CN104558281A - Spherical carrier used for olefin polymerization catalyst and preparation method thereof - Google Patents
Spherical carrier used for olefin polymerization catalyst and preparation method thereof Download PDFInfo
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- CN104558281A CN104558281A CN201310491393.6A CN201310491393A CN104558281A CN 104558281 A CN104558281 A CN 104558281A CN 201310491393 A CN201310491393 A CN 201310491393A CN 104558281 A CN104558281 A CN 104558281A
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Abstract
The invention relates to a spherical carrier used for an olefin polymerization catalyst and a preparation method thereof. The preparation method comprises the following steps: (1) in the presence of at least one macromolecular dispersion stabilizer, reacting magnesium halide with an organic compound containing reactive hydrogen to form a coordination compound solution; (2) reacting the coordination compound solution with epoxy alkane compounds, and separating out solid particles; (3) recycling the solid particles to obtain spherical carriers. When the catalyst prepared from the spherical carrier is used for propylene polymerization, the catalyst has relatively high polymerization activity and relatively high stereotactic ability.
Description
Technical field
The present invention relates to a kind of preparation method of the ball type carrier for olefin polymerization catalysis, and the ball type carrier prepared by the method.
Background technology
Catalyzer for olefinic polymerization is mostly obtained by being loaded in by halogenated titanium on inactive anhydrous magnesium chloride.Wherein, a kind of common method being used for preparing active magnesium chloride is by anhydrous MgCl
2react with alcohol that to form general formula be MgCl
2mROHnH
2the magnesium dichloride-alcohol adducts of O, and then prepare catalyst solid component of olefin polymerization with this adducts load halogenated titanium.This type of alcohol adduct is extruded by spraying dry, spray cooling, high pressure or the method preparation such as high-speed stirring.As: the magnesium chloride alcohol adduct disclosed in US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US6323152.Carry out subcooling after the preparation process of above-mentioned magnesium chloride alcohol adduct carrier generally all needs high-temperature fusion more shaping, process power consumption is large, and gained alcohol adduct carrier also needs to carry out dealcoholation treatment, and technique is comparatively complicated.
Activated magnesium chloride carrier can alkoxyl magnesium be also that raw material is prepared.Such as, CN1033385A discloses a kind of preparation method of Ziegler-Natta type solid catalyst, and it is under the existence of transition metal alkoxide, and solubility dialkyl magnesium and transition metal halide are reacted, and reusable liquid hydrocarbon is settled out solid ingredient and obtains.Alkoxyl group in the dialkoxy magnesium wherein adopted is the branched alkoxy of linear alkoxide groups containing 6-12 carbon atom or 5-12 carbon atom, can form the alcohol magnesium solution being dissolved in liquid hydrocarbon, but this alkoxyl magnesium is difficult to obtain.
CN1177868C discloses a kind of preparation method for olefin polymerization catalysis precursor, and this precursor makes alkoxyl magnesium and titan-alkoxide react to form solid complexes to make under the existence blocking agent.Wherein alkoxyl magnesium is diethoxy magnesium, and titan-alkoxide is purity titanium tetraethoxide.
CN101056894A discloses a kind of catalyzer for propylene polymerization, and it is by dialkoxy magnesium and halogenated titanium compound or silane halide compound and inner electron donor are reacted obtained in presence of organic solvent.Wherein the general formula of dialkoxy magnesium is Mg (OR)
2, wherein R is the alkyl of C1-C6, and reacts obtained by magnesium metal and alcohol.
US4727051 discloses a kind of compound that can be used as carrier for olefin polymerization catalyst, and its structural formula is X
nmg (OR)
2-n, in formula, X is halogen, and R is the alkyl of C1-C10, and n value is 0.2-1.9.Described compound is by being MgX by formula
2magnesium halide and formula be after the alcohol of ROH reacts, then react obtained with MAGNESIUM METAL.
CN1255436C discloses a kind of preparation method of olefin polymerization catalysis, and its preparation process is as follows: be Mg (OR ") with halogenating agent and general formula
2the contact of solubility dialkoxy magnesium, this halogenating agent can with halogen displacement alkoxyl group, forming reactions product A, contact with reaction product A with the first halogenation/titanizing agent again, forming reactions product B, contacts with reaction product B with the second halogenation/titanizing agent, forms catalyst component.Wherein R in dialkoxy magnesium " for containing the alkyl of 1-20 carbon atom or substituted hydrocarbon radical, and this solubility magnesium diaikoxide compound be the alkyl magnesium of MgRR ' and general formula by general formula is R " reaction product that is obtained by reacting of the alcohol of OH.Wherein R and R ' of alkyl magnesium is the alkyl containing 1-10 carbon atom, can be identical or different.Described alcohol is straight or branched alcohol, wherein R " be the alkyl containing 4-20 carbon atom.
