CN101550205B - Spherical magnesium halide alcohol polymer as well as preparation method and application thereof - Google Patents
Spherical magnesium halide alcohol polymer as well as preparation method and application thereof Download PDFInfo
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- CN101550205B CN101550205B CN2008101032288A CN200810103228A CN101550205B CN 101550205 B CN101550205 B CN 101550205B CN 2008101032288 A CN2008101032288 A CN 2008101032288A CN 200810103228 A CN200810103228 A CN 200810103228A CN 101550205 B CN101550205 B CN 101550205B
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Abstract
The invention relates to a catalyst component for olefinic polymerization particularly for propylene polymerization or copolymerization, in particular to a novel alcohol polymer containing three components of magnesium halide, alcohol and polyester and an application of the alcohol polymer in the preparation of an olefin polymerization catalyst. When a catalyst prepared by using the alcohol polymer as a carrier is used for the olefinic polymerization, particularly the propylene polymerization, the catalyst shows better polymerization activity, and a polymer has higher isotacticity. The catalyst is used in the field of petrochemical engineering.
Description
Technical field
The present invention relates to a kind of olefinic polymerization particularly propylene polymerization or copolymerization catalyst component of being used for, be specifically related to comprise the alcohol adduct of the ternary component of magnesium halide, pure and mild polyester.
Background technology
As everyone knows, being carried on Titanium series catalyst on the magnesium halide carrier is a kind of important catalyst on polypropylene is produced.After magnesium halide and alcohol form alcohol adduct, be used for olefinic polymerization particularly during propylene polymerization, have very high catalytic efficiency and stereospecificity with the formed supported catalyst of halogenated titanium and electron donor compound reaction back.Especially, has good particle form and higher apparent density by spherical alcohol adduct as the catalyzer synthetic polymkeric substance that carrier makes when using.
The magnesium halide alcohol adduct of industrial extensive employing is the alcohol adduct of magnesium chloride mostly, mainly comprises magnesium chloride and two kinds of components of alcohol.The method for preparing spherical alcohol adduct has spraying drying, spray cooling, high pressure to extrude or high-speed stirring etc.
The preparation of carrier is the basis and the committed step of Preparation of Catalyst.The form of carrier has directly determined catalyst form, and the composition of carrier and texture can produce great effect to the performance of catalyzer.Such as with pure magnesium halide as carrier, the inorganic ash content of in polymkeric substance, introducing, limited polypropylene at some special occasions as the application in the capacitance material.If use organism as carrier purely, not only Zhi Bei catalyst activity is lower, and because organic fusing point is generally lower, the rigidity deficiency, the form that can have influence in the polymerization process is duplicated, and can not get the polymkeric substance of relatively good form.Then can overcome their shortcomings separately with inorganics and the common complex carrier of forming of organism.
Based on the critical role of carrier in Preparation of Catalyst, investigators just obtain novel carriers by diverse ways.For example: in Chinese patent CN1463990 and CN1563112A technology, known internal electron donor of the industry such as phthalate compound were introduced in synthesizing of carrier, form the spherical carrier of " magnesium dichloride-alcohol-phthalic ester " mixture, the load titanium tetrachloride forms catalyzer then.But because the spherical carrier of described mixture is clamminess in preparation process easily, be difficult to form the suitable spheroidal particle of size, its disclosed ball type carrier is of a size of D50:70～200, the catalytic activity that is used for propylene polymerization only is 406g PP/gcath, and for example Chinese patent CN101050245 discloses a kind of C, C-two hydrocarbon oxy compounds are introduced in the carrier, gained carrier median size is about 50 μ m, the catalyzer of load has better hydrogen regulation sensitivity, and fine powder content has certain minimizing in the polymkeric substance.
Therefore, providing novel carriers to be used for supported catalyst is the focus that the investigator pays close attention to.
Summary of the invention
The technical problem to be solved in the present invention is:
At the deficiencies in the prior art, the purpose of this invention is to provide the compound alcohol adduct of a kind of novel magnesium halide/polyester.With the catalyzer of this alcohol adduct as preparing carriers, be used for olefinic polymerization particularly during propylene polymerization, when keeping good polymerization activity, polymkeric substance has higher degree of isotacticity.
