conversion ratio (w t%) | |||||||
| ????A ??g??mmol | ????B ??g??mmol | ????C ??g??mmol | ??H 2??℃ (pisg) | DAB?COD | ||||||
| ????16 | ?0.098 | ?0.016 | ?0.090 | 0.32 | ?0.082 | ?0.48 | ????15 | ?60 | ??46 | ??86 |
| ????17 | ?0.098 | ?0.016 | ?0.090 | 0.32 | 0.164 | ?0.96 | ????15 | ?60 | ??51 | ??92 |
Use following method to determine the effect of reaction temperature.Preparation is by [(RuCl
2(p-cymol)]
2(0.049g, 0.08mmol), tricyclohexyl phosphine (0.056g, 0.20mmol), 1,4-diacetoxy-2-butine (0.082g, 0.48mmol-Narchem Corp.), suitable-1,4-DAB (7.4ml, 47mmol), 1, (30.0ml 244mmol) and the reaction solution formed of 10ml chlorobenzene, is put in the 6-ounce glass Fisher-Porter bottle of nitrogen atmosphere (15psia) 5-COD.The sealing bottle, and be immersed in the oil bath of the temperature that requires, the solution magnetic agitation is all dissolved up to solid.Then, bottle hydrogen (H
2) be forced into 15-20psig.After the pressurization, bottle seal (is closed the valve of sources of hydrogen) under quiet Hydrogen Vapor Pressure, and solution (temperature of oil bath) under desired temperature stirs 4 hours (after pressurized with hydrogen).Then, bottle cool to room temperature and decompression.With FID GC analytical solution to determine conversion ratio.Response data and reaction-ure conversion-age see Table 5.
Table 5
Embodiment 22-25
| Embodiment | Catalytic component | Reaction condition | Conversion ratio (wt%) | |||||||
| ????A ??g??mmol | ????B ??g??mmol | ????C ??g??mmol | ??H 2??℃ (pisg) | DAB?COD | ||||||
| ????18 | ?0.049 | 0.080 | ?0.056 | ?0.20 | 0.082 | ?0.48 | ??15 | ??45 | ????5 | ????19 |
| ????19 | ?0.049 | ?0.080 | ?0.056 | ?0.20 | 0.082 | ?0.48 | ??16 | ??60 | ??33 | ??76 |
| ????20 | ?0.049 | ?0.080 | ?0.056 | ?0.20 | 0.082 | ?0.48 | ????15 | ????82 | ????51 | ????91 |
| ????21 | ?0.049 | ?0.080 | ?0.056 | ?0.20 | 0.082 | ?0.48 | ??19 | ??90 | ??41 | ??84 |
Following examples are undertaken by the method for embodiment 4, exception be to use different ruthenium component (catalytic component A).The ruthenium component all is [(RuCl
2(aromatic hydrocarbons)]
2Structure, but use the aromatic hydrocarbons that is different from the p-cymol.
