CN102372804A - Novel polyolefin spherical catalyst carrier, solid catalyst thereof and preparation method thereof - Google Patents
Novel polyolefin spherical catalyst carrier, solid catalyst thereof and preparation method thereof Download PDFInfo
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- CN102372804A CN102372804A CN2010102614067A CN201010261406A CN102372804A CN 102372804 A CN102372804 A CN 102372804A CN 2010102614067 A CN2010102614067 A CN 2010102614067A CN 201010261406 A CN201010261406 A CN 201010261406A CN 102372804 A CN102372804 A CN 102372804A
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Abstract
The invention provides a polyolefin spherical catalyst carrier, which has a general formula of MgClmOR<1>2-m*nR<2>OH, in the formula, 0<m<2, R<1> is C1-C8 alkyl, R2 is identical or different C1-C8 alkyl with R<1>, 1.5<=n<=5.0. The invention also provides an obtained solid catalyst and a preparation method thereof. The solid catalyst has the outstanding characteristics of high polymerization activity, less usage amount of TiCl4 and the like.
Description
Technical field
The present invention relates to a kind of polyolefin catalyst carrier, specifically, relate to a kind of polyolefine spherical carrier of catalyst, its solid catalyst and preparation method thereof, belong to the polyolefin catalyst field.
Background technology
Along with the continuous development of polyolefine industry, various dissimilar polyolefin catalysts have appearred, wherein spherical catalyst have that particle is regular, outstanding feature such as powder is carried easily, outward appearance is good, be widely used on the present polyolefin industry device.
The spherical catalyst that is adopted at present adopts the carrier of single spherical magnesium chloride alcohol adduct as polyolefin catalyst mostly, and then forms the polyolefine solid catalyst with active transition metallic compound in halogenide dealcoholysis and the load.
Such as, ZL03800552.2 discloses a kind of MgCl
2The adducts of mEtOH; Wherein the m value is between 2.5 to 3.2; Alternatively can contain the moisture based on adducts gross weight meter 1 weight %, high melting temperature (Tm) peak value surpasses 109 ℃ and have 103 joule/gram or lower relevant fusion enthalpy in the DSC figure that it is characterized by at him.Catalyst component by this adducts of the present invention obtains can be given the catalyzer of the olefinic polymerization of sening as an envoy to.
Publication number is that the patent specification of CN 1617893A discloses a kind of MgCl
2MEtOHnH
2The O adducts; Wherein 3.4＜m≤4.4,0≤n≤0.7 is characterised in that in the X-ray diffraction spectrum that obtains under these conditions; In the scope of 5-10 ° 2 θ diffraction angle; Under diffraction angle 2 θ of 9.3 ± 0.2 ° and 9.9 ± 0.2 °, have at least two diffracted rays, the strongest diffracted ray is the diffracted ray under 9.3 ± 0.2 ° 2 θ, and the intensity of another diffracted ray is lower than 0.4 times of intensity of diffracted ray the most by force.
Publication number is that the patent specification of CN 1726080A discloses a kind of magnesium chloride that comprises, the solid lewis adducts of ether, ester, ketone, silane or amine Lewis base (LB) and alcohol roh, and wherein R is the optional substituted C of heteroatom group that contained
1-C
15Alkyl, the mol ratio between said each compound is by formula MgCl
2(ROH) m (LB) n confirms, wherein the value of m is 0.05 to 6, and the value of n is 0.08 to 6.
Summary of the invention
The object of the present invention is to provide a kind of polyolefine spherical carrier of catalyst, it helps improving the polymerization activity of solid catalyst.
Another object of the present invention is to provide the preparation method of this polyolefin catalyst carrier.
A purpose more of the present invention is to provide the catalyst component that is made up of this polyolefin catalyst carrier.
An also purpose of the present invention is to provide the preparation method of this catalyst component.
In order to realize the object of the invention, the present invention provides a kind of polyolefine spherical carrier of catalyst, and its general formula is: MgCl
mOR
1 2-mNR
2OH, in the formula, 0＜m＜2, R
1Be C
1～C
8Alkyl, R
2For with R
1Identical or different C
1～C
8Alkyl, 1.5≤n in the formula≤5.0.
Wherein, preferably: 1.0＜m＜2.0, R
1For carbonatoms is 1～4 alkyl, R
2For carbonatoms is 1～4 alkyl, 2.0≤n≤5.0.
The size-grade distribution of support of the catalyst according to the invention is: D50:10～120 micron are preferably 20～70 microns.
The preparation method of polyolefine spherical carrier of catalyst according to the invention, it is employed in and adds a mole MgCl in the inert solvent respectively
2, b mole MgOR
1 2, the mole of n * (a+b) R
2OH reacts 0～300min time down at 30～150 ℃; Get spherical carrier of catalyst through balling-up curing, drying treatment then; Wherein, m=2a/ (a+b).
