CN102453133B - Olefin polymeric catalyst system and olefin polymerization method by using catalyst system thereof - Google Patents
Olefin polymeric catalyst system and olefin polymerization method by using catalyst system thereof Download PDFInfo
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- CN102453133B CN102453133B CN 201010517800 CN201010517800A CN102453133B CN 102453133 B CN102453133 B CN 102453133B CN 201010517800 CN201010517800 CN 201010517800 CN 201010517800 A CN201010517800 A CN 201010517800A CN 102453133 B CN102453133 B CN 102453133B
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- 0 CCCCCc1c(C)c(*(C)(CCC)Cc2cc(*)cc(Cc3cc(*)cc(Cc4cc(*)cc(CCCC)c4*)c3C)c2O)cc(*)c1 Chemical compound CCCCCc1c(C)c(*(C)(CCC)Cc2cc(*)cc(Cc3cc(*)cc(Cc4cc(*)cc(CCCC)c4*)c3C)c2O)cc(*)c1 0.000 description 2
Abstract
The present invention provides an olefin polymeric catalyze system, the catalyst system comprises a solid component and an external electron donor compound. The solid component contains titanium, magnesium and the external electron donor compound, wherein the external electron donor compound is a silane compound containing calixarene and amino and a diether compound. The polymerization activity of the olefin polymeric catalyst is increased by comparing with exclusive use of PPDE, the hydrogen modulation susceptibility of the catalyst is substantially enhanced. The molecular weight distribution of the obtained polymer is wider than the molecular weight distribution of the polymer obtained by individually using the diether compound.
Description
Technical field
The olefine polymerizing process that the present invention relates to olefin polymerization catalyst system and use this catalyst system.
Background technology
The catalyzer of propylene polymerization generally includes Ziegler-Natta type (Ziegler-Natta type) Primary Catalysts, organoaluminum promotor, internal electron donor compound and external donor compound.
Since the fifties, polypropylene catalyst has experienced following development course: first-generation catalyzer is TiCl
3alCl
3/ AlEt
2the Cl system; S-generation catalyzer is TiCl
3/ AlEt
2the Cl system; Third generation catalyzer be take magnesium chloride as carrier, take benzoic ether as the internal electron donor compound, with TiCl
4as Primary Catalysts, using aluminum alkyls as promotor; The 4th generation catalyzer take phthalic ester as the internal electron donor compound, take silane as external donor compound, with TiCl
4as Primary Catalysts, with MgCl
2as carrier, using aluminum alkyls as promotor.
In olefin polymerization catalyst system, external donor compound is combined with the purpose that can reach the degree of isotacticity that improves polymkeric substance with the internal electron donor compound.The external donor compound of widespread use at present is organosilicone compounds.The organosilicone compounds of usining is applied to as the catalyst system of external donor compound the polypropylene that propylene polymerization can obtain high isotactic, medium molecular weight distributions.But the organo-siloxane of usining exists as the olefin polymerization catalysis of external donor compound the problem that hydrogen response is not high, the melting index of polymkeric substance changes not obvious with the add-on of hydrogen.
For this reason, someone attempts using diether compounds as external donor compound, for example, CN1143651 discloses with ring polyenoid 1, effect when the 3-diether is applied to propylene polymerization as external donor compound, this catalyst system has the advantages that hydrogen response is high, but molecular weight distribution is narrower, and activity also has much room for improvement in addition.
Therefore, development of new is for the external donor compound of olefin polymerization catalysis, thereby the hydrogen response that further improves olefin polymerization catalysis remains a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to overcome the problem that is difficult to take into account hydrogen response and molecular weight distribution that the olefin polymerization catalyst system of existing external donor compound exists, provide a kind of and using the compound that contains calixarene radical and diether compounds as the olefin polymerization catalyst system of external donor compound and the olefine polymerizing process that uses this catalyst system, the compound that described olefin polymerization catalyst system is used diether compounds and contains calixarene radical is as external donor compound, thereby there is high hydrogen response, and can the preparation of high reactivity ground there is the polymkeric substance than wide molecular weight distribution.
The invention provides a kind of olefin polymerization catalyst system, this catalyst system comprises solid ingredient and external donor compound, and described solid ingredient contains titanium, magnesium and internal electron donor compound, wherein, described external donor compound contains the compound shown in formula 1 and diether compounds
In formula 1:
B is the calixarene radical shown in formula 2;
Two R
1identical or different, C respectively does for oneself
1-C
8the straight or branched alkyl in a kind of;
Two R
3identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl, C
6-C
12replacement or unsubstituted aryl, C
7-C
12arylalkyl, C
8-C
12aryl alkenyl and C
2-C
10the straight or branched thiazolinyl in a kind of, and two R
3when different, be hydrogen; Perhaps two R
3with together with N condenses to form saturated or undersaturated assorted monocycle or assorted dicyclo,
In formula 2:
A plurality of R
5identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl,
and C
6-C
12replacement or unsubstituted aryl in a kind of;
A plurality of R
6identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
1-C
12the straight or branched alkoxyl group,
and C
6-C
12replacement or unsubstituted aryl in a kind of,
R
12and R
13c respectively does for oneself
1-C
12straight or branched alkyl, C
7-C
12arylalkyl, C
8-C
12aryl alkenyl, C
3-C
10replacement or unsubstituted cycloalkyl, C
2-C
10straight or branched thiazolinyl and C
6-C
12replacement or unsubstituted aryl in a kind of, R
14for C
1-C
12the straight or branched alkylidene group;
The integer that n is 1-5.
The present invention also provides a kind of olefine polymerizing process, and the method is included under the olefinic polymerization condition, and one or more alkene are contacted with organo-aluminium compound with catalyzer, and wherein, described catalyzer is olefin polymerization catalyst system provided by the invention.
The compound that uses diether compounds and contain calixarene radical and silicon amine groups according to alkene catalyst system of the present invention is as external donor compound, thereby there is high hydrogen response, and can the preparation of high reactivity ground there is the polymkeric substance than wide molecular weight distribution.
Embodiment
The invention provides a kind of olefin polymerization catalyst system, this catalyst system comprises solid ingredient and external donor compound, and described solid ingredient contains titanium, magnesium and internal electron donor compound, wherein, described external donor compound contains the compound shown in formula 1 and diether compounds
In formula 1:
B is the calixarene radical shown in formula 2;
Two R
1identical or different, C respectively does for oneself
1-C
8the straight or branched alkyl in a kind of;
Two R
3identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl, C
6-C
12replacement or unsubstituted aryl, C
7-C
12arylalkyl, C
8-C
12aryl alkenyl and C
2-C
10the straight or branched thiazolinyl in a kind of, and two R
3when different, be hydrogen; Perhaps two R
3with together with N condenses to form saturated or undersaturated assorted monocycle or assorted dicyclo,
In formula 2:
A plurality of R
5identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl,
and C
6-C
12replacement or unsubstituted aryl in a kind of;
A plurality of R
6identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
1-C
12the straight or branched alkoxyl group,
and C
6-C
12replacement or unsubstituted aryl in a kind of,
R
12and R
13c respectively does for oneself
1-C
12straight or branched alkyl, C
7-C
12arylalkyl, C
8-C
12aryl alkenyl, C
3-C
10replacement or unsubstituted cycloalkyl, C
2-C
10straight or branched thiazolinyl and C
6-C
12replacement or unsubstituted aryl in a kind of, R
14for C
1-C
12the straight or branched alkylidene group;
The integer that n is 1-5.
In the present invention, C
1-C
12the straight or branched alkoxyl group can there is following chemical formula: R
2o-, wherein, R
2for C
1-C
12the straight or branched alkyl.
