CN102850386B - A kind of silane compound containing oxaza and its preparation method and application and olefine polymerizing process - Google Patents
A kind of silane compound containing oxaza and its preparation method and application and olefine polymerizing process Download PDFInfo
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- CN102850386B CN102850386B CN201110183047.2A CN201110183047A CN102850386B CN 102850386 B CN102850386 B CN 102850386B CN 201110183047 A CN201110183047 A CN 201110183047A CN 102850386 B CN102850386 B CN 102850386B
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Abstract
The present invention relates to a kind of silane compound containing oxaza and preparation method and application and the olefine polymerizing process of the silane compound of oxaza should be contained, wherein, the structure shown in formula (I) should be had containing the silane compound of oxaza.When the silane compound containing oxaza using method of the present invention to prepare is used as the external donor compound of olefin polymerization catalysis, the degree of isotacticity of the high and obtained polymkeric substance of the activity of catalyzer can be made to meet the demands, and should have containing preparation method of silane compound of oxaza and react completely, by product is few, product is easy to be separated, the advantages such as product cost is lower.
Description
Technical field
The present invention relates to a kind of silane compound containing oxaza and preparation method and application and the olefine polymerizing process of the silane compound of oxaza should be contained.
Background technology
As everyone knows, for the catalyzer, particularly catalyst for polymerization of propylene of olefinic polymerization and copolymerization, silane compound be used as external electron donor, to improve the degree of isotacticity of polymkeric substance, thus improve the machining property of polymkeric substance.
Its general structure of silane compound conventional is at present: R
nsi (OR ')
4-n(wherein, n is the natural number of 1-3), as dimethoxydiphenylsilane (WO8805056, EP283011), Cyclohexylmethyldimethoxysilane (JP02-170803, JP02-229807), diisopropyl dimethoxy silane (EP350170), second, isobutyl dimethoxy silane (EP250229, EP376145) and dicyclopentyl dimethoxyl silane (JP02-229807) etc.
But, the above-mentioned silane compound that oneself knows, some contains phenyl ring, in use likely discharges harmful benzene, thus causes health and health problem; Some, owing to a Siliciumatom being connected with two sterically hindered very high cyclic alkyls, prepare more difficult, and cost is higher; Although some preparation is than being easier to, cost is also lower, is not that the activity of the catalyzer of gained is not high, and the degree of isotacticity of polymkeric substance obtained exactly can not meet the demands.
Therefore, be necessary to synthesize new silane compound, to solve existing silane compound Problems existing.
Such as, the human hair such as TomokoAoki of Japanese TonenCorporation understands the cyclohexyl dimethoxy oxa--3-cyclopentyloxy silane (US5,248,803) containing tetrahydrofuran (THF) group; The C.A.Stewort of U.S. HimontIncorporated has invented nitrogenous heterocyclic organosilane (EP0410443A1); The research of the people such as the HiroyukiIkeuchi of Japan UBEIndustriesLtd. finds, the silane containing one or two piperidines group is substantially identical with hydrocarbyl si lanes in performance, is also the external electron donor of a class height isotactic.
The preparation method of existing silane compound, take normally halogenated alkane as raw material, reacts, make Grignard reagent under the condition of absolute with MAGNESIUM METAL, then reacts obtained product with organoalkoxysilane.The method operational condition is very harsh, as material adds speed or temperature controls bad during reaction, very easily bumping occurs, even sets off an explosion.
Summary of the invention
The object of this invention is to provide a kind of silane compound containing oxaza and its preparation method and application and olefine polymerizing process, when should be used as the external donor compound of olefin polymerization catalysis containing the silane compound of oxaza, the degree of isotacticity of the high and obtained polymkeric substance of the activity of catalyzer can be made to meet the demands, and should have containing preparation method of silane compound of oxaza and react completely, by product is few, product is easy to be separated, the advantages such as product cost is lower.
The invention provides a kind of silane compound containing oxaza, it is characterized in that, the structure shown in formula (I) should be had containing the silane compound of oxaza,
Wherein, m and n is 0 or 1, and is asynchronously 0; R
1, R
2being identical or not identical, is straight or branched C separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20one in aralkyl; A is C, N or O, and when A is C, o is 1, p is 2, R
3for hydrogen; When A is oxygen, o=p=2, R
3do not exist; When A is N, o=p=2, R
3for straight or branched C
1-C
20alkyl.
