CN106543315B - A kind of catalyst support used for olefinic polymerization and its preparation method and application - Google Patents
A kind of catalyst support used for olefinic polymerization and its preparation method and application Download PDFInfo
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- CN106543315B CN106543315B CN201510614090.8A CN201510614090A CN106543315B CN 106543315 B CN106543315 B CN 106543315B CN 201510614090 A CN201510614090 A CN 201510614090A CN 106543315 B CN106543315 B CN 106543315B
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Abstract
The present invention relates to field of olefin polymerisation, a kind of catalyst support used for olefinic polymerization and its preparation method and application is disclosed.The carrier has structure shown in formula (I), wherein R1For C1‑C12Alkyl or C3‑C12Naphthenic base；X and Y is each independently selected from by halogen element, C1‑C14Alkyl or alkoxy, C6‑C14The group of aryl or aryloxy group composition；M is 0.1-1.9, n 2-m；The sum of amount of substance of X and Y and the mass ratio of the material of Mg are not less than 3 in the carrier.Above-mentioned catalyst support used for olefinic polymerization pattern provided by the invention is preferable and is not susceptible to adhesion.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular, to a kind of catalyst support used for olefinic polymerization and its preparation side
Method and application.
Background technique
It is well known that the Ziegler-Natta catalyst of chlorination magnesium alcoholate load is poly- for alkene (especially propylene)
When conjunction, performance is substantially better than the catalyst that other carriers are loaded.Therefore, it is mostly currently used for the catalyst of olefinic polymerization
It is prepared and halogenated titanium is carried on chlorination magnesium alcoholate.It, can be by being spray-dried, spraying in order to obtain ball type carrier
The methods of mist cooling, high pressure extrusion, high-speed stirred, mulser method and high-gravity rotating bed method preparation, such as WO1999044009A1
It discloses and can be quenched by under high temperature after high-speed stirred emulsified magnesium chloride alcohol adduct system with shape with US4399054 etc.
At spherical alcohol adduct.
But when the catalyst for preparing the chlorination magnesium alcoholate as disclosed in the above-mentioned prior art is used for olefinic polymerization,
It is easy to that the Fragmentation Phenomena of polymer particle occurs in the course of the polymerization process, to cause fine polymer powder more.In order to overcome this
One disadvantage, people attempt to introduce electron donor compound in advance in the carrier preparation of chlorination magnesium alcoholate again, such as:
Internal electron donor phthalate compound commonly understood in the industry is introduced into chlorination by CN1169840C and CN1286863C
In the synthesis of magnesium alcoholate carrier, to obtain " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier, then by the carrier with
Titanium tetrachloride reaction is to form catalyst.But the compound ball type carrier is easy tacky during the preparation process, it is difficult to be formed
The suitable spheric granules of particle size.
In addition, above-mentioned chlorination magnesium alcoholate is to use cryogenic quenching means to solidify the alcohol adduct melt of high temperature and be made,
It is not only larger to the consumption of the energy, preparation process is complicated, multiple reactors is needed to carry out joint preparation, but also obtained alcohol adduct
Particle diameter distribution it is wider.In order to solve this problem, CN102040683A discloses a kind of by magnesium halide alcohol adduct and epoxy second
The method that alkyl compound reacts to prepare carrier, and specifically disclose after magnesium halide alcohol adduct melting dispersion, epoxy is added
Ethane compound；Either the reaction containing oxirane compound will be added directly into after magnesium halide alcohol adduct melting dispersion
In device.The feature of this method is to react to obtain solid at high temperature with the alcohol adduct of melting using epoxychloropropane.However, using
This method prepares catalyst carrier, and that there are preparation process is unstable, is easy to happen carrier adhesion, and carrier molding effect is bad
Disadvantage, therefore, it is necessary to other surfactants, such as stearic acid, sapn, quaternary ammonium compound are added during the preparation process.These objects
The addition of matter not only increases cost, and has an adverse effect to the recovery processing of by-product, in addition, in by-product
In post-processing recycling, the recycling of ethyl alcohol and epoxy compounds is more difficult, and which increases operating costs.
Therefore, developing one kind can overcome the new catalyst support used for olefinic polymerization of the drawbacks described above of the prior art to have
Significance.
Summary of the invention
The purpose of the present invention is overcoming the drawbacks described above of the prior art, provide a kind of pattern preferably, be not susceptible to adhesion and
The low catalyst support used for olefinic polymerization of production cost.
To achieve the goals above, on the one hand, the present invention provides a kind of catalyst support used for olefinic polymerization, which has
Structure shown in formula (I),
Wherein,
R1For C1-C12Alkyl or C3-C12Naphthenic base；X and Y is each independently selected from by halogen element, C1-C14Alkyl or
Alkoxy, C6-C14The group of aryl or aryloxy group composition；M is 0.1-1.9, n 2-m；
The sum of amount of substance of X and Y and the mass ratio of the material of Mg are not less than 3 in the carrier.
