CN1222531A - Catalyst for polymerization of alpha-olefins containing substituted amino silane compounds - Google Patents
Catalyst for polymerization of alpha-olefins containing substituted amino silane compounds Download PDFInfo
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- CN1222531A CN1222531A CN 98125937 CN98125937A CN1222531A CN 1222531 A CN1222531 A CN 1222531A CN 98125937 CN98125937 CN 98125937 CN 98125937 A CN98125937 A CN 98125937A CN 1222531 A CN1222531 A CN 1222531A
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Abstract
An aminosilane of the formula: where R1 is a linear or branched C1-22 alkyl or C3-22 cycloalkyl, which may be substituted with at least one halogen atom; R2 is a bis(linear or branched C1-22 alkyl or C3-22 cycloalkyl)amino, a substituted piperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl, 1,2,3,4-tetrahydroquinolinyl or 1,2,3,4-tetrahydroisoquinolinyl, with the substituent selected from the group consisting of C1-8 alkyl, pheny. C1-8 linear or branched alkylsubstituted phenyl and trimethylsilyl, with the proviso that when the substituent is C1-8 alkyl, there must be at least two such substituent groups present and R1 must contain halogen; and R3 is a linear or branched C1-8 alkyl or C3-8 cycloalkyl. The aminosilane may be reacted with an aluminum-alkyl compound and a solid component comprising a titanium compound having at least one titanium-halogen bond and an electron donor, both supported on an activated anhydrous magnesium dihalide, to form a catalyst for polymerization of olefins.
Description
The present invention relates to ziegler-natta catalyst systems, this system uses the amino silane electron donor that replaces as the promotor component.The olefin polymer of producing with this catalyst system has required high degree of isotacticity and high polydispersity index simultaneously.
The degree of isotacticity of polymkeric substance is the important factor when determining whether polymkeric substance is fit to a certain specific end use.Degree of isotacticity is normally measured like this: the weight percent of soluble polymer (XSRT) in the dimethylbenzene under the mensuration room temperature deducts this per-cent then from 100%.High degree of isotacticity greater than 90 is preferred, is most preferred greater than 95.
Polydispersity index (P.I.) is the observed value of molecular weight distribution.Wide molecular weight ranges distribution (＞4.0 high P.I.) can provide better melt strength, and this is favourable in the operation of thermoforming, formation film and fiber.4.0 high PI represented wide molecular weight distribution.Preferably, PI is 5.0 or higher greater than 4.5 best.
Organic silane compound has been used to catalyst system, (1) they in solid catalytic ingredient (comprising the halogen-containing Ti compound that loads on the anhydrous active magnesium dihalide), be used as electron donor and (2) they with the promotor component that contains organometallic compound as electron donor.Usually, they are to have Si-OR, Si-OCOR or Si-NR
2The organic silane compound of key, wherein R is alkyl, alkenyl, aryl, aralkyl or the cycloalkyl of 1-20 carbon atom, and Si is as central atom.This compounds is disclosed in U.S. Patent No. 4,180, and 636,4,242,479,4,347,160,4,382,019,4,435,550,4,442,276,4,465,782,4,473,660; 4,530,912 and 4,560,671, they are used as the electron donor in the solid catalytic ingredient in these patents; Also be disclosed in U.S. Patent No. 4,472,524,4,522,930,4,560,671,4,581,342,4,657,882 and european patent application 45976 and 45977, they are used as electron donor with promotor in these documents.
U.S. Patent No. 5,102,892 disclose replace and the silane that also contain piperidyl (piperidinyl) or pyrrolidyl (pyrrolidinyl) ring of trifluoro propyl, for example 3,3,3-trifluoro propyl (pyrrolidyl) dimethoxy silane and 3,3,3-trifluoro propyl (4-methyl piperidine base) dimethoxy silane.Even nearest European patent publication No.658,577 also talk about, with use have conventional electrical donor (as phenyl triethoxysilane, dicyclopentyl dimethoxyl silane and dimethoxydiphenylsilane) polymerization catalyst and the fiber of alfon compare, with with trifluoro propyl (alkyl) dimethoxy polymerizable silane alfon be the fiber that raw material makes, have lower bonding (bonding) temperature and wideer sticking temperature scope.
An object of the present invention is to provide new aminosilane, it can be used as the electron donor in the olefin polymerization catalyst system.Another object of the present invention provides a kind of catalyst system of improvement, and it can be produced has the required high degree of isotacticity and the olefin polymer of high polydispersity index simultaneously.
In one aspect, the present invention relates to a kind of amino silane compounds of following formula:
Wherein, R
1Be the straight or branched C that can be replaced by at least one halogen atom
1-22Alkyl or C
3-22Cycloalkyl;
R
2Be two (straight or branched C
1-22Alkyl or C
3-22Cycloalkyl) piperidyl, the pyrrolidyl of replacement, the decahydroquinolyl (decahydroquinolinyl), 1,2,3 of amino, replacement, 4-tetrahydric quinoline group or 1,2,3, the 4-tetrahydro isoquinolyl, substituting group wherein is selected from down group: straight or branched C
1-8Alkyl, phenyl, straight or branched C
1-8Alkyl-substituted phenyl or trimethyl silyl, condition be when substituting group be C
1-8During alkyl, must there be 2 such substituting groups and R at least
1Must contain halogen atom; With
R
3Be the C of straight or branched
1-8Alkyl or C
3-8Cycloalkyl.
On the other hand, the present invention relates to a kind of catalyzer that is used for olefin polymerization, this catalyzer comprises the reaction product of following material:
(A) alkylaluminium cpd;
(B) above-mentioned amino silane compounds; With
(C) solid constituent, this component comprise titanium compound and the electron donor with at least one titanium-halogen key, on the both loads on active, the anhydrous magnesium dihalide.
As mentioned above, amino silane compounds of the present invention has following formula:
Wherein, R
1Be the straight or branched C that can be replaced by at least one halogen atom
1-22Alkyl or C
3-22Cycloalkyl;
R
2Be two (straight or branched C
1-22Alkyl or C
3-22Cycloalkyl) piperidyl, the pyrrolidyl of replacement, the decahydroquinolyl (decahydroquinolinyl), 1,2,3 of amino, replacement, 4-tetrahydric quinoline group or 1,2,3, the 4-tetrahydro isoquinolyl, substituting group wherein is selected from down group: straight or branched C
1-8Alkyl, phenyl, straight or branched C
1-8Alkyl-substituted phenyl or trimethyl silyl, condition be when substituting group be C
1-8During alkyl, must there be 2 such substituting groups and R at least
1Must contain halogen atom; With
R
3Be the C of straight or branched
1-8Alkyl or C
3-8Cycloalkyl.
Preferably, R
1Be 3,3,3-trifluoro propyl, and R
3Be methyl or ethyl.Representative compounds within preferred definition comprises:
3,3,3-trifluoro propyl (2-trimethyl silyl piperidyl) dimethoxy silane;
3,3,3-trifluoro propyl (2-trimethyl silyl pyrrolidyl) dimethoxy silane;
3,3,3-trifluoro propyl (2-(3-aminomethyl phenyl) piperidyl) dimethoxy silane;
3,3,3-trifluoro propyl (2 (3-aminomethyl phenyl) pyrrolidyl) dimethoxy silane;
3,3,3-trifluoro propyl (1,2,3, the 4-tetrahydric quinoline group) dimethoxy silane;
3,3,3-trifluoro propyl (1,2,3, the 4-tetrahydro isoquinolyl) dimethoxy silane;
3,3,3-trifluoro propyl (decahydroquinolyl) dimethoxy silane;
3,3,3-trifluoro propyl (two (2-ethylhexyl) amino) dimethoxy silane; With
3,3,3-trifluoro propyl (suitable-the lupetidine base) dimethoxy silane.