Wherein, the mol ratio of each composition is:
MgOR
1 2/ MgCl
2: (0.01～10): 1, preferred (0.05～1.0): 1;
Inert solvent/MgCl
2: (1～500): 1, preferred (1～40): 1;
R
2OH/MgCl
2: (0.01～10): 1, preferred (1～5): 1.
Thus, polyolefine spherical carrier of catalyst of the present invention forms complex compound or the mixture that contains chlorination alkoxyl magnesium or dialkoxy magnesium compound and magnesium chloride and alcohol.The support of the catalyst of this formation can make the polymerization activity of catalyzer improve.
Said dialkoxy magnesium compound can adopt magnesium methylate, magnesium ethylate, propoxy-magnesium, butoxy magnesium, oxyethyl group methoxy base magnesium, oxyethyl group propoxy-magnesium or butoxy magnesium ethylate etc.It is magnesium ethylate or propoxy-magnesium preferably.Can separately or mix and use.
Said dialkoxy magnesium compound can be processed such as pure and mild reactive magnesium in the presence of halogen or metal halide through this area method preparation commonly used, can be granular or pulverous.
Said general formula R
2The alcohol of OH is methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, and it can adopt one or more to mix and use.Ethanol preferably.
Said inert solvent is the solvent that chemical reaction does not take place with other materials of participating in reaction, is higher than 120 ℃ inert solvent such as boiling points such as white oil, silicone oil, Vaseline, can one or more mix use.
Described balling-up is solidified can adopt the emulsification pretreatment processing, stirs through cryogenic quenching again, can form the solid spherical powder.
Said drying treatment can adopt modes such as vacuum-drying or spraying drying, is this area drying mode commonly used.
Support of the catalyst according to the invention can be used to prepare the solid catalyst that polyolefine is used.Thus obtained solid catalyst has polymerization activity height, TiCl
4Advantages such as consumption is few.
The solid catalyst that said polyolefine is used, it adopts following method to process: with said general formula is MgCl
mOR
1 2-mNR
2OH is (in the formula: 0＜m＜2, R
1Be C
1～C
8Alkyl, R
2For with R
1Identical or different C
1～C
8Alkyl, 1.5≤n in the formula≤5.0) support of the catalyst and general formula be Ti (OR
3)
yX
4-y(R
3Be C
1～C
4Alkyl, X is a halogen, y is 0～3 integer) the titanium compound reaction, add inert solvent in the reaction process and carry out to promote reaction, add electron donor in the reaction process, also can in subsequent processes, add electron donor; Use general formula to be Ti (OR then
3)
yX
4-yThe mixture process of titanium compound and inert solvent more than 2 times, again with inert solvent washing and the dry final solid spherical polyolefin catalyst that forms.
Said inert solvent is that a kind of room temperature is liquid aromatic hydrocarbons or alkane.Described aromatic hydrocarbons is: benzene,toluene,xylene, ethylbenzene, propyl benzene or trimethylbenzene etc., preferably use toluene or YLENE.Said alkane is hexane, heptane or hexanaphthene, and aromatic hydrocarbons and alkane can use separately also can mix use.
Said electron donor is the diester (like Bisphthalate or bis--terephthalate) of aromatic series monoesters or aromatic binary carboxylic acid.
Bisphthalate comprises: dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, Methyl Benzene-o-dicarboxylate ethyl ester, Methyl Benzene-o-dicarboxylate isopropyl ester, Methyl Benzene-o-dicarboxylate n-propyl, the positive butyl ester of ethyl phthalate(DEP), ethyl phthalate(DEP) isobutylate, amyl phthalate, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid (2; 2-dimethyl-hexyl) diester, phthalic acid (2-ethylhexyl) diester, 2-nonyl-phthalate ester, Di Iso Decyl Phthalate, phthalic acid (2; 2-dimethyl-heptyl) diester, n-butyl phthalate isohexyl ester, n-butyl phthalate (2-ethylhexyl) ester, the just own ester of phthalic acid n-pentyl ester, phthalic acid n-pentyl ester ester in the different ninth of the ten Heavenly Stems, isoamyl phthalate ester in the positive last of the ten Heavenly stems, phthalic acid n-pentyl ester undecane ester, phthalic acid isopentyl isohexyl ester, the just own ester of phthalic acid (2-methyl polyhexamethylene), phthalic acid n-hexyl (2-(ethyl hexyl) ester), the just own ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), phthalic acid n-hexyl (positive the last of the ten Heavenly stems ester), the positive heptyl ester of phthalic acid (2-(ethyl hexyl) ester), the positive heptyl ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), the positive heptyl ester of phthalic acid ester in the new ninth of the ten Heavenly Stems and phthalic acid 2-ethylhexyl (different the ninth of the ten Heavenly Stems ester).These esters can use in independent or multiple mixing.
