CN105646749A - Beta-diiminosilicon bridged dimethylamino zirconium catalyst and preparation thereof - Google Patents
Beta-diiminosilicon bridged dimethylamino zirconium catalyst and preparation thereof Download PDFInfo
- Publication number
- CN105646749A CN105646749A CN201610011699.0A CN201610011699A CN105646749A CN 105646749 A CN105646749 A CN 105646749A CN 201610011699 A CN201610011699 A CN 201610011699A CN 105646749 A CN105646749 A CN 105646749A
- Authority
- CN
- China
- Prior art keywords
- dimethylamino
- beta
- catalyst
- lithium
- silicon bridge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CCCO[C@](C)C(CC)=CC(CN1CC1)=CC(*1(CC)CC1)=C Chemical compound CCCO[C@](C)C(CC)=CC(CN1CC1)=CC(*1(CC)CC1)=C 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/01—High molecular weight, e.g. >800,000 Da.
Abstract
The invention provides a beta-diiminosilicon bridged dimethylamino zirconium catalyst, relating to an ethylene polymerization IVB transition metal catalyst, particularly an iminosilicon bridged dimethylamino ligand zirconium complex catalyst with an N-C-C-C-N-Si-N framework. The preparation method comprises the following steps: in a nitrogen protective atmosphere, dehydrogenating kitimines by using diisopropylamido lithium (LDA) to obtain a ligand lithium salt, adding an equivalent mole of silanes to obtain an oily liquid, and carrying out secondary dehydrogenation to obtain a colorless allyl lithium ligand compound; dissolving the ligand compound in tetrahydrofuran, adding nitriles in an ice water bath, extracting with toluene to obtain beta-diiminosilicon bridged dimethylamino lithium salts; and finally, reacting the beta-diiminosilicon bridged dimethylamino lithium salts with early transition metal halides to obtain the beta-diiminosilicon bridged dimethylamino metal catalyst. The preparation method is simple, and has the advantages of accessible materials, low price and higher yield. When being used for ethylene polymerization, the catalyst has high catalytic activity, and obtains the ultrahigh-molecular-weight polyethylene.
Description
Technical field
The present invention relates to vinyl polymerization IVB transition-metal catalyst, there is N-C-C-C-N-Si-N in particular to oneThe imines silicon bridge amido zirconium complex catalyst of skeleton, more specifically says the catalysis of a kind of beta-diimine silicon bridge dimethylamino zirconiumAgent and its preparation method and application.
Background technology
Polyvinyl resin is the kind of output maximum in general synthetic resin, because of features such as its price are low, performance is good, in ChinaApply quite extensive, as film, injection-molded item, electric wire, hollow product etc. all occupy larger ratio in its consumption structureExample. Industrialized olefin polymerization catalysis has the catalyst such as Ziegler-Natta type catalyst, Phillips type catalyst and metallocene-type,These catalyst can reach the control to catalytic activity and polymer performance by the structure that regulates part. Wherein β-bis-AsiaThe report of amine metallic compound class catalyst has, but has raw materials complex process, and productive rate is low, and catalytic activity is low,The shortcomings such as fluoropolymer resin molecular weight is low, have limited the application of this type of beta-diimine metal compound catalyst.
Summary of the invention
The object of this invention is to provide a kind of beta-diimine silicon bridge dimethylamino Zr catalyst and preparation method thereof, and this is urgedThe application of agent in vinyl polymerization.
A kind of beta-diimine silicon bridge dimethylamino Zr catalyst provided by the invention, has the structural formula of following C:
Wherein:
R1、R2Be selected from independently of one another hydrogen, alkyl, aryl, alkaryl, aralkyl and the alkoxyl of 1-10 carbon atomIn one; R3、R4Be selected from independently of one another alkyl, aryl, alkaryl, aralkyl and the alkane of 1-10 carbon atomOne in oxygen base;
X is halogen, preferably chlorine or bromine.