Aminosilane can be prepared with the rapid route of synthesis of multistep.First step is C
1-22The negatively charged ion of alkane or halogenated alkane, with the silane that can obtain by market (as tetraalkyl original silica ester (SiOR
4) or tetrachloro silicane) between reaction.When using tetrachloro silicane, form (alkyl) trichlorosilane or (haloalkyl) trichlorosilane.By handling, can be converted into corresponding (alkyl) trialkoxy silane or (haloalkyl) trialkoxy silane with suitable alkoxide (as methylate or ethylate).When using tetraalkyl original silica ester (tretraalkylorthosilicate), can directly make (alkyl) trialkoxy silane or (haloalkyl) trialkoxy silane.
Final step is the secondary amine of (alkyl) trialkoxy silane or (haloalkyl) trialkoxy silane and replacement or the substitution reaction between the cyclammonium.By handling, can produce amine-negatively charged ion with n-Butyl Lithium or isopropyl-magnesium chloride.Allow this negatively charged ion and (alkyl) trialkoxy silane or (haloalkyl) trialkoxy silane react then, thereby generate aminosilane.
When some amine of preparation, need use blocking group.Suitable blocking group is t-butyl carbamate (" BOC "), and it can be used for preparing 2-trimethyl silyl piperidines, 2-trimethyl silyl tetramethyleneimine, 2-(3-aminomethyl phenyl) piperidines and 2-(3-aminomethyl phenyl) tetramethyleneimine.By producing negatively charged ion from piperidines or tetramethyleneimine, can connect the BOC group with the sodium hydride in the tetrahydrofuran (THF).This solution is cooled to 5 ℃, and adds excessive slightly hydrogen-carbonate di-t-butyl ester (di-tert-butyldicarbonate).After 2 hours, solution is poured in the saturated sodium bicarbonate into layering.The organic layer dried over mgso is removed by rotary evaporation and to be desolvated.Underpressure distillation obtains piperidyl-N-tertiary butyl carbamate (bp95 ℃, 3mmHg, 89% productive rate) or pyrrolidyl-N-tertiary butyl carbamate (bp69 ℃, 1mmHg, 95% productive rate).
Aminosilane of the present invention can react with alkylaluminium cpd (A) and solid constituent (C), be applicable to the catalyzer of olefinic polymerization with formation, wherein solid constituent (C) comprises titanium compound and the electron donor with at least one titanium-halogen key, on the both loads on active, the anhydrous magnesium dihalide.
The component (A) (this component be not halogen atom) that is used to form alkylaluminium cpd comprising: trialkylaluminium such as triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium; Dialkyl aluminum hydride such as diethyl aluminium hydride; And contain 2 or a plurality of aluminium atom and the aluminium atom compound continuous mutually by oxygen, nitrogen or sulfur heteroatom, for example: (C
2H
5)
2Al-O-Al (C
2H
5)
2 
With
Preferably, alkylaluminium cpd is a triethyl aluminum.
In solid constituent (C), the suitable example with titanium compound of at least one Ti-halogen key is a titanium tetrahalide, especially TiCl
4Yet, also can use alkoxy halide.
The electron donor compound that is adopted in component (C) comprises: alkyl ester, aryl ester and the cycloalkyl ester of aromatic acid (especially phenylformic acid or phthalic acid), and their derivative.Object lesson comprises: ethyl benzoate, the positive butyl ester of phenylformic acid, methyl p toluate (methyl p-toluate), diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate and dioctyl phthalate (DOP).Except above-mentioned ester, also alkyl or alkyl aryl ether, ketone, monoamine or polyamine, aldehyde and phosphorus compound (for example phosphine and phosphamide) can be used as electron donor.
The active anhydrous magnesium dihalide that constitutes component (C) carrier is such magnesium dihalide, and it shows the strongest diffracted ray (this strongest diffracted ray appears in the powder power spectrum of corresponding dihalide that surface-area is 1 meters squared per gram) broadening at least 30% in the powder X-ray ray energy spectrum of component (C); Or such magnesium dihalide, this strongest diffracted ray is replaced by haloing in its powder X-ray ray energy spectrum, the intensity peak of this haloing with respect to this spacing of strong diffracted ray move; And/or be the magnesium dihalide of surface-area greater than 3 meters squared per gram.
The measurement of magnesium dihalide surface-area is to use ebullient TiCl
4Handle after 2 hours, component (C) is carried out.The value that records is considered to the surface-area of magnesium dihalide.
Magnesium dihalide can be activated in advance, can be by in-situ activation in the titanizing process, can form in position and then activation magnesium compound (when handling with suitable halogen-containing transistion metal compound, this magnesium compound can form magnesium dihalide), perhaps use magnesium dihalide C
1-3The alkanol adducts (wherein magnesium chloride is 1 with the mol ratio of alcohol: 1-1: 3, and MgCl for example
23ROH) form.
The very active form of magnesium dihalide is that those are in the powder X-ray ray energy spectrum; at surface-area is that the strongest diffracted ray generation relative intensity descends and broadens and forms the magnesium dihalide of haloing in the corresponding halid power spectrum of 1 meters squared per gram; or those the strongest diffracted rays are by the magnesium dihalide that haloing replaced, wherein the intensity peak of this haloing with respect to this spacing of strong diffracted ray move.Usually, the surface-area of above-mentioned form magnesium dihalide especially comprises the 100-300 meters squared per gram greater than the 30-40 meters squared per gram.
Activity form can also be by thermal treatment component (C) in inert hydrocarbon solvent from the formation of deriving of above-mentioned form, and in X-ray energy spectrum, demonstrate the kind that the obvious diffraction line replaces haloing.With respect to surface-area is the diffracted ray of the corresponding magnesium dihalide of 1 meters squared per gram, and the significantly the strongest diffracted ray of these forms under any circumstance all demonstrates and broadens at least 30%.
Preferred magnesium dihalide is MgCl
2And MgBr
2, that best is MgCl
2Halid water-content is usually less than 1 weight %.
" load on titanium halide or titanium alkoxy halide and electron donor on the active magnesium dihalide ", mean above-mentioned component by chemically or physical method be fixed on the carrier, and, when handling its 2 hours, the 2-ethylene dichloride can not be extracted from component (C) with ebullient 1.
The available various different methods of component (C) are prepared.A kind of method is: magnesium dihalide and electron donor compound are ground together, after under standard conditions, extracting with triethyl aluminum, the surface-area of product is greater than 20 meters squared per gram (as top described to the magnesium dihalide power spectrum), subsequently with grinding product and titanium compound reaction.
The additive method of preparation solid constituent (C) is disclosed in U.S. Patent No. 4,220, and 554,4,294,721,4,315,835 and 4,439,540, these methods are incorporated herein by reference.
In all aforesaid methods, component (C) also has the above-mentioned magnesium dihalide that is in activity form.
Other cause forming active magnesium dihalide, or cause forming the method for titaniferous magnesium dihalide carrier component (wherein dihalide is an activity form), can be based on following reaction:
(ⅰ) Grignard reagent or MgR
2Compound (R is an alkyl) or this MgR
2The title complex that compound and trialkylaluminium form is with AlX3 or AlR
mX
n(X is a halogen atom to compound, and R is an alkyl, m+n=3), SiCl
4Or HSiCl
3Deng the reaction between the halogenating agent;
(ⅱ) Grignard compound and silanol or polysiloxane, water reaction, perhaps with the alcohol reaction, and then with halogenating agent or TiCl
4Reaction;
(ⅲ) reaction of magnesium and pure and mild haloid acid (halogen halide acid), the perhaps reaction of magnesium and alkyl halogen and alcohol;
(ⅳ) MgO and Cl
2Or AlCl
3Reaction;
(ⅴ) MgX2nH
2O (X=halogen, n are 1-3) and halogenating agent or TiCl
4Reaction; Or
(ⅵ) reaction of monoalkoxy magnesium or dialkoxy magnesium or magnesium carboxylates and halogenating agent.
