CN113527555A - Catalyst component containing epoxy resin, preparation method and application thereof - Google Patents
Catalyst component containing epoxy resin, preparation method and application thereof Download PDFInfo
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- CN113527555A CN113527555A CN202010319591.4A CN202010319591A CN113527555A CN 113527555 A CN113527555 A CN 113527555A CN 202010319591 A CN202010319591 A CN 202010319591A CN 113527555 A CN113527555 A CN 113527555A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a catalyst component containing epoxy resin, a preparation method thereof, a catalyst and application thereof, wherein the catalyst component comprises: titanium element, magnesium element, electron donor, epoxy resin and inorganic oxide carrier, wherein the epoxy value of the epoxy resin is 0.10-0.90, the preferable epoxy value is 0.15-0.75, and the most preferable epoxy value is 0.18-0.60; the catalyst component is obtained by spray drying of raw materials. The catalyst comprises the catalyst component and an organic aluminum compound, and has the characteristics of high activity, good hydrogen regulation performance, high bulk density of the obtained polymer powder and low content of fine powder of the polymer powder when the catalyst is used for olefin polymerization, particularly for the polymerization of ethylene and alpha-olefin.
Description
Technical Field
The invention relates to a catalyst component, in particular to a catalyst component containing epoxy resin, a preparation method and application thereof.
Background
In polymerization reactions, the properties of the polymer are affected by the catalyst. In the gas phase polymerization process, since polymer fines are detrimental to the polymerization process, the polymer fines cause problems with fluidized bed control and entrainment of recycle gas, resulting in equipment failure, impaired operability and reduced efficiency. Thus, not only is it desirable for the catalyst to have high polymerization activity, good hydrogen regulation and copolymerization properties, but it is also desirable to minimize polymer fines in the olefin polymerization process, one factor in reducing such polymer fines is by reducing or eliminating procatalyst fines which can produce polymer fines. The polymer fines are mainly derived from the fines in the catalyst, from the breakup of hollow catalyst particles during fluidization impingement due to poor strength, and from the breakup due to too rapid release of activity during catalyst polymerization. It is also desirable to have a higher bulk density of the polymer powder during the polymerization, and a suitably high bulk density of the polymer powder makes the fluidized bed control more stable, which is advantageous for the production of the reactor under high load conditions.
Spray drying is an efficient method for preparing high efficiency Ziegler-Natta catalysts for olefin polymerization. The method is that dissolved liquid or suspension liquid is sprayed into a hot inert gas drying chamber by gas through a specially designed nozzle for drying, and dispersed atomized micro-droplets are dried into powder or granular products. Once the mist droplets are contacted with the dry carrier gas, evaporation takes place on a saturated vapor film on the surface of the rapidly building droplets. During evaporation, the size distribution of the droplets changes and different products show different characteristics. During evaporation, the droplets tend to swell, collapse, break up or disintegrate, resulting in a porous, irregular shape, which is related to the characteristics of the droplets formed in the spray process. The structural modification of the particles can be influenced by the change of the composition, volume and size of the droplets. Adjusting the conditions of the spray drying process, large, small or aggregated particles can be obtained.
CN1668654A discloses a spray-dried polymerization catalyst and a polymerization process using the same, the catalyst comprising a spray-dried composition of an inert porous filler and the reaction product of: magnesium halide, solvent, electron donor compound, transition metal compound mixture or reaction product. The catalyst contains an alcohol compound as an electron donor, and uses an inert porous filler with a spherical average particle size of 1-12 mu m to reduce small catalyst particles in the catalyst, so as to reduce the content of particles in a polymer.
CN1993391A discloses a strong spray-dried Ziegler-Natta catalyst composition, which comprises inert porous filler, magnesium halide, solvent or diluent, Lewis base electron donor compound, and mixture or reaction product of transition metal compound, wherein the magnesium halide compound exists in the solvent or diluent in an amount of at least 90% of saturation concentration, and the catalyst particles obtained by spray-drying have an average diameter (D) of 10-70 μm50) Wherein at least 5% of the particles have an internal void volume substantially or completely surrounded by a single surface layer (shell), said layer being characterized in that the particles having a particle diameter of more than 30 μm have an average shell thickness/particle diameter (thickness ratio) determined by SEM techniques of more than 0.2. The catalyst reduces polymer fines by reducing catalyst breakage or catalyst fragments remaining larger after breakage.
CN1802391A discloses a catalyst for ethylene polymerization prepared by spray drying process, which has better activity, but still generates more severe crumbling and causes the fine powder content to increase in gas phase polymerization.
Some of the above catalysts can only improve the performance of the olefin polymerization catalyst in one aspect, and some of the catalysts can improve several performances, but the catalysts are still not ideal. Therefore, there is a need to develop a catalyst that can improve the performance parameters of the catalyst and its polymerization powder more completely.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a catalyst component containing epoxy resin, a preparation method and application thereof. The catalyst is used for olefin polymerization, especially for the polymerization of ethylene and alpha-olefin, and has the characteristics of high activity, good hydrogen-regulating copolymerization performance, high bulk density of the obtained polymer powder and low content of fine powder of the polymer powder.