[(RuCl
2(aromatic hydrocarbons)]
2Compound is by heating [(RuCl
2(p-cymol)]
2Suspension preparation in pure aromatic hydrocarbons.Embodiment 22
At N
2In, by making [(RuCl
2(p-cymol)]
2(3g, StremChemicals) backflow preparation in 2 hours [(RuCl in the suspension of 100ml 4-t-butyltoluene (Aldrich, 95%, b.p.190 ℃)
2(t-butyltoluene)]
2Cooling solution.By filtering and collecting solid with heptane wash.At N
2In, the solid of separating of a 2 grams refluxed 6 hours in the fresh 4-t-butyltoluene of 100ml.Cool off this solution, and by filtering to isolate solid.Use the heptane wash solid, and 70 ℃ of following vacuum drying.Obtain about 1.95 gram red crystals.This product
1H NMR analyzes and 91% pure [(RuCl
2(t-butyltoluene)]
2With about 9% unreacted [(RuCl
2(p-cymol)]
2The material unanimity.[(RuCl
2(t-butyltoluene)]
2 1H NMR data (CDCl
3Solvent): δ 1.40 (s, 9H), 2.11 (s, 3H), 5.3 (d, 2H), 5.8 (d, 2H).Embodiment 23
At N
2In, under 190 ℃, by making [(RuCl
2(p-cymol)]
2(3g) at 100ml 1, stir 8 hours preparation [(RuCl in the suspension of 3-diisopropyl benzene (Aldrich, 96%)
2(1, the 3-diisopropyl benzene)]
2Cooling solution.By solid collected by filtration, and use heptane wash, 70 ℃ of following vacuum drying.Obtain about 2.6 gram light brown solids.This product
1H NMR analyzes and the pure [(RuCl of 90+%
2(1, the 3-diisopropyl benzene)]
2Unreacted on a small quantity [(RuCl
2(p-cymol)]
2The material unanimity.[(RuCl
2(1, the 3-diisopropyl benzene)]
2 1H NMR data (CDCl
3Solvent): δ 1.27 (d, 12H), 2.95 (m, 2H), 5.23 (s, 1H), 5.4 (d, 2H), 5.7 (t, 1H).Embodiment 24
At N
2In, under 190 ℃, by making [(RuCl
2(p-cymol)]
2(3g) at 100ml 1, stir 8 hours preparation [(RuCl in the suspension of 4-diisopropyl benzene (Aldrich, 97%)
2(1, the 4-diisopropyl benzene)]
2Cooling solution.By solid collected by filtration, and use heptane wash, 70 ℃ of following vacuum drying.Obtain about 2.95 gram red solid.The solid that the redness of a 2.6 grams are come out is in 100ml is fresh 1, and the 4-diisopropyl benzene stirred 6 hours.After the cooling,, and use heptane wash, 70 ℃ of following vacuum drying by solid collected by filtration.Obtain rufous solid (about 2.95 grams).This product
1H NMR analyzes and the pure [(RuCl of 90+%
2(1, the 4-diisopropyl benzene)]
2Unreacted on a small quantity [(RuCl
2(p-cymol)]
2The material unanimity.[(RuCl
2(1, the 4-diisopropyl benzene)]
2 1H NMR data (CDCl
3Solvent): δ 1.28 (d, 12H), 2.9 (m, 2H), 5.45 (s, 4H).Embodiment 25
At N
2In, under 190 ℃, by making [(RuCl
2(p-cymol)]
2(3g) at 120ml 1,3, stir 8 hours preparation [(RuCl in the suspension of 5-triisopropylbenzene (Aldrich, 97%)
2(1,3, the 5-triisopropylbenzene)]
2With the solution cool to room temperature, be placed in the refrigerator 2-3 days then.By cold solid collected by filtration, and use heptane wash, 70 ℃ of following vacuum drying.Obtain rufous solid product (3.25 gram).This product
1H NMR analyzes and the pure [(RuCl of 90+%
2(1,3,5 triisopropylbenzene)]
2Unreacted on a small quantity [(RuCl
2(p-cymol)]
2The material unanimity.[(RuCl
2(1,3, the 5-triisopropylbenzene)]
2 1H NMR data (CDCl
3Solvent): δ 1.3 (d, 18H), 3.1 (m, 3H), 5.2 (s, 3H).
Make in the following method and carry out 1,5-COD and suitable-1, the olefin metathesis reactions of 4-DAB.
By [(RuCl
2(aromatic hydrocarbons)]
2(0.084mmol,), tricyclohexyl phosphine (0.028g, 0.10mmol), 1,4-diacetoxy-2-butine (0.041g, 0.24mmo1), suitable-1,4-DAB (7.4ml, 47mmol), 1, (30.0ml 244mmol) and the reaction solution formed of 10ml chlorobenzene, is put in the 6-ounce glass Fisher-Porter bottle of nitrogen atmosphere (15psia) 5-COD.Sealing bottle, and being immersed in 60 ℃ the oil bath, solution magnetic agitation a few minutes are with dissolved solid.Then, bottle hydrogen (H
2) be forced into 15-17psig.After the pressurization, bottle seal (is closed the valve of sources of hydrogen) under quiet Hydrogen Vapor Pressure, and solution stirs 4 hours (after pressurized with hydrogen) down at 60 ℃.Then, bottle cool to room temperature and decompression.With FID GC analytical solution to determine conversion ratio.Response data and reaction-ure conversion-age see the following form.