In component (C), the mol ratio of magnesium dihalide and load halogenated titanium compound thereon is between the 1-500, and this halogenated titanium compound and the mol ratio that loads on the electron donor on the magnesium dihalide are between the 0.1-50.
Catalyzer, i.e. component (A), (B) and (C), the mode that can separate almost joins in the polymerization reactor simultaneously, no matter and monomer whether already in reactor; Perhaps added successively, if monomer is joined in the reactor after a while.Preferably, be pre-mixing component (A) and (B), before polyreaction, allow this premixture and component (C) at room temperature contact 3 minutes to about 10 minutes then.
Olefinic monomer can catalyzer is added to polymerization reactor before, add afterwards or simultaneously.Be preferably after adding catalyzer and add monomer.
Can add hydrogen on demand, reduce the molecular weight of polymkeric substance as chain-transfer agent.Use an amount of hydrogen and suitably select amino silane compounds, can realize greater than/10 minutes melt flow rate (MFR) of 1500 grams.Referring to the following examples IX.
Polyreaction can be carried out with slurry process, liquid phase method or vapor phase process, perhaps uses the liquid and gas method with different combination of reactors, and all these methods can be carried out in batches or continuously.
Polyreaction is carried out under 40-90 ℃ and normal atmosphere or higher pressure usually.
Catalyzer can contact (prepolymerization) in advance with the small amounts of olefins monomer, make catalyzer keep suspended state in varsol, then 60 ℃ or more under the low temperature the enough time of polymerization a certain amount of to produce, be catalyst weight 0.5-3 polymkeric substance doubly.
This prepolymerization reaction also can be carried out in liquid state or gaseous monomer, can produce quantity in this case and be the polymkeric substance within 1000 times of the catalyst weights.
The suitable alpha-olefin of available the inventive method polymeric comprises formula CH
2The alkene of=CHR, R is H or C in the formula
1-10 straight or branched alkyl are as ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene and 1-octene.
The following example is used to set forth the present invention, and is not used in the qualification scope of the invention.
Unless otherwise indicated, all umbers and per-cent in this application all is by weight.
Embodiment
The preparation electron donor compound
Universal program:
The purity chromatographically or the spectrophotometric analysis of all reagent are confirmed.Suitable, reagent was purified before using.All non-aqueous reactions are in drying nitrogen or argon atmosphere, carry out with the glassware of heat drying under the vacuum.Solution to air and moisture-sensitive shifts by syringe or intubate.Boiling point and fusing point are revised.
NMR spectrum is with Varian Unity 300 spectrometers, writes down under 300MHz, and carries out reference at inner and tetramethylsilane or residual proton impurity.For
1The following record that carries out of the data of H: chemical shift, (, ppm), (s-is unimodal for multiplicity; D-is bimodal; The t-triplet; The q-quartet; The qn-quintet; The m-multiplet), integration.(δ ppm) carries out record to the datumization displacement study of 13C NMR.Infrared spectra is to use the KBr plate, on the mid-IR spectrometer of BioRad FT430 series, measures, and with absorption frequency (v, cm
-1) carry out record.
It is to carry out with Hewlett Packard 6890 type chromatographic instruments that GC analyzes, and adopts the flame ionization detector (" FID ") that is coupled to HP6890 type totalizing instrument.In standard analysis, with syringe (50: 1 the splitting ratio of 250 ℃ of 1.0 microlitres injections; The 10psi column head pressure, the shunting of 106 ml/min; The total flux of 111 ml/min).With helium as by (the carrier gas of 30m * 0.32mm * 0.3m) of Alltech Heliflex AT-1 post.Keep 50 ℃ of starting temperatures, 2 minutes, increase to 300 ℃ of outlet temperatures with 10 ℃/minute then.Fid detector is maintained at 300 ℃ of (40 ml/min H
2400 ml/min air; Use the constant arbitrary way of 30 ml/min He).
Use 2 kinds of GC/MS systems.A kind of system selects instrument (massselective, ＂ MSD ＂) bonded Hewlett Packard 5890 type GC with Hewlett Packard 5970 type matter.In standard analysis, 2.0 microlitre samples are injected the injection orifice of 290 ℃ nothing shunting.Helium is used as the carrier gas of passing through HP-1 (Hewlett Packard, 25m * 0.33mm * 0.2 μ m).Kept 75 ℃ of starting temperatures 4 minutes.With 10 ℃/minute speed post is heated up.The acquisition of MSD is to use 10-800 AMU.Spectrogram carries out record with m/z (relative abundance).
Second kind of GC/MS system selects detector bonded HewlettPackard 6890 type GC with Hewlett Packard 5973 type matter.In standard analysis, 1.0 microlitre samples are injected the injection orifice of shunting/nothing shunting of 290 ℃.Helium is used as the carrier gas of passing through HP-5 (Hewlett Packard, 30m * 0.25mm * 0.25 μ m).Starting temperature is 50 ℃ and kept 4 minutes.With 10 ℃/minute speed post is heated up.Quality obtains (mass acquisition) and uses 10-800 AMU.Spectrogram carries out record with m/z (relative abundance).
The embodiment I
3,3,3-trifluoro propyl (2-trimethyl silyl piperidyl) dimethoxy silane
2-trimethyl silyl piperidyl-N-tertiary butyl carbamate-(25.0 restrain to add piperidyl-N-tertiary butyl carbamate in 1000 ml flasks, 135mmol), Tetramethyl Ethylene Diamine (" TMEDA ", 44 milliliters, 290mmol) and anhydrous ether (300 milliliters).Material in the bottle is cooled to-78 ℃.In 25 minutes, and the adding s-butyl lithium (cyclohexane solution of 125 milliliters of 1.3M, 162mmol).Material 3.5 hours and keep temperature of reaction and be-78 ℃ in the blender jar.(" TMS-Cl ", 165mmol), allows a bottle interior material be warming up to room temperature then and stirred 18 hours by 21.0 milliliters to add the chloro trimethyl silane in 15 minutes.With solution pour into dilute hydrochloric acid (400 milliliters, 0.2N) in.Separate each phase, with 0.2N HCl (3 * 100 milliliters) washing organic layer, dry then (MgSO
4).Except that desolvating, obtain 53.3 gram 2-trimethyl silyl piperidyl-N-tertiary butyl carbamate: C by rotary evaporation
13H
27NO
2Si (molecular weight=257.44); MS:m/z (relative abundance) 200 (18.2), 186 (40.2), and 156 (47.7), 128 (26.9), 84 (45.5), 73 (100), 57 (87.3).