In the present invention, C
1-C
12the example of straight or branched alkyl can include, but are not limited to: 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.
In the present invention, C
1-C
12the example of straight or branched alkylidene group can include but not limited to: methylene radical, ethylidene, inferior n-propyl, isopropylidene, inferior normal-butyl, inferior sec-butyl, isobutylidene, the inferior tertiary butyl, inferior n-pentyl, isopentylidene, inferior tert-pentyl, inferior neo-pentyl, inferior n-hexyl, inferior n-heptyl, inferior n-octyl, inferior positive decyl and inferior dodecyl.
In the present invention, C
3-C
10replacement or the example of unsubstituted cycloalkyl can include but not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethyl cyclohexyl, 4-n-propyl cyclohexyl and 4-normal-butyl cyclohexyl.
In the present invention, C
6-C
12replacement or the example of unsubstituted aryl can include but not limited to: phenyl, naphthyl, 4-aminomethyl phenyl and 4-ethylphenyl.
In the present invention, C
2-C
10the example of straight or branched thiazolinyl can include but not limited to: vinyl and allyl group.
In the present invention, C
7-C
12the example of arylalkyl can include but not limited to: phenyl methyl, phenylethyl, phenyl n-propyl, phenyl normal-butyl, the phenyl tertiary butyl, propyloxy phenyl base, phenyl n-pentyl and phenyl normal-butyl.
In the present invention, C
8-C
12the example of aryl alkenyl can include but not limited to: phenyl vinyl, phenyl n-butene base, the positive pentenyl of phenyl, phenyl n-hexylene base and cinnamyl.
Preferably, in formula 2, a plurality of R
5identical or different, hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl,
and
in a kind of; R
12and R
13c respectively does for oneself
1-C
8straight or branched alkyl, C
3-C
8replacement or unsubstituted cycloalkyl, phenyl and cinnamyl in a kind of, R
14for C
1-C
4the straight or branched alkylidene group.
In formula 2, a plurality of R
6be preferably separately hydrogen or C
1-C
8the straight or branched alkyl.More preferably, a plurality of R
6hydrogen or C respectively do for oneself
1-C
4the straight or branched alkyl.From the angle of being easy to get property of raw material, a plurality of R
6for hydrogen or the tertiary butyl.
Most preferably, in formula 2, a plurality of R
6identical, be hydrogen or the tertiary butyl; A plurality of R
5identical, a kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, ethanoyl, positive propionyl, isopropyl acyl group, positive butyryl radicals, isobutyryl, tertiary butyryl radicals, positive pentanoyl, isovaleryl, ring pentanoyl, positive caproyl, hexamethylene acyl group, positive capryloyl, benzoyl, cinnamoyl, acetic acid ethanoyl, acetic acid propionyl, the positive butyryl radicals of acetic acid and acetic acid isobutyryl.
Particularly, the example of the calixarene radical shown in formula 2 can for but be not limited to:
4-tert-butyl-calix [4] aryl-O, O ', O " trimethylammonium,
4-tert-butyl-calix [4] aryl-O, O ', O " triethyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-n-propyls,
4-tert-butyl-calix [4] aryl-O, O ', O " triisopropyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-normal-butyls,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-sec-butyls,
4-tert-butyl-calix [4] aryl-O, O ', O " triisobutyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-tert,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-n-pentyls,
4-tert-butyl-calix [4] aryl-O, O ', O " triisopentyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-cyclopentyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-n-hexyls,
4-tert-butyl-calix [4] aryl-O, O ', O " thricyclohexyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-n-octyls,
4-tert-butyl-calix [4] aryl-O, O ', O " triacetyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive propionyls,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-isopropyl acyl groups,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive butyryl radicalies,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-tertiary butyryl radicalies,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive pentanoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-isovaleryl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-ring pentanoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive caproyls,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-hexamethylene acyl groups,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive capryloyls,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-benzoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-cinnamoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " the nitrilotriacetic ethanoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " the nitrilotriacetic propionyl,
4-tert-butyl-calix [4] aryl-O, O ', O " the positive butyryl radicals of nitrilotriacetic,
4-tert-butyl-calix [4] aryl-O, O ', O " nitrilotriacetic isobutyryl.
In formula 1, two R
1identical or different, can be C separately
1-C
8the straight or branched alkyl in a kind of, be preferably C
1-C
4the straight or branched alkyl, more preferably methyl or ethyl.In the present invention, two R
1be preferably identical.
In formula 1, two R
3identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl, C
6-C
12replacement or unsubstituted aryl, C
7-C
12arylalkyl, C
8-C
12aryl alkenyl and C
2-C
10the straight or branched thiazolinyl in a kind of, and two R
3when different, be H; Perhaps two R
3with together with N condenses to form saturated or undersaturated assorted monocycle or assorted dicyclo.
A kind of preferred embodiment in, in formula 1, two R
3hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl and C
3-C
8replacement or unsubstituted cycloalkyl in a kind of, and R
3when different, be hydrogen.
A kind of more preferred embodiment in, in formula 1, two R
3a kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, cyclopentyl, n-hexyl, cyclohexyl and n-octyl and two R respectively do for oneself
3when different, be hydrogen.
In another preferred embodiment, two R3 with together with N condenses to form
with
in a kind of ring.
Most preferably, in formula 1, two R
3a kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-and the tertiary butyl and two R respectively do for oneself
3when different, be hydrogen.
According to the present invention, the n in formula 1 can be the integer of 1-5, and for example: n can be 1,2,3,4 or 5.Preferably, the integer that n is 1-3.More preferably, n is 1 or 2.Most preferably, n is 1.
According to the present invention, the example of the compound that contains calixarene radical shown in formula 1 can include but not limited to: 4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl-O " '-(two n-butyl amine base diethoxies) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl-O " '-(the amino diethoxy of two isobutyls) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl-O " '-(the amino diethoxy of isobutyl) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive butyryl radicals-O " '-(the amino diethoxy of two isobutyls) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl-O " '-(diisopropylaminoethyl diethoxy) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl-O " '-(the amino dimethoxy of isobutyl) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl-O " '-(diethylin diethoxy) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl-O " '-(two n-propylamine base diethoxies) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " triacetyl-O " '-(two n-butyl amine base diethoxies) silane, 4-tert-butyl-calix [4] aryl-O, O ', O " tri-propionyls-O " '-(two n-butyl amine base diethoxies) silane and 4-tert-butyl-calix [4] aryl-O, O ', one or more in O " triacetyl-O " '-(diethylin diethoxy) silane.
According in olefin polymerization catalyst system of the present invention, as the compound that contains calixarene radical shown in the formula 1 of external donor compound, can prepare in accordance with the following methods: at the temperature of-70 ℃ to 10 ℃, calixarene compound shown in formula 3 is mixed with the tetraalkoxysilane shown in formula 4, the mixture obtained is reacted to 3-8 hour at the temperature of 40-80 ℃, then at the temperature of-70 ℃ to 10 ℃, by the product that obtains with the compound shown in formula 5 and react 1-2 hour at this temperature, then react again 2-8 hour at the temperature of 40-80 ℃
In formula 3, R
5, R
6and the definition of n and R above
5, R
6and the definition of n is identical, repeats no more herein; In formula 3, M
1for MgX
1or Li, X
1for halogen, for example can in chlorine, bromine and iodine-kind, X
1be preferably chlorine;
In formula 4, R
1definition with above in R
1definition identical, repeat no more herein;
In formula 5, R
3definition with above in R
3definition identical, repeat no more herein; In formula 5, M
2for MgX
2or Li, X
2for halogen, for example can be in chlorine, bromine and iodine a kind of, X
2be preferably chlorine.