Second aspect, the present invention provide the preparation method of above-mentioned catalyst support used for olefinic polymerization, this method comprises:
1) by formula M gX2Shown in magnesium halide, general formula R1OH compound represented and optional inert liquid medium into
Row first contacts, and obtained mixture after the first contact and oxirane compound are then carried out the at not higher than 30 DEG C
Two contacts, obtain liquefied mixture；
2) liquefied mixture for obtaining step 1) is warming up to not less than 40 DEG C；
Wherein, in formula M gX2In, two X are identical or different, are each independently selected from by halogen element, C1-C14Alkyl or
Alkoxy, C6-C14The group of aryl or aryloxy group composition；In general formula R1In OH, R1For C1-C12Alkyl or C3-C12Naphthenic base；
The oxirane compound has structure shown in formula (II),
Wherein, Y is selected from by halogen element, C1-C14Alkyl or alkoxy, C6-C14The group of aryl or aryloxy group composition.
The third aspect, the present invention provide above-mentioned catalyst support used for olefinic polymerization in preparing catalyst for olefines polymerizing
Using.
Above-mentioned catalyst support used for olefinic polymerization pattern provided by the invention is preferable and is not susceptible to adhesion.
When preparing catalyst support used for olefinic polymerization using the above method of the invention, it is only necessary to by magnesium halide, pure and mild ring
Oxidative ethane class compound mixes at low temperature, and after forming uniform solution, by simply heating up, to be obtained with pattern good
Carrier has not only saved cost of material, need not also separate alcohols and oxirane compound, operating cost is greatly saved.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the catalyst support used for olefinic polymerization pattern optical microscope that preparation example 1 of the invention is prepared.
Fig. 2 is the catalyst support used for olefinic polymerization pattern optical microscope that preparation example 2 of the invention is prepared.
Fig. 3 is the catalyst support used for olefinic polymerization pattern optical microscopy that comparison preparation example 1 of the invention is prepared
Figure.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In a first aspect, the carrier has to be tied shown in formula (I) the present invention provides a kind of catalyst support used for olefinic polymerization
Structure,
Wherein,
R1For C1-C12Alkyl or C3-C12Naphthenic base；X and Y is each independently selected from by halogen element, C1-C14Alkyl or
Alkoxy, C6-C14The group of aryl or aryloxy group composition；M is 0.1-1.9, n 2-m；
The sum of amount of substance of X and Y and the mass ratio of the material of Mg are not less than 3 in the carrier.
In the present invention, in the structure shown in formula (I), preferably R1For C1-C10Alkyl or C3-C10Naphthenic base；X and
Y is each independently selected from by chlorine, bromine, C1-C12Alkyl or alkoxy, C6-C12The group of aryl or aryloxy group composition；M is 0.1-
1.9 n 2-m.
In the present invention, in the structure shown in formula (I), more preferred R1For C1-C8Alkyl or C3-C8Naphthenic base；X
It is each independently selected from Y by chlorine, bromine, C1-C10Alkyl or alkoxy, C6-C10The group of aryl or aryloxy group composition；M is 0.1-
1.9, n 2-m.
In the present invention, in the structure shown in formula (I), particularly preferred R1For C1-C6Alkyl or C3-C6Naphthenic base；X
It is each independently selected from Y by chlorine, bromine, C1-C8Alkyl or alkoxy, C6-C10The group of aryl or aryloxy group composition；M is 0.1-
1.9, n 2-m.
A kind of preferred embodiment according to the present invention, in the structure shown in formula (I), R1For methyl, ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl groups, second
Cyclopropyl, cyclopenta, methylcyclopentyl or cyclohexyl；X and Y is each independently selected from by chlorine, bromine, methyl, ethyl, positive third
It is base, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, methoxyl group, ethyoxyl, positive propoxy, different
Propoxyl group, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isoamoxy, positive hexyloxy, phenyl, aminomethyl phenyl, second
Base phenyl, 3,5-dimethylphenyl, trimethylphenyl, phenoxy group, methylphenoxy, ethyl phenoxy group, dimethyl phenoxy, trimethyl
Phenoxy group；M is 0.1-1.9, n 2-m.
In the present invention, the sum of amount of substance of X and Y and the mass ratio of the material of Mg element are more preferably in the carrier
3-4。
In the present invention, it is preferred to include following characteristics peak: 605 ± 10cm in the infrared spectrogram of the carrier-1；1154±
10cm-1, 1284 ± 10cm-1, 1058 ± 10cm-1, 747 ± 10cm-1, 894 ± 10cm-1, 1211 ± 10cm-1。
, according to the invention it is preferred to which the average grain diameter of the carrier is 10-100 microns, particle diameter distribution is less than 1.2.More
Add under preferable case, the average grain diameter of the carrier is 30-90 microns, and particle diameter distribution is less than or equal to 0.9.This preferably and
In more preferred embodiment, the catalyst prepared by the catalyst support used for olefinic polymerization can obtain having higher accumulation
The olefin polymer of density.In the present invention, the average grain diameter and particle diameter distribution of the catalyst support used for olefinic polymerization
It can be measured using 2000 laser particle analyzer of MasterSizer (being manufactured by Malvern Instruments Ltd).