2-trimethyl silyl piperidines-in 1000 ml flasks, add 600 milliliters of ethyl acetate, and be cooled to 5 ℃.Anhydrous hydrogen chloride (＞99%) is frothed by ethyl acetate 15 minutes.Remove ice bath, (107 restrain, 416mmol) to add 2-trimethyl silyl piperidyl-N-tertiary butyl carbamate.Stirred solution 18 hours.Product is extracted (3 * 200 milliliters) in the entry, separate each layer, use the water after ether (200 milliliters) washing merges then.With 45% (weight/volume) potassium hydroxide the aqueous solution is transferred to pH14, use ether (3 * 150 milliliters) to extract then.The organic moiety dried over mgso that merges, and rotary evaporation is except that desolvating.(29 ℃ of bp 0.5mmHg) obtain 2-trimethyl silyl piperidines (it is 97.4% that 26% productive rate, GC are measured purity for 17.0 grams, 108mmol) in underpressure distillation; C
8H
19NSi (molecular weight=157.33);
1H NMR:(CDCl
3) δ 3.08 (m, 2H), 2.55 (m, 2H), 2.01 (m, 2H), 1.79 (s, 2H), 1.61-0.80 (m, 11H);
13C NMR:(CDCl
3) δ 49.0,48.4,27.6,27.0,26.2 ,-4.4; IR (capillary film) ν 2926,2851,1440,1258,1247,918,888,833,765,737,696; MS:m/z (relative abundance) 128 (7.5), 84 (100), and 73 (13.8), 56 (17.7), 28 (10.1).
3,3, and 3-trifluoro propyl (2-trimethyl silyl piperidyl) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 21.5 milliliters of 2.0M, 43mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add 2-trimethyl silyl piperidines (44.5 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (39.5 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filters, and then rotary evaporation removes ether, thereby finish separation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (2-trimethyl silyl piperidyl) dimethoxy silane (33.5 mmoles, 85.0% productive rate).C
13H
28NO
2SiF
3(molecular weight=343.53);
1HNMR:(CDCl
3) δ 3.5 (s, 6H), 3.1-2.9 (m, 1H), 2.8-2.6 (m, 2H), 2.2-2.0 (m, 2H), 1.8-1.35 (m, 5H), 1.32-1.15 (m, 1H), 0.9-0.7 (m, 2H), 0.1 (s, 9H);
13CNMR:(CDCl
3) 127.7 (qJ=275Hz), 50.1,42.6,42.2,28.0 (qJ=30Hz), 27.8,23.4,3.0,0.2 ,-4.2; MS:m/z (relative abundance) 328 (1.2), 270 (100), and 246 (2.2), 155 (6.5), 125 (12.0), 84 (21.5).
The embodiment II
3,3,3-trifluoro propyl (2-trimethyl silyl pyrrolidyl) dimethoxy silane
2-trimethyl silyl pyrrolidyl-N-tertiary butyl carbamate-in 1000 ml flasks, add pyrrolidyl-N-tertiary butyl carbamate (23.2 grams, 136mmol), Tetramethyl Ethylene Diamine (44 milliliters, 290mmol) and anhydrous ether (300 milliliters).Material in the bottle is cooled to-78 ℃.In 25 minutes, and the adding s-butyl lithium (cyclohexane solution of 125 milliliters of 1.3M, 162mmol).Material 3.5 hours and keep temperature of reaction and be-78 ℃ in the stirring reaction bottle.In 15 minutes, add chloro trimethyl silane (21.0 milliliters 165mmol), allow a bottle interior material be warming up to room temperature then and stirred 18 hours.With solution pour into dilute hydrochloric acid (750 milliliters, 0.2NHCl) in.Separate each phase, with 0.2N HCl (3 * 100 milliliters) and salt solution (1 * 250 milliliter) washing organic layer, dry then (MgSO
4).Except that desolvating, obtain 93 gram crude products by rotary evaporation.Through underpressure distillation (85-92 ℃ obtains 45.9 grams (189 mmoles, 70% productive rate) after 1.8mmHg)
2-trimethyl silyl pyrrolidyl-N-tertiary butyl carbamate: C
12H
25NO
2Si (molecular weight=243.42).
2-trimethyl silyl tetramethyleneimine-in 1000 ml flasks, add 600 milliliters of ethyl acetate, and be cooled to 5 ℃.Anhydrous hydrogen chloride gas (greater than 99%) is frothed by ethyl acetate 15 minutes.Stop the HCl charging, and remove ice bath, (45.9 restrain, 189mmol) to add 2-trimethyl silyl pyrrolidyl-N-tertiary butyl carbamate.Stirred solution 18 hours.In solution, add entry (250 milliliters).Separate each layer, product is extracted (3 * 200 milliliters) in the entry.With 45% (weight/volume) potassium hydroxide the aqueous solution is transferred to pH14.Add ether (200 milliliters), separate each layer, product is extracted in the ether (3 * 150 milliliters).The organic moiety dried over mgso that merges, and rotary evaporation is except that desolvating.Through underpressure distillation (25 ℃ 1.5mmHg) obtain 2-trimethyl silyl tetramethyleneimine (64% productive rate, purity is greater than 99% for 16.0 grams, 112mmol); C
17H
11NSi (molecular weight=143.30);
1H NMR: δ 49.0,48.9,28.1,26.7 ,-3.3, and-3.6 ,-4.0; IR (capillary film) ν 2952,2866,2823,2752,1423,1247,1069,936,892,837,747,692,622; MS:m/z (relative abundance) 115 (11.9), 100 (14.9), and 73 (10.0), 70 (100), 43 (12.4), 28 (13.2).
3,3, and 3-trifluoro propyl (2-trimethyl silyl pyrrolidyl) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 28.25 milliliters of 2.0M, 56.5mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add 2-trimethyl silyl tetramethyleneimine (58.0 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (51.3 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filtration, and then remove ether, thereby finish separation by rotary evaporation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (2-trimethyl silyl pyrrolidyl) dimethoxy silane (46.7 mmoles, 91% productive rate).C
12H
26NO
2Si
2F
3(molecular weight=329.51);
1HNMR:(CDCl
3) δ 3.50 (s, 3H), 3.45 (s, 3H), 3.25-3.10 (m, 1H), 2.90-2.80 (m, 1H), 2.80-2.65 (m, 1H), 2.20-1.50 (m, 6H), 0.85-0.75 (m, 2H) ,-0.05 (s, 9H);
13C NMR:(CDCl
3) δ 129.6 (q J=275), 50.1,49.0,47.6,46.7,28.2 (qJ=30Hz), 28.0,27.5,2.9 ,-2.7;
29Si NMR:(CDCl
3) δ 2.07 ,-34.74; MS:m/z (relative abundance) 314 (1.5), 256 (100), and 232 (1.7), 155 (3.8), 125 (3.6), 70 (4.2).
The embodiment III
3,3,3-trifluoro propyl (2-(3-aminomethyl phenyl)-piperidyl) dimethoxy silane
(2-(3-aminomethyl phenyl)-piperidyl)-N-tertiary butyl carbamate-(18.5 restrain 1.00 * 10 to add piperidyl-N-tertiary butyl carbamate in 500 ml flasks
2Mmol), Tetramethyl Ethylene Diamine (33 milliliters, 220mmol) and THF (200 milliliters).Material in the bottle is cooled to-78 ℃.In 15 minutes, and the adding s-butyl lithium (cyclohexane solution of 93 milliliters of 1.3M, 120mmol).Being reflected at-78 ℃ stirred 3.5 hours down.In 1000 ml flasks, add THF (200 milliliters), 3-iodo toluene (25.7 milliliters, 2.00 * 10
2Mmole), cuprous cyanide (I) (0.896 gram, 1.00 * 10
2Mmole) and chlorination two (triphenylphosphine) palladium (3.5 gram, 5.0 mmoles).Material in the bottle is cooled to-78 ℃.With intubate piperidyl-N-tertiary butyl carbamate anion ion-transfer is gone in the iodo toluene solution.Allow reaction stir and carried out 18 hours, be heated to backflow (75 ℃) then and also kept again 18 hours.Material in the cooled bottle is added in the water (200 milliliters), separate each layer, with ether (2 * 150 milliliters) aqueous layer extracted.Organic phase after the merging is washed with salt solution (3 * 150 milliliters), dry then (MgSO
4).Except that desolvating, obtain thick 2-(3-aminomethyl phenyl)-piperidyl-N-tertiary butyl carbamate: the C of 59.5 grams by rotary evaporation
17H
25NO
2(molecular weight=275.39); MS:m/z (relative abundance) 275 (0.3), 219 (73.0), and 202 (12.4), 174 (97.3), 158 (34.8), 146 (20.6), 132 (14.6), 57 (100).