The bis--terephthalate comprises: DMT. Dimethyl p-benzenedicarboxylate, diethyl terephthalate, terephthalic acid di-n-propyl ester, terephthalic acid diisopropyl ester, di-n-butyl terephthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthaldehyde's acetoacetic ester methyl esters, terephthalic acid methyl esters isopropyl ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (positive butyl ester), terephthaldehyde's acetoacetic ester (isobutylate), terephthalic acid two n-pentyl esters, terephthalic acid diisoamyl ester, terephthalic acid dihexyl, terephthalic acid two positive heptyl esters, terephthalic acid di-n-octyl, terephthalic acid two different n-octyls, terephthalic acid two (2; 2-dimethyl-hexyl) ester, terephthalic acid two (2-ethylhexyl) ester, terephthalic acid two ester in the positive ninth of the ten Heavenly Stems, terephthalic acid dinonyl, terephthalic acid two isodecyl esters, terephthalic acid two (2,2-dimethyl ethyl heptyl) ester, the positive butyl ester dissident of terephthalic acid ester, the positive butyl ester of terephthalic acid (2 ethylhexyl) ester, the just own ester of terephthalic acid n-pentyl ester, terephthalic acid n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), terephthalic acid, terephthalic acid n-pentyl ester (2-ethylhexyl) ester, terephthalic acid n-pentyl ester (different the ninth of the ten Heavenly Stems ester), terephthaldehyde's isoamyl valerate (positive the last of the ten Heavenly stems ester), terephthalic acid n-pentyl ester undecane ester, terephthaldehyde's isoamyl valerate dissident ester, terephthalic acid n-hexyl (2-(ethyl hexyl) ester), terephthalic acid n-hexyl (different nonyl ester), the just own ester of terephthalic acid (positive the last of the ten Heavenly stems ester), terephthalic acid n-heptyl (2-(ethyl hexyl) ester), terephthalic acid n-heptyl (different nonyl ester), terephthalic acid n-heptyl (new the last of the ten Heavenly stems ester) and terephthalic acid 2-ethylhexyl (different nonyl ester).These esters can use in independent or multiple mixing.
In these diester, recommend to use diethyl phthalate; The dipropyl phthalic butyl ester; The terephthalic acid diisopropyl ester; N-butyl phthalate; Diisobutyl phthalate; Dinoctyl phthalate; Dimixo-octyl phthalate; Di-n-butyl terephthalate; Isobutyl terephthalate; The terephthalic acid di-n-octyl; The terephthalic acid di-isooctyl; The mixing of one or more in terephthalic acid two (2-ethylhexyl) ester or the Di Iso Decyl Phthalate.
The aromatic series monoesters comprises: a kind of in oil of Niobe, ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl-benzoate, phenylformic acid heptyl ester, n-octyl benzoate, phenylformic acid ester in the ninth of the ten Heavenly Stems, n-decyl benzoate methyl-formiate, ETHYLE ACETATE, ETHYLE ACETATE, propyl acetate, the butylacetate or their mixture.
Specifically, the solid catalyst that polyolefine of the present invention is used, its composition comprises:
1) said general formula is MgCl
mOR
1 2-mNR
2OH is (in the formula: 0＜m＜2, R
1Be C
1～C
8Alkyl, R
2For with R
1Identical or different C
1～C
8Alkyl, 1.5≤n in the formula≤5.0) support of the catalyst (be called for short component a);
2) Ti (OR
3)
yX
4-yTitanium compound (R
3Be the alkyl of C1～C4, X is a halogen, and y is 0～3 integer) (abbreviation components b);
3) electron donor: a kind of diester of aromatic binary carboxylic acid or aromatic series monoesters (abbreviation amount of component b);
4) aromatic hydrocarbons or alkane (being called for short component d);
5) alkane (being called for short component e)
Its preparation process is:
With spherical MgCl
mOR
1 2-mNR
2OH carrier adding components b or the adding component d of elder generation process suspension-s and add components b again; Be warming up to 0～100 ℃ then, add amount of component b again, continue to be warming up to 90～130 ℃ and kept 1～3 hour; Filter; Again with components b and component d mixed solution or handle and filter with components b separately,, the solids drying of gained is obtained the solid spherical polyolefin catalyst after 3～6 times (also can in subsequent washing or treating processes, add amount of component b once more) of component e washing.
Also can after filtering for the first time, filtrate be washed 2 times 0～130 ℃ of wash temperature, preferred 40～130 ℃ at least with component d;
Said components b is one or more titanium tetrachlorides or alkoxyl group halogenated titanium.Comprise titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, alkoxyl group halogenated titanium such as methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, n-butoxy titanous chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, two n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride or three n-butoxy titanium chlorides.Can use one or more in these halogenated titaniums and mix use.Wherein adopt the titanium tetrachloride best results.