The present invention also provides a kind of preparation method of the silane compound containing oxaza, under the method is included in conditions of replacement reaction, morpholine shown in formula (II) is carried out first with hydrocarbyl lithium in the presence of solvent contact, then the product after contact is carried out second with the silicone compounds shown in formula (III) and contact;
M, n, R in above-mentioned formula (III)
1, R
2identical with the definition in above-mentioned formula (I), R
4, R
5for H or carbonatoms are the alkyl of 1-2.
Present invention also offers a kind of preparation method of the silane compound containing oxaza, the method comprises the one in following method:
Method one: under conditions of replacement reaction, carries out first with hydrocarbyl lithium in the presence of solvent by the morpholine shown in formula (II) and contacts, and the product after then contacting first carries out second with the silicone compounds shown in formula (III) and contacts; By formula) shown in nitrogen-containing heterocycle compound carry out the 3rd with hydrocarbyl lithium in the presence of solvent and contact; Then the product after the product after contacting the 3rd contacts with second carries out the 4th contact;
Method two: under conditions of replacement reaction, nitrogen-containing heterocycle compound shown in formula () is carried out the 5th with hydrocarbyl lithium in the presence of solvent contact, the product after then contacting the 5th carries out the 6th with the silicone compounds shown in formula (III) and contacts; Morpholine shown in formula (II) is carried out the 7th with hydrocarbyl lithium in the presence of solvent contact; Then the product after the product after contacting the 7th contacts with the 6th carries out the 8th contact;
M, n, R in above-mentioned formula (III)
1, R
2, R
4, R
5identical with the definition of above-mentioned formula (I), o, p, A and R in formula (IV)
3identical with the definition of above-mentioned formula (I).
Present invention also offers the above-mentioned application of silane compound as the external electron donor in olefin polymerization catalysis containing oxaza.
Present invention also offers a kind of olefine polymerizing process, under the method is included in the existence of a kind of olefin polymerization catalyst system, alkene is polymerized, described olefin polymerization catalyst system comprises solids containing titanium catalyst component, alkylaluminium cpd and external electron donor, it is characterized in that, described external electron donor is the above-mentioned silane compound containing oxaza provided by the invention.
Silane compound containing oxaza provided by the invention is when using as olefin polymerization catalysis external electron donor component, the polymerization activity of catalyzer is higher, the degree of isotacticity of polymerisate is also higher, and the preparation method that the invention provides containing the silane compound of oxaza has reaction conditions gentleness, easy and simple to handle, raw materials usedly to be easy to get, the advantages such as product cost is lower.
Embodiment
According to a kind of silane compound containing oxaza provided by the invention, it is characterized in that, the structure shown in formula (I) should be had containing the silane compound of oxaza,
Wherein, m and n is 0 or 1, and is asynchronously 0; R
1, R
2being identical or not identical, is straight or branched C separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20one in aralkyl; A is C, N or O, and when A is C, o is 1, p is 2, R
3for hydrogen; When A is oxygen, o=p=2, R
3do not exist; When A is N, o=p=2, R
3for straight or branched C
1-C
20alkyl.
According to the present invention, the R in formula (I)
1and R
2preferably identical or not identical straight or branched C
1-C
5one in alkyl; R
3preferably straight or branched C
1-C
5one in alkyl.
According to the present invention, straight or branched C in formula (I)
1-C
20the example of alkyl can include but not limited to: the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl and dodecyl;
According to the present invention, C in formula (I)
3-C
20the example of cycloalkyl can include but not limited to: the one in cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1,2-Dimethylcyclohexyl, 1,3-Dimethylcyclohexyl, Isosorbide-5-Nitrae-Dimethylcyclohexyl, 1-ethylcyclohexyl.
According to the present invention, C in formula (I)
6-C
20the example of aryl can include but not limited to: the one in phenyl, naphthyl, 4-aminomethyl phenyl and 4-ethylphenyl.
According to the present invention, C in formula (I)
7-C
20the example of alkaryl can include but not limited to: 4-aminomethyl phenyl, 4-ethylphenyl, the one in 4-butyl phenyl.
According to the present invention, C in formula (I)
7-C
20the example of aralkyl can include but not limited to: phenmethyl, styroyl, the one in benzene butyl.
According to the present invention, R in formula (I)
1and R
2more preferably be methyl or ethyl separately; R
3be more preferably methyl.