CN101190953A discloses a kind of preparation method of catalyst solid component of olefin polymerization, comprise general formula be ClMg (OR) n (ROH) containing magnesium complex, react with electron donor compound and titanium tetrahalide respectively under unreactive hydrocarbons exist and obtains.Should react obtained containing magnesium complex by metal magnesium powder and alcohol, in its formula of, R is selected from the alkyl of C1-C5, and n is 0.1-1.0.
Above-mentioned alkoxyl magnesium compound adopts magnesium powder or alkyl magnesium to be raw material preparation mostly, and compared with magnesium chloride, cost of material is high, and complicated process of preparation.
In order to solve the problem, CN102040681A discloses a kind of compound that can be used as carrier for olefin polymerization catalyst, and it has following structure:
wherein R
1for C
1-C
12straight or branched alkyl; R
2and R
3identical or not identical, be hydrogen or C
1-C
5straight or branched alkyl, the hydrogen wherein on alkyl is optionally replaced by halogen atom; X is chlorine or bromine, but also one of them X by C
1-C
14alkyl or alkoxyl group, C
6-C
14aryl or aryloxy replace; M is 0.1-1.9, n is 0.1-1.9, p+m+n=2.The preparation process of this compound is as follows: under the existence of inert dispersion medium, by MgX
2, general formula R
1alcohol compound shown in OH, is heated to 30-160 DEG C of reaction, forms magnesium halide alcohol adduct solution; Afterwards itself and oxirane compound are reacted at 30-160 DEG C, form carrier; Wherein X is chlorine or bromine, R
1for C
1-C
12straight or branched alkyl.
Although the technical scheme disclosed in above-mentioned patent application reduces raw materials cost prepared by carrier, simplify carrier preparation technology, but owing to needing to use a large amount of inert dispersion medium in carrier preparation process, thus reduce the single-autoclave yield rate of carrier, and the recovery of inert dispersion medium adds solvent recuperation cost; In addition, the taxis of the polymkeric substance adopting the olefin polymerization catalysis of the carrier of this patent application to obtain in olefin polymerization process need further raising.
Summary of the invention
The object of the invention is the above-mentioned defect existed to overcome existing carrier for olefin polymerization catalyst and preparation method thereof, the preparation method that a kind of ball type carrier for olefin polymerization catalysis is newly provided and the ball type carrier prepared by the method.
The invention provides a kind of preparation method of the ball type carrier for olefin polymerization catalysis, the method comprises: under the existence of at least one macromolecular dispersion stabilizer, will be reacted by least following component and directly separate out to obtain solid product: (a) magnesium halide; (b) organic compound containing reactive hydrogen; And (c) alkylene oxides compound.
Present invention also offers the ball type carrier prepared by aforesaid method.
By above technical scheme, the present invention has the following advantages:
(1) can obtain without the need to adding inert dispersion medium the solid particulate that particle form is good, size distribution is narrower in the preparation process of described ball type carrier, thus improve the single-autoclave yield rate of ball type carrier;
(2) macromolecular dispersion stabilizer used in the preparation process of described ball type carrier is easier to reclaim relative to inert dispersion medium, thus relatively reduces the cost recovery of solvent;
(3) olefin polymerization catalysis adopting ball type carrier of the present invention to prepare as carrier resulting polymers when olefinic polymerization (particularly propylene polymerization or copolymerization) has higher taxis.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is ball type carrier prepared by embodiment 1
1h-NMR spectrogram;
Fig. 2 is ball type carrier prepared by embodiment 2
1h-NMR spectrogram;
Fig. 3 is ball type carrier prepared by embodiment 13
1h-NMR spectrogram;
Fig. 4 is ball type carrier prepared by embodiment 16
1h-NMR spectrogram;
Fig. 5 is the optical microscope photograph of ball type carrier prepared by embodiment 1;
Fig. 6 is the optical microscope photograph of block carrier prepared by comparative example 3.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Term used herein " ball type carrier " refers to that described carrier has the spherical particle form of class, and does not require that described carrier has perfect spherical morphology.
Described herein " carrier " refers to the material without olefin polymerizating activity, namely in the carrier not containing forming the active ingredient with olefin polymerizating activity, as titanium compound.
" directly separate out and obtain solid product " described in the present invention has following implication:
(1) in the present invention, gained solid product (i.e. ball type carrier) is obtained by chemical reaction precipitation, namely in original system, directly separate out shaping by chemical reaction in solid product preparation process, and do not need to make reactant precipitation obtain spherical solid particulate by means such as solvent flashing or change system temperatures (as spraying dry, reducing system temperature).