It is an object of the present invention to provide an epoxy resin-containing catalyst component comprising: titanium element, magnesium element, electron donor, epoxy resin and inorganic oxide carrier.
In a preferred embodiment, the catalyst component comprises, based on 100 wt% total weight:
0.1-5 wt% of titanium element;
0.2-10.2 wt% of magnesium element;
15-40 wt% of electron donor;
0.01-15 wt% of epoxy resin;
1-70 wt% of inorganic oxide carrier.
In a further preferred embodiment, the catalyst component comprises, based on 100 wt% total weight:
0.5-4 wt% of titanium element, preferably 1-3.5 wt%;
4-8 wt% of magnesium element, preferably 5.5-8 wt%;
20-35 wt% of electron donor, preferably 23-35 wt%;
0.1-10 wt% of epoxy resin, preferably 0.6-8 wt%;
10 to 60 wt%, preferably 15 to 53 wt% of an inorganic oxide carrier.
In a preferred embodiment, the epoxy resin is a polymer compound having a molecular structure containing at least two epoxy groups.
In a further preferred embodiment, the epoxy resin has an epoxy value (number of epoxy group species per 100g of epoxy resin) of from 0.10 to 0.90, preferably an epoxy value of from 0.15 to 0.75, most preferably an epoxy value of from 0.18 to 0.60.
Wherein: the epoxy value is the amount of species of epoxy groups in 100g of epoxy resin, the higher the epoxy value, the higher the epoxy group content therein for the same two types of epoxy resins. In the preparation process of the catalyst, except for the function of the adhesive, the epoxy resin has a competitive coordination reaction between oxygen in an epoxy group and oxygen in an electron donor (such as tetrahydrofuran) and magnesium chloride, and if the dosage of the epoxy resin is too small, a good adhesion effect cannot be achieved; however, the amount of epoxy resin used should not be too high (or the epoxy value should not be too high for the same amount), which would affect the electron-donating effect of the electron donor. Therefore, the selection of the dosage of the epoxy resin and the epoxy value needs to be controlled within a reasonable range, so that not only can the adhesion be realized, but also the coordination competition with the electron donor in a balanced state can be achieved, and the electron donor content in the product is controlled within a reasonable range.
Wherein, the epoxy resin is solid or liquid or a mixture of solid and liquid.
In a preferred embodiment, the epoxy resin is selected from the group consisting of glycidyl ether type epoxy resins (including at least one of bisphenol a epoxy resin, 4' -dihydroxydiphenylsulfone bisglycidyl ether, toluenediol diglycidyl ether, phloroglucinol triglycidyl ether, glycerol epoxy resin, polyethylene glycol epoxy resin, pentaerythritol epoxy resin), glycidyl ester type epoxy resins (including at least one of phthalic acid bisglycidyl ester, tetrahydrophthalic acid bisglycidyl ester, terephthalic acid glycidyl ester, trimesic acid triglycidyl ether), glycidyl amine type epoxy resins (including at least one of N, N-diglycidylaniline, N-diglycidylparaben glycidyl ether, amino tetrafunctional epoxy resins), linear aliphatic epoxy resins (including epoxidized polybutadiene, epoxy resins, and epoxy resins, and epoxy resins, and epoxy resins, and epoxy resins, At least one of diglycidyl ether and polyglycidyl ether), alicyclic epoxy resins (including dicyclopentadiene diepoxide and/or bis (2, 3-epoxycyclopentyl) ether, and the like).
In a further preferred embodiment, the epoxy resin is selected from glycidyl ether type epoxy resins, preferably glycidyl ether type bisphenol a epoxy resins, the molecular structure of which is shown in formula (I):
in formula (I), n represents polymerization degree, and n can be changed from 0 to 20. A resin having an average degree of polymerization n of 2 or more, which is solid at room temperature; the resin having an average degree of polymerization n of 2 or less is liquid at room temperature. The bisphenol A epoxy resin can be solid or liquid or a mixture of solid and liquid. The glycidyl ether type epoxy resin is obtained by condensation reaction of bisphenol A and epoxy chloropropane under the catalysis of alkali.
During the evaporation process of spray drying, the droplets tend to swell, collapse, break up or disintegrate, resulting in the production of porous, irregularly shaped catalyst fines, which are the primary cause of the production of polymer fines. Therefore, the invention creatively adds the epoxy resin into the raw material of the spray drying, thus, the expansion, collapse, breakage or splitting of the fog drops can be inhibited in the evaporation process of the spray drying, thereby reducing the generation of porous and irregularly-shaped catalyst fine particles, wherein, the epoxy resin is uniformly dispersed in the catalyst, so that the inorganic oxide carrier in the catalyst is more tightly gathered, the particle strength of the catalyst is improved, the breakage of the catalyst in the polymerization process is reduced, the content of fine powder in the polymer is reduced, and the bulk density of the polymer can be improved.
In a preferred embodiment, the weight ratio of the inorganic oxide carrier to the epoxy resin is (1-100) to 1, preferably (2-80) to 1, and more preferably (5-65) to 1.