According to the present invention, the silane compound with general formula (I) structure provided can be one or more in following compound:
Two morpholinyl dimethoxysilane,
Two morpholinyl diethoxy silane,
Pyrryl morpholinyl dimethoxysilane,
(N-methyl) piperazinyl morpholinyl dimethoxysilane,
Pyrryl morpholinyl A methoxylsilane,
(N-methyl) piperazinyl morpholinyl A methoxylsilane,
The preparation method of a kind of silane compound containing oxaza provided by the invention, under the method is included in conditions of replacement reaction, morpholine shown in formula (II) is carried out first with hydrocarbyl lithium in the presence of solvent contact, then the product after contact is carried out second with the silicone compounds shown in formula (III) and contact;
According to the present invention, m and n in above-mentioned formula (III) is 0 or 1, and is asynchronously 0, R
1, R
2identical with the definition in above-mentioned formula (I), R
4, R
5for H or carbonatoms are the alkyl of 1-2, do not repeat them here.
According to the present invention, under preferable case, the condition of described first contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 10-200 minute, is preferably 20-100 minute.
According to the present invention, under preferable case, the condition of described second contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 1-24 hour, is preferably 20-100 minute.
According to the present invention, the preparation method of the described silane compound containing oxaza, under preferable case, in mole, the morpholine shown in described formula (II): hydrocarbyl lithium: silicone compounds=1 shown in formula (III): 1-5: 0.1-5; Be more preferably 1: 1-3: 0.4-0.7.The 5-30 that the consumption of described solvent is the silicone compounds gross weight shown in the morpholine shown in formula (II), hydrocarbyl lithium and formula (III) doubly.
Another kind provided by the invention is containing the preparation method of the silane compound of oxaza, and the method comprises the one in following method:
Method one: under conditions of replacement reaction, carries out first with hydrocarbyl lithium in the presence of solvent by the morpholine shown in formula (II) and contacts, and the product after then contacting first carries out second with the silicone compounds shown in formula (III) and contacts; Nitrogen-containing heterocycle compound shown in formula (IV) is carried out the 3rd with hydrocarbyl lithium in the presence of solvent contact; Then the product after the product after contacting the 3rd contacts with second carries out the 4th contact;
Method two: under conditions of replacement reaction, nitrogen-containing heterocycle compound shown in formula (IV) is carried out the 5th with hydrocarbyl lithium in the presence of solvent contact, the product after then contacting the 5th carries out the 6th with the silicone compounds shown in formula (III) and contacts; Morpholine shown in formula (II) is carried out the 7th with hydrocarbyl lithium in the presence of solvent contact; Then the product after the product after contacting the 7th contacts with the 6th carries out the 8th contact;
According to the present invention, m, n, R in above-mentioned formula (III)
1, R
2, R
4, R
5identical with the definition of above-mentioned formula (I), o, p, A and R in formula (IV)
3identical with the definition of above-mentioned formula (I), do not repeat them here.
According to the present invention, described carbonatoms is the alkyl of 1-2 is such as methyl, ethyl.
The preparation method of silane compound containing oxaza of employing hydrocarbyl lithium provided by the invention, compared with aforementioned existing grignard reagent method, has reaction conditions gentleness, easy and simple to handle, is raw materials usedly easy to get, the advantage that product cost is lower.
According to the present invention, under preferable case, the condition of described first contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 10-200 minute, is preferably 20-100 minute.
According to the present invention, under preferable case, the condition of described second contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 1-24 hour, is preferably 20-100 minute.
According to the present invention, the condition of described 3rd contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 10-200 minute, is preferably 20-100 minute; The condition of described 4th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 1-24 hour, is preferably 20-100 minute; The condition of described 5th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 10-200 minute, is preferably 20-100 minute; The condition of described 6th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 1-24 hour, is preferably 20-100 minute; The condition of described 7th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 10-200 minute, is preferably 20-100 minute; The condition of described 8th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, is preferably 0 DEG C to 10 DEG C; Time is 1-24 hour, is preferably 20-100 minute.
It should be noted that, when reaction raw materials adopt drip mode carry out time, the described time from drip start timing.
Described rare gas element can be variously do not cause the gases of disadvantageous effect to reaction, such as, can be one or more in the periodic table of elements in neutral element gas and nitrogen.
According to the present invention, the alkyl in described hydrocarbyl lithium can be the alkyl of 1-10 for various carbonatoms, and preferred described hydrocarbyl lithium is one or more in lithium methide, n-Butyl Lithium, phenyl lithium.
According to the present invention, the silicone compounds shown in described formula (III) can be one or more in various alkyltrialkoxysilaneand (namely m or n is the situation of 0) and tetraalkoxysilane (i.e. m=n=1).Described alkyltrialkoxysilaneand be preferably in methyl trialkoxysilane and alkyl trimethoxysilane one or more, be particularly preferably methyltrimethoxy silane.Described tetraalkoxysilane be preferably selected from tetramethoxy-silicane, tetraethoxysilane one or more.