Second aspect, the present invention provides the preparation methods of above-mentioned catalyst support used for olefinic polymerization, this method comprises:
1) by formula M gX2Shown in magnesium halide, general formula R1OH compound represented and optional inert liquid medium into
Row first contacts, and obtained mixture after the first contact and oxirane compound are then carried out the at not higher than 30 DEG C
Two contacts, obtain liquefied mixture；
2) liquefied mixture for obtaining step 1) is warming up to not less than 40 DEG C；
Wherein, in formula M gX2In, two X are identical or different, are each independently selected from by halogen element, C1-C14Alkyl or
Alkoxy, C6-C14The group of aryl or aryloxy group composition；In general formula R1In OH, R1For C1-C12Alkyl or C3-C12Naphthenic base；
The oxirane compound has structure shown in formula (II),
Wherein, Y is selected from by halogen element, C1-C14Alkyl or alkoxy, C6-C14The group of aryl or aryloxy group composition.
In the present invention, described " and optional inert liquid medium " refer to the inert liquid medium may exist or
It is not present, that is to say, that can need or not need inert liquid medium in first contact of the invention.
In the present invention, the formula M gX2Shown in magnesium halide, general formula R1OH compound represented and ethylene oxide
The specific type for closing object is for obtaining the carrier of aforesaid kind of the present invention, and therefore, those skilled in the art can be according to need
The carrier wanted selects different types of MgX2Shown in magnesium halide, general formula R1OH compound represented and ethylene oxide
Close object.
According to the present invention, general formula MgX2Magnesium halide, general formula R1Compound, the structure ring as shown in formula (II) of OH
The dosage of oxidative ethane class compound can make appropriate choice according to the composition of expected catalyst support used for olefinic polymerization.?
In the present invention, relative to 1mol formula M gX2Shown in magnesium halide, the preferably described general formula R1The dosage of OH compound represented is 4-
30mol, the dosage of the oxirane compound are 1-10mol.
In more preferred situation, in the present invention, relative to 1mol formula M gX2Shown in magnesium halide, the general formula R1OH
The dosage of compound represented is 10-25mol, and the dosage of the oxirane compound is 3-6mol.
According to the present invention, the minor amount of water in above-mentioned each reactant can also participate in forming catalyst support used for olefinic polymerization
Reaction.
According to the present invention, in step 1), for by formula M gX2Shown in magnesium halide, general formula R1OH compound represented
And optional inert liquid medium carries out the condition that first contacts and is not particularly limited, as long as the condition makes formula M gX2
Shown in magnesium halide and general formula R1OH compound represented is sufficiently reacted., according to the invention it is preferred to first contact
Condition includes: that temperature is 80-120 DEG C；More preferably 80-100 DEG C.It is preferred that the condition of first contact includes: the time to be
0.5-5h；More preferably 0.5-3h.
According to the present invention, in step 1), by the mixture and oxirane compound that are obtained after the first contact 30
DEG C or less carry out second contact when, preferably carry out under agitation.
In the present invention, by formula M gX2Shown in magnesium halide, general formula R1OH compound represented and optional inert liquid
The temperature of gained mixture is usually above 30 DEG C after the first contact of body medium progress, again by the mixture of acquisition preferably after cooling
Second is carried out with oxirane compound to contact.
In the present invention, it is preferred to it is 0-28 DEG C that the condition of second contact, which includes: temperature, time 0.1-2h.
Under preferable case, in the present invention, in step 2), the liquefied mixture that step 1) is obtained is warming up to 40-120
℃。
According to the present invention, in step 2), the condition that the liquefied mixture that step 1) is obtained is warming up to 40 DEG C or more can
Think the existing various conditions for being capable of forming catalyst support used for olefinic polymerization, for example, heating rate can be controlled, it is excellent
Selecting heating rate is 0.0001-15 DEG C/min, from the aspect of economic angle and the final particle shape control of obtained carrier, is risen
Warm rate is particularly preferably 1-6 DEG C/min.
As previously mentioned, in step 2), the liquefied mixture for preferably obtaining step 1) is warming up to 40-120 DEG C, more excellent
The liquefied mixture for obtaining step 1) is selected to be warming up to 50-90 DEG C.In particular it is preferred to the stop of the outlet temperature in the heating
Time is 1-60 minutes, and the more preferable residence time is 15-50 minutes.The residence time of the outlet temperature of heating of the present invention
Namely in the soaking time of outlet temperature.
According to the present invention, the dosage of the optional inert liquid medium can be according to formula M gX2Shown in magnesium halide
Dosage selects.Generally, with 1mol formula M gX2Shown on the basis of magnesium halide, the dosage of the inert liquid medium can be with
For 0.8-10L, preferably 2-8L.The inert liquid medium can for it is commonly used in the art it is various not with reactant and react production
Chemically interactive liquid medium occurs for object.Such as: the inert liquid medium can be silicone oil and/or inert fluid hydro carbons
Solvent.Specifically, the inert liquid medium is preferably kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon
At least one of oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil are a variety of.Inert fluid of the present invention is situated between
Matter is particularly preferably white oil.
In the present invention, the specific example of structure oxirane compound as shown in formula (II) can be but unlimited
In: one of epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and epoxy bromobutane are a variety of.