In the invention, the limitation of the contents of the inorganic oxide carrier and the epoxy resin in the catalyst is obtained by theoretical calculation according to the using amounts of the inorganic oxide carrier and the epoxy resin in the raw materials, wherein, as the raw materials are directly subjected to spray drying treatment without other post-treatment in the preparation process, the inorganic oxide carrier and the epoxy resin are not lost in the treatment process, and therefore, the limitation of the contents of the two components in the catalyst according to the using amount of the raw materials is reasonable.
In the preparation process of the catalyst, besides the function of the epoxy resin as a binder, oxygen in an epoxy group and oxygen in an electron donor (such as tetrahydrofuran) react with magnesium chloride in a competitive coordination manner to affect the electron donating effect of the electron donor, so that the dosage of the epoxy resin needs to be controlled.
In a preferred embodiment, the source of elemental titanium is a titanium-containing compound.
In a further preferred embodiment, the titanium-containing compound is selected from at least one of titanium halide, a product of aluminum reduction of titanium halide, a product of magnesium reduction of titanium halide; preferably, the product of the aluminum reduction of titanium halide has the formula TiXm·nAlXpWherein n is more than 0 and less than or equal to 1, m is more than 0 and less than or equal to 3, p is more than 0 and less than or equal to 3, and X is halogen; the general formula of the product of magnesium reduction titanium halide is TiXmqMgXr, where q is greater than 0 and less than or equal to 1, m is greater than 0 and less than or equal to 3, r is greater than 0 and less than or equal to 3, and X is halogen.
In a still further preferred embodiment, the titanium halide is selected from titanium bromide and/or titanium chloride, preferably from at least one of titanium tribromide, titanium tetrabromide, titanium trichloride and titanium tetrachloride, more preferably from titanium trichloride and/or titanium tetrachloride; the product of the aluminum reduction of the titanium halide is TiCl3·1/3AlCl3The product of magnesium reduction of titanium halide is TiCl3·1/2MgCl2。
In a preferred embodiment, the source of the magnesium element is a magnesium halide.
In a further preferred embodiment, the magnesium halide is selected from at least one of magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, preferably magnesium chloride.
In a preferred embodiment, the electron donor is at least one selected from the group consisting of ester compounds, ether compounds and ketone compounds.
In a further preferred embodiment, the electron donor is selected from C1～C4Alkyl esters of saturated fatty carboxylic acids, C7～C8Alkyl esters of aromatic carboxylic acids, C2～C6Fatty ethers, C3～C4Cyclic ethers and C3～C6At least one saturated aliphatic ketone.
In a still further preferred embodiment, the electron donor is selected from at least one of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone.
In a still further preferred embodiment, the electron donor is selected from at least one of methyl formate, ethyl acetate, butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone; tetrahydrofuran is most preferred.
The electron donors can be used singly or in combination.
In a preferred embodiment, the inorganic oxide support is selected from oxides of silicon and/or oxides of aluminum, preferably silica.
In a further preferred embodiment, the particle size of the inorganic oxide support is 0.01 to 10 microns, preferably 0.01 to 5 microns, and more preferably 0.1 to 1 micron.
The inert carrier is used in spray drying to help control the shape and composition of catalyst particles, and is favorable for spray forming, and the generated catalyst particles have good shape, high strength and are not easy to break.
In a preferred embodiment, D is the particle size of the catalyst component measured10Greater than 6.6 μm, preferably greater than 6.9. mu.m.
Wherein D is10Representing the average diameter of 10% of the particles in the product.
In a further preferred embodiment, the particle size distribution is less than 1.77, preferably less than 1.75, in a particle size measurement of the catalyst component.
The catalyst component of the present invention has a relatively narrow particle size distribution, while D10Relatively large means that the catalyst component has relatively few fine particles, so that the formation of polymer fines during later polymerization can be largely avoided.
The second purpose of the invention is to provide a preparation method of the catalyst component of the first purpose of the invention, which comprises the following steps:
step 1, mixing raw materials including a titanium-containing compound, magnesium halide, an electron donor, epoxy resin and an inorganic oxide carrier to obtain slurry suspension;
and 2, carrying out spray drying to obtain the catalyst component.
In a preferred embodiment, in step 1, the titanium-containing compound, the magnesium halide and the electron donor are mixed to obtain a mother liquor.
In a further preferred embodiment, the inorganic oxide support and epoxy resin are added during or after the preparation of the mother liquor to obtain the slurry suspension.
The inorganic oxide carrier and the epoxy resin can be added at any time during the preparation of the mother liquor, for example, magnesium halide, a titanium-containing compound, the inorganic oxide carrier and the epoxy resin are mixed and reacted in an electron donor to obtain a slurry liquid material, and the obtained slurry liquid is subjected to spray drying to obtain the catalyst component.
In the above preparation method, a sufficient amount of the inorganic oxide support should be mixed with the mother liquor to form a slurry suitable for spray drying.
In a preferred embodiment, in step 1, the molar ratio of the electron donor to the magnesium halide is (5.0-50) to 1, the mass ratio of the epoxy resin to the magnesium halide is (0.01-1.0) to 1, the molar ratio of the titanium-containing compound to the magnesium halide is (0.1-1.0) to 1, and the molar ratio of the inorganic oxide to the magnesium halide is (1.0-5.0) to 1.