2-(3-aminomethyl phenyl) piperidines-in 1000 ml flasks, add 600 milliliters of ethyl acetate, and be cooled to 5 ℃.Anhydrous hydrogen chloride (99%) is frothed by ethyl acetate 15 minutes.Stop the HCl charging, and remove ice bath, (59.5 restrain, 216mmol) to add 2-(3-aminomethyl phenyl) piperidyl-N-tertiary butyl carbamate.Stirred solution 18 hours.Water (250 milliliters) is added solution.Separate each layer, and product is extracted in the entry (3 * 200 milliliters).With 45% (weight/volume) potassium hydroxide water is transferred to pH14.Product is extracted into ether (4 * 150 milliliters).The organic moiety dried over mgso that merges, and rotary evaporation is except that desolvating.Through underpressure distillation (75-90 ℃ 0.3mmHg) obtains 2-(3-aminomethyl phenyl) piperidines (10.4 grams, 59.3mmol, 27.5% productive rate); C
12H
17N (molecular weight=175.27);
1H NMR:(CDCl
3) δ 7.2-7.0 (m, 4H), 3.5 (m, 1H), 3.1 (m, 1H), 3.7 (t, 1H), 2.3 (s, 3H), 1.9-1.4 (m, 7H);
13C NMR: δ (CDCl
3) 145.4,137.6,128.0,127.5,127.0,123.5,62.1,47.6,34.8,25.6,25.3,21.1; IR (capillary film) ν 3319,3267,3022,2924,1932,1855,1777,1680,1441,1323,1108,783,701; MS:m/z (relative abundance) 175 (35.7), 160 (10.4), and 146 (45.0), 132 (34.6), 118 (100), 91 (31.7), 84 (48.4), 56 (7.7), 28 (23.3).
3,3, and 3-trifluoro propyl (2-(3-aminomethyl phenyl) piperidyl) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 15 milliliters of 2.0M, 30mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add 2-(3-aminomethyl phenyl) piperidines (34.3 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (31.1 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filters, and then rotary evaporation removes ether, thereby finish separation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (2-(3-aminomethyl phenyl)-piperidyl) dimethoxy silane (24.1 mmoles, 80.4% productive rate; Bp:101 ℃, under 0.2mmHg).C
17H
26NO
2SiF
3(molecular weight=361.47); MS:m/z (relative abundance) 361 (13.4), 332 (3.6), and 270 (100), 174 (5.6), 155 (9.1), 125 (12.0), 105 (12.2), 59 (19.4).
The embodiment IV
3,3,3-trifluoro propyl (2-(3-aminomethyl phenyl)-pyrrolidyl) dimethoxy silane
(2-(3-aminomethyl phenyl)-pyrrolidyl)-N-tertiary butyl carbamate-in 500 ml flasks, add pyrrolidyl-N-tertiary butyl carbamate (17.3 grams, 101mmol), Tetramethyl Ethylene Diamine (33 milliliters, 220mmol) and THF (200 milliliters).Material in the bottle is cooled to-78 ℃.In 15 minutes, add s-butyl lithium (cyclohexane solution of 93 milliliters of 1.3M, 120mmol), material 3.5 hours in-78 ℃ of following blender jars then.In 1000 ml flasks, add THF (200 milliliters), 3-iodo toluene (25.7 milliliters, 2.00 * 10
2Mmole), cuprous cyanide (I) (0.896 gram, 10.0 mmoles) and chlorination two (triphenylphosphine) palladium (3.5 grams, 5.0 mmoles).Material in the bottle is cooled to-78 ℃.With intubate pyrrolidyl-N-tertiary butyl carbamate anion ion-transfer is gone in the iodo toluene solution.Allow reaction stir and carried out 18 hours, be heated to backflow (75 ℃) 18 hours then.Material and it is added in the water (200 milliliters) in the cooling bottle.Separate each layer, with ether (2 * 150 milliliters) aqueous layer extracted.Organic phase after the merging is washed with salt solution (3 * 150 milliliters), dry then (MgSO
4).Except that desolvating, obtain 62.5 gram crude products by rotary evaporation.Through underpressure distillation (145 ℃ 0.2mmHg) obtain 2-(3-aminomethyl phenyl) pyrrolidyl-N-tertiary butyl carbamate (13.3 grams, 50.9 mmoles, 50% productive rate): C
16H
23NO
2(molecular weight=261.36).
2-(3-aminomethyl phenyl) pyrroline (pyrrolidene)-in 1000 ml flasks, add 600 milliliters of ethyl acetate, and be cooled to 5 ℃.Anhydrous hydrogen chloride (99%) is frothed by ethyl acetate 15 minutes.Stop the HCl charging, and remove ice bath, (35.0 restrain, 134mmol) to add 2-(3-aminomethyl phenyl) pyrrolidyl-N-tertiary butyl carbamate.Stirred solution 18 hours.Water (250 milliliters) is added solution, separate each layer, and product is extracted in the entry (3 * 200 milliliters).With 45% (weight/volume) potassium hydroxide water is transferred to pH 14.Product is extracted in the ether (4 * 150 milliliters).The organic moiety dried over mgso that merges, and rotary evaporation is except that desolvating.Through underpressure distillation (115-122 ℃ 2mmHg) obtains 70: 30 2-(3-aminomethyl phenyl) tetramethyleneimine and the mixture of 2-(3-aminomethyl phenyl) pyrroline (pyrrolidene) (14 grams, 65% productive rate).
2-(3-aminomethyl phenyl) tetramethyleneimine-in pressure reactor, add alkene/product mixtures (14 gram), dehydrated alcohol (140 milliliters) and platinum oxide (2.8 restrain 12 mmoles).With in hydrogen (99.99%) injecting reactor to pressure be 50psig.Reaction stirred 18 hours, pressure is reduced to 3psig during this period.Remove ethanol by distillation under the nitrogen.Residue is carried out underpressure distillation (63-74 ℃ 0.1mmHg), obtains 2-(3-aminomethyl phenyl)-tetramethyleneimine (10.8 grams, 67 mmoles, 77% productive rate, 97% purity); C
11H
15N (molecular weight=161.24);
1HNMR: δ (CDCl
3) 7.3-6.9 (m, 4H), 4.1 (t, 1H), 3.1 (m, 1H), 2.9 (m, 1H), 2.3 (s, 3H), 2.1 (m, 1H), 1.9 (m, 3H), 1.6 (M, 1H);
13C NMR: δ (CDCl
3) 144.9,137.9,128.2,127.5,127.2,123.6,62.6,47.0,34.3,25.6,21.4; IR (capillary film) ν 3327,3014,2953,2866,1937,1861,1783,1399,781,709; MS:m/z (relative abundance) 160 (62.9), 146 (40.5), and 132 (100), 118 (92.6), 92 (25.2), 70 (45.3), 43 (6.0), 28 (14.8).