Said amount of component b is the diester of aromatic binary carboxylic acid; Like Bisphthalate or bis--terephthalate; Bisphthalate comprises: dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, Methyl Benzene-o-dicarboxylate ethyl ester, Methyl Benzene-o-dicarboxylate isopropyl ester, Methyl Benzene-o-dicarboxylate n-propyl, the positive butyl ester of ethyl phthalate(DEP), ethyl phthalate(DEP) isobutylate, amyl phthalate, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid (2; 2-dimethyl-hexyl) diester, phthalic acid (2-ethylhexyl) diester, 2-nonyl-phthalate ester, Di Iso Decyl Phthalate, phthalic acid (2; 2-dimethyl-heptyl) diester, n-butyl phthalate isohexyl ester, n-butyl phthalate (2-ethylhexyl) ester, the just own ester of phthalic acid n-pentyl ester, phthalic acid n-pentyl ester ester in the different ninth of the ten Heavenly Stems, isoamyl phthalate ester in the positive last of the ten Heavenly stems, phthalic acid n-pentyl ester undecane ester, phthalic acid isopentyl isohexyl ester, the just own ester of phthalic acid (2-methyl polyhexamethylene), phthalic acid n-hexyl (2-(ethyl hexyl) ester), the just own ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), phthalic acid n-hexyl (positive the last of the ten Heavenly stems ester), the positive heptyl ester of phthalic acid (2-(ethyl hexyl) ester), the positive heptyl ester of phthalic acid (different the ninth of the ten Heavenly Stems ester), the positive heptyl ester of phthalic acid ester in the new ninth of the ten Heavenly Stems and phthalic acid 2-ethylhexyl (different the ninth of the ten Heavenly Stems ester).These esters can use in independent or multiple mixing.
The bis--terephthalate comprises: DMT. Dimethyl p-benzenedicarboxylate, diethyl terephthalate, terephthalic acid di-n-propyl ester, terephthalic acid diisopropyl ester, di-n-butyl terephthalate, di-n-butyl terephthalate, isobutyl terephthalate, terephthaldehyde's acetoacetic ester methyl esters, terephthalic acid methyl esters isopropyl ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (positive butyl ester), terephthaldehyde's acetoacetic ester (isobutylate), terephthalic acid two n-pentyl esters, terephthalic acid diisoamyl ester, terephthalic acid dihexyl, terephthalic acid two positive heptyl esters, terephthalic acid di-n-octyl, terephthalic acid two different n-octyls, terephthalic acid two (2; 2-dimethyl-hexyl) ester, terephthalic acid two (2-ethylhexyl) ester, terephthalic acid two ester in the positive ninth of the ten Heavenly Stems, terephthalic acid dinonyl, terephthalic acid two isodecyl esters, terephthalic acid two (2,2-dimethyl ethyl heptyl) ester, the positive butyl ester dissident of terephthalic acid ester, the positive butyl ester of terephthalic acid (2 ethylhexyl) ester, the just own ester of terephthalic acid n-pentyl ester, terephthalic acid n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), terephthalic acid, terephthalic acid n-pentyl ester (2-ethylhexyl) ester, terephthalic acid n-pentyl ester (different the ninth of the ten Heavenly Stems ester), terephthaldehyde's isoamyl valerate (positive the last of the ten Heavenly stems ester), terephthalic acid n-pentyl ester undecane ester, terephthaldehyde's isoamyl valerate dissident ester, terephthalic acid n-hexyl (2-(ethyl hexyl) ester), terephthalic acid n-hexyl (different nonyl ester), the just own ester of terephthalic acid (positive the last of the ten Heavenly stems ester), terephthalic acid n-heptyl (2-(ethyl hexyl) ester), terephthalic acid n-heptyl (different nonyl ester), terephthalic acid n-heptyl (new the last of the ten Heavenly stems ester) and terephthalic acid 2-ethylhexyl (different nonyl ester).These esters can use in independent or multiple mixing.
In these diester, recommend to use diethyl phthalate; The dipropyl phthalic butyl ester; The terephthalic acid diisopropyl ester; N-butyl phthalate; Diisobutyl phthalate; Dinoctyl phthalate; Dimixo-octyl phthalate; Di-n-butyl terephthalate; Isobutyl terephthalate; The terephthalic acid di-n-octyl; The terephthalic acid di-isooctyl; The mixing of one or more in terephthalic acid two (2-ethylhexyl) ester or the Di Iso Decyl Phthalate.
Said amount of component b comprises for the aromatic series monoesters: a kind of in oil of Niobe, ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl-benzoate, phenylformic acid heptyl ester, n-octyl benzoate, phenylformic acid ester in the ninth of the ten Heavenly Stems, n-decyl benzoate methyl-formiate, ETHYLE ACETATE, ETHYLE ACETATE, propyl acetate, the butylacetate or their mixture.
The component d that is used to prepare solid catalyst according to the invention is that a kind of room temperature is liquid aromatic hydrocarbons or alkane.
Described aromatic hydrocarbons is: benzene,toluene,xylene, ethylbenzene, propyl benzene or trimethylbenzene etc., preferably use toluene or YLENE.In addition, also can use other solvents of inert, these organic solvents are saturated hydro carbons-alkane, comprising: hexane, heptane or hexanaphthene, aromatic hydrocarbons and alkane can use separately also can mix use.
Said component e is an alkane, comprises hexane, heptane or hexanaphthene.