In a more preferred embodiment, in step 1, the molar ratio of the electron donor to the magnesium halide is (10 to 45) to 1, the mass ratio of the epoxy resin to the magnesium halide is (0.01 to 0.5) to 1, the molar ratio of the titanium-containing compound to the magnesium halide is (0.1 to 0.5) to 1, and the molar ratio of the inorganic oxide to the magnesium halide is (1.0 to 4.0) to 1.
In the invention, the electron donor has an electron donating effect and also serves as a solvent of the system.
In a preferred embodiment, the mixing in step 1 is performed at room temperature to 85 ℃ for 0.1 hour or more.
Wherein the normal temperature is 25 +/-5 ℃.
In a further preferred embodiment, the mixing of step 1 is performed at 45 to 75 ℃ for 1.0 to 10.0 hours.
In a preferred embodiment, in step 2, the spray drying conditions are: the inlet temperature is 100-240 ℃; the outlet temperature is 60-130 ℃.
In a further preferred embodiment, in step 2, the spray drying conditions are: the inlet temperature is 120-160 ℃; the outlet temperature is 90-115 ℃.
It is a further object of the present invention to provide a catalyst for olefin polymerization comprising: (A) a catalyst component according to one of the objects of the present invention or a catalyst component obtained by the preparation method according to the second object of the present invention; (B) the general formula is AlRbX’3-bWherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x' is halogen, preferably chlorine, bromine or iodine; b is more than 0 and less than or equal to 3, preferably more than 1 and less than or equal to 3.
In a preferred embodiment, the organoaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum monochloride.
In a preferred embodiment, the molar ratio of the organoaluminum compound to the catalyst component is (5 to 1000) to 1, preferably (10 to 200) to 1.
Wherein the molar amount of the organoaluminum compound is based on the molar amount of the aluminum element therein, and the molar amount of the catalyst component is based on the molar amount of the titanium element therein.
In order to make the solid catalyst component obtained after spray-drying suitable for the production of ethylene polymers, it is necessary to activate the catalyst component with an activator component, an organoaluminum compound.
In a preferred embodiment, the catalyst component and the organoaluminum compound are reacted in a hydrocarbon solvent to obtain the catalyst.
In a further preferred embodiment, the hydrocarbon solvent is selected from at least one of isopentane, hexane, heptane, toluene, xylene, naphtha and mineral oil.
In another preferred embodiment, the catalyst component and the organoaluminum compound are added to react during the olefin polymerization to initiate the olefin polymerization reaction.
The fourth object of the present invention is to provide the use of the catalyst of the third object of the present invention in the polymerization of olefins, preferably in the homopolymerization or copolymerization of ethylene.
The catalyst of the invention is suitable for homopolymerization of various ethylene or copolymerization of ethylene and other alpha-olefin, wherein the alpha-olefin is one or a mixture of more of propylene, butene, pentene, hexene, octene and 4-methylpentene-1. The polymerization process adopts a gas phase method, a slurry method and a solution method, and is more suitable for gas phase polymerization.
Compared with the prior art, the invention has the following beneficial effects: the catalyst containing the epoxy resin is prepared by mixing the epoxy resin and an inorganic oxide carrier as fillers to prepare a slurry suspension and forming by using a spray drying method. The catalyst has few fine particles, is used for catalyzing ethylene polymerization, and has the advantages of high activity, good hydrogen regulation performance, high bulk density of the obtained polymer powder and low fine powder content of the polymer powder.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The test method comprises the following steps:
1. activity: expressed as the weight of resin obtained per gram of catalyst;
2. polymer Melt Index (MI): determined according to ASTM D1238-99, load 2.16kg, 190 ℃;
3. polymer apparent Bulk Density (BD): the test was performed with reference to ASTM D1895-69 standard.
4. The values of the sieve analysis were based on: refer to the astm d-1921 standard.
5. The particle size of the catalyst is as follows: measured using a MasterSIZER2000 particle sizer, termed D10、D50、D90Expressed, i.e. a particular percentage of the standard logarithmic particle size distribution, e.g. the catalyst particle size having D50The median particle diameter is 24 μm when the particle diameter is 24 μm; d10By 7 μm is meant that 10% of the particles are less than 7 μm in diameter. D90By 45 μm is meant that 90% of the particles have a particle size of less than 45 μm.
6. The catalyst comprises the following components: the contents of titanium and magnesium are measured by a Spectrumlab 752s ultraviolet-visible spectrophotometer; the THF content was determined by means of an Aglient 7890A gas chromatograph from the company Aglient, USA.