Table 6
Annotate: A=[(RuCl
2(aromatic hydrocarbons)]
2
| Embodiment | Aromatic hydrocarbons among the catalytic component A | Catalytic component | Reaction condition | Conversion ratio (wt%) | |||||||
| ????A | ????B | ????C | |||||||||
| ????g | ?mmol | ????g | mmol | ????g | mmol | ?H 2(psig) | ??℃ | DAB | ??COD | ||
| ??22 | The 4-t-butyltoluene | 0.026 | ?0.040 | ?0.028 | ?0.10 | ?0.041 | ?0.24 | ????15-17 | ?60 | ?32 | ????71 |
| ??23 | 1,3-dipropyl benzene | 0.027 | ?0.040 | ?0.028 | ?0.10 | ?0.041 | ?0.24 | ????15-17 | ?60 | ????7 | ????34 |
| ??24 | 1,4-dipropyl benzene | 0.027 | ?0.040 | ?0.028 | ?0.10 | ?0.041 | ?0.24 | ????15-17 | ?60 | ?22 | ????60 |
| ??25 | 1,3,5-tripropyl benzene | 0.030 | ?0.040 | ?0.028 | ?0.10 | ?0.041 | ?0.24 | ????15-17 | ?60 | ?28 | ????67 |
The B=tricyclohexyl phosphine
C=1,4-diacetoxy-2-butine
Therefore, according to described above, a part of the present invention relates to:
The antigravity system of a kind of cyclic olefin ring-opening metathesis polymerization, acyclic olefin transposition, acyclic dienes metathesis polymerization, ring-type or acyclic cross metathesis, closed loop transposition, unsaturated polymer transposition depolymerization and sense olefin metathesis, wherein said catalyst comprises ruthenium compound (A), phosphorus compound (B) and contains the compound (C) of carbon-to-carbon triple bond, the molar ratio A that represents with compound wherein: B: C is about 1.0: 0.01-100: in the scope of 0.01-100
Described ruthenium compound (A) is Ru (II), the Ru (III) that contains anion ligand (X) and optional aromatic hydrocarbons ligand and optional phosphorus ligand (as phosphine or phosphite ester), or Ru (IV) compound;
Condition is, if described compound ruthenium compound contains the phosphorus compound ligand, then described phosphorus compound (B) is chosen wantonly.
The above-mentioned available following general formula of ruthenium-based catalyst system (A) that contains ruthenium compound (A) is represented:
[RuX
n(PR '
3)
q(aromatic hydrocarbons)
p]
z
N=2 wherein, 3 or 4; Q=0,1,2,3 or 4; P=0 or 1; And z=1 or 2.
In above-mentioned ruthenium-based catalyst system, the A that represents with compound: B: the C mol ratio is about 1.0: 0.1-40: 0.1-40 (or about 1.0: 0.2-20: 0.2-20).
In the above-mentioned ruthenium-based catalyst system, wherein X is fatty anion ligand methyl, ethyl, propyl group, isopropyl, butyl or the hexyl of about 8 or about 6 carbon atoms of as many as of as many as about 20 or as many as about 12 or as many as (as contain), or X is the aromatics ligand phenyl or the benzyl of about 8 or about 6 carbon atoms of as many as of as many as about 20 or as many as about 12 or as many as (as contain), or X is halogen (F, Cl, Br and I), or hydroxide or alkoxide are (as OR
3, R wherein
3Be selected from alkyl, cycloalkyl, aryl and alkaryl (as containing as many as about 20 or as many as about 12 or as many as about 8 or about 6 carbon atoms of as many as)), or X is selected from nitrate anion, nitrite anions, acetate, trifluoroacetic acid root, acetylacetone,2,4-pentanedione acid group, hexafluoroacetylacetone acid group, or its mixture.