3,3, and 3-trifluoro propyl (2-(3-aminomethyl phenyl) pyrrolidyl) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 20 milliliters of 2.0M, 40mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add 2-(3-aminomethyl phenyl) tetramethyleneimine (39.1 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (36.3 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filters, and then rotary evaporation removes ether, thereby finish separation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (2-(3-aminomethyl phenyl)-pyrrolidyl) dimethoxy silane (24.3 mmoles, 62.2% productive rate).CH
16H
21NO
2SiF
3(molecular weight=347.45); Boiling point under 0.2mmHg=128 ℃;
1H NMR:(CDCl
3) δ 7.3-6.9 (m, 4H), 4.5 (t, 1H), 3.41 (s, 3H), 3.40 (s, 3H), 3.3 (t, 2H), 2.3 (s, 3H), 2.2-2.1 (m, 2H), 2.0-1.7 (m, 4H), 1.7-1.6 (m, 2H);
13C NMR:(CDCl
3) δ 147.8,137.7,128.1,127.6 (q, J=275.9Hz), 127.2,126.8,123.2 61.7,50.3,47.4,37.0,27.7 (q, J=30.1Hz) 21.4,3.0; MS:m/z (relative abundance) 347 (18.0), 318 (8.3), and 304 (3.7), 256 (100), 155 (12.0), 125 (15.9), 59 (24.6).
3,3,3-trifluoro propyl (suitable-the lupetidine base) dimethoxy silane
Suitable-lupetidine-as in 1000 ml flasks, to add 600 milliliters of 5M KOH, 3 moles) and lutidine (15.0 restrain 1.50 * 10
2Mmole).In 48 hours, add solid-state aluminium/nickelalloy (1200 gram).During adding alloy, the gas generation is arranged and make internal temperature rise to 65 ℃ (adding the alloys that are no more than 15 grams by portion) from 35 ℃.Pass through diatomite
1And filter salts, with ether and water washing filter cake.Separate each layer.Product is extracted into ether (3 * 150 milliliters), uses dried over mgso, form thick lupetidine (8.13 grams, 71.2mmol, 51% productive rate).
3,3, and 3-trifluoro propyl (suitable-the lupetidine base) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 31 milliliters of 2.0M, 62mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add suitable-lupetidine (64 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (57 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filters, and then rotary evaporation removes ether, thereby finish separation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (suitable-the lupetidine base) dimethoxy silane (27.4 mmoles, 48% productive rate).C
12H
24NO
2SiF
3(molecular weight=299.40), the boiling point under 0.3mmHg=66 ℃;
1H NMR:(CDCl
3) δ 3.5 (s, 6H), 3.4-3.3 (m, 2H), 2.2-2.0 (m, 2H), 1.9-1.7 (m, 1H), 1.6-1.4 (m, 5H), 1.2-1.0 (m, 6H), 0.8-0.7 (m, 2H);
13C NMR:(CDCl
3) δ 128 (q, J=275Hz), 50.1,44.2,31.6 28.3 (q, J=30Hz), 24.6,20.5,14.3; MS:m/z (relative abundance) 299 (0.7), 284 (100), and 202 (6.7), 155 (7.9), 98 (12.7), 59 (12.5).
1Attention: on diatomite, can stay flammable Raney nickel type solid.If filtration cakes torrefaction, so this material can be lighted in air.Preferably by it is stirred this solid that neutralized in 48 hours with a large amount of rare nitric acid.
The embodiment VI
3,3, and 3-trifluoro propyl (1,2,3, the 4-tetrahydric quinoline group) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 30 milliliters of 2.0M, 60mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add 1,2,3,4-tetrahydroquinoline (60 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (54.5 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filters, and then rotary evaporation removes ether, thereby finish separation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (1,2,3, the 4-tetrahydric quinoline group) dimethoxy silane (54 mmoles, 99% productive rate).C
14H
20NO
2SiF
3(molecular weight=319.39), the boiling point under 0.35mmHg=110 ℃;
1H NMR:(CDCl
3) δ 7.1-6.4 (m, 4H), 3.6-3.2 (m has an overlapping with unimodal, 8H), 2.9-2.7 (m, 2H), 2.2-1.7 (m, 4H), 1.3-0.7 (m, 2H);
13C NMR:(CDCl
3) δ 130.2,129.6,128 (q, J=275Hz), 126.8,126.5,119.2,117.0,50.5,43.5,27.8 (q, J=30Hz), 23.8,22.4,3.4; MS:m/z (relative abundance) 319 (100), 222 (11.7), and 190 (6.5), 182 (6.2), 155 (10.7), 132 (55.0), 125 (21.8), 117 (12.1), 59 (32.6).
The embodiment VII
3,3, and 3-trifluoro propyl (1,2,3, the 4-tetrahydro isoquinolyl) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 30 milliliters of 2.0M, 60mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add 1,2,3,4-tetrahydroisoquinoline (60 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (54.5 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filters, and then rotary evaporation removes ether, thereby finish separation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (1,2,3, the 4-tetrahydro isoquinolyl) dimethoxy silane (54 mmoles, 99% productive rate).C
14H
20NO
2SiF
3(molecular weight=319.39), the boiling point under 0.3mmHg=98 ℃;
1H NMR:(CDCl
3) δ 7.2-6.9 (m, 4H), 4.2-4.0 (d, 2H), 3.6-3.4 (s, 6H), 3.3-3.1 (dt, 2H), 2.8-2.6 (m, 2H), 2.2-1.9 (m, 2H), 0.9-0.8 (m, 2H);
13C NMR:(CDCl
3) δ 135.9,135.1,129.4,128 (q, J=275Hz), 126.0,125.9,125.8,50.4,46.5,42.1,29.9,28 (q, J=30Hz), 2.8; MS:m/z (relative abundance) 319 (38.3), 318 (100), and 222 (7.9), 132 (21.0), 104 (21.4), 79 (9.8), 59 (13.4).
The embodiment VIII
3,3, and 3-trifluoro propyl (decahydroquinolyl) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 28.75 milliliters of 2.0M, 57.5mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add decahydroquinoline (57.5 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (52.3 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filters, and then rotary evaporation removes ether, thereby finish separation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (decahydroquinolyl) dimethoxy silane (53.1 mmoles, quantitative yield).C
14H
26NO
2SiF
3(molecular weight=325.44), the boiling point under 1.0mmHg=103 ℃;
1H NMR:(CDCl
3) δ 3.5 (s, 6H), 3.1-2.7 (m, 3H), 2.2-1.9 (m, 3H), 1.8-1.1 (m, 12H), 0.9-0.7 (m, 2H);
13C NMR:(CDCl
3) δ 127.9 (q, J=275Hz), 52.6,50.4,38.2,36.9,29.0,28.5,27.8 (q, J=30Hz), 26.4,26.3,20.5,3.1; MS:m/z (relative abundance) 325 (14.3), 282 (100), and 228 (4.1), 125 (6.8), 96 (11.3), 59 (12.6).