According to the present invention, the nitrogen-containing heterocycle compound shown in described formula (IV) be preferably in tetramethyleneimine and (N-alkyl) piperazine one or more, the alkyl in described (N-alkyl) piperazine can be the alkyl of carbonatoms 1-6; (N-alkyl) piperazine can be one or more in N methyl piperazine, NEP, N-normal-butyl piperazine, preferred N methyl piperazine.
According to the present invention, the preparation method of the described silane compound containing oxaza, the consumption of described solvent can be selected in relative broad range, under preferable case, in mole, morpholine shown in described formula (II): hydrocarbyl lithium: the silicone compounds shown in formula (III): nitrogen-containing heterocycle compound=1 shown in formula (IV): 1-5: 1-5: 1-5, is more preferably 1: 1-3: 1-3: 1-3; The 5-30 that the consumption of described solvent is the nitrogen-containing heterocycle compound shown in the morpholine shown in formula (II), hydrocarbyl lithium, formula (IV) and the silicone compounds gross weight shown in formula (III) doubly, is more preferably 5-20 times of weight.
According to the present invention, described solvent is preferably various aprotic solvent, described aprotic solvent be preferably selected from acid amides, halohydrocarbon, hydrocarbon, ether one or more, concrete as methylene dichloride, trichloromethane, benzene, toluene, normal hexane, hexanaphthene, sherwood oil, ether, tetrahydrofuran (THF), methyl tertiary butyl ether and N, one or more of dinethylformamide, are preferably normal hexane.
According to the present invention, under preferable case, the method also comprises carries out centrifugation to products therefrom after the second contact and separating obtained liquid is carried out purifying.Separating obtained liquid first can be carried out evaporation and desolventize by the method for purifying, then distills, and collects required cut.
A preferred embodiment of the invention, the preparation method of the described silane compound containing oxaza adopts following step to carry out: at N
2under protective condition, in aprotic solvent, in reaction flask, add morpholine successively, stir; Under the condition of preferred 0-10 DEG C, dropwise add n-Butyl Lithium-hexane solution, described n-Butyl Lithium-hexane solution is the reagent be purchased; Then the silicone compounds shown in formula (III) is dropwise added; Centrifugation reaction solution more after completion of the reaction, washes twice with above-mentioned aprotic solvent, collects filtrate, boils off above-mentioned aprotic solvent, underpressure distillation with Rotary Evaporators, collects cut.
According to another kind of preferred implementation of the present invention, the preparation method of the described silane compound containing oxaza adopts following step to carry out: at N
2under protective condition, in aprotic solvent, in reaction flask, add morpholine successively, stir; Under the condition of preferred 0-10 DEG C, dropwise add n-Butyl Lithium-hexane solution, described n-Butyl Lithium-hexane solution is the reagent be purchased; Then the silicone compounds shown in formula (III) is dropwise added; Centrifugation reaction solution more after completion of the reaction, wash twice with above-mentioned aprotic solvent, collect filtrate, above-mentioned aprotic solvent is boiled off with Rotary Evaporators, underpressure distillation, collect cut, the product after the alkoxyl group obtained in the silicone compounds shown in formula (III) is replaced by morpholinyl.Then, at N
2under protective condition, in aprotic solvent, in reaction flask, add the nitrogen-containing heterocycle compound shown in formula (IV) successively, stir; Under the condition of preferred 0-10 DEG C, dropwise add n-Butyl Lithium-hexane solution; Then the product after the alkoxyl group dropwise added in the above-mentioned silicone compounds shown in formula (III) prepared is replaced by morpholinyl; Centrifugation reaction solution more after completion of the reaction, washes twice with above-mentioned aprotic solvent, collects filtrate, boils off above-mentioned aprotic solvent, underpressure distillation with Rotary Evaporators, collects cut.