The present invention also provides a kind of preparation method of beta-diimine silicon bridge dimethylamino Zr catalyst, comprises the steps:
(1) preparation of lithium salts: under the protection of nitrogen, under acetone bath, by kitimine compound and lithium diisopropyl amidoAccording to reaction with same mole, solvent is oxolane, reacts after 4-6 hour, after solution is warmed up to room temperature naturally, keeps stirringMix reaction 8-10 hour, obtain the tetrahydrofuran solution of lithium salts L1; Under the protection of nitrogen, under ice-water bath, by equimolarSilane compound slowly adds wherein, after solution is warmed up to room temperature naturally, keeps stirring reaction 10-12 hour, uses tolueneExtraction obtains the neutral compound L2 of oily; Then under the protection of nitrogen, under ice-water bath, use equimolar diisopropyl amidoLithium is lithiumation again, keeps stirring reaction 8-10 hour, and in oxolane, crystallization obtains colourless pi-allyl lithium ligand compound L3;Again ligand compound L3 is dissolved in oxolane, under ice-water bath, adds nitrile compounds, with toluene extraction, concentrated obtain β-Diimine silicon bridge dimethylamino lithium salt compound L4.
(2) preparation of catalyst: under the protection of nitrogen, under acetone bath, transition metal halide MX4Join β-In the tetrahydrofuran solution of diimine silicon bridge dimethylamino lithium L4, MX4With the mol ratio of L4 be 1 ﹕ 1-2, when solution natureAfter being warmed up to room temperature, keep stirring reaction 20-24 hour, vacuum is drained, and adds carrene, filters, and filtrate is concentratedObtain beta-diimine silicon bridge dimethylamino Zr catalyst C. Concrete synthetic route is as follows:
The application of beta-diimine silicon bridge dimethylamino Zr catalyst in olefinic polymerization. Catalyst in the experiment of vinyl polymerizationPolymerization activity reaches as high as: 1.45 × 106g·mol(Zr)-1·h-1, molecular weight of polyethylene can reach: 4.32 × 106g·mol-1。
Compared with prior art advantage of the present invention and effect: synthetic catalyst is raw materials used to be easy to get, cheap, preparationMethod is simple, and productive rate is higher; Catalyst has high catalytic activity for vinyl polymerization, can obtain having super high molecular weightPolyethylene.
Brief description of the drawings
Fig. 1 is the crystal structure figure of catalyst C;
In the crystal structure of Fig. 1, the octahedral structure that coordination structure is distortion.
Detailed description of the invention
The embodiment only providing for explanation below, these embodiment are not for limiting the scope of the invention.
Embodiment 1
(1) preparation of lithium salts
Under the protection of nitrogen, under acetone bath, lithium diisopropyl amido (0.21g, 2mmol) is joined to N-methyl-2,6-bis-In the tetrahydrofuran solution of cumene imines (0.44g, 2mmol), react after 3 hours, when solution is warmed up to room temperature naturallyAfter, keeping stirring reaction 8 hours, vacuum is drained, n-hexane washing, recrystallization obtains 2,6-diisopropyl-methylphenylamineThe oxolane complex L1 of base lithium salts. Under the protection of nitrogen, under ice-water bath, by silica-based dimethylamino dimethyl chloride(0.3ml, 2mmol) slowly adds in the tetrahydrofuran solution of L1, after solution is warmed up to room temperature naturally, keeps stirring anti-Answer 6 hours, obtain the N-(2-dimethylamino dimethyl silica-based-1-methyl)-2 of oily with toluene extraction, 6-diisopropyl benzeneAmine neutral compound L2. Then under the protection of nitrogen, under acetone bath, use lithium diisopropyl amido (0.21g, 2mmol) againInferior lithiumation L2, keeps stirring reaction 6 hours, and in oxolane, crystallization obtains colourless N-(2-dimethylamino dimethyl is silica-based-1-methyl) the oxolane ligand compound L3 of-2,6-DIPA base lithium; Again ligand compound L3 is dissolved in to fourIn hydrogen furans, under ice-water bath, add tertiary butyronitrile (0.3ml, 2mmol), after being naturally warmed up to room temperature, keep stirring reaction 10 littleTime, with toluene extraction, concentrated, recrystallization obtains beta-diimine silicon bridge dimethylamino lithium salt compound L4.
The productive rate of intermediate L1, L2, L3 and L4 and the data of sign thereof are as follows:
L1: colourless crystalline thing, productive rate 98%.1HNMR(300MHzC6D6):δ1.11(d,12H,CH(CH3)2),2.23(s,3H,CH3),2.80–2.84(m,2H,CH(CH3)2),4.04,4.42(d,2H,CH2),6.85–6.89(m,3H,Aryl).13CNMR(75MHzC6D6):δ23.34,24.57(CH(CH3)2),27.53(CH3),28.93(CH(CH3)2),86.55(CH2),126.12(p-Ar),130.29(m-Ar),136.12(ipso-CAr),141.77(ipso-CAr-N), 150.29 (N=C). elementary analysis reasonOpinion value: C, 80.69; H, 9.93; N, 6.27%. measured value: C, 80.81; H, 9.90; N, 6.18.