Product technology scheme of the present invention is:
A kind of magnesium halide alcohol adduct, its general structure is shown in (I) formula:
MgX
2-mROH-kE
(I)
(I) in the formula, X is a chlorine or bromine, and perhaps one of them X is replaced by one of following group: C
1～C
14Alkyl, C
6～C
14Aryl, C
1～C
14Alkoxyl group, C
7～C
14Aryloxy;
R is a kind of in the following groups: C
1～C
12Alkyl, C
3～C
10Cycloalkyl, C
6～C
10Aryl; M is 1～5; K is 0.001～3; E is the petchem shown in the general formula (II);
In the general formula (II), R
1Or R
2Be and eliminate a kind of of any 1 subunit that hydrogen atom forms: C in the following groups
1～C
10Straight chained alkyl, C
3～C
10Branched-chain alkyl, C
3～C
10Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl, C
1～C
10Straight chain silylation, C
3～C
10The branched silicon alkyl; Hydrogen atom on the phenyl ring in wherein said aryl, alkaryl or the aralkyl is randomly replaced by halogen atom; R
1With R
2Identical or inequality; 2≤n≤10000.
Preferably, MgX in the general formula (I)
2The compound of representative is one of following: magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium.Described halogenated magnesium compound can be used alone or as a mixture.
X in the preferred formula (I) is a chlorine.
R is a kind of in the following groups in the general formula (I): C
1～C
4Alkyl.
Be specially ROH in the general formula (I) and be a kind of in following: methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, ethylene glycol, propylene glycol.
M is 1.5～3.5 in the preferred formula (I); K is 0.02～3.
General formula (II) R
1Or R
2All be selected from one of following: methylene radical, ethylene, propylene, 1,3-propylidene, 1,2-butylidene, 1, the inferior tertiary butyl, 1 of 2-, 2-pentylidene, 1,2-cyclopentylidene, 1,2-cyclohexylidene, 1,4-phenylene, 1, the halogenated phenyl of 4-Asia-2-, 1,4-Asia-2-aminomethyl phenyl, 2-are halogenated 1,4-Asia-5-aminomethyl phenyl, sub indenyl, 1,4 '-benzylidene, 1,4 '-phenylene ethyl; R
1With R
2Identical or different.
More preferably, R
1Or R
2It is one of following that group all is selected from: methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, isopropylidene, isobutylidene, isopentylidene.
It is one of following that petchem shown in the preferred formula (II) is selected from: polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, poly-succinic fourth diester.
Magnesium halide alcohol adduct of the present invention can adopt the known magnesium halide alcohol adduct preparation process of the industry to prepare, and for example can extrude or method such as high-speed stirring by spraying drying, spray cooling, high pressure.Usually, can be earlier with magnesium halide, pure and mild petchem three components contact reacts under the condition of heating, final temperature of reaction will reach and can make magnesium halide, the compound alcohol adduct fusing of pure and mild petchem form melt, be preferably 100 ℃～140 ℃, in inert media, further solidify to form solid particulate then.Described inert media generally adopts liquid aliphatic family hydro carbons inert solvent, as kerosene, paraffin oil, vaseline oil, white oil etc., when needing, also can randomly add some silicoorganic compound or tensio-active agent, as methyl-silicone oil etc.When the contact reacts of magnesium halide, pure and mild petchem three components, also can randomly add above-mentioned inert liquid medium.
Technical scheme as the preferred preparation method of the said products of the present invention is:
A kind of preparation method of magnesium halide alcohol adduct may further comprise the steps:
The first step, the preparation of magnesium halide alcohol adduct melt
In airtight container, magnesium halide, alcohol, petchem and optional inert media are heated to 100 ℃～140 ℃, fully the reaction back forms the mixture that contains the fused magnesium halide alcohol adduct; The add-on of magnesium halide is 0.1～1.0mol/L liquid medium, and the add-on of alcohol counts 1～5 with every mole of magnesium, and the add-on of petchem counts 0.001～5 with every mole of magnesium;
In the preparation of magnesium halide alcohol adduct melt, order of addition(of ingredients) in no particular order.
In second step, the magnesium halide alcohol adduct particulate forms
Above-mentioned magnesium halide alcohol adduct melted blend after high shear forces, by the moulding of low temperature inert media chilling, is formed the magnesium halide alcohol adduct particle; Obtain described product.
High shear forces can adopt conventional method, as the disclosed high-speed mixing method of Chinese patent CN1330086, as the disclosed spray method of US6020279, and disclosed high-gravity rotating bed as CN1580136A, as the disclosed mulser of CN1463990A etc.
Heat-eliminating medium can adopt the lower inert hydrocarbon solvent of boiling point, as pentane, hexane, heptane, gasoline or petrol ether etc.With before material contacts, the temperature of heat-eliminating medium is controlled at-40 ℃～0 ℃.
The above-mentioned magnesium halide alcohol adduct particle that obtains can be used for preparing the catalyzer of olefinic polymerization after inert hydrocarbon solvent washing, drying.