According to another kind of preferred implementation of the present invention, the preparation method of the described silane compound containing oxaza adopts following step to carry out: at N
2under protective condition, in aprotic solvent, in reaction flask, add the nitrogen-containing heterocycle compound shown in formula (IV) successively, stir; Under the condition of preferred 0-10 DEG C, dropwise add n-Butyl Lithium-hexane solution; Then the silicone compounds shown in formula (III) is dropwise added; Centrifugation reaction solution more after completion of the reaction, wash twice with above-mentioned aprotic solvent, collect filtrate, above-mentioned aprotic solvent is boiled off with Rotary Evaporators, underpressure distillation, collect cut, the product that the alkoxyl group obtaining the silicone compounds shown in formula (III) is replaced by the group of the nitrogen-containing heterocycle compound shown in formula (IV) except H.Then, at N
2under protective condition, in aprotic solvent, in reaction flask, add morpholine successively, stir; Under the condition of preferred 0-10 DEG C, dropwise add n-Butyl Lithium-hexane solution; Then the product that the alkoxyl group dropwise adding the above-mentioned silicone compounds shown in formula (III) prepared is replaced by the group of the nitrogen-containing heterocycle compound shown in formula (IV) except H; Centrifugation reaction solution more after completion of the reaction, washes twice with above-mentioned aprotic solvent, collects filtrate, boils off above-mentioned aprotic solvent, underpressure distillation with Rotary Evaporators, collects cut.
Because olefine polymerizing process provided by the invention relates generally to the improvement to external donor compound wherein, namely adopt the above-mentioned silane compound containing oxaza provided by the invention as external donor compound, and to other aspects of olefine polymerizing process as the kind of the kind of solids containing titanium catalyst component and consumption, alkylaluminium cpd and consumption and olefin polymerization conditions do not improve, namely can be same as the prior art.
Such as, the reaction product of solids containing titanium catalyst component generally containing adduct of magnesium halides, titanium compound and optional internal electron donor compound.Described aluminum alkyls is general formula AlR " '
3one or more in shown compound, in this general formula, three R " ' identical or different, be C separately
1-C
8alkyl, one in a chloro alkyl and dichloro-alkyl.Described in the alkylaluminium cpd of aluminium and in the mol ratio of the catalyst component of titanium for 1-2000: 1, be preferably 20-500: 1; The mol ratio of described external donor compound and alkylaluminium cpd is 0.005-0.5: 1, is preferably 0.01-0.4: 1.
Described polymerization can be mass polymerization, vapour phase polymerization, slurry polymerization or liquid-phase bulk-gas phase polymerization mix.Described alkene can be general formula CH
2=CHR
13shown alkene, wherein, R
13can be hydrogen, C
1-C
12straight or branched alkyl and C
6-C
12substituted or unsubstituted aryl in one.Be preferably propylene; Or propylene and CH
2=CHR
13shown alkene, wherein, R
13for C
1-C
12straight or branched alkyl and C
6-C
12substituted or unsubstituted aryl in one.According to olefine polymerizing process of the present invention, described olefin polymerization conditions can be the normal condition of this area, and such as, polymerization temperature can be 0-150 DEG C, is preferably 60-90 DEG C; Polymerization pressure can be normal pressure or pressurization.
Below in conjunction with embodiment, further explanation is explained to the present invention.In following examples, unless stated otherwise, agents useful for same is the chemically pure reagent be purchased.
Embodiment 1-6 is for illustration of silane compound containing oxaza provided by the invention and preparation method thereof.
Embodiment 1
Produced according to the present invention pair of morpholinyl dimethoxysilane
At N
2under protective condition, in reaction flask, add morpholine 0.916g successively, 10ml normal hexane, stir.Under temperature is 5 DEG C of conditions, dropwise add 4.2ml (2.87M) butyllithium-hexane solution, time for adding is 30min; In reaction solution, dropwise add tetramethoxy-silicane 0.85g after 30min, continue reaction 6h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 84 DEG C/80Pa cut, heavy 0.88g, content 99.0% (GC), carries out nucleus magnetic resonance test, obtains following spectrum peak:
1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：2.99(t，8H，4CH
2)，3.51(s，6H，2OCH
3)，3.58(t，8H，4CH
2)
Embodiment 2
Pyrryl morpholinyl dimethoxysilane produced according to the present invention
At N
2under protective condition, in reaction flask, add tetramethyleneimine 4.58g successively, 50ml normal hexane, stir.Under temperature is 10 DEG C of conditions, dropwise add 25.4ml (2.5M) butyllithium-hexane solution, time for adding is 30min.In reaction solution, dropwise add tetramethoxy-silicane 13.4g after 1h, continue reaction 17h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 86-91 DEG C/90Pa cut, be called intermediate A 2, heavy 7.7g, content 99.0% (GC).