Mole proportioning between each component:
Components b/spherical MgCl
mOR
1 2-mNR
2OH carrier: (1～40): 1, preferred (1～10): 1;
Amount of component b/spherical MgCl
mOR
1 2-mNR
2OH carrier: (0.01～5): 1, preferred (0.1～1): 1;
The spherical MgCl of component d/
mOR
1 2-mNR
2OH carrier: (1～100): 1, preferred (5～40): 1.
Solid catalyst of the present invention preferably adopts following method preparation:
1) with spherical MgCl
mOR
1 2-mNR
2The OH carrier adds components b or adds component d earlier processes suspension-s again at-30～100 ℃, preferred-30～30 ℃ of mixed solutions that add components b or components b and component d;
2) be warming up to 0～100 ℃, add amount of component b again, continue to be warming up to 90～130 ℃ and kept 1～3 hour, filter;
3) the gained solids washs (this process can be omitted and directly carried out next step) at least 2 times with component d; 0～130 ℃ of wash temperature, preferred 40～130 ℃;
4) the gained solids is through components b and component d mixed solution or handle and filter with components b separately;
5) the gained solids obtains the solid spherical polyolefin catalyst through 3～6 solids dryings with gained of component e washing.
Annotate: can add amount of component b once more in step 1～5, also can not add amount of component b and add amount of component b once more in step 2～5 then in step 1.
Adopt the solid catalyst of gained of the present invention to can be used for preparing olefin polymerization catalysis, described olefin polymerization catalysis comprises following component:
(A) spherical solid catalyzer of the present invention (being called for short component A)
(B) a kind of organo-aluminium compound (abbreviation B component), the general molecular formula is following: R
2 PAlQ
3-P(R
2The alkyl that refers to C1-4; Q refers to Wasserstoffatoms or halogen atom such as chlorine, bromine, iodine, and the value of P is 0-3)
(C) a kind of silicoorganic compound (being called for short component C), the general molecular formula is following: R
3 qSi (OR
4)
4-q(R
3And R
4Refer to C
1-12Alkyl, naphthenic base, phenyl, allyl group, aralkyl, vinyl, these groups can be the same or different, the value of q is: 1-3).
Wherein: B component is preferably triethyl aluminum, diethyl aluminum chloride, triisobutyl aluminium, diethylammonium aluminum bromide or ADEH.The organism of these aluminium can use separately or two or more use simultaneously.What effect was best is triethyl aluminum and triisobutyl aluminium.
Component C specifically can be: trimethylammonium methoxy silane, trimethylethoxysilane, three n-propyl methoxy silane, three n-propyl Ethoxysilanes, three normal-butyl methoxy silane, triisobutyl Ethoxysilane, thricyclohexyl methyl-monosilane, thricyclohexyl Ethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, di dimethoxy silane, diisopropyl dimethoxy silane, di diethoxy silane, di-isopropyl diethoxy silane, di-n-butyl diethoxy silane, diisobutyl diethoxy silane, di-t-butyl dimethoxy silane, di-t-butyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl diethoxy silane, di-n-butyl diethoxy silane, n-butylmethyldimethoxyforane, two (2-ethylhexyl) dimethoxy silane, two (2-ethylhexyl) diethoxy silane, dicyclohexyl dimethoxy silane, dicyclohexyl diethoxy silane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, cyclohexyl methyl dimethoxy silane, cyclohexyl methyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl ethyl diethoxy silane, cyclopentyl sec.-propyl diethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclohexyl n-propyl dimethoxy silane, cyclohexyl n-propyl diethoxy silane, cyclohexyl normal-butyl diethoxy silane, amyl group methyl dimethoxysilane, amyl group methyldiethoxysilane, amyl group ethyl dimethoxy silane, amyl group ethyl diethoxy silane, cyclohexyl dimethyl methyl TMOS, cyclohexyl diethylammonium methoxy silane, cyclohexyl diethylammonium methoxy silane, cyclohexyl diethylammonium Ethoxysilane, 2-ethylhexyl Trimethoxy silane, cyclohexyl dimethoxy silane, cyclohexyl diethoxy silane, 2-ethylhexyl triethoxyl silane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, sec.-propyl Trimethoxy silane, sec.-propyl triethoxyl silane, normal-butyl Trimethoxy silane, isobutyl-Trimethoxy silane, tert-butyl trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl trimethoxy silane, cyclohexyl triethoxyl silane, cyclopentyl Trimethoxy silane, cyclopentyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, 2-ethylhexyl Trimethoxy silane, 2-ethylhexyl triethoxyl silane, amyltrimethoxysilane, amyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl ring amyl group diethoxy silane, cyclohexyl ring amyl group dipropoxy silane, 3-methylcyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxy silane, 3; 5-Dimethylcyclohexyl cyclopentyl dimethoxy silane, 3-methylcyclohexyl cyclohexyl dimethoxy silane, two (3-methylcyclohexyl) dimethoxy silane, 4-methylcyclohexyl cyclohexyl dimethoxy silane, two (4-methylcyclohexyl) dimethoxy silane, 3; 5-Dimethylcyclohexyl cyclohexyl dimethoxy silane, two (3, the 5-Dimethylcyclohexyl) dimethoxy silane, tetrapropoxysilane, four butoxy silanes.First-selected in these silicoorganic compound: di dimethoxy silane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane, di-n-butyl diethoxy silane, tert-butyl trimethoxy silane, dicyclohexyl dimethoxy silane, dicyclohexyl diethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl ethyl diethoxy silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl ring amyl group diethoxy silane, 3-methylcyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxy silane and 3,5-dimethylcyclopentyl dimethoxy silane etc.Use can used or mix to these Compound C separately.