According to the present invention, general formula R1The specific example of OH compound represented can be but be not limited to: ethyl alcohol, propyl alcohol, different
One of propyl alcohol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol are a variety of.
In the present invention, formula M gX2Shown in the specific example of magnesium halide can be but be not limited to: magnesium chloride, bromination
One of magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium are a variety of.The angle ready availability from raw material
Degree sets out, preferably magnesium chloride.
According to the present invention, this method can also include being separated by solid-liquid separation the product obtained by step 2), by solid phase
Product is washed and is dried.The separation of solid and liquid can be the existing various methods that can be realized solid phase and liquid phase separation,
Such as filter, filters pressing or centrifuge separation, under preferable case, the method for the separation of solid and liquid is filter press technique.The present invention is to filters pressing
Condition is not particularly limited, be subject to as far as possible fully realize solid phase and liquid phase separation.The washing can be using this
Method well known to the technical staff of field washs obtained solid product, for example, can using inert hydrocarbon solvent (such as:
Pentane, hexane, heptane, petroleum ether and gasoline) obtained solid product is washed.Condition of the present invention for the drying
It is not particularly limited, such as: the temperature of the drying can be 20-70 DEG C, and the time of the drying can be 0.5-10 hours.
According to the present invention, the drying can carry out under normal pressure or reduced pressure.
The third aspect, the present invention provide above-mentioned catalyst support used for olefinic polymerization in preparing catalyst for olefines polymerizing
Using.
In the present invention, in the application for preparing catalyst for olefines polymerizing, preferably by above-mentioned catalyst for olefines polymerizing
Carrier is further reacted with titanium source and internal electron donor compound, and it is poly- can to obtain being suitable for alkene (especially propylene)
The catalyst of conjunction, i.e. catalyst for olefines polymerizing.
In the present invention, it is preferred to the titanium source in terms of titanium elements, the carrier in terms of magnesium elements and internal electron donor
The weight ratio of compound is 1:5-15:2-15；More preferably 1:6-13:3-12.
In the present invention, the internal electron donor compound can be conventional during preparing catalyst for olefines polymerizing
The various internal electron donor compounds used, the preferably described internal electron donor compound are carboxylate, alcohol ester, ether, ketone, nitrile, amine
At least one of with silane；The more preferred internal electron donor compound is unitary or polyhydric aliphatic race carboxylate, unitary
Or at least one of polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether.In the present invention, the unitary or polyhydric aliphatic race
The specific kind of selection of carboxylate, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether can refer to existing skill
Art is selected, and the present invention is no longer described in detail herein.
According to the present invention, the titanium source can be conventional use of during preparing catalyst for olefines polymerizing various contains
Titanium compound.In step 2), the preferably described titanium source has general formula Ti (ORn)4-mXmShown in structure, wherein RnFor C1-C14's
Aliphatic group, X F, Cl or Br, m are the integer of 1-4；In more preferred situation, the titanium source be titanium tetrachloride, titanium tetrabromide,
Titanium tetrafluoride, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy titanium trichloride, triethoxy titanium chloride, diethoxy
At least one of base titanium chloride and ethyoxyl titanium trichloride.
In the present invention, it is described by above-mentioned catalyst support used for olefinic polymerization further with titanium source and internal electron donor compound
There is no particular limitation for the condition reacted, and under preferable case, the condition of the reaction may include: that reaction temperature is 80-130
DEG C, the reaction time is 0.5-10 hours.
In the present invention, it is preferred to which it is mixed that titanium source and the catalyst support used for olefinic polymerization are first carried out contact at low temperature
It closes, then slowly heats up again to reach above-mentioned reaction temperature.Those skilled in the art understood technical solution of the present invention it
It can be operated afterwards according to Conventional wisdom in the art, details are not described herein by the present invention.
Under preferable case, the present invention also provides a kind of catalyst for olefinic polymerization, which contains: institute of the present invention
Catalyst for olefines polymerizing, alkyl aluminum compound and the optional external donor compound stated.It is described that " optional is outer to electricity
Donor compound " refers to that external donor compound can have or be not present in the catalyst for olefinic polymerization of the invention
In, that is to say, that the catalyst of the present invention for olefinic polymerization can contain or without containing external electron donor chemical combination
Object.
In the present invention, detailed description has been carried out in the composition of the catalyst for olefines polymerizing above,
This is repeated no more.
In the present invention, it is catalyzed in the catalyst for olefinic polymerization containing olefin polymerization of the present invention
Agent, therefore, the catalyst according to the present invention for olefinic polymerization is when being used as the catalyst of olefin polymerization, polymerization
The heap density of obtained polymer greatly improves.
Moreover, the catalyst according to the present invention for olefinic polymerization is for alkyl aluminum compound and external electron donor
The type and dosage for closing object are not particularly limited.
Generally, in the catalyst for olefinic polymerization, alkyl aluminum compound in terms of aluminium element and with titanium member
The molar ratio of the catalyst for olefines polymerizing of element meter can be 1-2000:1, preferably 20-500:1；The external electron donor
The molar ratio for closing object and alkyl aluminum compound can be 0.005-0.5:1, preferably 0.01-0.4:1.