At N
2under protective condition, in reaction flask, add morpholine 1.58g successively, 20ml normal hexane, stir.Under temperature is 10 DEG C of conditions, dropwise add 8.3ml (2.5M) butyllithium-hexane solution, time for adding is 40min; In reaction solution, dropwise add the above-mentioned intermediate A 2 of 3.8g after 20min, continue reaction 17h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 106 DEG C/25Pa cut, heavy 2.3g, content 98.0% (GC), carries out nucleus magnetic resonance test, obtains following spectrum peak:
1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：1.72(m，4H，2CH
2)，2.99(t，4H，2CH
2)，3.05(m，4H，2CH
2)，3.51(s，6H，2OCH
3)，3.58(t，4H，2CH
2)
Embodiment 3
(N-methyl) produced according to the present invention piperazinyl morpholinyl dimethoxysilane
At N
2under protective condition, in reaction flask, add morpholine 5.5g successively, 60ml normal hexane, stir.Under temperature is 0 DEG C of condition, dropwise add 29ml (2.5M) butyllithium-hexane solution, time for adding is 30min; In reaction solution, dropwise add tetramethoxy-silicane 15.3g after 30min, continue reaction 5h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 1110 DEG C/50hPa cut, be called intermediate A 3, heavy 5.2g, content 98.0% (GC).
At N
2under protective condition, in reaction flask, add N methyl piperazine 2.5g successively, 30ml normal hexane, stir.Under temperature is 0 DEG C of condition, dropwise add 10.5ml (2.5M) butyllithium-hexane solution, time for adding is 30min; In reaction solution, dropwise add the above-mentioned intermediate A 3 of 5.2g after 30min, continue reaction 17h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 130 DEG C/45Pa cut, heavy 2.8g, carry out nucleus magnetic resonance test, obtain following spectrum peak:
1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：2.27(s+m，7H，2NCH
2，NCH
3)，3.00(m，8H，4CH
2)，3.51(s，6H，2OCH
3)，3.57(t，4H，2CH
2)
Embodiment 4
Pyrryl morpholinyl A methoxylsilane produced according to the present invention
At N
2under protective condition, in reaction flask, add tetramethyleneimine 5.2g successively, 45ml normal hexane, stir.Under temperature is 8 DEG C of conditions, dropwise add 30ml (2.5M) butyllithium-hexane solution, time for adding is 20min; In reaction solution, dropwise add methyltrimethoxy silane 14.9g after 40min, continue reaction 17h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 132-140 DEG C/45hPa cut, be called intermediate A 4, heavy 6.2g.
At N
2under protective condition, in reaction flask, add morpholine 2.0g successively, 20ml normal hexane, stir.Under temperature is 8 DEG C of conditions, dropwise add 10.3ml (2.5M) butyllithium-hexane solution, time for adding is 20min; In reaction solution, dropwise add the above-mentioned intermediate A 4 of 4.3g after 40min, continue reaction 17h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 102-104 DEG C/30Pa cut, heavy 2.7g, carry out nucleus magnetic resonance test, obtain following spectrum peak:
1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：0.07(s，3H，CH
3)，1.70(m，4H，2CH
2)，2.94(t，4H，2CH
2)，3.00(m，4H，2CH
2)，3.43(s，3H，OCH
3)，3.54(t，4H，2CH
2)
Embodiment 5
(N-methyl) produced according to the present invention piperazinyl morpholinyl A methoxylsilane
At N
2under protective condition, in reaction flask, add N methyl piperazine 2.7g successively, 30ml normal hexane, stir.Under temperature is 5 DEG C of conditions, dropwise add 12ml (2.5M) butyllithium-hexane solution, time for adding is 40min; In reaction solution, dropwise add methyltrimethoxy silane 5.5g after 20min, continue reaction 17h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 73 DEG C/90Pa cut, be called intermediate A 5, heavy 2.2g.