(2) in the present invention the shape (spherical) of solid product acquisition without the need to add in preparation process there is good particle form inert support compound (as SiO
2, metal oxide etc.) just can realize.
The invention provides a kind of preparation method of the ball type carrier for olefin polymerization catalysis, the method comprises: under the existence of at least one macromolecular dispersion stabilizer, will be reacted by least following component and directly separate out to obtain solid product: (a) magnesium halide; (b) organic compound containing reactive hydrogen; And (c) alkylene oxides compound.
In the preferred case, the process of described component reaction is comprised:
(1) under the existence of at least one macromolecular dispersion stabilizer, by magnesium halide with containing the organic compound reaction of reactive hydrogen to form complex solution;
(2) described complex solution and alkylene oxides compound are reacted, separate out solid particulate.
In step (1), relative to the consumption of every mole of magnesium halide, the consumption of the described organic compound containing reactive hydrogen can be 3-30 mole, is preferably 4-20 mole.
In the present invention, the consumption of described macromolecular dispersion stabilizer can be the 0.1-10 % by weight of total consumption of described magnesium halide and the described organic compound containing reactive hydrogen, is preferably 0.2-5 % by weight.
Reaction conditions in step (1) can comprise: temperature of reaction is 30-160 DEG C, preferred 40-120 DEG C; Reaction times is 0.1-5 hour, is preferably 0.5-2 hour.Reaction in step (1) can be carried out in the reactor of routine or container, and preferably, the reaction in step (1) is carried out in airtight container, such as, can carry out in a kettle..
In the present invention, the general formula of magnesium halide is MgX
2, wherein, X is preferably bromine, chlorine or iodine.More preferably, described magnesium halide is selected from least one in magnesium dichloride, dibrominated magnesium and diiodinating magnesium, most preferably is magnesium dichloride.
In the present invention, the described organic compound containing reactive hydrogen is preferably Organic Alcohol R
1oH, wherein, R
1be preferably C
1-C
8straight or branched alkyl, be more preferably C
2-C
5straight or branched alkyl, as ethyl, propyl group, butyl or amyl group.Particularly, described Organic Alcohol such as can be selected from methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and the 2-ethyl-1-at least one in alcohol.
In invention, " polymer " in macromolecular dispersion stabilizer is not particularly limited molecular weight, but adopt IUPAC(International Union of Pure and Applied Chemistry, IUPAC) in the definition of polymer (or macromole) namely " molecule of relative high molecule mass, its structure mainly by low relative molecular mass molecule by fact or conceptive derivative unit is multiple repeats to form ".In the present invention, the weight-average molecular weight of the macromolecular dispersion stabilizer in step (1) is preferably greater than 1000, more preferably greater than 3000, and more preferably 6,000-2,000,000.Particularly, described macromolecular dispersion stabilizer can be selected from polyacrylate, styrene-maleic anhydride copolymer, poly styrene sulfonate, naphthalene sulfonic acidformaldehyde condensation product, condensation alkyl phenyl ether sulfuric ester, condensation polyoxyethylene alkylphenol ether phosphoric acid ester, the modification of oxygen base alkyl acrylate copolymer gathers ethyleneimine, the polymkeric substance of 1-12-4-vinylpyridine bromide, polyvinyl benzyl front three amine salt, polyvinyl alcohol, polyacrylamide, ethylene oxide propylene oxide segmented copolymer, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone vinylacetate copolymers, polyoxyethylene glycol (PEG), at least one in alkyl phenyl polyethylene oxides ether and polyalkyl methacrylate compounds, be preferably polyvinylpyrrolidone, at least one in polyvinylpyrrolidone vinylacetate copolymers and polyoxyethylene glycol.
In the present invention, described magnesium halide, described organic compound containing reactive hydrogen and described macromolecular dispersion stabilizer can participate in the process of formation magnesium halide alcohol adduct solution with the form containing minor amount of water.The water that these minor amount of water refer in industrial production or store or inevitably introduce in transportation, instead of people is the water added.
In step (1), described magnesium halide, described organic compound containing reactive hydrogen and described macromolecular dispersion stabilizer, the order of addition(of ingredients) between three in no particular order, can add with arbitrary order of addition(of ingredients).
In the present invention, relative to the consumption of magnesium halide every mole described, the consumption of described alkylene oxides compound can be 1-10 mole, is preferably 2-6 mole.
Reaction conditions in step (2) can comprise: temperature of reaction is 30-160 DEG C, preferred 40-120 DEG C; Reaction times is 0.1-5 hour, is preferably 0.2-1 hour.