In the above-mentioned ruthenium-based catalyst system, R ' is selected from R and (OR), wherein R is identical or different, be independently selected from hydrogen, alkyl, cycloalkyl aryl and aralkyl (as containing as many as about 20 or as many as about 12 or as many as about 8 or about 6 carbon atoms of as many as), that replace or unsubstituted (wherein substituting group can be halogen (F, Cl, Br and I) or alkyl or aryl (as containing as many as about 20 or as many as about 12 or as many as about 8 or about 6 carbon atoms of as many as)) adds fruit R ' is OR, then R ' and R are not hydrogen, if R ' is R, then at least one R is not a hydrogen.
In the above-mentioned ruthenium-based catalyst system, in the described ruthenium compound (A) described aromatic hydrocarbons ligand be selected from unsubstituted aromatic hydrocarbons ligand (as containing as many as about 30 or as many as about 20 or about 15 carbon atoms of as many as); Or substituted arene ligand ((as containing as many as about 30 or as many as about 20 or about 15 carbon atoms of as many as), with its mixture, the substituting group of the described substituted arene ligand of the described aromatic hydrocarbon group in the wherein said ruthenium compound (A) can be selected from halogen (F, Cl, Br and I), alkyl and aryl (as containing as many as about 25 or as many as about 20 or as many as about 12 or about 8 carbon atoms of as many as), trialkylsilkl and diarye silyl (as containing as many as about 25 or as many as about 20 or as many as about 15 or about 8 carbon atoms of as many as), or its mixture.Wherein the aryl ligand can be selected from alkylbenzene, polyalkylbenzene, aryl benzene, polyaryl benzene, halogeno-benzene, haloalkyl benzene, halogenated aryl benzene, Fluhyzon, arylnaphthalene, many Fluhyzons, polyaryl naphthalene, naphthalene halide, haloalkyl naphthalene and halogenated aryl naphthalene.The aryl ligand can be benzene,toluene,xylene, cumene, cymol, P-cymol, durene, trimethyl silyl benzene, 1, two (trimethyl silyl) benzene of 4-, or naphthalene.
In the above-mentioned ruthenium-based catalyst system, described phosphorus compound (B) can be selected from general formula PR
3, P (OR)
3, PH
2R, PHRR
1, PRR
1R
2And P (OR) (OR
1) (OR
2) phosphine and phosphite ester.Wherein R, R
1And R
2Identical or phase not, be selected from replacement or unsubstituted alkyl, cycloalkyl, aryl and alkaryl (as containing as many as about 20 or as many as about 12 or as many as about 8 or about 6 carbon atoms of as many as), wherein substituting group can be halogen (F, Cl, Br and I), about 20 carbon atoms of as many as (preferred about 12 carbon atoms of as many as, further preferred about 8 carbon atoms of as many as, preferred especially about 6 carbon atoms of as many as) alkyl or aryl.Phosphorus compound (B) is phosphine compound preferably, further preferred C
3-C
8Trialkyl or tricyclic alkyl phosphine for example, are selected from tricyclohexyl phosphine, tri isopropyl phosphine and three cyclopenta phosphines.
In the above-mentioned ruthenium-based catalyst system, compound (C) be replace or unsubstituted alkynes (as containing as many as about 20 or as many as about 12 or as many as about 8 or about 6 carbon atoms of as many as), or be selected from Terminal Acetylenes, interior alkynes (internal alkyne), or have one or more aliphatic or aromatic functional group substituting group, halogen (F, Cl, Br and I), ester, hydroxyl, ketone, aldehyde, ether, carboxyl, acid amides, acid anhydride, nitrile, silicyl or amine functional group substituting group, or the alkynes of its mixture.Preferred acetylene (C
2H
2), propine, the 1-butine, the 2-butine, the 1-pentyne, valerylene, the 1-hexin, the 2-hexin, the 3-hexin, the 1-heptyne, the 1-octyne, the 1-decine, the 1-dodecyne, trimethyl silyl acetylene, phenylacetylene, dibenzenyl, 2-butine-1, the 4-glycol, 2-butine-1, the ester derivant of 4-glycol, as 1,4-acetoxyl group-2-butine, 2-butine-1,4-diol monoacetate, 2-butine-1, the 4-glycol diacetate, 2-butine-1,4-glycol mono-propionate, 2-butine-1,4-glycol dipropionate, 2-butine-1,4-glycol mono benzoate, 2-butine-1,4-glycol dibenzoate.