[ example 1 ]
(1) Preparation of the catalyst component
Into a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and a nitrogen purge and guard were charged, while stirring, 120mL of Tetrahydrofuran (THF), 4.2g of magnesium chloride and 1.0mL of TiCl in succession4Heating to 68 ℃ under stirring, and carrying out reflux reaction at constant temperature for 4 hours to obtain mother liquor;
adding 5.5g of silica gel (Cabot Corporation TS-610, particle size less than 1 μm) and 1.0g of bisphenol A epoxy resin (Phoenix brand E51, epoxy value 0.48-0.54) in a 250mL four-neck flask equipped with a temperature controller, a stirrer, a reflux condenser and protected by nitrogen gas blowing, in a weight ratio of silica gel to epoxy resin of 5.5, adding the above mother liquor under stirring, and continuing constant-temperature reflux stirring at 68 ℃ for 2 hours to completely disperse the silica gel in the mother liquor to obtain a slurry suspension;
in closed-cycle gas-flow spray dryers (e.g. for drying solid material)
Mini Spray Dryer B-290), introducing nitrogen gas at a carrier gas inlet temperature of 145 ℃ into the Spray Dryer, adding the resulting slurry suspension at 43 ℃ to the circulating Dryer, adjusting the slurry suspension feed rate and the Spray gas (N) at room temperature2) The flow rates are respectively 8mL/min and 30m3About/h, carrier gas (N) is adjusted2) Flow rate, so that the outlet temperature was 95 ℃ to obtain a solid catalyst component. The resulting catalyst component has a desired particle diameter D50About 20 to 23 μm. The structural analysis of the catalyst obtained is shown in Table 1.
(2) Ethylene slurry polymerization
Adding 1L of hexane into a 2L polymerization kettle which is blown off by nitrogen and hydrogen firstly, adding 1mL of triethyl aluminum (1M) and 20mg of dry powder catalyst simultaneously, heating to 70 ℃, adding hydrogen to 0.28MPa, adding ethylene to 1.03MPa after hydrogenation, heating to 85 ℃, reacting for 2 hours at constant temperature and constant pressure of 85 ℃, cooling and discharging. The polymerization results are shown in Table 2.
[ example 2 ]
In comparison with example 1, except that "5.5 g of silica gel (Cabot Corporation TS-610, particle size less than 1 μm) and 1.0g of bisphenol A epoxy resin (Phoenix brand E51, epoxy value 0.48-0.54) were added in the preparation of the catalyst component in step (1)" the weight ratio of silica gel to epoxy resin 5.5 "was changed to" 6.4 g of silica gel (Cabot Corporation TS-610, particle size less than 1 μm) and 0.1g of bisphenol A epoxy resin (Phoenix brand E51, epoxy value 0.48-0.54), weight ratio of silica gel to epoxy resin 64 ", and the other was the same as in example 1.
[ example 3 ]
In comparison with example 1, except that "5.5 g of silica gel (Cabot Corporation TS-610, particle size less than 1 μm) and 1.0g of bisphenol A epoxy resin (Phoenix brand E51, epoxy value 0.48-0.54) were added in the preparation of the catalyst component in step (1)" the weight ratio of silica gel to epoxy resin 5.5 "was changed to" 6.0 g of silica gel (Cabot Corporation TS-610, particle size less than 1 μm) and 0.5g of bisphenol A epoxy resin (Phoenix brand E51, epoxy value 0.48-0.54), weight ratio of silica gel to epoxy resin 12 ", and the other was the same as in example 1.
[ example 4 ]
The procedure of example 1 was repeated except that "1.0 g of bisphenol A epoxy resin (Phoenix brand E51, epoxy value 0.48 to 0.54)" was changed to "1.0 g of bisphenol A epoxy resin (Phoenix brand E42, epoxy value 0.38 to 0.45)" in the preparation of the catalyst component in step (1).
[ example 5 ]
In contrast to example 1, except that "1.0 mL of TiCl was used in the preparation of the catalyst component in step (1)41.4g of TiCl "instead3·1/3AlCl3", the others are the same as in example 1.
[ example 6 ]
In contrast to example 1, except that "1.0 mL of TiCl was used in the preparation of the catalyst component in step (1)41.5g of TiCl "instead3·1/2MgCl2", the others are the same as in example 1.
[ example 7 ]
The same as in example 1 was repeated except that "1.0 g of bisphenol A epoxy resin (Phoenix brand E51, epoxy value 0.48 to 0.54)" was changed to "1.0 g of bisphenol S epoxy resin (U.S. Compton brand No. 185S, epoxy value 0.38)" in the preparation of the catalyst component in step (1).
[ example 8 ]
(1) Preparation of the catalyst component
Into a 500mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and a nitrogen purge and guard were charged 160mL of ethyl acetate, 8.1g of magnesium bromide and 2.5mL of TiCl in succession with stirring4Heating to 75 ℃ under stirring, and carrying out reflux reaction at constant temperature for 2 hours to obtain a mother solution;
adding 10.5g of alumina (particle size less than 1 μm) and 2.08g of 1, 1, 2, 2-tetra (p-hydroxyphenyl) ethane tetraglycidyl ether epoxy resin (epoxy value is 0.45-0.5) into a 500mL four-neck flask which is provided with a temperature controller, a stirrer and a reflux condenser and is blown off by nitrogen and protected, wherein the weight ratio of silica gel to epoxy resin is 5.04, adding the mother liquor under stirring, and continuing to stir at constant temperature for 1 hour under reflux at 75 ℃ to completely disperse the silica gel in the mother liquor to obtain a slurry suspension;
in closed-cycle gas-flow spray dryers (e.g. for drying solid material)
Mini Spray Dryer B-290), introducing nitrogen gas at a carrier gas inlet temperature of 160 ℃ into the Spray Dryer, adding the resulting slurry suspension at 43 ℃ to the circulating Dryer, adjusting the slurry suspension feed rate and the Spray gas (N) at room temperature2) The flow rates are respectively 8mL/min and 30m3About/h, carrier gas (N) is adjusted2) Flow rate, so that the outlet temperature was 115 ℃ to obtain a solid catalyst component.