In the present invention, described alkylene oxides compound is preferably structural formula compound as the formula (1),
formula (1)
Wherein, R
2and R
3identical or different, and be hydrogen or C independently of one another
1-C
5straight or branched alkyl, the hydrogen wherein on alkyl is optionally optionally substituted by halogen, particularly, R
2and R
3be preferably hydrogen, methyl, ethyl, propyl group, chloromethyl, Chloroethyl, chloro propyl group, bromomethyl, bromoethyl or Bromopropyl independently of one another.Particularly, described alkylene oxides compound can be selected from least one in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
In described method provided by the invention, can add in step (1) or not add inert dispersion medium.Described inert dispersion medium is the inert dispersion medium that this area routine uses, such as can be selected from least one in liquid aliphatic series, aromatics or cycloaliphatic hydrocarbons and silicone oil, particularly, at least one in the straight or branched liquid alkane of 6 carbon, aromatic hydrocarbons (as toluene), kerosene, paraffin oil, vaseline oil, white oil and methyl-silicone oil such as can be greater than for carbon chain lengths.When adding described inert dispersion medium in step (1), the volume ratio of the consumption of described inert dispersion medium and the consumption of the described organic compound containing reactive hydrogen can be 1:0.2-20, is preferably 1:0.5-10.In more preferably embodiment, in step (1) and (2), all do not add inert dispersion medium.
In described method provided by the invention, the raw material at least comprising component (a), component (b) and component (c) is being carried out in the process of reacting, except component (a), component (b) and component (c), conventional binder component can also be added, as electron donor.Described electron donor can be the electron donor compound that this area routine uses, as ether, ester, ketone, aldehyde, amine, amide, organoalkoxysilane etc., and at least one in preferred ether, ester and organoalkoxysilane.
In described method provided by the invention, preferably, the raw material at least comprising component (a), component (b) and component (c) is being carried out, in the process of reacting, not adding titanium tetrachloride.
In a preferred embodiment, the preparation method of described ball type carrier comprises:
(1) in airtight container, under the existence of at least one macromolecular dispersion stabilizer, by magnesium halide MgX
2with Organic Alcohol R
1the mixture of OH reacts 0.1-5 hour (preferred 0.5-2 hour) under 30-160 DEG C (preferred 40-120 DEG C), forms magnesium halide alcohol adduct solution, i.e. complex solution;
(2) the alkylene oxides compound shown in described magnesium halide alcohol adduct solution and above-mentioned formula (1) is reacted 0.1-5 hour (preferred 0.2-1 hour) under 30-160 DEG C (preferred 40-120 DEG C), separate out solid particulate;
(3) reclaim described solid particulate by solid-liquid separation technique and obtain ball type carrier.
In the preferred embodiment of one, the preparation method of described ball type carrier comprises:
(1) in airtight container, under agitation the mixture of magnesium halide, Organic Alcohol and at least one macromolecular dispersion stabilizer is heated to 30-160 DEG C, preferred 40-120 DEG C, reaction 0.1-5 hour, preferred 0.5-2 hour, form magnesium halide alcohol adduct solution, wherein, in every mole of magnesium, the consumption of described Organic Alcohol is 3-30 mole, is preferably 4-25 mole; The consumption of described macromolecular dispersion stabilizer is the 0.1-10 % by weight of described magnesium halide and the total consumption of described Organic Alcohol, is preferably 0.2-5 % by weight.
(2) under agitation, the alkylene oxides compound shown in above-mentioned formula (1) is added in above-mentioned magnesium halide alcohol adduct solution, 0.1-5 hour is reacted under 30-160 DEG C (preferred 40-120 DEG C), preferred 0.2-1 hour, form solid particulate, wherein, in every mole of magnesium, the consumption of described alkylene oxides compound is 1-10 mole, preferred 2-6 mole;
(3) reclaim described solid particulate by solid-liquid separation technique and obtain ball type carrier.
In above-mentioned preferred implementation, the process reclaiming solid particulate can be implemented according to the conventional solid-liquid isolation technique of this area, such as, the modes such as filtration, decantation, centrifugation can be adopted to implement.And step (3) can also comprise is undertaken washing and drying by the spherical carrier particle inert hydrocarbon solvent obtained.Described inert hydrocarbon solvent is preferably straight chain or straight chain liquid alkane, the aromatic hydrocarbons that carbon chain lengths is greater than 4 carbon, particularly, such as, can be hexane, heptane, octane, decane, toluene etc.
Present invention also offers the ball type carrier prepared by aforesaid method.