In the above-mentioned ruthenium-based catalyst system, hydrogen (H wherein
2) exist as the activator of antigravity system, wherein the dividing potential drop of hydrogen is about 1 * 10
-2MmHg-200 atmospheric pressure (approximately or 0.1mmHg-100 atmospheric pressure or about 20 atmospheric pressure of 1mmHg-).
In above-mentioned ruthenium catalyst system, described ruthenium compound (A) is selected from [(RuCl
2(p-cymol)]
2, [(RuCl
2(4-t-butyltoluene)]
2, [(RuCl
2(1, the 3-diisopropyl benzene)]
2, [(RuCl
2(1, the 4-diisopropyl benzene)]
2, [(RuCl
2(1,3, the 5-triisopropylbenzene)]
2, described phosphorus compound (B) is a tricyclohexyl phosphine, the described compound (C) that contains carbon-to-carbon triple bond is selected from 1,4-diacetoxy-2-butine, 3-hexin and 1-decine.
In the above-mentioned ruthenium-based catalyst system, described ruthenium compound (A) is selected from [RuX
2(aromatic hydrocarbons)]
2, RuX
2(aromatic hydrocarbons) (PRR
1R
2), RuX
2(aromatic hydrocarbons) (PHRR
1), RuX
2(aromatic hydrocarbons) (PH
2R), RuX
2(aromatic hydrocarbons) [P (OR) (OR
1) (OR
2), RuX
3, RuX
3-hydrate, RuX
2(PRR
1R
2)
3, RuX
2(PHRR
1)
3, RuX
2(PH
2R)
3, RuX
2[P (OR) (OR
1) (OR
2)]
3, RuX
2(PRR
1R
2)
4, RuX
2(PHRR
1)
4, RuX
2(PH
2R)
4, and RuX
2[P (OR) (OR
1) (OR
2)]
4Wherein P is a phosphorus, X is selected from aliphatic anion ligand, aromatics anion ligand, halogen (F, Cl, Br and I), hydroxyl, alkoxy radical nitrate anion, nitrite anions, acetate, trifluoroacetic acid root, acetylacetone,2,4-pentanedione acid group, hexafluoroacetylacetone acid group, or its mixture, wherein R, R
1, R
2Identical or different, be selected from the alkyl, cycloalkyl, aryl and the aralkyl that do not replace or replace, the aromatic hydrocarbons in the wherein said ruthenium compound (A) is selected from unsubstituted aromatics ligand, the aromatics ligand of replacement and its mixture.
A kind of under the condition that has antigravity system to exist, the olefin metathesis method of cyclic olefin ring-opening metathesis polymerization, acyclic olefin transposition, acyclic dienes metathesis polymerization, ring-type or acyclic cross metathesis, closed loop transposition, unsaturated polymer transposition depolymerization and sense olefin metathesis, described method comprise makes at least a alkene contact with above-described antigravity system.
In the said method, wherein hydrogen exists as catalyst activator, and its dividing potential drop is 1 * 10
-2About 200 atmospheric pressure of mmHg-(about or about 100 atmospheric pressure of 0.1mmHg-or about 20 atmospheric pressure of 1mmHg-).
In the said method, wherein this method under about 0 ℃-Yue 250 ℃ temperature (or about 0 ℃-Yue 200 ℃ or about 0 ℃-Yue 150 ℃) is carried out.
In the said method, wherein this method is about 1 * 10
-2Carry out under the pressure of mmHg-200 atmospheric pressure (about or 0.1mmHg-100 atmospheric pressure or about 1mmHg-20 atmospheric pressure).