Catalyst according to the present invention for olefinic polymerization, the alkyl aluminum compound can be commonly used in the art each
Kind alkyl aluminum compound.For example, the alkyl aluminum compound can be for triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, three just
Hexyl aluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, one ethyl of dichloro
One of aluminium, one n-hexyl aluminium of one aluminium isobutyl of dichloro, one n-butylaluminum of dichloro and dichloro are a variety of.
Catalyst according to the present invention for olefinic polymerization, the external donor compound can be commonly used in the art
Various external donor compounds, for example, the external donor compound can for carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol,
One of organic phosphorus compound and silicon compound are a variety of；Preferably, the external electron donor is with general formula R8 aR9 bSi
(OR10)cSilicon compound, wherein a and b is respectively 0, an integer of 1 or 2, and c is the integer of 1-3, and a+b+c's and be 4, R8、
R9、R10It is each independently C1-C18Substituted or unsubstituted alkyl；It is highly preferred that a and b are respectively 1, c 2, R8、R9Respectively
It independently is C3-C10Substituted or unsubstituted alkyl, R10For C1-C10Substituted or unsubstituted alkyl.Specifically, described to have
The example of organic silicon compound can be but be not limited to: Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, two
Normal-butyl dimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl tertbutyl dimethoxy
Silane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- t-butyldimethoxysilane and (the fluoro- 2- third of 1,1,1- tri-
Base) -2- ethyl piperidine base dimethoxysilane and (the fluoro- 2- propyl of 1,1,1- tri-)-methyl dimethoxysilane.
The present invention also provides a kind of methods of olefinic polymerization, will at least one this method comprises: under olefin polymerization conditions
Kind alkene and catalyst for olefines polymerizing of the present invention carry out olefin polymerization.
The method of olefinic polymerization according to the present invention, by using the catalyst for olefines polymerizing of the invention,
The polymer that particle shape is good, heap density is high can be prepared.The method of the olefinic polymerization of the invention is for olefinic polymerization
Condition and used alkene are not particularly limited.The alkene for example can be ethylene, propylene, 1- butylene, 2- butylene, 2- first
One of base -1- butylene, 3-methyl-1-butene, 2- methyl-2-butene, 1- amylene, 2- amylene, 1- hexene and styrene or
It is a variety of, preferably one of ethylene, propylene, 1- butylene, 2- butylene and styrene or a variety of.
The method of olefinic polymerization according to the present invention, the olefinic polymerization can carry out according to conventional methods in the art.
For example, the olefinic polymerization can be bulk polymerization, gas-phase polymerization or slurry polymerization.Olefine polymerizing process according to the present invention,
The olefin polymerization conditions can be the normal condition of this field, for example, polymerization temperature can be 0-150 DEG C, preferably 60-90
℃；Polymerization pressure can be normal pressure or pressurization.
In particularly preferred situation, the method for olefinic polymerization of the invention include: under olefin polymerization conditions, will be at least one
Alkene and the catalyst of the present invention for olefinic polymerization carry out olefin polymerization.
The present invention will be described in detail by way of examples below.
In following preparation example, embodiment and comparative example, in case of no particular description, used various raw materials
It is all from commercially available.
1, the average grain diameter and particle diameter distribution of catalyst support used for olefinic polymerization use Masters Sizer 2000
Particle size analyzer (being manufactured by Malvern Instruments Ltd) is measured；
2, the apparent form of catalyst support used for olefinic polymerization is by being commercially available from the model Eclipse of Nikon company
The optical microscopy of E200 is observed；
3, the heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008.
In order to verify the catalyst that the carrier that method of the invention obtains is prepared have better catalytic performance and
So that the heap density of obtained polymerizate is higher, in following embodiment illustratively using one of conventional techniques come
Explanation.Specific experimental method is as shown in the following example.Those skilled in the art should not be construed as to technology of the invention
The limitation of scheme.
Preparation example 1
The preparation example is for illustrating catalyst support used for olefinic polymerization provided by the invention and preparation method thereof.
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.7mol ethyl alcohol is added, is warming up to 90 DEG C under stiring.Constant temperature
After reaction 1 hour, 15 DEG C are cooled to, the epoxychloropropane of the pre- 0.3mol for being cooled to 15 DEG C is added and continues to stir, is existed to temperature
It after 15 DEG C of stable 0.5h, starts to warm up, heating rate is 2 DEG C/min, until maintaining 20min after 50 DEG C.Filters pressing, by filters pressing product
It is washed 5 times with hexane, is dried in vacuo, obtains catalyst support used for olefinic polymerization Z1.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z1 is 70 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 1.It can be seen from the figure that olefinic polymerization
Particle shape with catalyst carrier Z1 is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no that irregular particle exists.
The catalyst support used for olefinic polymerization Z1 is by x-ray fluorescence spectrum analysis, the wherein amount of the substance of chlorine and Mg
The mass ratio of the material is 3.8.
The catalyst support used for olefinic polymerization Z1 is by infrared spectrum analysis, in 605.4cm-1；1154.2cm-1,
1284.4cm-1, 1058.7cm-1, 747.3cm-1, 894.6cm-1, 1211.4cm-1There is characteristic peak.