For the catalyzer of using among the present invention carries out olefinic polymerization, homopolymerization and copolymerization can be used above-mentioned through component A, B, the prepared catalyzer of C.Usually the mol ratio of B component and component A is that the every mol of 1～1000mol is contained in the titanium atom among the component A, is preferably the every mol of 50～800mol and is contained in the titanium atom among the component A; The mol ratio of component C and B component is 0.002～10, is preferably 0.01～2, is preferably 0.01～0.5.
The order of addition(of ingredients) of each component is arbitrarily, joins at first in the paradigmatic system with B component, adds component C then, and it is good adding component A at last.
Polymerization technique among the present invention can carry out under the situation of solvent solvent being arranged or do not have.Olefinic monomer can be gas phase or liquid phase.Further add hydrogen and can be used as molecular weight regulator.Certainly polymerization also can be carried out under the situation of molecular weight regulator not having.Polymerization temperature is not higher than 200 ℃, had better not be above 100 ℃.Polymerization pressure does not surpass 10MPa, had better not surpass 5MPa.Successive polymerization or batchwise polymerization technology can be used.And polyreaction can divide a step, two steps or multistep to carry out.
Use the alkene that catalyzer according to the invention carries out homopolymerization or copolymerization and comprise normal olefine: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-nonene, 1-decene; Branched-chain alkene is like 3-methyl-1-butene and 4-methyl-1-pentene; Diolefine is like divinyl, vinyl cyclopentenes and VCH.Catalyzer of the present invention preferably is applied in Vilaterm and the Vestolen PP 7052.These alkene can use in independent or multiple mixing.
Use the polymerization (referring to the main body polymerization here) of the alkene that catalyst component A, B, C of the present invention carried out, recommend to carry out the degree of isotacticity, particle performance of the incompatible increase activity of such catalysts of pre-polymerization polymkeric substance etc.This prepolymerization technology can be used for the vinylbenzene homopolymerization equally.
Each component and monomeric order of addition(of ingredients) are arbitrarily in prepolymerization technology.Preferably earlier B component is joined and contain inertia and maybe will carry out in the polymeric alkene gas, after adding component A, add then and want one or more alkene of polymeric.In the prepolymerized process of alkene of using organosilane, suggestion joins rare gas element with B component maybe will be carried out adding component C then in the prepolymerization system of polymeric olefin gas, adds component A then, adds alkene at last again.
The present invention is through with magnesium chloride and the compound spherical carrier of catalyst of processing of alkoxyl magnesium; And then the active transition metallic compound forms the polyolefine solid catalyst in the load, and the prepared catalyzer of the present invention has outstanding features such as polymerization activity height, titanium tetrachloride consumption are few.
Embodiment
Further describe the present invention with embodiment below, help understanding, but said embodiment only is used to explain the present invention rather than restriction the present invention the present invention and advantage thereof, better effects if.
Embodiment 1
Spherical MgCl
mOR
1 2-mNR
2The preparation of OH carrier:
In the abundant metathetical flask of nitrogen, add white oil 400ml at 1000ml, absolute ethyl alcohol 46ml, magnesium chloride 20g, diethoxy magnesium 5g stirs and is warming up to 130 ℃ of reactions 3 hours.Be transferred to mulser emulsification 20min under 5000rpm then, with in reactant transfer to-20 ℃ the 5000ml hexane, low temperature stirred 5 hours then; Use hexane wash then 3～6 times, cross and filter white powder, remove hexane through drying; Get ball type carrier (wherein, m is 1.66, and n is 3.11).Test gained ball type carrier size-grade distribution is the D10:20 micron; The D50:36 micron; The D90:69 micron.
The preparation of solid catalyst:
Have in 5 mouthfuls of flasks of stirring through the abundant metathetical of nitrogen at 500ml; Add the 100ml titanium tetrachloride; Stirring is cooled to-20 ℃, adds the above-mentioned carrier of 10g then, is warming up to 10 ℃ then and drips 20ml toluene; Continue to be warming up to 60 ℃ and add 3mlDNBP (Witcizer 300), continued to be warming up to 110 ℃ and constant temperature then 1 hour.Sedimentation and elimination clear liquid add the 100ml toluene wash 1 time then, and the titanium tetrachloride toluene solution that adds volume ratio 20% is then handled 20 minutes 4 times at 110 ℃, uses hexane wash then 4 times, and the gained solid drying gets the solid polyolefin catalyzer.Analyzing titanium content is 2.52 (wt) %.