According to the present invention, the example of four oxyalkylsiloxane shown in formula 4 can include but not limited to: a kind of in tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane and four (2-ethyl hexyl oxy) silane.Preferably, four oxyalkylsiloxane shown in formula 4 are a kind of in tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan and four n-butoxy silane.More preferably, four oxyalkylsiloxane shown in formula 4 are tetramethoxy-silicane or tetraethoxysilane.Most preferably, four oxyalkylsiloxane shown in formula 4 are tetraethoxysilane.
According to the present invention, the mol ratio of the compound shown in the tetraalkoxysilane shown in the calixarene compound shown in formula 3, formula 4 and formula 5 can be 1: 1-3: 1-5.Under the prerequisite of the productive rate of guaranteeing the compound shown in formula 1, angle from the cost of further reduction olefin polymerization catalyst system of the present invention, the mol ratio of the compound shown in the tetraalkoxysilane shown in the calixarene compound shown in formula 3, formula 4 and formula 5 is preferably 1: 1-2: 1-2, more preferably 1: 1-1.2: 1-1.2.
According to the present invention, mixing temperature, temperature of reaction and the time of the tetraalkoxysilane shown in the calixarene compound shown in formula 3 and formula 4 can be carried out appropriate selection according to the structure of the tetraalkoxysilane shown in the calixarene compound shown in formula 3 and formula 4.Usually, the temperature that the calixarene compound shown in formula 3 is mixed with the tetraalkoxysilane shown in formula 4 can be-70 ℃ to 10 ℃, is preferably-30 ℃ to 10 ℃; The mixture of the calixarene compound shown in formula 3 and the tetraalkoxysilane shown in formula 4 can 40-80 ℃, be preferably at the temperature of 50-60 ℃ and react 3-8 hour, be preferably 2-5 hour.
According to the present invention, the temperature of the reaction product of the tetraalkoxysilane shown in the calixarene compound shown in formula 3 and formula 4 and the compound shown in formula 5 can be-70 ℃ to 10 ℃, be preferably-30 ℃ to 10 ℃, the reaction times at this temperature can be 1-2 hour; Calixarene compound shown in formula 3 and the reaction product of the tetraalkoxysilane shown in formula 4 and the compound reaction product at low temperatures shown in formula 5 can 40-80 ℃, be preferably at the temperature of 50-60 ℃ and continue to react 2-8 hour, be preferably 2-5 hour.
According to the present invention, the calixarene compound shown in formula 3 and the tetraalkoxysilane shown in formula 4 react and formula 3 shown in calixarene compound react the product obtained with the tetraalkoxysilane shown in formula 4 and can carry out in the organic solvent commonly used in this area with reacting of the compound shown in formula 5.Preferably, described organic solvent is tetrahydrofuran (THF) (THF), toluene, hexanaphthene, 1, one or more in 2-ethylene dichloride and vinyl trichloride.The consumption of described organic solvent is not particularly limited, and usually, it is the 5-20 % by weight that the consumption of described organic solvent makes the concentration of the calixarene compound shown in formula 3.According to the present invention, before being used, described organic solvent preferably adopt this area method commonly used to carry out drying, for example: when using tetrahydrofuran (THF) as solvent, can be by sodium, refluxing tetrahydrofuran (THF) carried out to drying.
According to the present invention, calixarene compound shown in formula 3 and the tetraalkoxysilane shown in formula 4 react and formula 3 shown in calixarene compound react the product obtained with the tetraalkoxysilane shown in formula 4 and carry out under inert gas atmosphere with reacting preferably of the compound shown in formula 5, can avoid like this detrimentally affect of airborne water and oxygen.In the present invention, described rare gas element do not refer to, with reactant, chemically interactive gas occurs, for example: the neutral element gas (as argon gas) in nitrogen and the periodic table of elements.
According to the present invention, the compound shown in formula 3 can adopt the ordinary method in organic synthesis field to be synthesized, and is not particularly limited.Preferably, in the present invention, the preparation method of the calixarene compound shown in formula 3 comprises: under etherification conditions or enzymatic synthesis condition, by calixarene and the R shown in formula 6
5x
3take mol ratio as 1: 3-3.6 is contacted, then by the product and the R that obtain
7mgX
5(that is, Grignard reagent) or R
8li (that is, organolithium compound) be take mol ratio as 1: 1-1.2-70 ℃ to 10 ℃, preferably at the temperature of-30 ℃ to 10 ℃, mix, and by the mixture that obtains 40-80 ℃, preferably at the temperature of 40-60 ℃, reacted, wherein, R
7and R
8c respectively does for oneself
1-C
5direct-connected or branched-chain alkyl, X
3and X
5the halogen of respectively doing for oneself, for example can be in chlorine, bromine and iodine a kind of, be preferably chlorine or bromine, chlorine more preferably,
In formula 6, R
6definition with above in R
6definition identical, repeat no more herein;
R
5x
3in R
5definition with above in R
5definition identical, repeat no more herein.
Wherein, at R
5for C
1-C
12straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl and C
6-C
12replacement or during unsubstituted aryl, the calixarene shown in formula 6 and R
5x
3contact under etherification conditions, carry out; At R
5for
the time, the calixarene shown in formula 6 and R
5x
3contact under enzymatic synthesis condition, carry out.
According to the present invention, R
5x
3be preferably monochloro methane, monobromethane, methyl iodide, monochloroethane, monobromethane, iodoethane, the chloro n-propane, n-propyl bromide, propyl iodide, Iso-Propyl iodide, chloroisopropane, bromination of n-butane, n-propylcarbinyl chloride, iodo-n-butane, sec-butyliodide, chloro-chung butane, chung-bromo butane, isobutane bromide, chloro-iso-butane, iodo isobutane, tert-bromo butane, tert-butyl chloride, iodo-tert-butane, the iodo Skellysolve A, the chloro iso-pentane, chlorocyclopentane, the iodo pentamethylene, bromocyclopentane, the chloro normal hexane, chlorocyclohexane, bromocyclohexane, n-octane bromide, the bromo tetramethylene, bromocyclohexane, Acetyl Chloride 98Min., positive propionyl chloride, the isopropyl acyl chlorides, n-butyryl chloride, isobutyryl chloride, 2, 2-dimethyl propylene acyl chlorides, n-amyl chloride, isoveryl chloride, positive caproyl chloride, cyclohexanecarbonyl chloride, positive capryl(yl)chloride, Benzoyl chloride, acetoxyacetyl chloride, the acetic acid propionyl chloride, the acetic acid n-butyryl chloride, a kind of in acetic acid isobutyryl chloride and cinnamyl chloride.
According to the present invention, the calixarene shown in formula 6 and R
5x
3take mol ratio as 1: 3-3.6 is contacted.At calixarene and the R shown in formula 6
5x
3mol ratio within above-mentioned scope the time, can be with the calixarene shown in high productive rate preparation formula 3.More preferably, the calixarene shown in formula 6 and R
5x
3take mol ratio as 1: 3.15-3.3 is contacted.
According to the present invention, the esterification that described esterification or etherification conditions can be known to the skilled person or etherification conditions, be not particularly limited.Preferably, described enzymatic synthesis condition can comprise: at the temperature of-50 ℃ to 10 ℃ by calixarene and the R shown in formula 6
5x
3mix, then reaction 1-3 hour at the temperature of 15-30 ℃, then reaction 0.5-6 hour at the temperature of 50-80 ℃.Preferably, described etherification conditions can comprise: at the temperature of-50 ℃ to 10 ℃ by calixarene and the R shown in formula 6
5x
3mix, then reaction 1-3 hour at the temperature of 15-30 ℃, then reaction 0.5-6 hour at the temperature of 50-80 ℃.