Compare preparation example 1
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 0.96mol ethyl alcohol is added, is warming up to 90 DEG C under stiring.It is permanent
Epoxychloropropane 0.48mol is added after 2 hours in temperature reaction, reacts filters pressing after half an hour, filters pressing product is washed 5 with hexane
Secondary, vacuum drying obtains catalyst support used for olefinic polymerization D-Z1.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization D-Z1 is 100 microns, particle diameter distribution
((D90-D10)/D50) is 1.6.Particle morphology using optical microphotograph sem observation is as shown in Figure 3.It can be seen from the figure that alkene
There are a large amount of irregular particles in polymerized hydrocarbon catalyst carrier D-Z1, and surface is more coarse.
Catalyst support used for olefinic polymerization D-Z1 passes through x-ray fluorescence spectrum analysis, wherein the object of the amount of the substance of chlorine and Mg
The amount ratio of matter is 2.4.
The catalyst support used for olefinic polymerization D-Z1 is by infrared spectrum analysis, in 701.1cm-1；758.4cm-1,
1658.3cm-1, 1054.8cm-1, 1077.6cm-1, 830.1cm-1, 1294.5cm-1There is characteristic peak.
Preparation example 2
The preparation example is for illustrating catalyst support used for olefinic polymerization provided by the invention and preparation method thereof.
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.2mol ethyl alcohol is added, is warming up to 80 DEG C under stiring.Constant temperature
After reaction 1.5 hours, 20 DEG C are cooled to, the epoxychloropropane of the pre- 0.35mol for being cooled to 20 DEG C is added, to temperature in 20 DEG C of stabilizations
It after 20min, starts to warm up, heating rate is 3 DEG C/min, until maintaining 20min after 60 DEG C.Filters pressing washes filters pressing product with hexane
It washs 5 times, is dried in vacuo, obtains catalyst support used for olefinic polymerization Z2.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z2 is 72 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 2.It can be seen from the figure that olefinic polymerization
Particle shape with catalyst carrier Z2 is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares collection
In, and there is no that irregular particle exists.
Catalyst support used for olefinic polymerization Z2 passes through x-ray fluorescence spectrum analysis, wherein the substance of the amount of the substance of chlorine and Mg
Amount ratio be 3.4.
The catalyst support used for olefinic polymerization Z2 is by infrared spectrum analysis, in 606.3cm-1；1152.9cm-1,
1285.4cm-1, 1057.9cm-1, 746.6cm-1, 894.9cm-1, 1210.6cm-1There is characteristic peak.
Preparation example 3
The preparation example is for illustrating catalyst support used for olefinic polymerization provided by the invention and preparation method thereof.
In the reaction kettle of 0.6L, 0.08mol magnesium chloride, 1.44mol ethyl alcohol is added, is warming up to 100 DEG C under stiring.It is permanent
After temperature reaction 1 hour, 5 DEG C are cooled to, the epoxychloropropane of the pre- 0.35mol for being cooled to 5 DEG C is added, to temperature in 5 DEG C of stabilizations
It after 40min, starts to warm up, heating rate is 3 DEG C/min, until maintaining 30min after 70 DEG C.Filters pressing washes filters pressing product with hexane
It washs 5 times, is dried in vacuo, obtains catalyst support used for olefinic polymerization Z3.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z3 is 75 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.It can be seen that catalyst support used for olefinic polymerization Z3's using the particle morphology of optical microphotograph sem observation
Particle shape is more regular, and surface is smooth, is essentially all spherical shape, particle size distribution compares concentration, and there is no
Irregular particle exists.
Catalyst support used for olefinic polymerization Z3 passes through x-ray fluorescence spectrum analysis, wherein the substance of the amount of the substance of chlorine and Mg
Amount ratio be 3.5.
The catalyst support used for olefinic polymerization Z3 is by infrared spectrum analysis, in 605.9cm-1；1155.4cm-1,
1283.2cm-1, 1056.9cm-1, 748.4cm-1, 892.7cm-1, 1211.5cm-1There is characteristic peak.
Preparation example 4
The preparation example is for illustrating catalyst support used for olefinic polymerization provided by the invention and preparation method thereof.
In the reaction kettle of 0.6L, be added 0.08mol magnesium chloride, 1.7mol ethyl alcohol, 0.3mol epoxychloropropane and
It persistently stirring at 15 DEG C, after temperature after 15 DEG C of stable 1.5h, starts to warm up, heating rate is 2 DEG C/min, until after 50 DEG C, dimension
Hold 20min.Filters pressing washs filters pressing product 5 times with hexane, and vacuum drying obtains catalyst support used for olefinic polymerization Z4.
The average grain diameter (D50) of the catalyst support used for olefinic polymerization Z4 is 72 microns, particle diameter distribution ((D90-
D10)/D50) it is 1.1.The particle shape of catalyst support used for olefinic polymerization Z4 is more regular, and surface is smooth, is essentially all ball
Shape, particle size distribution compares concentration, and there is no that irregular particle exists.