Carry out the polymerization evaluation with solid catalyst as the component of olefin polymerization catalysis:
At 5 liters of stainless steel cauldrons after nitrogen is fully replaced; Add 5 ml concns and be 10 milligrams of the catalyzer of the triethyl aluminum hexane solution of 0.5 mol and methylcyclohexyl dimethoxy silane (CMMS) hexane solution that 1 ml concn is 1 mol and embodiment 1 preparation, add 10 milliliters of hexane charge lines then, add 2 liters of (under the standard state) hydrogen again; With 2.5 liters of refining propylene; Control is reflected at 20 ℃ of pre-polymerizations 5 minutes, is warming up to 70 ℃, and polyreaction is 2 hours under this temperature.After reaction finishes, with the reaction kettle cooling and stop stirring and discharge reaction product, weighing polymkeric substance after dry, getting catalyst activity is 7.52 myriagrams Vestolen PP 7052/gram catalyzer, polymer bulk density is 0.45g/cm
3(tap density of polymkeric substance adopts JIS K6721 method), polymkeric substance degree of isotacticity II98.6wt%, melting index 3.8g/10min.
Embodiment 2
The preparation of solid catalyst:
Have in 5 mouthfuls of flasks of stirring through the abundant metathetical of nitrogen at 500ml; Add the 80ml titanium tetrachloride; Stirring is cooled to-20 ℃, adds the 10g carrier of embodiment 1 preparation then, is warming up to 10 ℃ then and drips 40ml toluene; Continue to be warming up to 60 ℃ and add 3mlDNBP, continued to be warming up to 110 ℃ and constant temperature then 1 hour.Sedimentation and elimination clear liquid add the 100ml toluene wash 1 time then, and the titanium tetrachloride toluene solution that adds volume ratio 20% is then handled 20 minutes 4 times at 110 ℃, uses hexane wash then 4 times, and the gained solid drying gets the solid polyolefin catalyzer.Analyzing titanium content is 2.34 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result is seen table 1.
Embodiment 3
The preparation of solid catalyst:
Have in 5 mouthfuls of flasks of stirring through the abundant metathetical of nitrogen at 500ml; Add the 60ml titanium tetrachloride; Stirring is cooled to-20 ℃, adds the 10g carrier of embodiment 1 preparation then, is warming up to 10 ℃ then and drips 60ml toluene; Continue to be warming up to 60 ℃ and add 3mlDNBP, continued to be warming up to 110 ℃ and constant temperature then 1 hour.Sedimentation and elimination clear liquid add the 100ml toluene wash 1 time then, and the titanium tetrachloride toluene solution that adds volume ratio 20% is then handled 20 minutes 4 times at 110 ℃, uses hexane wash then 4 times, and the gained solid drying gets the solid polyolefin catalyzer.Analyzing titanium content is 2.21 (wt) %.
The polymerization evaluation method of solid catalyst is with embodiment 1, and evaluation result is seen table 1.
Table 1: catalyst performance contrast table
| Sequence number | Catalyst activity gpp/gcat | The close g/cm of polymer stacks 3 | II?wt％ | MI?g/10min |
| Embodiment 1 | 75200 | 0.45 | 98.6 | 3.8 |
| Embodiment 2 | 82100 | 0.44 | 98.7 | 4.1 |
| Embodiment 3 | 88600 | 0.43 | 98.5 | 4.4 |
Can find out that through table 1 adopt the catalyzer of the present invention's preparation to have higher catalyst activity, used titanium tetrachloride amount is less in the preparation process.
Although oneself has done detailed explanation and has quoted some specific exampless as proof to the present invention, for a person skilled in the art, only otherwise leave the spirit and scope of the present invention, it is obvious doing various variations or correction.
Claims (9)
1. polyolefine spherical carrier of catalyst, its general formula is: MgCl
mOR
1 2-mNR
2OH, in the formula, 0＜m＜2, R
1Be C
1～C
8Alkyl, R
2For with R
1Identical or different C
1～C
8Alkyl, 1.5≤n≤5.0.
2. support of the catalyst according to claim 1 is characterized in that, the m value is 1.0＜m＜2.0, R
1For carbonatoms is 1～4 alkyl, R
2For carbonatoms is 1～4 alkyl, the n value is 2.0≤n≤5.0.
3. prepare the method for claim 1 or 2 described support of the catalyst, it is characterized in that, it is employed in and adds a mole MgCl in the inert solvent respectively
2, b mole MgOR
1 2, the mole of n * (a+b) R
2OH reacts 0～300min down at 30～150 ℃; Get ball type carrier through balling-up curing, drying treatment then, wherein, m=2a/ (a+b).