According to the present invention, the calixarene shown in formula 6 and R
5x
3contact preferably under the existence of basic cpd, carry out, the calixarene shown in formula 6 and R
5x
3while being contacted, can generate HX under enzymatic synthesis condition
3, described basic nitrogen compound can with HX
3form salt, thereby further improve the productive rate of the compound shown in formula 3.The mol ratio of the compound shown in described basic cpd and formula 6 can be 3-3.9: 1, be preferably 3.15-3.3: 1.Described basic cpd can form the basic nitrogen compound of salt for commonly used various in organic synthesis field with acid, for example: triethylamine, pyridine.
According to the present invention, the calixarene shown in formula 6 and R
5x
3contact can in organic solvent commonly used, carry out.For example,, at calixarene and the R shown in formula 6
5x
3while being contacted, described organic solvent can be one or more in ether, ethyl acetate, toluene, methylene dichloride and trichloromethane.From the angle of the productive rate of the calixarene compound shown in further raising formula 3, described organic solvent, before using, preferably adopts the method that well known to a person skilled in the art to carry out drying treatment.
According to the present invention, by calixarene and the R shown in formula 6
5x
3product and R that reaction obtains
7mgX
5(that is, Grignard reagent) or R
8li (, organolithium compound) take mol ratio as 1: 1-1.5, preferably take mol ratio as 1: 1-1.2 is at-70 ℃ to 10 ℃, be preferably-30 ℃ and mixed to the temperature of 10 ℃, and the mix products obtained is reacted at the temperature of 40-80 ℃, preferred 40-60 ℃.
According to the present invention, the compound shown in formula 5 can adopt those skilled in the art's method preparation commonly used.Preferably, the preparation method of the compound shown in formula 5 comprises :-70 ℃ to 10 ℃, preferably-30 ℃ to the temperature of 10 ℃, by amine and the R shown in formula 7
4mgX
6(that is, Grignard reagent) or R
9li (that is, organolithium compound) be take mol ratio as 1: the 1-1.2 mixing, and react 2-8 hour, preferred 2-6 hour at the temperature of 40-80 ℃, preferred 40-60 ℃; R
4and R
9c respectively does for oneself
1-C
5alkyl; X
6for example, for halogen (: chlorine, bromine, iodine), be preferably chlorine or bromine, more preferably chlorine;
In formula 7, R
3definition with above in R
3definition identical, repeat no more herein.
According to the present invention, the amine shown in formula 7 is preferably a kind of in methylamine, dimethylamine, ethamine, diethylamine, Tri N-Propyl Amine, di-n-propylamine, Isopropylamine, Diisopropylamine, n-Butyl Amine 99, Di-n-Butyl Amine, isobutylamine, diisobutylamine, TERTIARY BUTYL AMINE, two TERTIARY BUTYL AMINE, sec-butylamine, di-sec-butylamine, n-amylamine, two n-amylamines, isobutylcarbylamine, di-iso-amylamine, tertiary amylamine, two tertiary amylamines, neopentyl amine, two neopentyl amines, cyclopentamine, hexahydroaniline and n-octyl amine.More preferably, the amine shown in formula 7 is a kind of in methylamine, dimethylamine, ethamine, diethylamine, Tri N-Propyl Amine, di-n-propylamine, Isopropylamine, Diisopropylamine, n-Butyl Amine 99, Di-n-Butyl Amine, isobutylamine, diisobutylamine, TERTIARY BUTYL AMINE, two TERTIARY BUTYL AMINE, sec-butylamine and di-sec-butylamine.
According to the present invention, the calixarene compound shown in formula 6 can adopt the method for well known to a person skilled in the art synthetic, also can be commercially available.
According to the present invention, the calixarene shown in formula 6 most preferably is 4-tert-butyl-calix [4] aromatic hydrocarbons.
According to olefin polymerization catalysis of the present invention, described external donor compound also contains diether compounds.The present invention is not particularly limited for the kind of described diether compounds, can be the diether compounds of this area various external donor compounds as olefin polymerization catalysis commonly used.Preferably, described diether compounds has the structure shown in formula 10:
Wherein: R, R
i, R
iI, R
iII, R
iVand R
videntical or different, hydrogen or C respectively do for oneself
1-C
18straight chain or branched-alkyl, C
3-C
8cycloalkyl, C
6-C
12a kind of in aryl, and R and R
ican not be all H or CH
3;
R
vIand R
vIIidentical or different, C respectively does for oneself
1-C
18straight chain or branched-alkyl, C
3-C
8cycloalkyl, C
6-C
12a kind of in aryl; Perhaps
R, R
i, R
iI, R
iII, R
iVand R
videntical or different, hydrogen or C respectively do for oneself
1-C
18straight chain or branched-alkyl, C
3-C
8cycloalkyl, C
6-C
12a kind of in aryl, and R and R
ican not be all H or CH
3;
R
vIand R
vIIidentical or different, C respectively does for oneself
1-C
18straight chain or branched-alkyl, C
3-C
8cycloalkyl, C
6-C
12a kind of in aryl; And R, R
i, R
iI, R
iII, R
iV, R
vand R
vIIin two Cheng Huan.
More preferably, in formula 10, R, R
i, R
iI, R
iII, R
iVand R
videntical or different, hydrogen or C respectively do for oneself
1-C
5straight chained alkyl or branched-alkyl in a kind of, and R and R
ican not be all H or CH
3; R
vIand R
vIIidentical or different, C respectively does for oneself
1-C
3straight chained alkyl.
Most preferably, described diether compounds can be 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (PPDE).
According to olefin polymerization catalysis of the present invention, the ratio of the compound shown in formula 1 and described diether compounds can in very large range change.The present inventor finds in research process, in the mol ratio of the compound shown in formula 1 and described diether compounds in 0.5-20: in the time of in 1 scope, olefin polymerization catalysis according to the present invention has high stereoselectivity and high hydrogen response.More preferably, the mol ratio of the compound shown in formula 1 and described diether compounds is 1-15: 1.Guaranteeing under the prerequisite of hydrogen response, from the angle of the cost of further reduction olefin polymerization catalysis of the present invention, the mol ratio of the compound shown in formula 1 and described diether compounds most preferably is 1-10: 1.
According to olefin polymerization catalysis of the present invention, the amount of described external donor compound can be the conventional amount used of this area.Preferably, the mol ratio of the silicon in the titanium in described solid ingredient and described external donor compound can be 1: 10-500 is preferably 1: 25-100.
According to the present invention, the mol ratio of described titanium compound, internal electron donor compound and magnesium compound is well known to a person skilled in the art.Usually, the mol ratio of described titanium compound, internal electron donor compound and magnesium compound can be 0.5-150: 0.02-0.4: 1, be preferably 2-50: 0.06-0.2: 1.
According to the present invention, described internal electron donor compound can be field of olefin polymerisation various internal electron donor compounds commonly used.Preferably, described internal electron donor compound is n-butyl phthalate and/or diisobutyl phthalate.
According to the present invention, described magnesium compound can be one or more in the alcohol adducts of the magnesium compound shown in the magnesium compound shown in formula 8 and formula 8,
MgR
11R
15 (8)
In formula 8, R
11and R
15halogen, C respectively do for oneself
1-C
5straight or branched alkoxyl group and C
1-C
5the straight or branched alkyl in a kind of.In the present invention, described alcohol adducts refers to MgR
11r
15pR
10oH, wherein, R
10for C
1-C
18alkyl, be preferably C
1-C
5the straight or branched alkyl, more preferably methyl, ethyl, n-propyl and sec.-propyl; Within the scope of the numerical value of p in 0.1-6, preferably within the scope in 2-3.5.Preferably, in formula 8, R
11and R
15the halogen of respectively doing for oneself, for example can be in chlorine, bromine and iodine a kind of.