In the preferred case, the main composition of the ball type carrier prepared by aforesaid method be: the alkylene oxides compound shown in the magnesium compound shown in formula (2) and formula (1),
formula (1)
formula (2)
Wherein, R
1for C
1-C
12straight or branched alkyl; R
2and R
3identical or different, and be hydrogen or C independently of one another
1-C
5straight or branched alkyl, the hydrogen wherein on alkyl is optionally optionally substituted by halogen; X is halogen; M is 0.1-1.9, n is 0.1-1.9, and m+n=2;
Wherein, relative to the magnesium compound shown in every mole of formula (2), the content of the alkylene oxides compound shown in formula (1) is 0.01-0.8 mole, is preferably 0.02-0.5 mole, is more preferably 0.02-0.3 mole.
Preferably, X is bromine, chlorine or iodine, is more preferably chlorine.
Preferably, m is 0.5-1.5, n is 0.5-1.5, and m+n=2.Most preferably, m is 1, n is 1.
The median size (D50) of described ball type carrier is preferably 30-125 μm, is more preferably 40-85 μm.The particle size distribution values (SPAN=(D90-D10)/D50) of described ball type carrier is preferably 0.6-2.5, is more preferably 0.6-0.85.In the present invention, the median size of ball type carrier and particle size distribution values adopt MastersSizer 2000 particle size analyzer (being manufactured by Malvern Instruments Ltd) mensuration.
The invention will be further described by the following examples.
(1) composition of ball type carrier: dissolve ball type carrier with TRI N BUTYL PHOSPHATE and deuterated toluene, and test with nuclear magnetic resonance spectrometer
1h-NMR spectrogram.
(2) melt index: the method according to ASTM D1238-99 measures.
(3) polymkeric substance isotactic index: adopt heptane extraction process to measure (heptane boiling extracting 6 hours), namely the polymer samples of 2g drying is got, be placed in extractor boiling heptane extracting 6 hours, afterwards, residuum is dried to constant weight, resulting polymers weight (g) with 2 ratio be isotactic index.
(4) size distribution test: the median size of spherical carrier particle and size-grade distribution MastersSizer 2000 particle size analyzer (being manufactured by Malvern Instruments Ltd) measure, wherein, particle size distribution values SPAN=(D90-D10)/D50.
Embodiment 1-22
These embodiments are for illustration of ball type carrier for olefin polymerization catalysis of the present invention and preparation method thereof.
In the closed reactor of 500mL, add magnesium chloride, Organic Alcohol (R successively
1and macromolecular dispersion stabilizer OH), and in embodiment 19-22, additionally add toluene as inert dispersion medium (wherein respectively, for the volume ratio of the add-on of toluene and Organic Alcohol, embodiment 19 is 1:10, embodiment 20 is 1:3, embodiment 21 is 1:1, embodiment 22 is 1:2), under agitation be warming up to temperature of reaction (T), isothermal reaction is after 1 hour, add alkylene oxides compound (E), holding temperature reacts 0.5 hour, elimination liquid, 5 times are washed with hexane, vacuum-drying, obtain spherical carrier particle, concrete preparation condition is as shown in table 1, thus obtain ball type carrier A1-A22 respectively, wherein, these ball type carriers median size separately (D50) and particle size distribution values (SPAN) as shown in table 1, ball type carrier A1's
1h-NMR spectrogram as shown in Figure 1, ball type carrier A2's
1h-NMR spectrogram as shown in Figure 2, ball type carrier A13's
1h-NMR spectrogram as shown in Figure 3, ball type carrier A16's
1as shown in Figure 4, the optical microscope photograph of ball type carrier A1 as shown in Figure 5 for H-NMR spectrogram.
Table 1
As can be seen from table 1 and Fig. 5, the form of prepared according to the methods of the invention spherical carrier particle is for being essentially spherical, and particle size distribution is narrow.
At ball type carrier A1 prepared by embodiment 1
1in H-NMR spectrogram, Spectra peak recognition and integral area as shown in table 2 below.
Table 2
| Belonging to group | Chemical shift ppm | Integral area |
| CH 3（Ⅴ） | 1.40 | 3.01 |
| CH 2（Ⅴ） | 3.93 | 7.10-5.10=2 |
| CH（Ⅴ） | 4.29 | 1.00 |
| CH 2Cl（Ⅴ） | 3.79 | 4.00 |
| CH 2Cl（Ⅵ） | 2.87 | 0.08 |
| C-CH-C（Ⅵ） | 2.60 | 0.04 |
| C-CH-O（Ⅵ） | 2.16 | 0.04 |
| C-CH-O（Ⅵ） | 1.95 | 0.04 |
Note: do not mark peak position person in Fig. 1 for solvent peak
It can thus be appreciated that ball type carrier A1 prepared by embodiment 1 is primarily of the compound composition shown in formula V and formula (VI), and the mol ratio of the content of the compound shown in formula V and formula (VI) is 1:0.04.
formula V
formula (VI)
At ball type carrier A2 prepared by embodiment 2
1in H-NMR spectrogram, Spectra peak recognition and integral area as shown in table 3 below.