L2: light yellow oil, productive rate: 97%.1HNMR(300MHzCDCl3):δ0.01(d,6H,Si(CH3)2),1.31-1.43(d,12H,CH(CH3)2),2.23(s,3H,CH3),2.32-2.37(d,6H,N(CH3)2),2.99(m,2H,CH(CH3)2),4.05(s,H,NH),4.08(s,H,CH),6.89(s,2H,m-Ar),7.03(d,1H,p-Ar).
L3: colourless crystalline thing, productive rate: 98%.1HNMR(300MHzC6D6)δ0.05(d,6H,Si(CH3)2),0.67-0.71(m,12H,CH(CH3)2),0.76-0.83(q,12H,3THF),2.25(s,3H,CH3),2.33-2.36(d,6H,N(CH3)2),2.80(q,12H,3THF),3.01-3.05(m,2H,CH(CH3)2),4.06(d,1H,CH),6.68(d,1H,p-Ar),7.10-7.13(d,2H,m-Ar).13CNMR(75MHzC6D6)δ1.60(Si(CH3)2),23.85-24.58(CH3,iPr),26.03(CH2,THF),28.38-29.45(CH,iPr),31.56(CH3),40.86(N(CH3)2),68.43(o-CH2,THF),87.36(CH),121.34(p-Ar),123.51(m-Ar),136.35(ipso-CAr),142.14(ipso-CAr-N),152.90(N-C-CH3).C19H33LiN2Si elementary analysis theoretical value: C, 70.32; H, 10.25; N, 8.63%. measured value: C, 70.39; H, 10.21; N,8.60.
L4: colourless crystalline thing, productive rate: 95%.1HNMR(300MHzC6D6)δ0.14(d,6H,Si(CH3)2),0.67-0.71(m,9H,C(CH3)3),0.97-1.01(m,12H,CH(CH3)2),2.33(s,3H,CH3),2.35-2.39(d,6H,N(CH3)2),3.15-3.18(m,2H,CH(CH3)2),5.06(d,1H,CH),6.68(d,1H,p-Ar),7.10-7.13(d,2H,m-Ar).13CNMR(75MHzC6D6)δ1.53(Si(CH3)2),23.75-23.78(CH3,iPr),27.85-27.88(CH3,tBu),28.36-28.45(CH,iPr),31.50(CH3),40.76(N(CH3)2),50.96(CH,tBu),87.66(CH),122.34(p-Ar), 125.51(m-Ar),136.95(ipso-CAr),142.34(ipso-CAr-N),148.90(N-C-CH3),164.60(N-C-tBu).C48H84Li2N6Si2Elementary analysis theoretical value: C, 70.71; H, 10.39; N, 10.31%. measured value: C, 70.79; H, 10.32; N,10.30.
(2) preparation of catalyst C: Schlenk bottle is vacuumized to logical N2Replace after three times, add L4 (0.82g, 1mmol)With oxolane 25ml, add ZrCl at-78 DEG C4(0.46g, 2mmol) stirs lower recovery room temperature reaction 24 hours, and vacuum is taken outDry 50 milliliters of the carrene that add, filter, concentrated, n-hexane washing, and crystallization in carrene, obtains pale yellow crystals chemical combinationThing C0.80 gram, productive rate: 67%. Decomposition temperature: 152 155 DEG C of –. Elementary analysis theoretical value C24H42Cl3N3SiZr:C,48.18;H, 7.08; N, 7.02%. measured value: C, 48.16; H, 7.14; N, 6.98.1HNMR(300MHzCDCl3)δ0.19-0.22(d,6H,Si(CH3)2),0.70-0.73(m,9H,C(CH3)3),1.15-1.19(m,12H,CH(CH3)2),2.43(s,3H,CH3),2.45-2.49(d,6H,N(CH3)2),3.17(m,2H,CH(CH3)2),5.10(d,1H,CH),6.98(d,1H,p-Ar),7.16-7.19(d,2H,m-Ar).13CNMR(75MHzC6D6)δ14.53(Si(CH3)2),22.79-28.78(CH3,iPr),27.80-29.98(CH3,tBu),30.01-30.05(CH,iPr),31.60(CH3),40.86(N(CH3)2),51.46(CH,tBu),89.56(CH),124.24(p-Ar),127.41(m-Ar),131.95(ipso-CAr),147.34(ipso-CAr-N),149.90(N-C-CH3),165.60(N-C-tBu). crystal structure is shown in Fig. 1.