Above-mentioned magnesium halide alcohol adduct is applied to prepare olefin polymerization catalysis.
The synthetic of catalyzer can be adopted known synthetic method, as with as described in the magnesium halide alcohol adduct particle directly with the halogenated titanium reaction, common needs according to practical application can randomly add the known internal electron donor compound of some industry.
The invention has the beneficial effects as follows:
The compound alcohol adduct of spherical organic/inorganic of magnesium halide of the present invention, pure and mild petchem ternary component, for catalyzer provides a kind of novel carriers, overcome the shortcoming of pure inorganic carrier and pure organic carrier, and the preparation route is simple, it is good that the catalyst activity of institute's load keeps, and the polymerisate degree of isotacticity is higher.
Description of drawings
Fig. 1 is the differential scanning calorimetric-thermogravimetry analytical results figure of embodiment 1 carrier.
Fig. 2 is the differential scanning calorimetric-thermogravimetry analytical results figure of Comparative Examples 1 carrier.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Testing method:
(1) heat analysis is carried out on Netzsch STA 449C, and temperature rise rate is 10 ℃/minute, uses nitrogen to do carrier gas.
(2) polypropylene degree of isotacticity (II) is measured with the boiling n-heptane extraction process: by recording behind the boiling heptane extracting 4h.
Embodiment 1
The preparation of carrier:
In the withstand voltage reactor of 500mL, add 250ml silicone oil successively, add 15 gram magnesium chlorides, 26ml ethanol and 25 gram polyethylene terephthalates (PET, it is 89 ℃ that DSC measures fusing point) are put into refrigerative hexane in advance with mixture through mulser emulsification after temperature reaction is finished, suction filtration is also used hexane wash three times, vacuum-drying obtains ball type carrier, abbreviates Sp-p as.
Preparation of catalysts:
In the glass reaction bottle of 300mL, add the titanium tetrachloride of 100ml, be cooled to-20 ℃, add above-mentioned Sp-p ball type carrier 8 grams, be warming up to 100 ℃.Add diisobutyl phthalate 1.5ml in temperature-rise period, elimination liquid washs secondary with titanium tetrachloride, with hexane wash three times, vacuum-drying, obtains the catalyzer that made by the Sp-p ball type carrier, abbreviates SpC-p as.
Propylene polymerization:
Liquid phase bulk propylene polymerization is to carry out in the stainless steel autoclave of 5L.In nitrogen protection downhill reaction still, add the 1mmol triethyl aluminium solution successively; 0.05mmol methylcyclohexyl dimethoxy silane (CHMDMS) solution; the above-mentioned SpC-p catalyzer of 10mg; propylene 2.5L and 1L hydrogen (standard volume) are warming up to 70 ℃, react after 1 hour; cooling; release, discharging will be weighed after the gained alfon drying.
Comparative Examples 1
Except that not adding the polyethylene terephthalate all the other same embodiment.Obtain ball type carrier and abbreviate Sp-n as, the catalyzer that is made by the Sp-n carrier is called for short SpC-n.
The catalyst performance of embodiment and Comparative Examples sees Table 1.
Table 1 catalyst performance
Fig. 1 is differential scanning calorimetric-thermogravimetry (DSC-TG) analytical results of embodiment Sp-p carrier, and Fig. 2 is differential scanning calorimetric-thermogravimetry (DSC-TG) analytical results of Comparative Examples Sp-n carrier.As can be seen from Figure 1, complex carrier locates to have occurred one at 83.8 ℃, and the fusing point of pairing temperature and PET is very approaching in the unexistent endotherm(ic)peak of pure magnesium chloride support, should be the endotherm(ic)peak that belongs to PET.The PET that is added is described behind Over emulsfication, enters in the magnesium chloride alcohol adduct, form complex carrier with it.
From the data of table 1 as can be seen, the spherical alcohol adduct of magnesium halide of the present invention, pure and mild petchem ternary component is as the catalyzer of preparing carriers, when being used for propylene polymerization, demonstrate when keeping good polymerization activity, polymer product has higher degree of isotacticity.