The embodiment IX
3,3, and 3-trifluoro propyl (two (2-ethylhexyl) amino) dimethoxy silane-in 500 milliliters of round-bottomed flasks, add tetrahydrofuran (THF) (300 milliliters) and isopropyl-magnesium chloride (the THF solution of 25 milliliters of 2.0M, 50mmol).Material in the bottle is cooled to 15 ℃.In 15 minutes, add two (2-ethylhexyl) amine (50 mmole) by pressure balanced feed hopper.Remove ice bath, material is 2 hours in the blender jar.Add 3,3 by pressure balanced feed hopper, 3-trifluoro propyl Trimethoxy silane (45 mmole).With material backflow (65-70 ℃) in the bottle 2 hours, with the progress of GC monitoring reaction.Remove THF by rotary evaporation, residue is dissolved in ether (250 milliliters) and filters, and then rotary evaporation removes ether, thereby finish separation.Purifying is realized by distillation, thereby is obtained 3,3,3-trifluoro propyl (two (2-ethylhexyl) amino) dimethoxy silane (44 mmoles, 98% productive rate).C
21H
44NO
2SiF
3(molecular weight=427.66), the boiling point under 1.4mmHg=200 ℃;
1H NMR:(CDCl
3) δ 3.5 (s, 6H), 2.6-2.4 (dd, 4H), 2.2-2.0 (m, 2H), 1.6-1.1 (m, 18H), 1.0-0.7 (m, 14H);
13C NMR:(CDCl
3) δ 128 (q, J=275Hz), 50.4,48.5,39.4,36.9,30.8,29.1,28.2 (q, J=30Hz), 23.2,14.2,10.3,3.2; MS:m/z (relative abundance) 328 (100), 230 (25.6), and 155 (7.4), 109 (2.9).
The embodiment X
Polymerization procedure
Amino silane compounds in embodiment I-IX is come the polypropylene monomer as electron donor.Polymerization reactor was heated to 70 ℃, with argon gas stream purge slowly 1 hour.With 70 ℃ of argon gas reactor is forced into 100psig then, emptying again.Repeat this step 4 time again.Then with reactor cooling to 30 ℃.
Individually, in the feed hopper that the argon gas purge is crossed, add material: 75 milliliters of hexanes by following order, 4.47 milliliter 1.5M triethyl aluminum (TEAL) (0.764 gram, 0.0067 hexane solution mole), the aminosilane electron donor of about 3.4 milliliters of 0.1M embodiment I-IX (0.00034 mole) solution was placed 5 minutes then.From this mixture, get 35 milliliters and add in the flask.Then 0.0129 gram FT4S solid catalytic ingredient (is loaded on active MgCl
2Halogenated titanium on the compound catalyst component and electron donor can be buied from Montell ItaliaSpA) join the flask and vortex mixed 5 minutes.Catalyst complex with obtaining like this under argon gas purge and room temperature, adds above-mentioned polymerization reactor.Hexane/TEAL/ solution of silane with remainder enters the flask from feed hopper then, and flask is carried out the vortex vibration, then it is entered reactor and closes the injection valve.
In polymerization reactor, stir lentamente and add 2.2 liters of propylene liquids and 0.25 mole of % hydrogen.Reactor is heated to 70 ℃ then, under steady temperature and pressure, allows reaction begin to carry out about 2 hours.After about 2 hours, stop to stir and remaining propylene being discharged lentamente.Reactor is heated to 80 ℃,, is cooled to room temperature then and opens with argon gas purge 10 minutes.Take out polymkeric substance, in vacuum drying oven,, test again in 80 ℃ times dry 1 hour.
Unless otherwise indicated, the limiting viscosity IV of polymkeric substance is in naphthane, in 135 ℃, with Ubbelohde type viscometer, presses people J.Applied Polymer Sci. such as J.H.Elliot, 14, and the method for 2947-63 (1970) is measured.The output of polymkeric substance (mileage) is calculated as follows:
Output=polypropylene gram number/catalyzer gram number
At room temperature polymkeric substance solvable percentage composition (%XSRT) in dimethylbenzene is to measure like this: 2 gram polymer dissolution in 200 milliliters 135 ℃ dimethylbenzene, are cooled off in 22 ℃ thermostatic bath, then by quick filter paper filtering.A filtrate is evaporated to drying, residue is weighed and calculated the weight percent of soluble composition.
Test result is listed in the table below 1.
Table 1
| Aminosilane | % hydrogen | Output (g pp/g cat) | Limiting viscosity (dL/g) | Melt flow rate (MFR) | ????XSRT ???(wt％) | ????P.I. |
| The embodiment I | ????0 | ????22.353 | ?4.94 | ?????0 | ????2.19 | |
| ???0.2 | ????47,168 | ?3.7 | ????0.56 | ????3.03 | ????5.6 | |
| ???0.75 | ????57,767 | ?2.63 | ????3.18 | ????1.93 | ||
| ???1.5 | ????56,486 | ?1.83 | ???12.49 | ????2.57 | ????4.5 | |
| ???2.5 | ????55,208 | ?1.57 | ???31.27 | ????2.31 | ????4.6 | |
| ????5 | ????54,222 | ?1.16 | ???98.89 | ????2.6 | ????4.6 | |
| The embodiment II | ????0 | ????21,329 | ?9.4 | ????0.02 | ????2.79 | |
| ???0.2 | ????45,487 | ?3.48 | ????0.75 | ????2.21 | ????5.5 | |
| ???0.75 | ????57,714 | ?2.4 | ????4.29 | ????2.18 | ||
| ???1.5 | ????54,528 | ?1.82 | ???12.66 | ????2.47 | ????5.2 | |
| ???2.5 | ????53,555 | ?1.48 | ???34.54 | ????2.79 | ????4.9 | |
| ????5 | ????56,153 | ?1.25 | ???96.27 | ????2.75 | ????4.6 | |
| The embodiment III | ????0 | ????19,805 | ?6.47 | ????0.01 | ????3.39 | |
| ???0.2 | ????43,750 | ?2.39 | ????4.3 | ????2.45 | ????5.0 | |
| ???0.75 | ????51,386 | ?1.56 | ???25.23 | ????2.24 | ||
| ???1.5 | ????46,818 | ?1.22 | ???88.09 | ????2.74 | ????4.4 | |
| ???2.5 | ????43,297 | ?1.01 | ??213.06 | ????2.86 | ????4.4 | |
| The embodiment IV | ????0 | ????20,952 | ?11.1 | ????0.01 | ????3.43 | |
| ???0.2 | ????47,211 | ?2.78 | ????1.6 | ????2.1 | ????4.8 | |
| ???0.75 | ????52,444 | ?1.95 | ????9.03 | ????2.42 | ||
| ???1.5 | ????49,285 | ?1.54 | ???30.43 | ????2.42 | ????4.5 | |
| ???2.5 | ????46,333 | ?1.22 | ???77.65 | ????2.15 | ????4.4 | |
| ????5 | ????42,755 | ?0.91 | ??307.31 | ????2.85 | ????4.5 | |
| The embodiment V | ????0 | ????14,601 | ?7.72 | ????0.03 | ????5.15 | |
| ???0.2 | ????33,465 | ?2.28 | ????5.04 | ????3.5 | ????6.6 | |
| ???0.75 | ????41,456 | ?1.58 | ???25.3 | ????2.87 | ||
| ???1.5 | ????42,391 | ?1.26 | ???75.38 | ????2.95 | ????4.5 | |
| ???2.5 | ????42,173 | ?1.11 | ??153.6 | ????3 | ????4.7 | |
| The embodiment VI | ????0 | ????18,216 | ?6.12 | ????0.03 | ????4.49 | |
| ???0.2 | ????45,398 | ?2.04 | ????6.82 | ????2.85 | ????4.5 | |
| ???0.75 | ????54,857 | ?1.5 | ???29.56 | ????2.77 | ||
| ???1.5 | ????46,923 | ???74.7 | ????2.94 | ????4.3 | ||
| ???2.5 | ????48,620 | ???96.1 | ????2.85 | ????4.3 | ||
| ????5 | ????42,058 | ???551 | ????2.97 | ????4.4 |
| The embodiment VII | ????0 | ?17,939 | ?6.88 | ??0.03 | ?3.37 | |
| ????0.2 | ?37,804 | ?2.05 | ??14.2 | ?2.55 | ?4.4 | |
| ????0.75 | ?44,151 | ?1.47 | ??32.63 | ?2.45 | ||
| ????1.5 | ?37,378 | ??101.4 | ?2.64 | ?4.3 | ||
| ????2.5 | ?39,754 | ??149.3 | ?2.41 | ?4.3 | ||
| ????5 | ?36,090 | ??694.8 | ?2.83 | ?4.2 | ||
| The embodiment VIII | ????0 | ?19,000 | 10.23 | ??0.01 | ?2.95 | |
| ????0.2 | ?40,280 | ?2.57 | ??2.77 | ?2.15 | ?N.D.* | |
| ????0.75 | ?47,407 | ?1.93 | ??11.75 | ?2.2 | ||
| The embodiment IX | ????0 | ?19,655 | ?5.16 | ??0.11 | ?8.27 | |
| ????0.2 | ?36,272 | ?2.08 | ??13.24 | ?7.29 | ?4.4 | |
| ????0.75 | ?40,540 | ?1.21 | ???75 | ?5.94 | ||
| ????1.5 | ?38,867 | ??179.1 | ?5.86 | ?4.6 | ||
| ????2.5 | ?36,581 | ??344.4 | ?8.48 | ?4.5 | ||
| ????5 | ?33.966 | ??1,598 | ?6.55 | ?4.4 |
N.D.