Embodiment 2
1. the preparation of catalyst C is with embodiment 1.
2. vinyl polymerization: 250 milliliters of polymerization bottles that magnetic stick is housed, 130 DEG C of continuous dryings 6 hours, are taken out while hotVacuum is also used N2Gas displacement 3 times. Add catalyst C (3.0mg, 5 μ mol), and then vacuumize and replace with ethene2 times. Inject a certain amount of toluene (26.6ml) with syringe, then add MAO (1.46mol/L, 3.4ml)Make Al/Zr=1000, at 50 DEG C, keep 1 atmospheric ethylene pressure, vigorous stirring 30 minutes. In reactant liquorAdd 5% ethanol solution hydrochloride neutralization, have a small amount of white solid to separate out. Filter final vacuum dry 3 hours. Obtain product0.036g, polymerization activity: 1.42 × 104g·mol(Zr)-1·h-1, the fusing point of polymer: 134.9 DEG C.
Embodiment 3
1. the preparation of catalyst C is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical agitation and thermocouple are housed is vacuumized and use nitrogen replacement3 times, then with ethene displacement 2 times. Be cooled to after 30 DEG C, add successively catalyst C's (3.0mg, 5 μ mol)Toluene solution and a certain amount of toluene, then add MAO (1.46mol/L, 3.4ml) to make Al/Zr=1000,After to add the cumulative volume of a certain amount of toluene be 100 milliliters. Immediately the pressure of ethene is increased to 10 atmospheric pressure, at 30 DEG CLower vigorous stirring 30 minutes. Reactant liquor is poured out, added 5% ethanol solution hydrochloride neutralization, adularescent solid is separated out.Filter final vacuum dry 3 hours. Obtain 1.29 grams of products, polymerization activity: 5.16 × 105g·mol(Zr)-1·h-1, polymerFusing point: 134.0 DEG C, molecular weight: 4.32 × 106g·mol-1, molecular weight distribution: 4.47.
Embodiment 4
1. the preparation of catalyst a1 is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical agitation and thermocouple are housed is vacuumized and use nitrogen replacement3 times, then with ethene displacement 2 times. Be cooled to after 50 DEG C, add successively catalyst C's (3.0mg, 5 μ mol)Toluene solution and a certain amount of toluene, then add MAO (1.46mol/L, 3.4ml) to make Al/Zr=1000,After to add the cumulative volume of a certain amount of toluene be 100 milliliters. Immediately the pressure of ethene is increased to 10 atmospheric pressure, at 50 DEG CLower vigorous stirring 30 minutes. Reactant liquor is poured out, added 5% ethanol solution hydrochloride neutralization, adularescent solid is separated out.Filter final vacuum dry 3 hours. Obtain 1.78 grams of products, polymerization activity: 7.12 × 105g·mol(Zr)-1·h-1, polymerFusing point: 133.9 DEG C.
Embodiment 5
1. the preparation of catalyst C is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical agitation and thermocouple are housed is vacuumized and use nitrogen replacement3 times, then with ethene displacement 2 times. Add successively the toluene solution of catalyst C (3.0mg, 5 μ mol) and a certain amount ofToluene, is warming up to 70 DEG C, finally adds a certain amount of MAO (1.46mol/L, 3.4ml) to make Al/Zr=1000,The cumulative volume of toluene is 100 milliliters. Immediately the pressure of ethene is increased to 10 atmospheric pressure, vigorous stirring 30 at 70 DEG CMinute, add 5% ethanol solution hydrochloride, there is a large amount of polymer to swim in container top after static. Filtration drying,Obtain white polymer 3.63g, polymerization activity: 1.45 × 106g·mol(Zr)-1·h-1, the fusing point of polymer: 133.1 DEG C,Molecular weight: 3.56 × 106g·mol-1, molecular weight distribution: 5.12.
Embodiment 6
1. the preparation of catalyst C is with embodiment 1.