(2) Ethylene slurry polymerization
Adding 1L of hexane into a 2L polymerization kettle which is blown off by nitrogen and hydrogen firstly, adding 1mL of triethyl aluminum (1M) and 20mg of dry powder catalyst simultaneously, heating to 70 ℃, adding hydrogen to 0.28MPa, adding ethylene to 1.03MPa after hydrogenation, heating to 85 ℃, reacting for 2 hours at constant temperature and constant pressure of 85 ℃, cooling and discharging.
[ example 9 ]
(1) Preparation of the catalyst component
To one is provided with a temperature controller72mL of ethyl propyl ether, 2.75g of magnesium fluoride and 0.5mL of TiCl were added successively with stirring to a 250mL four-neck flask with stirrer and reflux condenser, purged with nitrogen and protected4Heating to 50 ℃ under stirring, and carrying out reflux reaction at constant temperature for 10 hours to obtain mother liquor;
adding 8g of silica gel (Cabot Corporation TS-610, particle size less than 1 μm) and 0.42g of resorcinol bisglycidyl ether type epoxy resin (680#, epoxy value 0.78-0.85) in a 250mL four-neck flask equipped with a temperature controller, a stirrer, a reflux condenser and protected with nitrogen gas, in a weight ratio of silica gel to epoxy resin of 8, adding the above mother liquor under stirring, and continuing to stir at constant temperature for 5 hours under reflux at 50 ℃ to completely disperse the silica gel in the mother liquor to obtain a slurry suspension;
in closed-cycle gas-flow spray dryers (e.g. for drying solid material)
Mini Spray Dryer B-290), introducing nitrogen gas at a carrier gas inlet temperature of 120 ℃ into the Spray Dryer, adding the resulting slurry suspension at 43 ℃ to the circulating Dryer, adjusting the slurry suspension feed rate and the Spray gas (N) at room temperature2) The flow rates are respectively 8mL/min and 30m3About/h, carrier gas (N) is adjusted2) Flow rate, so that the outlet temperature was 90 ℃, to obtain a solid catalyst component.
(2) Ethylene slurry polymerization
Adding 1L of hexane into a 2L polymerization kettle which is blown off by nitrogen and hydrogen firstly, adding 1mL of triethyl aluminum (1M) and 20mg of dry powder catalyst simultaneously, heating to 70 ℃, adding hydrogen to 0.28MPa, adding ethylene to 1.03MPa after hydrogenation, heating to 85 ℃, reacting for 2 hours at constant temperature and constant pressure of 85 ℃, cooling and discharging.
[ example 10 ]
(1) Preparation of the catalyst component
Into a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and a nitrogen purge and guard were charged, with stirring, 100mL of Tetrahydrofuran (THF), 4.2g of magnesium chloride and 4mL of TiCl in succession4Stirring the mixtureHeating to 85 ℃ while stirring, and carrying out reflux reaction for 3 hours at constant temperature to obtain mother liquor;
to a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and protected by nitrogen purging, 2.65g of silica gel (Cabot Corporation TS-610, particle size less than 1 μm) and 0.21g of glycidyl ester type epoxy resin (711#, epoxy value of 0.63-0.67) were added in a weight ratio of silica gel to epoxy resin of 12.6, the mother liquor was added under stirring, and stirring was continued at constant temperature at 85 ℃ under reflux for 1 hour to completely disperse the silica gel in the mother liquor to obtain a slurry suspension;
in closed-cycle gas-flow spray dryers (e.g. for drying solid material)
Mini Spray Dryer B-290), introducing nitrogen gas at a carrier gas inlet temperature of 150 ℃ into the Spray Dryer, adding the resulting slurry suspension at 43 ℃ to the circulating Dryer, adjusting the slurry suspension feed rate and the Spray gas (N) at room temperature2) The flow rates are respectively 8mL/min and 30m3About/h, carrier gas (N) is adjusted2) Flow rate, so that the outlet temperature was 100 ℃ to obtain a solid catalyst component.
(2) Ethylene slurry polymerization
Adding 1L of hexane into a 2L polymerization kettle which is blown off by nitrogen and hydrogen firstly, adding 1mL of triethyl aluminum (1M) and 20mg of dry powder catalyst simultaneously, heating to 70 ℃, adding hydrogen to 0.28MPa, adding ethylene to 1.03MPa after hydrogenation, heating to 85 ℃, reacting for 2 hours at constant temperature and constant pressure of 85 ℃, cooling and discharging.
Comparative example 1
The procedure of example 1 was repeated except that no epoxy resin was added at the time of preparation of the catalyst component.