*: not test
Comparing embodiment
According to the polymerization procedure of embodiment X, be 20/1 Al/Si with 0.25% hydrogen and ratio, and with 3,3,3-trifluoro propyl (4-methyl piperidine base) dimethoxy silane is as aminosilane.The polypropylene production that catalyzer shows is every gram catalyzer 43,900 gram polypropylene.The limiting viscosity of the polymkeric substance that forms is 2.35, and XSRT is 1.51%, and polydispersity index is 4.22.
After having read above-mentioned disclosure, other features of the present invention disclosed herein, advantage and example are clearly for those skilled in the art.Based on this, although specific embodiments of the invention quite at length are described, however can be in the scope of the invention and spirit of the described and claim that proposes, these examples are changed and changed.
Claims (15)
1. the aminosilane of a following formula is characterized in that,
In the formula,
R
1Be the straight or branched C that can be replaced by at least one halogen atom
1-22Alkyl or C
3-22Cycloalkyl;
R
2Be two (straight or branched C
1-22Alkyl or C
3-22Cycloalkyl) piperidyl, the pyrrolidyl of replacement, the decahydroquinolyl, 1,2,3 of amino, replacement, 4-tetrahydric quinoline group or 1,2,3, the 4-tetrahydro isoquinolyl, substituting group wherein is selected from down group: straight or branched C
1-8Alkyl, phenyl, straight or branched C
1-8Alkyl-substituted phenyl or trimethyl silyl, condition be when substituting group be C
1-8During alkyl, must there be 2 such substituting groups and R at least
1Must contain halogen atom; With
R
3Be the C of straight or branched
1-8Alkyl or C
3-8Cycloalkyl.
2. aminosilane as claimed in claim 1 is characterized in that R
1Be 3,3, the 3-trifluoro propyl.
3. aminosilane as claimed in claim 2 is characterized in that R
3Be methyl or ethyl.
4. aminosilane as claimed in claim 3 is characterized in that R
2Be two (straight or branched C
1-22Alkyl or C
3-22Cycloalkyl) amino.
5. aminosilane as claimed in claim 3 is characterized in that R
2Be two (2-ethylhexyl) amino.
6. aminosilane as claimed in claim 3 is characterized in that R
2It is decahydroquinolyl.
7. aminosilane as claimed in claim 3 is characterized in that R
2Be 1,2,3, the 4-tetrahydric quinoline group.
8. aminosilane as claimed in claim 3 is characterized in that R
2Be 1,2,3, the 4-tetrahydro isoquinolyl.
9. aminosilane as claimed in claim 3 is characterized in that R
2It is 2-trimethyl silyl piperidyl.
10. aminosilane as claimed in claim 3 is characterized in that R
2It is 2-(3-aminomethyl phenyl) piperidyl.
11. aminosilane as claimed in claim 3 is characterized in that, R
2It is suitable-lupetidine base.
12. aminosilane as claimed in claim 3 is characterized in that, R
2It is 2-trimethyl silyl pyrrolidyl.
13. aminosilane as claimed in claim 3 is characterized in that, R
2It is 2-(3-aminomethyl phenyl) pyrrolidyl.
14. a catalyzer that is used for olefin polymerization is characterized in that, this catalyzer comprises the reaction product of following material:
(A) alkylaluminium cpd;
(B) amino silane compounds of following formula;
In the formula,
R
1Be the straight or branched C that can be replaced by at least one halogen atom
1-22Alkyl or C
3-22Cycloalkyl;
R
2Be two (straight or branched C
1-22Alkyl or C
3-22Cycloalkyl) piperidyl, the pyrrolidyl of replacement, the decahydroquinolyl, 1,2,3 of amino, replacement, 4-tetrahydric quinoline group or 1,2,3, the 4-tetrahydro isoquinolyl, substituting group wherein is selected from down group: straight or branched C
1-8Alkyl, phenyl, straight or branched C
1-8Alkyl-substituted phenyl or trimethyl silyl, condition be when substituting group be C
1-8During alkyl, must there be 2 such substituting groups and R at least
1Must contain halogen atom; With
R
3Be the C of straight or branched
1-8Alkyl or C
3-8Cycloalkyl,
(C) solid constituent, this component comprise titanium compound and the electron donor with at least one titanium-halogen key, on the both loads on active, the anhydrous magnesium dihalide.
15. catalyzer as claimed in claim 14 is characterized in that, this alkylaluminium cpd is a triethyl aluminum, and this solid constituent comprises: the reaction product of electron donor, active magnesium chloride and titanium tetrachloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98125937 CN1222531A (en) | 1997-12-23 | 1998-12-22 | Catalyst for polymerization of alpha-olefins containing substituted amino silane compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/996,854 | 1997-12-23 | ||
| CN 98125937 CN1222531A (en) | 1997-12-23 | 1998-12-22 | Catalyst for polymerization of alpha-olefins containing substituted amino silane compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1222531A true CN1222531A (en) | 1999-07-14 |
Family
ID=5229428
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98125937 Pending CN1222531A (en) | 1997-12-23 | 1998-12-22 | Catalyst for polymerization of alpha-olefins containing substituted amino silane compounds |
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| Country | Link |
|---|---|
| CN (1) | CN1222531A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387626C (en) * | 2003-03-05 | 2008-05-14 | 伊奎斯塔化学有限公司 | Propylene polymerization process |
| CN104072534A (en) * | 2005-10-05 | 2014-10-01 | 田边三菱制药株式会社 | Dermatitis treating agent |
| CN106916097A (en) * | 2017-02-13 | 2017-07-04 | 中节能万润股份有限公司 | A kind of preparation method of cis 3,5 lupetidine of high-purity |
-
1998
- 1998-12-22 CN CN 98125937 patent/CN1222531A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387626C (en) * | 2003-03-05 | 2008-05-14 | 伊奎斯塔化学有限公司 | Propylene polymerization process |
| CN104072534A (en) * | 2005-10-05 | 2014-10-01 | 田边三菱制药株式会社 | Dermatitis treating agent |
| CN106916097A (en) * | 2017-02-13 | 2017-07-04 | 中节能万润股份有限公司 | A kind of preparation method of cis 3,5 lupetidine of high-purity |
| CN106916097B (en) * | 2017-02-13 | 2019-06-07 | 中节能万润股份有限公司 | A kind of preparation method of the cis- -3,5- lupetidine of high-purity |
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