Table 3
| Belonging to group | Chemical shift ppm | Integral area |
| CH 3（Ⅴ） | 1.41 | 3.03 |
| CH 2（Ⅴ） | 3.94 | 7.26-5.23=2.03 |
| CH（Ⅴ） | 4.31 | 1.00 |
| CH 2Cl（Ⅴ） | 3.81 | 3.99 |
| CH 2Cl（Ⅵ） | 2.88 | 0.13 |
| C-CH-C（Ⅵ） | 2.61 | 0.06 |
| C-CH-O（Ⅵ） | 2.17 | 0.07 |
| C-CH-O（Ⅵ） | 1.95 | 0.07 |
Note: do not mark peak position person in Fig. 2 for solvent peak
It can thus be appreciated that ball type carrier A2 prepared by embodiment 2 is primarily of the compound composition shown in formula V and formula (VI), and the mol ratio of the content of the compound shown in formula V and formula (VI) is 1:0.07.
At ball type carrier A13 prepared by embodiment 13
1in H-NMR spectrogram, Spectra peak recognition and integral area as shown in table 4 below.
Table 4
| Belonging to group | Chemical shift ppm | Integral area |
| CH 3（Ⅶ） | 1.09 | 3.00 |
| CH 2（Ⅶ） | 3.87 | 2.00 |
| CH 2（Ⅶ） | 1.76 | 2.00 |
| CH 2（Ⅶ） | 1.48 | 8.60-6.60=2.00 |
| CH（Ⅶ） | 4.28 | 1.00 |
| CH 2Cl（Ⅶ） | 3.78 | 6.00-2.00=4.00 |
| CH 2Cl（Ⅵ） | 2.87 | 0.04 |
| C-CH-C（Ⅵ） | 2.60 | 0.02 |
| C-CH-O（Ⅵ） | 2.14 | 0.02 |
| C-CH-O（Ⅵ） | 1.94 | 0.02 |
Note: do not mark peak position person in Fig. 3 for solvent peak
It can thus be appreciated that ball type carrier A13 prepared by embodiment 13 is primarily of the compound composition shown in formula (VII) and formula (VI), and the mol ratio of the content of the compound shown in formula (VII) and formula (VI) is 1:0.02.
formula (VII)
formula (VI)
At ball type carrier A16 prepared by embodiment 16
1in H-NMR spectrogram, Spectra peak recognition and integral area as shown in table 5 below.
Table 5
| Belonging to group | Chemical shift ppm | Integral area |
| CH 3（Ⅴ） | 1.40 | 9.08-6.88-1.18=1.02 |
| CH 2（Ⅴ） | 3.95 | 5.86-4-1.18=0.68 |
| CH 3（Ⅶ） | 1.06 | 1.77 |
| CH 2（Ⅶ） | 3.86 | 1.18 |
| CH 2（Ⅶ） | 1.74 | 1.18 |
| CH 2（Ⅶ） | 1.51 | 1.18 |
| CH（Ⅶ） | 4.34 | 1.00 |
| CH 2Cl（Ⅶ） | 3.84 | 4.00 |
| CH 2Cl（Ⅵ） | 2.86 | 0.49 |
| C-CH-C（Ⅵ） | 2.60 | 0.23 |
| C-CH-O（Ⅵ） | 2.15 | 0.24 |
| C-CH-O（Ⅵ） | 1.94 | 0.24 |
Note: do not mark peak position person in Fig. 4 for solvent peak
It can thus be appreciated that, ball type carrier A16 prepared by embodiment 16 is primarily of the compound composition shown in formula V, formula (VI) and formula (VII), and the mol ratio of the content sum of the compound shown in the content of the compound shown in formula (VI) and formula V and formula (VII) is 0.24:1, the mol ratio of the content of the compound shown in the compound shown in formula (VI) and formula (VII) is 1:1.74.
Comparative example 1
In the reactor of 500mL, add 7.2g magnesium chloride, 180ml white oil and 82ml ethanol successively, and content is under agitation warming up to 90 DEG C, and react after 1 hour at such a temperature, in reactor, add 24ml epoxy chloropropane, and make reaction proceed 0.5 hour at such a temperature, elimination liquid afterwards, residual solid hexane is washed 5 times, then vacuum-drying, obtain ball type carrier D1.
Comparative example 2
Method according to comparative example 1 prepares ball type carrier, and difference is, do not add inert dispersion medium white oil, result does not obtain solid particulate.
Comparative example 3
Method according to embodiment 1 prepares carrier, and difference is, replaces the PVP added in embodiment 1 with the nonionic surface active agent sorbester p17 of identical weight, thus obtained block carrier D3, the optical microscope photograph of this block carrier is as shown in Figure 6.