2. vinyl polymerization: the stainless steel still of 250 milliliters that mechanical agitation and thermocouple are housed is vacuumized and use nitrogen replacement3 times, then with ethene displacement 2 times. Add successively the toluene solution of catalyst C (3.0mg, 5 μ mol) and a certain amount ofToluene, is warming up to 80 DEG C, finally adds a certain amount of MAO (1.46mol/L, 3.4ml) to make Al/Zr=1000,The cumulative volume of toluene is 100 milliliters. Immediately the pressure of ethene is increased to 10 atmospheric pressure, vigorous stirring 30 at 70 DEG CMinute, add 5% ethanol solution hydrochloride, there is a large amount of polymer to swim in container top after static. Filtration drying,Obtain white polymer 2.53g, polymerization activity: 1.01 × 106g·mol(Zr)-1·h-1, the fusing point of polymer: 132.8 DEG C.
Claims (5)
1. a beta-diimine silicon bridge dimethylamino Zr catalyst, is characterized in that, structural formula is as follows:
Wherein:
R1、R2Be selected from independently of one another hydrogen, alkyl, aryl, alkaryl, aralkyl and the alkoxyl of 1-10 carbon atomIn one; R3、R4Be selected from independently of one another alkyl, aryl, alkaryl, aralkyl and the alkane of 1-10 carbon atomOne in oxygen base;
X is halogen.
2. a kind of beta-diimine silicon bridge dimethylamino Zr catalyst as claimed in claim 1, is characterized in that, describedR1、R2Be selected from independently of one another hydrogen, methyl, ethyl, the one in isopropyl and methoxyl group.
3. a kind of beta-diimine silicon bridge dimethylamino Zr catalyst as claimed in claim 1 or 2, is characterized in that instituteThe halogen of stating is chlorine or bromine.
4. the preparation method of a kind of beta-diimine silicon bridge dimethylamino Zr catalyst as claimed in claim 1 or 2, its spyLevy and be, comprise the steps:
(1) preparation of lithium salts: under the protection of nitrogen, under acetone bath, by kitimine compound and lithium diisopropyl amidoAccording to reaction with same mole, solvent is oxolane, reacts after 4-6 hour, after solution is warmed up to room temperature naturally, keeps stirringMix reaction 8-10 hour, obtain the tetrahydrofuran solution of lithium salts; Under the protection of nitrogen, under ice-water bath, by equimolar silaneCompound slowly adds wherein, after solution is warmed up to room temperature naturally, keeps stirring reaction 10-12 hour, extracts with tolueneObtain the neutral compound of oily; Then under the protection of nitrogen, under ice-water bath, with equimolar lithium diisopropyl amido againLithiumation, keeps stirring reaction 8-10 hour, and in oxolane, crystallization obtains colourless pi-allyl lithium ligand compound; Again will joinBody compound is dissolved in oxolane, under ice-water bath, adds nitrile compounds, with toluene extraction, and the concentrated beta-diimine silicon bridge that obtainsDimethylamino lithium salts.
(2) preparation of catalyst: under the protection of nitrogen, under acetone bath, transition metal halide MX4Join β-In the tetrahydrofuran solution of diimine silicon bridge dimethylamino lithium, MX4With the mol ratio of beta-diimine silicon bridge dimethylamino lithium salts be1 ﹕ 1-2, after solution is warmed up to room temperature naturally, keeps stirring reaction 20-24 hour, and vacuum is drained, and adds carrene,Filter, by the concentrated filtrate beta-diimine silicon bridge dimethylamino Zr catalyst that obtains.