(1) Preparation of the catalyst component
Into a 250mL four-necked flask equipped with a temperature controller, a stirrer, a reflux condenser and a nitrogen purge and guard were charged, while stirring, 120mL of Tetrahydrofuran (THF), 4.2g of magnesium chloride and 1.0mL of TiCl in succession4Heating to 68 deg.C under stirring, and refluxing at constant temperature4 hours, obtaining mother liquor;
into a 250mL four-necked flask equipped with a temperature controller, a stirrer, and a reflux condenser, purged with nitrogen and protected, 6.5g of silica gel (Cabot Corporation TS-610, particle size less than 1 μm) was added, the above mother liquor was added under stirring, and the stirring was continued at a constant temperature of 68 ℃ under reflux for 2 hours to completely disperse the silica gel in the mother liquor to obtain a slurry suspension;
in closed-cycle gas-flow spray dryers (e.g. for drying solid material)
Mini Spray Dryer B-290), introducing nitrogen gas at a carrier gas inlet temperature of 145 ℃ into the Spray Dryer, adding the resulting slurry suspension at 43 ℃ to the circulating Dryer, adjusting the slurry suspension feed rate and the Spray gas (N) at room temperature2) The flow rates are respectively 8mL/min and 30m3About/h, carrier gas (N) is adjusted2) Flow rate, so that the outlet temperature was 95 ℃ to obtain a solid catalyst component. The resulting catalyst component has a desired particle diameter D50About 20 to 23 μm. The structural analysis of the catalyst obtained is shown in Table 1.
(2) Ethylene slurry polymerization
Adding 1L of hexane into a 2L polymerization kettle which is blown off by nitrogen and hydrogen firstly, adding 1mL of triethyl aluminum (1M) and 20mg of dry powder catalyst simultaneously, heating to 70 ℃, adding hydrogen to 0.28MPa, adding ethylene to 1.03MPa after hydrogenation, heating to 85 ℃, reacting for 2 hours at constant temperature and constant pressure of 85 ℃, cooling and discharging. The polymerization results are shown in Table 2.
Comparative example 2
The procedure of example 1 was repeated except that the epoxy resin used was phoenix brand E06, having an epoxy value of 0.04-0.07. The results are shown in tables 1 and 2.
Comparative example 3
Aromatic amine glycidyl type epoxy resin with the trade name of AF6-90#, and the epoxy value of 0.85-0.95. The results are shown in tables 1 and 2.
TABLE 1 analysis of catalyst Structure
As can be seen from Table 1, the addition of the epoxy resin in the present invention is effective in increasing the adhesion between catalyst carriers, D of the catalyst particles10The size of the catalyst is increased, the fine particles are reduced, the particle size distribution of the catalyst is narrowed, and the tetrahydrofuran content in the catalyst component is reduced to reach a reasonable content range (wherein, the reduction of the tetrahydrofuran content is directly related to the addition of the epoxy resin, because the epoxy resin and the tetrahydrofuran have competitive coordination with the magnesium halide).
TABLE 2 polymerization Properties of the catalysts
a. Polymerization conditions: t85 ℃ and P (H)2)/P(C2H4)＝0.28/0.75，TEA(1M)1mL，t 2hr。
As shown in Table 2, the addition of the epoxy resin in the invention increases the particle strength of the catalyst, and the catalyst has higher activity when used for catalyzing ethylene polymerization, so that the bulk density of the obtained polyethylene powder is improved, the content of fine powder is reduced, and the hydrogen regulation responsiveness is better.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (14)
1. An epoxy-containing catalyst component, the catalyst component comprising: titanium element, magnesium element, electron donor, epoxy resin and inorganic oxide carrier.
2. The catalyst component according to claim 1, comprising, based on 100 wt% of the total weight:
0.1-5 wt% of titanium;
0.2-10.2 wt% of magnesium;
15-40 wt% of electron donor;
0.01-15 wt% of epoxy resin;
1-70 wt% of inorganic oxide carrier.
3. The catalyst component according to claim 1, comprising, based on 100 wt% of the total weight:
0.5-4 wt% of titanium;
4-8 wt% of magnesium;
20-35 wt% of electron donor;
0.1-10 wt% of epoxy resin;
10-60 wt% of inorganic oxide carrier.
4. The catalyst component according to claim 1, wherein the epoxy resin is a polymer compound having at least two epoxy groups in its molecular structure, and the epoxy value of the epoxy resin is 0.10 to 0.90, preferably 0.15 to 0.75, and most preferably 0.18 to 0.60;
preferably, the epoxy resin is selected from at least one of glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, linear aliphatic epoxy resins, and alicyclic epoxy resins.
5. The catalyst component according to claim 1, wherein the weight ratio of the inorganic oxide support to the epoxy resin is (1-100) to 1, preferably (2-80) to 1.