At N
2under protective condition, in reaction flask, add morpholine 2.0g successively, 20ml normal hexane, stir.Under temperature is 5 DEG C of conditions, dropwise add 10.3ml (2.5M) butyllithium-hexane solution, time for adding is 40min; In reaction solution, dropwise add the above-mentioned intermediate A 5 of 5g after 20min, continue reaction 17h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 120-122 DEG C/23Pa cut, heavy 2.9g, content 99.3% (GC), carries out nucleus magnetic resonance test, obtains following spectrum peak:
1HNMR(CDCl
3/TMS，300MHz)δ(ppm)：0.07(s，3H，CH
3)，2.26(s+m，7H，2NCH
2，NCH
3)，2.94(m，8H，4CH
2)，3.44(s，3H，OCH
3)，3.55(t，4H，2CH
2)
Embodiment 6
Produced according to the present invention pair of morpholinyl diethoxy silane
Under N2 protective condition, in reaction flask, add morpholine 3.7g successively, 40ml normal hexane, stir.Under the condition of 5 DEG C, dropwise add 19.4ml (2.5M) butyllithium-hexane solution, time for adding is 30min.In reaction solution, dropwise add tetraethoxysilane 4.8g after 1h, continue reaction 17h.Centrifugation reaction solution, precipitation normal hexane washes twice, collects filtrate.Boil off normal hexane solvent with Rotary Evaporators, underpressure distillation, collect 128-140 DEG C/45Pa cut, heavy 3.65g, carry out nucleus magnetic resonance test, obtain following spectrum peak:
1HNMR(CDCl3/TMS，300MHz)δ(ppm)：1.23(t，6H，2CH3)，3.00(t，8H，4NCH2)，3.58(t，8H，4NCH2)，3.82(q，4H，2OCH2)
Embodiment 7-12 for illustration of the above-mentioned silane compound containing oxaza as the application of the external electron donor in olefin polymerization catalysis and olefine polymerizing process
Embodiment 7
In the double glazing reaction flask of 300mL, add the anhydrous MgCl of 5.0g successively
2, 120ml toluene, 8.0ml epoxy chloropropane, 10.0ml tributyl phosphate, after dissolving completely at 60 DEG C, this solution is cooled to-25 DEG C, drip 50ml titanium tetrachloride, half an hour is maintained at-25 DEG C, add silica gel (DavisonXP02485, before using at 600 DEG C dry 4 hours) 3.0g, diisobutyl phthalate (DIBP) 5mmol is added in temperature-rise period, then elimination liquid after being slowly warming up to 90 DEG C, secondary is washed with titanium tetrachloride, with hexanes wash four times, after vacuum-drying, obtain spherical solid catalyst component.
In 5L autoclave, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, 1.25ml in stream of nitrogen gas as the hexane solution (concentration is 0.1mmol/ml) of the embodiment 1 gained piperazinyl silane compound of external electron donor, 10ml anhydrous n-hexane and above-mentioned spherical solid catalyst component 10mg.Close autoclave, introduce hydrogen 1L (standard volume) and liquid propene 2.3L, be warmed up to 70 DEG C, maintain this temperature 1 hour, cooling, bleed off pressure, obtain PP resin, polymerization result is in table 1.
The testing method related in the embodiment of the present invention is as follows:
1, melt index (MI): measure according to the method specified in ASTMD1238-99.
2, polymkeric substance isotactic index (II): adopt normal heptane extraction process to measure (normal heptane boiling extracting 6 hours), concrete operations are: the polymer samples taking 2g drying, be placed in the normal heptane extracting 6 hours of Soxhlet extractor boiling, then, residuum is dried to constant weight, and the weight (g) of gained residuum and the ratio of 2 are isotactic index.
Embodiment 8-12
Carry out according to the mode of embodiment 7, replaced by the silane compound containing oxaza of the embodiment 2-6 gained of identical weight respectively unlike the silane compound of embodiment 1 gained containing oxaza, obtain PP resin, polymerization result is in table 1.
Table 1
Result as can be seen from above table 1, the polymerization activity of compound prepared by embodiment 1-6, degree of isotacticity and melting index MI are higher.
Claims (11)
1. the preparation method containing the silane compound of oxaza, under the method is included in conditions of replacement reaction, morpholine shown in formula (II) is carried out first with hydrocarbyl lithium in the presence of solvent contact, then the product after contact is carried out second with the silicone compounds shown in formula (III) to contact, to obtain the silane compound containing oxaza shown in formula (I);
Wherein, m and n is 0 or 1, and is asynchronously 0; R
1, R
2identical or not identical, be methyl or ethyl separately, R
4, R
5for H or carbonatoms are the alkyl of 1-2, when A is oxygen, o=p=2, R
3do not exist;
Wherein, in mole, the morpholine shown in described formula (II): hydrocarbyl lithium: the silicone compounds=1:1-3:0.4-0.7 shown in formula (III); The 5-30 that the consumption of described solvent is the silicone compounds gross weight shown in the morpholine shown in formula (II), hydrocarbyl lithium and formula (III) doubly.
2. the preparation method of the silane compound containing oxaza according to claim 1, wherein, the condition of described first contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 10-200 minute; The condition of described second contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 1-24 hour.