5. a kind of beta-diimine silicon bridge dimethylamino Zr catalyst as claimed in claim 1 or 2 answering in olefinic polymerizationWith.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610011699.0A CN105646749B (en) | 2016-01-08 | 2016-01-08 | Beta diimine silicon bridge dimethylamino Zr catalyst and its preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610011699.0A CN105646749B (en) | 2016-01-08 | 2016-01-08 | Beta diimine silicon bridge dimethylamino Zr catalyst and its preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105646749A true CN105646749A (en) | 2016-06-08 |
CN105646749B CN105646749B (en) | 2017-11-03 |
Family
ID=56484085
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610011699.0A Expired - Fee Related CN105646749B (en) | 2016-01-08 | 2016-01-08 | Beta diimine silicon bridge dimethylamino Zr catalyst and its preparation |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105646749B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030130448A1 (en) * | 2002-01-10 | 2003-07-10 | Jia-Chu Liu | Preparation of ultra-high-molecular-weight polyethylene |
US20050148744A1 (en) * | 2003-12-30 | 2005-07-07 | Univation Technologies, Llc | Polymerization process using a supported, treated catalyst system |
CN101786018A (en) * | 2010-02-09 | 2010-07-28 | 山西大学 | Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof |
CN101798360A (en) * | 2010-04-08 | 2010-08-11 | 山西大学 | Bridged diamidino group-IV metal catalyst and method for preparing same |
-
2016
- 2016-01-08 CN CN201610011699.0A patent/CN105646749B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030130448A1 (en) * | 2002-01-10 | 2003-07-10 | Jia-Chu Liu | Preparation of ultra-high-molecular-weight polyethylene |
US20050148744A1 (en) * | 2003-12-30 | 2005-07-07 | Univation Technologies, Llc | Polymerization process using a supported, treated catalyst system |
CN101786018A (en) * | 2010-02-09 | 2010-07-28 | 山西大学 | Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof |
CN101798360A (en) * | 2010-04-08 | 2010-08-11 | 山西大学 | Bridged diamidino group-IV metal catalyst and method for preparing same |
Non-Patent Citations (1)
Title |
---|
CHUNYAN WEN ET AL: "Tailoring Polyethylenes by Nickel Complexes Bearing Modified 1‑(2-Benzhydrylnaphthylimino)-2-phenyliminoacenaphthylene Derivatives", 《ORGANOMETALLICS》 * |
Also Published As
Publication number | Publication date |
---|---|
CN105646749B (en) | 2017-11-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Edwards et al. | Early transition metal-catalyzed C–H alkylation: hydroaminoalkylation for C sp3–C sp3 bond formation in the synthesis of selectively substituted amines | |
Zhou et al. | Synthesis, Structure, and Diverse Catalytic Activities of [Ethylenebis (indenyl)] lanthanide (III) Amides on N− H and C− H Addition to Carbodiimides and ϵ-Caprolactone Polymerization | |
Hultzsch et al. | New yttrium complexes bearing diamidoamine ligands as efficient and diastereoselective catalysts for the intramolecular hydroamination of alkenes and alkynes | |
US11052384B2 (en) | Chrome compound, catalyst system using same, and method for preparing ethylene oligomer | |
WO2006023296A2 (en) | Alkene polymerization using beta-ketoiminato metal complexes | |
Gribkov et al. | Kinetic resolution of chiral aminoalkenes via asymmetric hydroamination/cyclisation using binaphtholate yttrium complexes | |
CN107298727B (en) | A kind of preparation and application of double salicylaldehyde imines-anthracene bimetallic titanium catalyst | |
CN101786018B (en) | Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof | |
WO2009062171A1 (en) | Preparation of saturated imidazolinium salts and related compounds | |
JP4564010B2 (en) | Process for producing optically active aziridine compound and amine compound, and complex and intermediate used in the process | |
CN105646749A (en) | Beta-diiminosilicon bridged dimethylamino zirconium catalyst and preparation thereof | |
Ji et al. | Synthesis of Ti, Zr, and Hf complexes with a new tetra-azane ligand by one-pot HCl-elimination and their properties as catalysts for production of UHMWPE | |
CN101591360B (en) | Ionic liquid type monophosphine monoimidazolium salt nickel (II) complex and preparation and application thereof | |
CN102993226A (en) | Method for preparing phenyl dimethylchlorosilane | |
CN105237568A (en) | Preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine and bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride | |
CN101376663B (en) | 6-benzimidazole-pyridine-2- formiate amide metal complexe, preparation and use | |
CN104231003B (en) | Bridging indenes fluorenes zirconium, hafnium compound and preparation method and the application in oligomerization of propene | |
CN105646599B (en) | Pyrido cycloheptane imine nickel complex catalyst and preparation method and application | |
CN100556910C (en) | Bibridge binucleus cyclopentadienyl metal compound and its production and application | |
CN105482007B (en) | Bis diimines silicon bridge Zr catalyst and preparation method thereof | |
CN101575387B (en) | Olefin polymerization catalyst and application thereof | |
CN105754020B (en) | Aromatic amine zirconium complex catalyst and preparation method thereof | |
CN105884819B (en) | A kind of pentacoordinate imines titanium compound and its preparation method and application | |
Kiasat et al. | A Novel One‐Step Synthesis of Symmetrical Dialkyl Trithiocarbonates in the Presence of Phase‐Transfer Catalysis | |
CN106519088A (en) | Oxygen bridge dicaryon allyl silicon bridge amino zirconium catalyst and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171103 Termination date: 20210108 |