Preferably, the alcohol adducts that described magnesium compound is magnesium dihalide and/or magnesium dihalide.One or more in the alcohol adducts of the alcohol adducts that more preferably, described magnesium compound is magnesium dichloride, dibrominated magnesium, two magnesium iodides, magnesium dichloride, the alcohol adducts of dibrominated magnesium and two magnesium iodides.Most preferably, described magnesium compound is magnesium dichloride.
According to the present invention, described titanium compound can be various titanium compounds commonly used in olefin polymerization catalysis.Preferably, described titanium compound has the structure shown in formula 9,
TiX
4 m(OR
16)
4-m (9)
In formula 9, X
4for halogen, R
16for C
1-C
20alkyl, the integer that m is 0-4.In formula 9, m can be for example 0,1,2,3 or 4.Described halogen can be chlorine, bromine or iodine.
Preferably, in formula 9, X
4for halogen, R
16for C
1-C
5alkyl, for example: one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.More preferably, in formula 9, X
4for halogen, R
16for C
1-C
5alkyl, the integer that m is 1-4, for example: one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.Most preferably, described titanium compound is titanium tetrachloride.
Can adopt the method for well known to a person skilled in the art to prepare described solid ingredient.Usually, the preparation method of described solid ingredient comprises: described magnesium compound is contacted in solvent with epoxy compounds, organo phosphorous compounds, product after contact is contacted with described titanium compound, and temperature is increased to 70-90 ℃, add again described internal electron donor compound, then carry out solid-liquid separation.A kind of preferred embodiment in, under the existence of precipitation additive, temperature is increased to 70-90 ℃.In another preferred embodiment, the method also comprises that the solid phase that solid-liquid separation is obtained contacts with the solution that contains titanium tetrahalide, this preferred embodiment under, the amount of the titanium elements in the described solid ingredient finally obtained also comprises the titanium in titanium tetrahalide.
Described epoxy compounds can be C for carbonatoms
2-C
8oxide compound, the C of alkene
2-C
8glycidyl ether and C
2-C
8inner ether in one or more.Preferably, one or more in the oxide compound that described epoxy compounds is oxyethane, propylene oxide, butylene oxide ring, divinyl, double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether and the tetrahydrofuran (THF) of divinyl.
Described organo phosphorous compounds can be the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate and/or phosphorous acid.Preferably, described organo phosphorous compounds is one or more in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, tributyl phosphate and triphenyl phosphite.
Described precipitation additive can be one or more in organic acid anhydride, organic acid, ether and ketone, is preferably C
2-C
20organic acid anhydride, C
2-C
20organic acid, C
2-C
20ether and C
2-C
20ketone in one or more.More preferably, described precipitation additive is one or more in diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, 2-butanone, benzophenone, methyl ether, ether, propyl ether, butyl ether and amyl ether.
The consumption of described epoxy compounds, organo phosphorous compounds and precipitation additive can be conventional amount used, preferably, with respect to 1 mole of magnesium compound, the consumption of described epoxide is 0.2-10 mole, the consumption of described organo phosphorous compounds is 0.1-3 mole, and the consumption of described precipitation additive is 0.005-1 mole.
For the solvent that described magnesium compound is contacted with epoxy compounds, organo phosphorous compounds, can, for the conventional solvent of this area, be not particularly limited.Preferably, the solvent contacted with epoxy compounds, organo phosphorous compounds for described magnesium compound is one or more of toluene, benzene and chlorobenzene.The present invention also is not particularly limited for the consumption of described solvent, can be the conventional amount used of this area.
According to the present invention, described external donor compound separates and deposits with described solid ingredient.Can adopt the method for well known to a person skilled in the art to use olefin polymerization catalyst system of the present invention.In embodiments of the invention, according to the using method of olefin polymerization catalyst system of the present invention, be: described external donor compound is mixed with to solution, during use, external donor compound solution and solid ingredient is added in olefin polymerization system successively.
The solvent of preparing the solution of described external donor compound can be the various organic solvents that can dissolve described external donor compound and can not have a negative impact to olefinic polyreaction.Preferably, described organic solvent can be one or more in trimethyl aluminium, triethyl aluminum, diethyl aluminum chloride and ethylaluminum dichloride.The concentration of solution can be the concentration of this area routine.
The present invention also provides a kind of olefine polymerizing process, and the method is included under the olefinic polymerization condition, and one or more alkene are contacted with organo-aluminium compound with catalyzer, and wherein, described catalyzer is described catalyst system provided by the invention.
Described organo-aluminium compound can be the field of olefin polymerisation various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst commonly used.Described organo-aluminium compound for example can trimethyl aluminium, one or more in triethyl aluminum, triisobutyl aluminium, three hexyl aluminium, aluminium diethyl monochloride, trioctylaluminum and three decyl aluminium.Preferably, described aluminum alkyls is one or more in trimethyl aluminium, triethyl aluminum and aluminium diethyl monochloride.
The consumption of described organo-aluminium compound can be the conventional amount used of this area.Usually, in the titanium in described solid ingredient and described organo-aluminium compound, the mol ratio of aluminium can be 1: 5-1000.Preferably, the mol ratio of the titanium in described solid ingredient and the aluminium in described organo-aluminium compound is 1: 5-500.More preferably, the mol ratio of the titanium in described solid ingredient and the aluminium in described organo-aluminium compound is 1: 5-250.
Can be for the equal polymerization of alkene according to olefine polymerizing process of the present invention, also can be for multiple alkene be carried out to copolymerization.Described alkene can be ethene, C
3-C
101-alkene and C
4-C
8diolefin in one or more.The specific examples of described alkene comprises: ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.Preferably, described alkene is one or more in ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene.
Olefine polymerizing process according to the present invention is specially adapted to the equal polymerization of propylene and the copolymerization of propylene, for example the copolymerization of one or more in propylene and ethene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.
According to olefine polymerizing process of the present invention, described olefinic polymerization condition can be the normal condition of this area.Usually, described olefinic polymerization condition comprises: temperature is 0-150 ℃, and the time is 0.5-5 hour, and pressure is 0.01-10MPa.Preferably, described olefinic polymerization condition comprises: temperature is 60-90 ℃, and the time is 0.5-2 hour, and pressure is 0.05-1.5MPa.
According to olefine polymerizing process of the present invention, when described contact is carried out under solvent exists, described olefinic polymerization condition comprises: temperature can be 0-150 ℃, time can be 0.5-5 hour, pressure can be 0.01-10MPa, in the titanium elements in solid ingredient, the concentration of described catalyzer in solvent can be 0.1 * 10
-5-5 * 10
-5mol/L.Preferably, described olefinic polymerization condition comprises: temperature is 60-90 ℃, and the time is 0.5-2 hour, and pressure is 0.05-1.5MPa, and in the titanium elements in solid ingredient, the concentration of described catalyzer in solvent is 0.5 * 10
-5-2 * 10
-5mol/L.
According to olefine polymerizing process of the present invention, can adopt this area various polymerization methodses commonly used to realize, for example: can be in gas phase or liquid phase for example, carry out on the tank reactor commonly used in this area or successive polymerization still (: tubular reactor or tower reactor) in the mode of mass polymerization or slurry polymerization.
Describe the present invention in detail below in conjunction with embodiment.
In following examples, on the nuclear magnetic resonance spectrometer that proton nmr spectra is AVANCE300 in the model be purchased from Bruke company, carry out; Under the pressure of the temperature of 230 ℃ and 2.16kg, according in ASTMD1238-99, stipulate method measure the melting index of polymkeric substance; Be purchased on the 721 type ultraviolet spectrophotometers of Tianjin Tuopu Equipment Co., Ltd., adopting the content of titanium in the colorimetric method for determining solid ingredient; The testing method of polymkeric substance degree of isotacticity comprises: the 2g polymer samples is placed in Soxhlet extractor, with heptane extracting 6 hours, then by remaining polymkeric substance drying to constant weight, calculate degree of isotacticity by following formula:
Polymer quality after degree of isotacticity (%)=extracting/2 * 100%.