3., containing a preparation method for the silane compound of oxaza, the method comprises the one in following method:
Method one: under conditions of replacement reaction, carries out first with hydrocarbyl lithium in the presence of solvent by the morpholine shown in formula (II) and contacts, and the product after then contacting first carries out second with the silicone compounds shown in formula (III) and contacts; Nitrogen-containing heterocycle compound shown in formula (IV) is carried out the 3rd with hydrocarbyl lithium in the presence of solvent contact, then the product after the product after contacting the 3rd contacts with second carries out the 4th contact, to obtain the silane compound containing oxaza shown in formula (I);
Method two: under conditions of replacement reaction, nitrogen-containing heterocycle compound shown in formula (IV) is carried out the 5th with hydrocarbyl lithium in the presence of solvent contact, the product after then contacting the 5th carries out the 6th with the silicone compounds shown in formula (III) and contacts; Morpholine shown in formula (II) is carried out the 7th with hydrocarbyl lithium in the presence of solvent contact; Then the product after the product after contacting the 7th contacts with the 6th carries out the 8th contact, to obtain the silane compound containing oxaza shown in formula (I);
Wherein, m and n is 0 or 1, and is asynchronously 0; R
1, R
2identical or not identical, be methyl or ethyl separately; A is C, N or O, and when A is C, o is 1, p is 2, R
3for hydrogen; When A is oxygen, o=p=2, R
3do not exist; When A is N, o=p=2, R
3for methyl; R
4, R
5for H or carbonatoms are the alkyl of 1-2;
Wherein, in mole, the morpholine shown in described formula (II): hydrocarbyl lithium: the silicone compounds shown in formula (III): the nitrogen-containing heterocycle compound=1:1-5:1-5:1-5 shown in formula (IV); The 5-30 that the consumption of described solvent is the nitrogen-containing heterocycle compound shown in the morpholine shown in formula (II), hydrocarbyl lithium, formula (IV) and the silicone compounds gross weight shown in formula (III) doubly.
4. the preparation method of the silane compound containing oxaza according to claim 3, wherein, the condition of described first contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 10-200 minute; The condition of described second contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 1-24 hour; The condition of described 3rd contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 10-200 minute; The condition of described 4th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 1-24 hour; The condition of described 5th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 10-200 minute; The condition of described 6th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 1-24 hour; The condition of described 7th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 10-200 minute; The condition of described 8th contact comprises protection of inert gas atmosphere, and temperature is-15 DEG C to 20 DEG C, and the time is 1-24 hour.
5. the preparation method of the silane compound containing oxaza according to claim 3, wherein, in mole, the morpholine shown in described formula (II): hydrocarbyl lithium: the silicone compounds shown in formula (III): the nitrogen-containing heterocycle compound=1:1-5:1-5:1-5 shown in formula (IV); The 5-30 that the consumption of described solvent is the nitrogen-containing heterocycle compound shown in the morpholine shown in formula (II), hydrocarbyl lithium, formula (IV) and the silicone compounds gross weight shown in formula (III) doubly.
6. according to the preparation method of the silane compound containing oxaza in claim 3-5 described in any one, wherein, described hydrocarbyl lithium is selected from one or more in n-Butyl Lithium, lithium methide and phenyl lithium; Silicone compounds shown in described formula (III) be selected from tetramethoxy-silicane, tetraethoxysilane one or more; Nitrogen-containing heterocycle compound shown in described formula (IV) is one or more in tetramethyleneimine and (N-alkyl) piperazine, and described alkyl is the alkyl of carbonatoms 1-6; Described solvent is aprotic solvent.
7. the preparation method of the silane compound containing oxaza according to claim 6, wherein, described hydrocarbyl lithium is n-Butyl Lithium; Described (N-alkyl) piperazine is (N-methyl) piperazine; Described solvent is one or more in acid amides, halohydrocarbon, hydrocarbon, ether.
8. the preparation method of the silane compound containing oxaza according to claim 7, wherein, described solvent is one or more in methylene dichloride, trichloromethane, benzene, toluene, normal hexane, hexanaphthene, sherwood oil, ether, tetrahydrofuran (THF), methyl tertiary butyl ether and DMF.
9. the preparation method of the silane compound containing oxaza according to claim 8, wherein, described solvent is normal hexane.
10. the silane compound containing oxaza prepared by the preparation method in claim 1-2 and claim 3-9 described in any one is as the application of the external electron donor in olefin polymerization catalysis.
11. 1 kinds of olefine polymerizing process, under the method is included in the existence of a kind of olefin polymerization catalyst system, alkene is polymerized, described olefin polymerization catalyst system comprises solids containing titanium catalyst component, alkylaluminium cpd and external electron donor, it is characterized in that, the silane compound containing oxaza that described external electron donor is prepared for the preparation method in claim 1-2 and claim 3-9 described in any one.
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