The catalyst support used for olefinic polymerization Z4 is by x-ray fluorescence spectrum analysis, the wherein amount of the substance of chlorine and Mg
The mass ratio of the material is 3.0.
The catalyst support used for olefinic polymerization Z4 is by infrared spectrum analysis, in 606.2cm-1；1153.8cm-1,
1284.4cm-1, 1057.5cm-1, 747.9cm-1, 893.5cm-1, 1211.2cm-1There is characteristic peak.
Embodiment 1
The embodiment is for illustrating that catalyst support used for olefinic polymerization provided by the invention is preparing olefin polymerization catalysis
Application in agent and prepare alkene.
(1) preparation of catalyst for olefines polymerizing
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, subzero 20 DEG C are cooled to, by 40 grams by making
The catalyst support used for olefinic polymerization Z1 that standby example 1 obtains is added thereto, and stirs 30min at subzero 20 DEG C.Later, it opens
Beginning is to slowly warm up to 110 DEG C, and the diisobutyl phthalate of 1.5mL is added in temperature-rise period, maintains at 110 DEG C
Liquid is filtered off after 30min.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain olefinic polymerization after dry
With catalyst C1.
(2) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
The hydrogen of catalyst for olefines polymerizing C1,1.5L (normal volume) of silane, the anhydrous hexane of 10mL and 10mg and the liquid of 2.5L
Body propylene.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, and discharging is dried to obtain polypropylene powder.
As a result, the heap density of gained polypropylene powder is 0.44g/cm3, in addition, the polypropylene powder particle shape is good,
Special-shaped material is substantially not present.
Comparative example 1
This comparative example is carried out using method similar to Example 1, in particular:
(1) preparation of catalyst for olefines polymerizing
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, subzero 20 DEG C are cooled to, by 40 grams by right
The catalyst support used for olefinic polymerization D-Z1 obtained than preparation example 1 is added thereto, and stirs 30min at subzero 20 DEG C.
Later, start to be to slowly warm up to 110 DEG C, the diisobutyl phthalate of 1.5mL is added in temperature-rise period, at 110 DEG C
Liquid is filtered off after maintaining 30min.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain alkene after dry
Catalyst for polymerization D-C1.
(2) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
The hydrogen of catalyst for olefines polymerizing D-C1,1.5L (normal volume) of silane, the anhydrous hexane of 10mL and 10mg and 2.5L's
Liquid propene.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, and discharging is dried to obtain polypropylene powder.
As a result, the heap density of the polypropylene powder is 0.38g/cm3, in addition, being all abnormity in the polypropylene powder particle
Material, mobility are bad.
Embodiment 2
The embodiment is for illustrating that catalyst support used for olefinic polymerization provided by the invention is preparing olefin polymerization catalysis
Application in agent and prepare alkene.
(1) preparation of catalyst for olefines polymerizing
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, subzero 20 DEG C are cooled to, by 40 grams by making
The catalyst support used for olefinic polymerization Z2 that standby example 2 obtains is added thereto, and stirs 30min at subzero 20 DEG C.Later, it opens
Beginning is to slowly warm up to 110 DEG C, and the diisobutyl phthalate of 1.5mL is added in temperature-rise period, maintains at 110 DEG C
Liquid is filtered off after 30min.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain olefinic polymerization after dry
With catalyst C2.
(2) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
The hydrogen of catalyst for olefines polymerizing C2,1.5L (normal volume) of silane, the anhydrous hexane of 10mL and 10mg and the liquid of 2.5L
Body propylene.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, and discharging is dried to obtain polypropylene powder.
As a result, the heap density of gained polypropylene powder is 0.45g/cm3, in addition, the polypropylene powder particle shape is good,
Special-shaped material is substantially not present.
Embodiment 3
(1) preparation of catalyst for olefines polymerizing
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, subzero 20 DEG C are cooled to, by 40 grams by making
The catalyst support used for olefinic polymerization Z3 that standby example 3 obtains is added thereto, and stirs 30min at subzero 20 DEG C.Later, it opens
Beginning is to slowly warm up to 110 DEG C, and the diisobutyl phthalate of 1.5mL is added in temperature-rise period, maintains at 110 DEG C
Liquid is filtered off after 30min.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain olefinic polymerization after dry
With catalyst C3.
(2) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
The hydrogen of catalyst for olefines polymerizing C3,1.5L (normal volume) of silane, the anhydrous hexane of 10mL and 10mg and the liquid of 2.5L
Body propylene.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, and discharging is dried to obtain polypropylene powder.
As a result, the heap density of gained polypropylene powder is 0.44g/cm3, in addition, the polypropylene powder particle shape is good,
Special-shaped material is substantially not present.
Embodiment 4
The embodiment is for illustrating that catalyst support used for olefinic polymerization provided by the invention is preparing olefin polymerization catalysis
Application in agent and prepare alkene.