In the said method, wherein said ruthenium compound (A) is selected from [(RuCl
2(p-cymol)]
2, [(RuCl
2(4-t-butyltoluene)]
2, [(RuCl
2(1, the 3-diisopropyl benzene)]
2, [(RuCl
2(1, the 4-diisopropyl benzene)]
2, [(RuCl
2(1,3, the 5-triisopropylbenzene)]
2, described phosphorus compound (B) is a tricyclohexyl phosphine, the described compound (C) that contains carbon-to-carbon triple bond is selected from 1,4-diacetoxy-2-butine, 3-hexin and l-decine.
In said method, in the wherein said antigravity system, the A that represents with compound: B: C is about 1: 0.01-100: in the scope of 0.01-100 (or about 1.0: in the scope of 0.1-40: 0.1-40 or about 1.0: in the scope of 0.2-20: 0.2-20).
Said method comprises makes suitable, suitable-1,5 cyclo-octadiene and suitable-1, it be 1 of end that acetic acid esters is produced in the reaction of 4-diacetoxy-2-butylene and described antigravity system, 4-polybutadiene or make suitable, suitable-1,5-cyclo-octadiene and the reaction of described antigravity system produce 1, the 4-polybutadiene.
Any product as described herein or method.
Antigravity system is used for the purposes of above-mentioned cyclic olefin ring-opening metathesis polymerization, acyclic olefin transposition, acyclic dienes metathesis polymerization, ring-type or acyclic cross metathesis, closed loop transposition, unsaturated polymer transposition depolymerization and sense olefin metathesis.
Above-mentioned antigravity system be used for the manufacture order functional polymer (by NMR spectrum (
13CNMR) measure, average functionality is 0.7) and telechelic two functional polymers (by NMR spectrum (
13C NMR) measure, average functionality is 1.7) purposes.
The antigravity system that can be used for olefin metathesis reactions comprises nail compound, phosphorus-containing compound and the product that contains the compound of carbon-to-carbon triple bond.In the antigravity system, phosphorus-containing compound is a phosphine, can be included in the described ruthenium compound.
For a person skilled in the art,, further change and improve and to become clearly, all be included in the appended claim according to the description of front.
Claims (10)
1. ruthenium base metathesis catalyst system, comprise ruthenium compound (A), phosphorus compound (B) and contain the compound (C) of carbon-to-carbon triple bond, wherein the molar ratio A that represents with compound: B: C is about 1.0: 0.01-100: in the scope of 0.01-100,
Wherein said ruthenium compound (A) is Ru (II), the Ru (III) that contains anion ligand (X) and optional aromatic hydrocarbons ligand and optional phosphorus compound ligand, or Ru (IV) compound;
Condition is if described ruthenium compound contains the phosphorus compound ligand, and then described phosphorus compound (B) is chosen wantonly.
2. the ruthenium-based catalyst system of claim 1, wherein said ruthenium compound (A) has following general formula:
[RuX
n(PR '
3)
q(aromatic hydrocarbons)
p]
z
N=2 wherein, 3 or 4; Q=0,1,2,3 or 4; P=0 or 1; And z=1 or 2.
3. the ruthenium-based catalyst system of claim 2, wherein said ruthenium compound (A) is selected from [RuX
2(aromatic hydrocarbons)]
2, RuX
2(aromatic hydrocarbons) (PRR
1R
2), RuX
2(aromatic hydrocarbons) (PHRR
1), RuX
2(aromatic hydrocarbons) (PH
2R), RuX
2(aromatic hydrocarbons) [P (OR) (OR
1) (OR
2), RuX
3, RuX
3-hydrate, RuX
2(PRR
1R
2)
3, RuX
2(PHRR
1)
3, RuX
2(PH
2R)
3, RuX
2[P (OR) (OR
1) (OR
2)]
3, RuX
2(PRR
1R
2)
4, RuX
2(PHRR
1)
4, RuX
2(PH
2R)
4, and RuX
2[P (OR) (OR
1) (OR
2)]
4, wherein P is a phosphorus.
4. the ruthenium-based catalyst system of claim 1, wherein X is aliphatic anion ligand or aromatics anion ligand.