6. The catalyst component according to any one of claims 1 to 5, wherein the source of the titanium element is a titanium-containing compound; preferably, the titanium-containing compound is selected from at least one of titanium halide, a product of aluminum reduction of titanium halide, a product of magnesium reduction of titanium halide;
more preferably, the titanium halide is selected from titanium bromide and/or titanium chloride; and/or the product of the reduction of titanium halide by aluminium has the general formula TiXm·nAlXpWherein n is more than 0 and less than or equal to 1, m is more than 0 and less than or equal to 3, p is more than 0 and less than or equal to 3, and X is halogen; and/or the product of magnesium reduction of titanium halide has the general formula TiXmqMgXr, where q is greater than 0 and less than or equal to 1, m is greater than 0 and less than or equal to 3, r is greater than 0 and less than or equal to 3, and X is halogen.
7. The catalyst component according to any of claims 1 to 5, characterized in that,
the source of the magnesium element is magnesium halide, preferably, the magnesium halide is at least one selected from magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, and more preferably, the magnesium chloride; and/or
The electron donor is at least one selected from ester compounds, ether compounds and ketone compounds; preferably, the electron donor is selected from C1～C4Alkyl esters of saturated fatty carboxylic acids, C7～C8Alkyl esters of aromatic carboxylic acids, C2～C6Fatty ethers, C3～C4Cyclic ethers and C3～C6At least one of saturated aliphatic ketones; more preferably, the electron donor is selected from at least one of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone; and/or
The inorganic oxide support is selected from oxides of silicon and/or oxides of aluminum, preferably silica; more preferably, the particle size of the inorganic oxide carrier is 0.01 to 10 micrometers, preferably 0.01 to 5 micrometers, and more preferably 0.1 to 1 micrometer.
8. The process for preparing a catalyst component according to any one of claims 1 to 7, comprising the steps of:
step 1, mixing raw materials including a titanium-containing compound, magnesium halide, an electron donor, epoxy resin and an inorganic oxide carrier to obtain slurry suspension;
and 2, carrying out spray drying to obtain the catalyst component.
9. The preparation method according to claim 8, wherein in step 1, the titanium-containing compound, the magnesium halide and the electron donor are mixed to obtain a mother liquor; adding an inorganic oxide carrier and an epoxy resin during or after the preparation of the mother liquor to obtain the slurry suspension.
10. The preparation method of claim 8, wherein in the step 1, the molar ratio of the electron donor to the magnesium halide is (5.0-50) to 1, preferably (10-45) to 1; and/or the mass ratio of the epoxy resin to the magnesium halide is (0.01-1.0) to 1, preferably (0.01-0.5) to 1; and/or the molar ratio of the titanium-containing compound to the magnesium halide is (0.1-1.0) to 1, preferably (0.1-0.5) to 1; and/or the molar ratio of the inorganic oxide carrier to the magnesium halide is (1.0-5.0) to 1, preferably (1.0-4.0) to 1.
11. The production method according to any one of claims 8 to 10,
the mixing in the step 1 is carried out for more than 0.1h at the normal temperature of 25 +/-5 ℃; and/or
In step 2, the spray drying conditions are: the inlet temperature is 100-240 ℃; the outlet temperature is 60-130 ℃.
12. A catalyst for the polymerization of olefins comprising: (A) the catalyst component according to any one of claims 1 to 7 or the catalyst component obtained by the production method according to any one of claims 8 to 11; (B) the general formula is AlRbX’3-bWherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x' is halogen, preferably chlorine, bromine or iodine; b is more than 0 and less than or equal to 3, preferably more than 1 and less than or equal to 3.
13. The catalyst according to claim 12, wherein the organoaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum monochloride; and/or
The molar ratio of the organic aluminum compound to the catalyst component is (5-1000) to 1, preferably (10-200) to 1.
14. Use of a catalyst according to claim 12 or 13 in the polymerization of olefins, preferably in the homopolymerization or copolymerization of ethylene.
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|---|---|---|---|---|
| US20060287446A1 (en) * | 2004-04-30 | 2006-12-21 | Mingzhi Gao | Catalyst component for olefin polymerization and catalyst comprising the same |
| CN101003586A (en) * | 2002-02-14 | 2007-07-25 | 诺沃伦技术控股公司 | Solid catalytic component and catalytic system of the ziegler-natta type, process for their preparation and their use in the polymerisation of alk-1-enes |
| JP2010235923A (en) * | 2009-03-09 | 2010-10-21 | Asahi Kasei Chemicals Corp | Manufacturing method for solid catalyst for olefin polymerization, and manufacturing method for polyolefin |
| WO2019094216A1 (en) * | 2017-11-13 | 2019-05-16 | W.R. Grace & Co.-Conn. | Catalyst components for propylene polymerization |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003586A (en) * | 2002-02-14 | 2007-07-25 | 诺沃伦技术控股公司 | Solid catalytic component and catalytic system of the ziegler-natta type, process for their preparation and their use in the polymerisation of alk-1-enes |
| US20060287446A1 (en) * | 2004-04-30 | 2006-12-21 | Mingzhi Gao | Catalyst component for olefin polymerization and catalyst comprising the same |
| JP2010235923A (en) * | 2009-03-09 | 2010-10-21 | Asahi Kasei Chemicals Corp | Manufacturing method for solid catalyst for olefin polymerization, and manufacturing method for polyolefin |
| WO2019094216A1 (en) * | 2017-11-13 | 2019-05-16 | W.R. Grace & Co.-Conn. | Catalyst components for propylene polymerization |
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