(1) preparation of catalyst for olefines polymerizing
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, subzero 20 DEG C are cooled to, by 40 grams by making
The catalyst support used for olefinic polymerization Z4 that standby example 4 obtains is added thereto, and stirs 30min at subzero 20 DEG C.Later, it opens
Beginning is to slowly warm up to 110 DEG C, and the diisobutyl phthalate of 1.5mL is added in temperature-rise period, maintains at 110 DEG C
Liquid is filtered off after 30min.Then, titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, obtain olefinic polymerization after dry
With catalyst C4.
(2) propylene polymerization
It in the autoclave of a 5L, is purged using stream of nitrogen gas, 1mmol is then introduced in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum be 0.5mmol/mL) of triethyl aluminum, 0.05mmol methylcyclohexyl dimethoxy
The hydrogen of catalyst for olefines polymerizing C4,1.5L (normal volume) of silane, the anhydrous hexane of 10mL and 10mg and the liquid of 2.5L
Body propylene.70 DEG C are warming up to, and is reacted 1 hour at such a temperature, cooling is bled off pressure, and discharging is dried to obtain polypropylene powder.
As a result, the heap density of gained polypropylene powder is 0.40g/cm3, in addition, the polypropylene powder particle shape is good,
Special-shaped material is substantially not present.
It can be seen that the olefinic polymerization being prepared using method of the invention from the result of above embodiments and comparative example
With the particle shape of catalyst carrier is good, surface is smooth, is substantially not in irregular particle, and with the preparation of resulting carrier
Catalyst for alkene (especially propylene) polymerize when, additionally it is possible to improve polymerizate heap density, substantially without the opposite sex material
Occur, great prospects for commercial application.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (16)
1. a kind of catalyst support used for olefinic polymerization, which has structure shown in formula (I),
Wherein,
R1For C1-C12Alkyl or C3-C12Naphthenic base；X and Y is each independently selected from by halogen element, C1-C14Alkyl or alcoxyl
Base, C6-C14The group of aryl or aryloxy group composition；M is 0.1-1.9, n 2-m；
The sum of amount of substance of X and Y and the mass ratio of the material of Mg are not less than 3 in the carrier.
2. carrier according to claim 1, wherein the substance of the sum of amount of substance of X and Y and Mg element in the carrier
Amount ratio be 3-4:1.
3. carrier according to claim 1, wherein include following characteristics peak in the infrared spectrogram of the carrier: 605 ±
10cm-1；1154±10cm-1, 1284 ± 10cm-1, 1058 ± 10cm-1, 747 ± 10cm-1, 894 ± 10cm-1, 1211 ± 10cm-1。
4. carrier according to claim 1, wherein the average grain diameter of the carrier is 10-100 microns, partial size point
Cloth is less than 1.2.
5. carrier according to claim 4, wherein the average grain diameter of the carrier is 30-90 microns, particle diameter distribution
Less than or equal to 0.9.
6. the preparation method of catalyst support used for olefinic polymerization described in any one of claim 1-5, this method comprises:
1) by formula M gX2Shown in magnesium halide, general formula R1OH compound represented and optional inert liquid medium carry out the
Then the mixture obtained after first contact and oxirane compound are carried out at not higher than 30 DEG C second and connect by one contact
Touching, obtains liquefied mixture；
2) liquefied mixture for obtaining step 1) is warming up to not less than 40 DEG C；
Wherein, in formula M gX2In, two X are identical or different, are each independently selected from by halogen element, C1-C14Alkyl or alcoxyl
Base, C6-C14The group of aryl or aryloxy group composition；In general formula R1In OH, R1For C1-C12Alkyl or C3-C12Naphthenic base；It is described
Oxirane compound has structure shown in formula (II),
Wherein, Y is selected from by halogen element, C1-C14Alkyl or alkoxy, C6-C14The group of aryl or aryloxy group composition.
7. according to the method described in claim 6, wherein, relative to 1mol formula M gX2Shown in magnesium halide, the general formula R1OH
The dosage of compound represented is 4-30mol, and the dosage of the oxirane compound is 1-10mol.
8. according to the method described in claim 7, wherein, relative to 1mol formula M gX2Shown in magnesium halide, the general formula R1OH
The dosage of compound represented is 10-25mol, and the dosage of the oxirane compound is 3-6mol.
9. it is 80-120 DEG C that the condition of first contact, which includes: temperature, according to the method described in claim 6, wherein, the time
For 0.5-5h.
10. it is 0-28 DEG C that the condition of second contact, which includes: temperature, according to the method described in claim 6, wherein, the time
For 0.1-2h.
11. according to the method described in claim 6, wherein, in step 2), the liquefied mixture that step 1) is obtained is warming up to
40-120℃。
12. according to the method described in claim 6, wherein, in step 2), the rate of the heating is 0.0001-15 DEG C/
min。
13. according to the method for claim 12, wherein in step 2), the rate of the heating is 1-6 DEG C/min.
14. according to the method described in claim 6, wherein, in step 1), the inert liquid medium is silicone oil and/or lazy
Property liquid hydrocarbon solvent.
15. according to the method for claim 14, wherein the inert liquid medium be kerosene, paraffin oil, vaseline oil,
At least one of white oil, methyl-silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
16. catalyst support used for olefinic polymerization described in any one of claim 1-5 is preparing catalyst for olefines polymerizing
In application.
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