4. the preparation method of support of the catalyst according to claim 3 is characterized in that, the mol ratio of each composition is:
MgOR
1 2/ MgCl
2: (0.01～10): 1, preferred (0.05～1.0): 1;
Inert solvent/MgCl
2: (1～500): 1, preferred (1～40): 1;
R
2OH/MgCl
2: (0.01～10): 1, preferred (1～5): 1.
5. according to claim 3 or 4 described methods, it is characterized in that said general formula R
2The alcohol of OH is methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, and it can adopt one or more to mix and use.
6. according to any described method of claim 3-5, it is characterized in that, said inert solvent be in white oil, silicone oil or the Vaseline one or more.
7. the solid catalyst that polyolefine is used is characterized in that, it adopts following method to process: with claim 1 or 2 said general formulas is MgCl
mOR
1 2-mNR
2The support of the catalyst of OH and general formula are Ti (OR
3)
yX
4-yTitanium compound reaction, wherein, R
3Be C
1～C
4Alkyl, X is a halogen, y is 0～3 integer, adds inert solvent in the reaction process and carries out to promote reaction, adds electron donor in the reaction process, or in subsequent processes, adds electron donor; Use general formula to be Ti (OR then
3)
yX
4-yThe mixture process of titanium compound and inert solvent more than 2 times, again with inert solvent washing and the dry final solid spherical polyolefin catalyst that forms.
8. the solid catalyst of using according to the said polyolefine of claim 7 is characterized in that, its composition comprises:
1) component a: said general formula is MgCl
mOR
1 2-mNR
2OH is (in the formula: 0＜m＜2, R
1Be C
1～C
8Alkyl, R
2For with R
1Identical or different C
1～C
8Alkyl, the support of the catalyst of 1.5≤n in the formula≤5.0=;
2) components b: Ti (OR
3)
yX
4-yTitanium compound (R
3Be C
1～C
4Alkyl, X is a halogen, y is 0～3 integer);
3) amount of component b: the electron donor of a kind of diester of aromatic binary carboxylic acid or aromatic series monoesters;
4) component d: aromatic hydrocarbons or alkane;
5) component e: alkane;
Its preparation process is:
With spherical MgCl
mOR
1 2-mNR
2OH carrier adding components b or the adding component d of elder generation process suspension-s and add components b again; Be warming up to 0～100 ℃ then, add amount of component b again, continue to be warming up to 90～130 ℃ and kept 1～3 hour; Filter; Again with components b and component d mixed solution or handle and filter with components b separately,, the solids drying of gained is obtained the solid spherical polyolefin catalyst after component e washing 3～6 times.
9. the solid catalyst of using according to claim 7 or 8 said polyolefine is characterized in that the mol ratio of each composition is:
General formula is Ti (OR
3)
yX
4-yTitanium compound/spherical MgCl
mOR
1 2-mNR
2OH carrier: (1～40): 1, preferred (1～10): 1;
Electron donor/spherical MgCl
mOR
1 2-mNR
2OH carrier: (0.01～5): 1, preferred (0.1～1): 1;
Inert solvent/spherical MgCl
mOR
1 2-mNR
2OH carrier: (1～100): 1, preferred (5～40): 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107108802A (en) * | 2014-12-31 | 2017-08-29 | 博里利斯股份公司 | The method for preparing propylene copolymer |
| CN107446070A (en) * | 2017-08-29 | 2017-12-08 | 营口风光新材料股份有限公司 | A kind of carrier for olefin polymerization catalysis, preparation method and applications |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399054A (en) * | 1978-08-22 | 1983-08-16 | Montedison S.P.A. | Catalyst components and catalysts for the polymerization of alpha-olefins |
| CN101671409A (en) * | 2008-09-11 | 2010-03-17 | 中国石油天然气股份有限公司 | Solid catalyst for olefin polymerization |
| CN101671408A (en) * | 2008-09-11 | 2010-03-17 | 中国石油天然气股份有限公司 | Propylene polymerization solid catalyst composition |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399054A (en) * | 1978-08-22 | 1983-08-16 | Montedison S.P.A. | Catalyst components and catalysts for the polymerization of alpha-olefins |
| CN101671409A (en) * | 2008-09-11 | 2010-03-17 | 中国石油天然气股份有限公司 | Solid catalyst for olefin polymerization |
| CN101671408A (en) * | 2008-09-11 | 2010-03-17 | 中国石油天然气股份有限公司 | Propylene polymerization solid catalyst composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107108802A (en) * | 2014-12-31 | 2017-08-29 | 博里利斯股份公司 | The method for preparing propylene copolymer |
| US10696764B2 (en) | 2014-12-31 | 2020-06-30 | Borealis Ag | Process for preparing propylene copolymers |
| CN107108802B (en) * | 2014-12-31 | 2021-03-09 | 博里利斯股份公司 | Process for preparing propylene copolymers |
| CN107446070A (en) * | 2017-08-29 | 2017-12-08 | 营口风光新材料股份有限公司 | A kind of carrier for olefin polymerization catalysis, preparation method and applications |
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