5. the ruthenium-based catalyst system of claim 2, wherein R ' is selected from R and (OR), and wherein R is identical or different, is independently selected from hydrogen, alkyl, cycloalkyl aryl and aralkyl, can be that replace or unsubstituted; If R ' is OR, then R ' and R are not hydrogen, if R ' is R, then at least one R is not a hydrogen.
6. the ruthenium-based catalyst system of claim 1, the aromatic hydrocarbons ligand in the wherein said ruthenium compound (A) is selected from unsubstituted aromatics ligand, the aromatics ligand of replacement and its mixture.
7. the ruthenium-based catalyst system of claim 1, wherein said phosphorus compound (B) is selected from general formula PR
3, P (OR)
3, PH
2R, PHRR
1, PRR
1R
2And P (OR) (OR
1) (OR
2) phosphine and bi-ester of phosphite, wherein R, R
1And R
2Identical or phase not, be independently selected from replacement or unsubstituted alkyl, cycloalkyl, aryl and alkaryl.
8. the ruthenium-based catalyst system of claim 1, wherein hydrogen (H
2) exist as the activator of antigravity system, wherein the dividing potential drop of hydrogen is about 1 * 10
-2MmHg-200 atmospheric pressure.
9. olefin metathesis method in the presence of the antigravity system of cyclic olefin ring-opening metathesis polymerization, acyclic olefin transposition, acyclic dienes metathesis polymerization, ring-type or acyclic cross metathesis, closed loop transposition, unsaturated polymer transposition depolymerization and sense olefin metathesis, described method comprises makes at least a alkene contact with antigravity system, wherein said antigravity system comprises the ruthenium-based catalyst system of claim 1, and wherein said method is chosen wantonly 1 * 10
-2Carry out under mmHg-200 the atmospheric pressure.
10. the purposes of the catalyst of claim 1 on cyclic olefin ring-opening metathesis polymerization, acyclic olefin transposition, acyclic dienes metathesis polymerization, ring-type or acyclic cross metathesis, closed loop transposition, unsaturated polymer transposition depolymerization and sense olefin metathesis.
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|---|---|---|---|
| CN97190460A CN1189784A (en) | 1996-04-30 | 1997-04-25 | Ruthenium-based catalyst system for olefin metathesis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/016,554 | 1996-04-30 | ||
| US60/033,257 | 1996-12-06 | ||
| US08/842,251 | 1997-04-24 | ||
| CN97190460A CN1189784A (en) | 1996-04-30 | 1997-04-25 | Ruthenium-based catalyst system for olefin metathesis |
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|---|---|
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ID=5178757
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103180045A (en) * | 2010-09-08 | 2013-06-26 | 卑尔根技术交易股份公司 | Novel olefin metathesis catalysts |
| CN102407159B (en) * | 2001-12-20 | 2015-05-20 | Sasol技术股份有限公司 | Trimerisation And Oligomerisation Of Olefins Using A Chromium Based Catalyst |
| CN105199025A (en) * | 2015-08-28 | 2015-12-30 | 江南大学 | Ruthenium catalyst used for norbornene polymerization and preparation method thereof |
| CN108495856A (en) * | 2016-01-27 | 2018-09-04 | 巴斯夫欧洲公司 | The method for generating inorganic thin film |
-
1997
- 1997-04-25 CN CN97190460A patent/CN1189784A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407159B (en) * | 2001-12-20 | 2015-05-20 | Sasol技术股份有限公司 | Trimerisation And Oligomerisation Of Olefins Using A Chromium Based Catalyst |
| CN103180045A (en) * | 2010-09-08 | 2013-06-26 | 卑尔根技术交易股份公司 | Novel olefin metathesis catalysts |
| CN103180045B (en) * | 2010-09-08 | 2016-04-13 | 卑尔根技术交易股份公司 | New olefin metathesis catalyst |
| CN105199025A (en) * | 2015-08-28 | 2015-12-30 | 江南大学 | Ruthenium catalyst used for norbornene polymerization and preparation method thereof |
| CN108495856A (en) * | 2016-01-27 | 2018-09-04 | 巴斯夫欧洲公司 | The method for generating inorganic thin film |
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