Comparative example 4
Method according to embodiment 1 prepares carrier, and difference is, does not add macromolecular dispersion stabilizer PVP, thus obtained block carrier D4.
Comparative example 5
In the closed reactor of 500mL, add magnesium chloride 22g, ethanol 188ml, PVP2.7g (Mw=10000) successively, be under agitation warming up to 80 DEG C, isothermal reaction, after 1 hour, slowly drips 4ml TiCl in solution
4, maintain after 0.5 hour, in above-mentioned solution, add epoxy chloropropane 57ml, holding temperature reacts 0.5 hour, elimination liquid, only obtains a small amount of amorphous powder solid.
Test example 1
(1) solid catalyst is prepared
In the glass reaction bottle of 300mL, add 100ml titanium tetrachloride successively, be cooled to-20 DEG C, add ball type carrier A1 prepared by 8g above-described embodiment 1, be warming up to 110 DEG C.In temperature-rise period, add diisobutyl phthalate 1.5ml, elimination liquid, washs secondary with titanium tetrachloride, with hexanes wash three times, obtains solid catalyst Cat-1 after vacuum-drying.
(2) liquid phase bulk propylene polymerization
Liquid phase bulk propylene polymerization carries out in the stainless steel autoclave of 5L.The hexane solution (concentration is 0.5mmol/ml) of 5ml triethyl aluminum, the hexane solution (concentration is 0.1mmol/ml) of 1ml Cyclohexyl Methyl Dimethoxysilane (CHMMS) and the above-mentioned solid catalyst Cat-1 of 9mg is added under nitrogen protection successively in reactor.Close autoclave, add the liquid propene of a certain amount of hydrogen (standard volume) and 2.3L.Be warming up to 70 DEG C, react after 1 hour, cooling, release, discharging, will weigh after the drying of gained alfon and analyze, result be as shown in table 6.
Test example 2-10
Prepare solid catalyst according to the method for test example 1 and implement liquid phase bulk propylene polymerization, difference is, respectively with embodiment 2 prepare ball type carrier A2, embodiment 3 prepare ball type carrier A3, embodiment 6 prepare ball type carrier A6, embodiment 8 prepare ball type carrier A8, embodiment 9 prepare ball type carrier A9, embodiment 11 prepare ball type carrier A11, embodiment 13 prepare ball type carrier A13, embodiment 16 prepare ball type carrier A16 and embodiment 20 prepare ball type carrier A20 replace described ball type carrier A1.Result is as shown in table 6.
Comparative experimental example 1
Prepare solid catalyst according to the method for test example 1 and implement liquid phase bulk propylene polymerization, difference is, replaces described ball type carrier A1 with ball type carrier D1 prepared by comparative example 1.Result is as shown in table 6.
Table 6
Data as can be seen from table 6, when the catalyzer prepared is for propylene polymerization, have compared with high polymerization activity and higher stereotaxis ability by ball type carrier of the present invention; Meanwhile, the hydrogen response of this catalyzer is better, and particularly under high melt index, polymkeric substance still has higher isotactic index.
Claims (14)
1. for a preparation method for the ball type carrier of olefin polymerization catalysis, the method comprises: under the existence of at least one macromolecular dispersion stabilizer, will be reacted by least following component and directly separate out to obtain solid product: (a) magnesium halide; (b) organic compound containing reactive hydrogen; And (c) alkylene oxides compound.
2. method according to claim 1, wherein, the process of described reaction comprises:
(1) under the existence of at least one macromolecular dispersion stabilizer, by magnesium halide with containing the organic compound reaction of reactive hydrogen to form complex solution;
(2) described complex solution and alkylene oxides compound are reacted.
3. method according to claim 1 and 2, wherein, in step (1), relative to the consumption of every mole of magnesium halide, the consumption of the described organic compound containing reactive hydrogen is 3-30 mole, is preferably 4-20 mole; The consumption of described macromolecular dispersion stabilizer is the 0.1-10 % by weight of total consumption of described magnesium halide and the described organic compound containing reactive hydrogen, is preferably 0.2-5 % by weight.
4. method according to claim 2, wherein, the reaction conditions in step (1) comprises: temperature of reaction is 30-160 DEG C, preferred 40-120 DEG C; Reaction times is 0.1-5 hour, is preferably 0.5-2 hour.
5. according to the method in claim 1-3 described in any one, wherein, the weight-average molecular weight of described macromolecular dispersion stabilizer is greater than 1000, is preferably greater than 3000, is more preferably 6,000-2, and 000,000.