In following examples, detect number-average molecular weight, weight-average molecular weight and the molecular weight distribution coefficient of polymkeric substance according to gel permeation chromatography (GPC), the tetrahydrofuran (THF) (THF) of take is solvent, at Waters-208 (band Waters 2410 RI detectors, 1.5ml/min flow velocity, 30 ℃) to measure on instrument, number-average molecular weight and weight-average molecular weight are calibrated with the vinylbenzene standard specimen.
Preparation example 1:4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl-O " '-bis-n-butyl amine base diethoxy silane (that is, and in formula I, R
1be ethyl, R
3be normal-butyl, in formula II, R
5be isobutyryl, R
6be the tertiary butyl) synthetic:
(1) preparation of 4-tert-butyl-calix [4] aromatic hydrocarbons
With reference to disclosed method in p-tert-butyl-calix [4] aromatic hydrocarbons (p-tert-Butylcalix[4] arene) (Org.Synth, 68,324,1990), according to following steps, prepare 4-tert-butyl-calix [4] aromatic hydrocarbons:
Under nitrogen protection, add the 10g p-tert-butylphenol in being equipped with the 250mL there-necked flask of whipping appts, dropping funnel and water trap, the formaldehyde that 7mL concentration is 37 % by weight and 0.1g sodium hydroxide (being dissolved in 5g water).Under nitrogen protection, after stirring, there-necked flask is placed in to oil bath, be heated to reflux, and separate water outlet from water trap, after not having moisture to go out in water trap, remove water trap, then 110-120 ℃ of temperature, continue reaction 2h.Then be cooled to room temperature; and add the 100mL phenyl ether in flask; under nitrogen protection, follow to stir to be warming up to backflow, be cooled to room temperature after 2h; with the salt acid for adjusting pH value, be 6-7; add the 125mL ethyl acetate, the rear standing 30min that stirs, and filtered; the ethyl acetate for solid product obtained (20mL * 2) is washed, the dry rear toluene recrystallization of using.
(2) the 4-tertiary butyl-O, O ', the O " preparation of tri-isobutyryl cup [4] aromatic hydrocarbons
Under nitrogen protection; 4-tert-butyl-calix [4] aromatic hydroxy compound that adds step (1) to prepare in being equipped with the 250mL there-necked flask of magnetic stirring apparatus and dropping funnel; after carrying out the vacuum pump drainage; add 150mL THF under nitrogen protection, add pyridine (mol ratio of pyridine and 4-tert-butyl-calix [4] aromatic hydroxy compound is 4: 1) after stirring.Add isobutyryl chloride (mol ratio of isobutyryl chloride and 4-tert-butyl-calix [4] aromatic hydroxy compound is 3: 1) in dropping funnel, and there-necked flask is placed in to ice-water bath, isobutyryl chloride is added drop-wise in there-necked flask.After being added dropwise to complete, remove ice-water bath, continue after reaction 2h, then to be heated to reflux, and to react 6h under refluxing under 25 ℃.Be cooled to room temperature after reaction finishes, and filtered, 30mL THF washing three times for filter cake, merge whole organic phases, and by saturated common salt water washing organic phase, then use the anhydrous sodium sulfate drying organic phase.Underpressure distillation removes desolventizing, and carries out vacuum-drying at the temperature of 50 ℃, obtains 4-tert-butyl-calix [4] aromatic hydrocarbons-O, O ', O " tri-isobutyryl.H
1nMR (300MHz, CDCl
3, δ): 7.05 (6H, phenyl), 6.72 (2H, phenyl), 5.5 (1H ,-OH), 3.85 (8H, CH
2), 2.70 (3H, CH), 1.39 (36H, CH
2), 1.1 (18H, CH
3).
The preparation of (3) two n-butyl amine base magnesium salts
Under nitrogen protection, add 20mL toluene and 4mL Di-n-Butyl Amine in being equipped with the 100mL there-necked flask of magnetic stirring apparatus and dropping funnel, bathe and temperature is cooled to-10 ℃ with cryosel.Add 15mL normal-butyl chlorination magnesium (that is, CH in dropping funnel
3cH
2cH
2cH
2mgCl), follow stirring that normal-butyl chlorination magnesium is added drop-wise in there-necked flask.After being added dropwise to complete, removing the cryosel bath temperature is risen to 50 ℃, continue reaction 4h, then be cooled to room temperature and obtain two n-butyl amine base magnesium salts (that is, (CH
3cH
2cH
2cH
2)
2nMgCl) solution.
(4) the 4-tertiary butyl-O, O ', the O " preparation of the lithium salts of tri-isobutyryl cup [4] aromatic hydrocarbons
Under nitrogen protection, " tri-isobutyryl cup [4] aromatic hydrocarbons, after carrying out the vacuum pump drainage for the 4-tertiary butyl-O that adds 11.5g step (2) to prepare in being equipped with the 250mL there-necked flask of magnetic stirring apparatus and dropping funnel, O ', O.There-necked flask is placed in to ice-water bath, opens and stir, in there-necked flask, add 80mL THF.To the hexane solution of the n-BuLi that adds 10mL 1.6M in dropping funnel and be added drop-wise in there-necked flask.After being added dropwise to complete, removing ice-water bath and be heated to 50 ℃ of reaction 2h.Then be cooled to room temperature, the product obtained is transferred in dropping funnel.
(5) 4-tert-butyl-calix [4] aryl-O, O ', the preparation of O " tri-isobutyryl-O " '-(two n-butyl amine base diethoxies) silane
Add 20mL THF and 3.5mL tetraethoxysilane in the 250mL there-necked flask that is equipped with magnetic stirring apparatus and dropping funnel, there-necked flask is placed in to the cryosel bath and is cooled to-10 ℃, the product of step (4) is added drop-wise in there-necked flask.Temperature is risen to 50 ℃ after being added dropwise to complete, continue reaction 4h.After having reacted, there-necked flask is transferred in the cryosel bath, temperature is reduced to-10 ℃, the product of step (3) is added drop-wise in there-necked flask, and continue reaction 1h.Then remove cryosel and bathe, temperature is increased to 50 ℃, and continue reaction 4h.Then cool the temperature to room temperature, filtered under nitrogen protection.Filtrate is through underpressure distillation except desolventizing, and solid matter carries out vacuum-drying, obtains product 4-tert-butyl-calix [4] aromatic hydrocarbons-O, O ', O " tri-isobutyryl-O " '-(two n-butyl amine base diethoxies) silane.H
1nMR (300MHz, CDCl
3, δ): 7.06 (6H, phenyl), 6.72 (2H, phenyl), 3.83 (4H, CH
2), 3.80 (8H, CH
2), 2.72 (3H, CH), 2.56 (4H, CH
2), 1.41 (4H, CH
2), 1.35 (36H, CH
3), 1.20 (6H, CH
3), 1.09 (18H, CH
3), 0.9 (6H, CH
3).