Claims (11)
1. magnesium halide alcohol adduct, its general structure is characterized in that shown in (I) formula:
MgX
2-mROH-kE
(Ⅰ)
In (I) formula, X is a chlorine or bromine, and perhaps one of them X is replaced by one of following group: C
1～C
14Alkyl, C
6～C
14Aryl, C
1～C
14Alkoxyl group, C
7～C
14Aryloxy;
R is a kind of in the following groups: C
1～C
12Alkyl; M is 1～5; K is 0.001～3; E is the petchem shown in the logical formula II;
In the logical formula II, R
1Or R
2Be and eliminate a kind of of any 1 subunit that hydrogen atom forms: C in the following groups
1～C
10Straight chained alkyl, C
3～C
10Branched-chain alkyl, C
3～C
10Cycloalkyl, C
6～C
10Aryl, C
7～C
10Alkaryl, C
7～C
10Aralkyl, C
1～C
10Straight chain silylation, C
3～C
10The branched silicon alkyl; Hydrogen atom on the phenyl ring in wherein said aryl, alkaryl or the aralkyl is randomly replaced by halogen atom; R
1With R
2Identical or inequality; 2≤n≤10000.
2. magnesium halide alcohol adduct according to claim 1 is characterized in that:
MgX in the logical formula I
2The compound of representative is one of following: magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium.
3. magnesium halide alcohol adduct according to claim 1 is characterized in that:
X in the logical formula I is a chlorine.
4. magnesium halide alcohol adduct according to claim 1 is characterized in that:
R is a kind of in the following groups in the logical formula I: C
1～C
4Alkyl.
5. magnesium halide alcohol adduct according to claim 1 is characterized in that:
ROH is a kind of in following in the logical formula I: methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, amylalcohol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol.
6. magnesium halide alcohol adduct according to claim 1 is characterized in that:
ROH is a kind of in following in the logical formula I: Virahol, primary isoamyl alcohol.
7. magnesium halide alcohol adduct according to claim 1 is characterized in that:
In the logical formula I, m is 1.5～3.5; K is 0.02～3.
8. magnesium halide alcohol adduct according to claim 1 is characterized in that:
Logical formula II R
1Or R
2All be selected from one of following: methylene radical, ethylene, propylene, 1,3-propylidene, 1,2-butylidene, 1, the inferior tertiary butyl, 1 of 2-, 2-pentylidene, 1,2-cyclopentylidene, 1,2-cyclohexylidene, 1,4-phenylene, 1, the halogenated phenyl of 4-Asia-2-, 1,4-Asia-2-aminomethyl phenyl, 2-are halogenated 1,4-Asia-5-aminomethyl phenyl, sub indenyl, 1,4 '-benzylidene, 1,4 '-phenylene ethyl; R1 and R
2Identical or different.
9. magnesium halide alcohol adduct according to claim 8 is characterized in that:
It is one of following that petchem shown in the logical formula II is selected from: polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, poly-succinic fourth diester.
10. the preparation method of the described magnesium halide alcohol adduct of one of claim 1 to 9 may further comprise the steps:
The first step, the preparation of magnesium halide alcohol adduct melt
In airtight container, magnesium halide, alcohol, petchem and optional inert media are heated to 100 ℃～140 ℃, fully the reaction back forms the mixture that contains the fused magnesium halide alcohol adduct; The add-on of magnesium halide is 0.1mol/L～1.0mol/L liquid medium, and the add-on of alcohol counts 1～5 with every mole of magnesium, and the add-on of petchem counts 0.001～5 with every mole of magnesium;
In second step, the magnesium halide alcohol adduct particulate forms
Above-mentioned magnesium halide alcohol adduct melted blend after high shear forces, by the moulding of low temperature inert media chilling, is formed the magnesium halide alcohol adduct particle; Obtain described product.
11. the application of the described magnesium halide alcohol adduct of one of claim 1 to 9 in the preparation olefin polymerization catalysis.
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| CN102432710A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Preparation method of ethylene polymerization catalyst carrier, catalyst components and catalyst |
| CN105482003B (en) * | 2014-10-10 | 2018-01-23 | 中国石油化工股份有限公司 | Carrier and its catalyst used in a kind of ethylene rolymerization catalyst |
| KR20230097111A (en) | 2020-10-26 | 2023-06-30 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Solid component for preparing olefin polymerization catalyst, method for preparing the same and application thereof |
| CN113004445A (en) * | 2021-03-29 | 2021-06-22 | 淄博新塑化工有限公司 | Regular carrier of polypropylene catalyst, preparation method thereof and polypropylene catalyst prepared by regular carrier |
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| CN1453298A (en) * | 2003-04-21 | 2003-11-05 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
| CN1803862A (en) * | 2005-01-13 | 2006-07-19 | 中国石油化工股份有限公司 | Catalyst components for olefinic polyreaction and catalyst thereof |
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| CN1453298A (en) * | 2003-04-21 | 2003-11-05 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
| CN1803862A (en) * | 2005-01-13 | 2006-07-19 | 中国石油化工股份有限公司 | Catalyst components for olefinic polyreaction and catalyst thereof |
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