6. according to the method in claim 1-3 and 5 described in any one, wherein, described macromolecular dispersion stabilizer is selected from polyacrylate, styrene-maleic anhydride copolymer, poly styrene sulfonate, naphthalene sulfonic acidformaldehyde condensation product, condensation alkyl phenyl ether sulfuric ester, condensation polyoxyethylene alkylphenol ether phosphoric acid ester, the modification of oxygen base alkyl acrylate copolymer gathers ethyleneimine, the polymkeric substance of 1-12-4-vinylpyridine bromide, polyvinyl benzyl front three amine salt, polyvinyl alcohol, polyacrylamide, ethylene oxide propylene oxide segmented copolymer, polyvinylpyrrolidone, polyvinylpyrrolidone vinylacetate copolymers, polyoxyethylene glycol, at least one in alkyl phenyl polyethylene oxides ether and polyalkyl methacrylate compounds, be preferably polyvinylpyrrolidone, at least one in polyvinylpyrrolidone vinylacetate copolymers and polyoxyethylene glycol.
7. according to the method in claim 1-3 described in any one, wherein, described magnesium halide is selected from least one in magnesium dichloride, dibrominated magnesium and diiodinating magnesium.
8. according to the method in claim 1-3 described in any one, wherein, the described organic compound containing reactive hydrogen is Organic Alcohol R
1oH, wherein, R
1for C
1-C
12straight or branched alkyl; Preferably, described Organic Alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and the 2-ethyl-1-at least one in alcohol.
9. method according to claim 2, wherein, in step (2), relative to the consumption of magnesium halide every mole described, the consumption of described alkylene oxides compound is 1-10 mole, is preferably 2-6 mole.
10. the method according to claim 2 or 9, wherein, the reaction conditions in step (2) comprises: temperature of reaction is 30-160 DEG C, preferred 40-120 DEG C; Reaction times is 0.1-5 hour, is preferably 0.2-1 hour.
11. according to the method in claim 1-3 described in any one, wherein, the structural formula of described alkylene oxides compound as the formula (1),
formula (1)
Wherein, R
2and R
3identical or different, and be hydrogen or C independently of one another
1-C
5straight or branched alkyl, the hydrogen wherein on alkyl is optionally optionally substituted by halogen;
Preferably, described alkylene oxides compound is selected from least one in oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide.
12. methods according to claim 2, wherein, all do not add inert dispersion medium in step (1) and (2), and described inert dispersion medium is selected from least one in liquid aliphatic series, aromatics or cycloaliphatic hydrocarbons and silicone oil.
13. methods according to claim 1 and 2, wherein, are not adding titanium tetrachloride by the process of described component reaction.
14. ball type carriers prepared by the method in claim 1-13 described in any one.
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| CN201310491393.6A CN104558281B (en) | 2013-10-18 | 2013-10-18 | It is a kind of for ball type carrier of olefin polymerization catalysis and preparation method thereof |
| TW103136036A TWI650335B (en) | 2013-10-18 | 2014-10-17 | Spherical carrier for olefin polymerization catalyst, catalyst component, catalyst and preparation method thereof |
| KR1020167012712A KR102019727B1 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| BR112016008605-8A BR112016008605B1 (en) | 2013-10-18 | 2014-10-17 | METHOD FOR PREPARING A SPHERICAL CONVEYOR OF A POLYMERIZATION DEOLEFINS, SPHERICAL CONVEYOR, PROCESS FOR PREPARING A SOLID COMPOSITION, COMPOSITION OF SOLID, CATALYST COMPONENT FOR POLYMERIZATION OF OLEFINES, METHODS OF PREPARATION OF OLEFINS AND METHOD FOR POLYMERIZING OLEFINS |
| EP14854726.8A EP3059263B1 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| RU2016118406A RU2668082C2 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerisation catalyst, catalyst components, catalyst and preparation methods therefor |
| JP2016524132A JP6397908B2 (en) | 2013-10-18 | 2014-10-17 | Spherical support for olefin polymerization catalyst, catalyst component, catalyst, and preparation method thereof |
| PCT/CN2014/088806 WO2015055136A1 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| US15/030,000 US9951157B2 (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| MYPI2016701399A MY172451A (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| SG11201603004RA SG11201603004RA (en) | 2013-10-18 | 2014-10-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| SA516370961A SA516370961B1 (en) | 2013-10-18 | 2016-04-17 | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor |
| CL2016000919A CL2016000919A1 (en) | 2013-10-18 | 2016-04-18 | Method for preparing a spherical carrier of a catalyst for the polymerization of olefins; spherical carrier; process to prepare a solid composition; solid composition; catalyst component; method for preparing a catalyst component; catalyst for the polymerization of olefins; use of the catalyst; and method for the polymerization of olefin (s). |
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