Preparation example 2:4-tert-butyl-calix [4] aromatic hydrocarbons-O, O ', O " tri-isobutyryl-O " '-(the amino diethoxy of two isobutyls) silane (that is, and in formula I, R
1be ethyl, R
3be isobutyl-, in formula II, R
5be isobutyryl, R
6be the tertiary butyl) synthetic
Adopt the method synthesising title compound identical with preparation example 1, different, replace Di-n-Butyl Amine with diisobutylamine.H
1nMR (300MHz, CDCl
3, δ): 7.06 (6H, phenyl), 6.71 (2H, Ph), 3.83 (4H, CH
2), 3.80 (8H, CH
2), 2.68 (3H, CH), 2.52 (4H, CH
2), 1.67 (2H, CH), 1.35 (36H, CH
3), 1.20 (6H, CH
3), 1.09 (18H, CH
3), 0.9 (12H, CH
3).
Preparation example 3:4-tert-butyl-calix [4] aromatic hydrocarbons-O, O ', O " tri-isobutyryl-O " '-(the amino dimethoxy of isobutyl) silane (that is, and in formula I, R
1be methyl, two R
3in, a R
3for hydrogen, a R
3for isobutyl-, in formula II, R
5be isobutyryl, R
6be the tertiary butyl) synthetic
Adopt the method synthesising title compound identical with preparation example 1, different, replace Di-n-Butyl Amine with isobutylamine, replace tetraethoxysilane with tetramethoxy-silicane.H
1nMR (300MHz, CDCl
3, δ): 7.05 (6H, phenyl), 6.70 (2H, phenyl), 3.81 (8H, CH
2), 3.56 (6H, CH
3), 2.68 (3H, CH), 2.60 (2H, CH
2), 2.5 (1H, NH) 1.67 (H, CH), 1.09 (18H, CH
3), 0.9 (6H, CH
3).
Preparation example 4:4-tert-butyl-calix [4] aromatic hydrocarbons-O, O ', O " tri-isobutyryl-O " '-(diethylin diethoxy) silane (that is, and in formula I, R
1be ethyl, R
3be ethyl, in formula II, R
5be isobutyryl, R
6be the tertiary butyl) synthetic
Adopt the method synthesising title compound identical with preparation example 1, different, replace Di-n-Butyl Amine with diethylamine.H
1nMR (300MHz, CDCl
3, δ): 7.06 (6H, phenyl), 6.71 (2H, phenyl), 3.83 (4H, CH
2), 3.80 (8H, CH
2), 2.68 (3H, CH), 2.59 (4H, CH
2), 1.35 (36H, CH
3), 1.20 (6H, CH
3), 1.09 (18H, CH
3), 1.0 (6H, CH
3).
Embodiment 1
The present embodiment is used for that olefin polymerization catalysis of the present invention is described and uses the olefine polymerizing process of this olefin polymerization catalysis.
(1) in the there-necked flask that carries out fully displacement with high pure nitrogen, add successively 4.8g magnesium chloride, 95mL toluene, 4mL epoxy chloropropane and 12.5mL tributyl phosphate.Follow to stir temperature is increased to 50 ℃, and maintain 2.5 hours.Then, add the 1.4g Tetra hydro Phthalic anhydride, maintain 1 hour under 50 ℃.Solution is cooled to-25 ℃, dripped 56mL TiCl in 1 hour
4.Be warming up to 80 ℃, separate out gradually solids in temperature-rise period.Add the 6mmol n-butyl phthalate, keep 1 hour under 80 ℃.After filtration, add toluene 70ml, washed twice, obtain solid sediment.Then, to the solid sediment obtained, add 60mL toluene, 40mL TiCl
4, be warmed up to 100 ℃, and keep venting filtrate after two hours, then add 60mL toluene, 40mL TiCl
4, be warmed up to 100 ℃, and keep venting filtrate after two hours.Add 60mL toluene, boiling washing three times, then add the 60mL hexane, the boiling washed twice, add the 60mL hexane, after the normal temperature washed twice, obtains the solid ingredient of catalyzer.
(2) use the stainless steel cauldron that volume is 5L, after fully replacing by gaseous propylene, add the AlEt that 4mL concentration is 1mol/L
3hexane solution, with the hexane solution of the organo-aluminium compound of 1mol/L, the compound that contains calixarene radical of preparation example 1 preparation is mixed with to the solution that concentration is 1mol/L, diether compounds (kind of diether compounds is shown in table 1) is mixed with to the hexane solution of 1mol/L, the total addition level of the solution of the compound that contains calixarene radical and the solution of diether compounds is 1mL, it is the ratio provided in table 1 that the solution of the compound that contains calixarene radical and the solution of diether compounds consumption separately make the compound and the diether compounds mol ratio that contain calixarene radical, the catalyst solid constituent that adds again 8mg step (1) to obtain, pass into hydrogen (amount of hydrogen is 0.52L/ (L propylene)) and 2.3L liquid propene, the temperature of reactor is increased to 70 ℃, and keep 1 hour at this temperature.Then cooling, pressure release, obtain polypropylene powder.The performance perameter of polymkeric substance is shown in Table 1.
(3) adopt the method identical with (2) to carry out the polymerization of propylene, the consumption of different is hydrogen is 4.1L/ (L propylene).
Embodiment 2-6
Embodiment 2-6 is used for that olefin polymerization catalysis of the present invention is described and uses the olefine polymerizing process of this olefin polymerization catalysis.
Adopt the method identical with embodiment 1 to prepare polypropylene, different, the composition of change external donor compound.The performance perameter of polymkeric substance is shown in Table 1.
Comparative Examples 1
Adopt the method identical with embodiment 1 to prepare polypropylene, different is, use separately 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (PPDE) is as the external donor compound of olefin polymerization catalysis, and the amount of external donor compound equates with the total amount of two kinds of external donor compounds in embodiment 1.The performance perameter of polymkeric substance is shown in Table 1.
The result of table 1 shows, olefin polymerization catalysis of the present invention not only polymerization activity increases than the independent PPDE that uses, and can find out that from the variation of melting index the hydrogen response of catalyzer also significantly improves, the molecular weight distribution of the polymkeric substance simultaneously obtained is wider than the molecular weight distribution of the polymkeric substance that uses separately diether compounds to obtain.
Claims (27)
1. an olefin polymerization catalyst system, this catalyst system comprises solid ingredient and external donor compound, and described solid ingredient contains titanium, magnesium and internal electron donor compound, it is characterized in that, described external donor compound contains the compound shown in formula 1 and diether compounds
In formula 1:
B is the calixarene radical shown in formula 2;
Two R
1identical or different, C respectively does for oneself
1-C
8the straight or branched alkyl in a kind of;
Two R
3identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl, C
6-C
12replacement or unsubstituted aryl, C
7-C
12arylalkyl, C
8-C
12aryl alkenyl and C
2-C
10the straight or branched thiazolinyl in a kind of, and two R
3when different, be hydrogen; Perhaps two R
3with together with N condenses to form saturated or undersaturated assorted monocycle or assorted dicyclo,
In formula 2:
A plurality of R
5identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
3-C
10replacement or unsubstituted cycloalkyl,
and C
6-C
12replacement or unsubstituted aryl in a kind of;
A plurality of R
6identical or different, hydrogen, C respectively do for oneself
1-C
12straight or branched alkyl, C
1-C
12the straight or branched alkoxyl group,
and C
6-C
12replacement or unsubstituted aryl in a kind of,
R
12and R
13c respectively does for oneself
1-C
12straight or branched alkyl, C
7-C
12arylalkyl, C
8-C
12aryl alkenyl, C
3-C
10replacement or unsubstituted cycloalkyl, C
2-C
10straight or branched thiazolinyl and C
6-C
12replacement or unsubstituted aryl in a kind of, R
14for C
1-C
12the straight or branched alkylidene group;
The integer that n is 1-5.
2. catalyst system according to claim 1, wherein, the mol ratio of the silicon in the titanium in described solid ingredient and described external donor compound is 1:10-500.
3. catalyst system according to claim 2, wherein, the mol ratio of the silicon in the titanium in described solid ingredient and described external donor compound is 1:25-100.
4. catalyst system according to claim 1, wherein, the mol ratio of the compound shown in formula 1 and diether compounds is 0.5-20:1.
5. according to the catalyst system shown in claim 4, wherein, the mol ratio of the compound shown in formula 1 and described diether compounds is 1-10:1.
6. according to the described catalyst system of any one in claim 1,4 and 5, wherein, in formula 1, two R
1c respectively does for oneself
1-C
4the straight or branched alkyl.
7. catalyst system according to claim 6, wherein, in formula 1, two R
1respectively do for oneself methyl or ethyl.
8. according to the described catalyst system of any one in claim 1,4 and 5, wherein, in formula 1, two R
3hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl and C
3-C
8replacement or unsubstituted cycloalkyl in a kind of, and R
3when different, be hydrogen.
9. according to the described catalyst system of any one in claim 1,4 and 5, wherein, in formula 1, two R
3condense to form with N and be selected from
in a kind of ring.
10. according to the described catalyst system of any one in claim 1,4 and 5, wherein, in formula 2, a plurality of R
5hydrogen, C respectively do for oneself
1-C
8straight or branched alkyl, C
3-C
8replacement or unsubstituted cycloalkyl,
and
in a kind of, R
12and R
13c respectively does for oneself
1-C
8straight or branched alkyl, C
3-C
8replacement or unsubstituted cycloalkyl, phenyl and cinnamyl in a kind of, R
14for C
1-C
4the straight or branched alkylidene group; A plurality of R
6hydrogen or C respectively do for oneself
1-C
8the straight or branched alkyl.
11. catalyst system according to claim 10, wherein, described calixarene radical is to be selected from a kind of in following calixarene radical:
4-tert-butyl-calix [4] aryl-O, O ', O " trimethylammonium,
4-tert-butyl-calix [4] aryl-O, O ', O " triethyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-n-propyls,
4-tert-butyl-calix [4] aryl-O, O ', O " triisopropyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-normal-butyls,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-sec-butyls,
4-tert-butyl-calix [4] aryl-O, O ', O " triisobutyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-tert,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-n-pentyls,
4-tert-butyl-calix [4] aryl-O, O ', O " triisopentyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-cyclopentyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-n-hexyls,
4-tert-butyl-calix [4] aryl-O, O ', O " thricyclohexyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-n-octyls,
4-tert-butyl-calix [4] aryl-O, O ', O " triacetyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive propionyls,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-isopropyl acyl groups,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive butyryl radicalies,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-isobutyryl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-tertiary butyryl radicalies,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive pentanoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-isovaleryl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-ring pentanoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive caproyls,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-hexamethylene acyl groups,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-positive capryloyls,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-benzoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " tri-cinnamoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " the nitrilotriacetic ethanoyl,
4-tert-butyl-calix [4] aryl-O, O ', O " the nitrilotriacetic propionyl,
4-tert-butyl-calix [4] aryl-O, O ', O " the positive butyryl radicals of nitrilotriacetic,
4-tert-butyl-calix [4] aryl-O, O ', O " nitrilotriacetic isobutyryl.
12., according to the described catalyst system of any one in claim 1,4 and 5, wherein, described diether compounds has the structure shown in formula 10:
Wherein: R, R
i, R
iI, R
iII, R
iVand R
videntical or different, hydrogen or C respectively do for oneself
1-C
18straight chain or branched-alkyl, C
3-C
8cycloalkyl, C
6-C
12a kind of in aryl, and R and R
ican not be all H or CH
3;
R
vIand R
vIIidentical or different, C respectively does for oneself
1-C
18straight chain or branched-alkyl, C
3-C
8cycloalkyl, C
6-C
12a kind of in aryl; Perhaps
R, R
i, R
iI, R
iII, R
iVand R
videntical or different, hydrogen or C respectively do for oneself
1-C
18straight chain or branched-alkyl, C
3-C
8cycloalkyl, C
6-C
12a kind of in aryl, and R and R
ican not be all H or CH
3;
R
vIand R
vIIidentical or different, C respectively does for oneself
1-C
18straight chain or branched-alkyl, C
3-C
8cycloalkyl, C
6-C
12a kind of in aryl; And R, R
i, R
iI, R
iII, R
iV, R
vand R
vIIin two Cheng Huan.
13. catalyst system according to claim 12, wherein, in formula 10, R
i, R
iI, R
iII, R
iVand R
videntical or different, hydrogen or C respectively do for oneself
1-C
5straight chained alkyl or branched-alkyl in a kind of, and R and R
ican not be all H or CH
3; R
vIand R
vIIidentical or different, C respectively does for oneself
1-C
3straight chained alkyl.
14. catalyst system according to claim 12, wherein, described diether compounds is 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal.
15. catalyst system according to claim 1, wherein, the reaction product that described solid ingredient is titanium compound, magnesium compound and internal electron donor compound.
16. catalyst system according to claim 15, wherein, the mol ratio of described titanium compound, internal electron donor compound and magnesium compound is 0.5-150:0.02-0.4:1.
17. according to the described catalyst system of any one in claim 1,15 and 16, wherein, described titanium compound is the titanium compound shown in formula 9,
TiX
4 m(OR
16)
4-mformula 9
In formula 9, X
4for halogen, R
16for C
1-C
20alkyl, the integer that m is 0-4.
18. catalyst system according to claim 17, wherein, described titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.
19. according to the described catalyst system of any one in claim 1,15 and 16, wherein, one or more in the alcohol adducts that described magnesium compound is the magnesium compound shown in the magnesium compound shown in formula 8 and formula 8,
MgR
11r
15formula 8
In formula 8, R
11and R
15halogen, C respectively do for oneself
1-C
5straight or branched alkoxyl group and C
1-C
5the straight or branched alkyl in a kind of.
20. catalyst system according to claim 19, wherein, described magnesium compound is one or more in magnesium dichloride, dibrominated magnesium and two magnesium iodides.
21., according to the described catalyst system of any one in claim 1,15 and 16, wherein, described internal electron donor compound is n-butyl phthalate or diisobutyl phthalate.
22. an olefine polymerizing process, the method is included under the olefinic polymerization condition, and one or more alkene are contacted with organo-aluminium compound with catalyzer, it is characterized in that, described catalyzer is the described catalyst system of any one in claim 1-21.
23. method according to claim 22, wherein, in the titanium in the solid ingredient of described catalyzer and described organo-aluminium compound, the mol ratio of aluminium is 1:5-1000.
24. method according to claim 23, wherein, described organo-aluminium compound is one or more in trimethyl aluminium, triethyl aluminum and aluminium diethyl monochloride.
25. method according to claim 22, wherein, described alkene is ethene, C
3-C
101-alkene and C
4-C
8diolefin in one or more.
26. method according to claim 25, wherein, described alkene is propylene; Perhaps propylene and be selected from one or more in ethene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene.
27. method according to claim 22, wherein, described olefinic polymerization condition comprises: temperature is 0-150 ℃, and the time is 0.5-5 hour, and pressure is 0.01-10MPa.
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| CN1143651A (en) * | 1995-02-21 | 1997-02-26 | 蒙特尔北美公司 | Component and catalysts for polymerization of olefins |
| CN1176256A (en) * | 1996-09-12 | 1998-03-18 | 中国科学院化学研究所 | Cup cyclo catalyst system and its preparation and use |
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| CN1143651A (en) * | 1995-02-21 | 1997-02-26 | 蒙特尔北美公司 | Component and catalysts for polymerization of olefins |
| CN1176256A (en) * | 1996-09-12 | 1998-03-18 | 中国科学院化学研究所 | Cup cyclo catalyst system and its preparation and use |
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