CN102260360A - Catalyst for ethylene polymerization, its preparation and application - Google Patents
Catalyst for ethylene polymerization, its preparation and application Download PDFInfo
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- CN102260360A CN102260360A CN2010101933949A CN201010193394A CN102260360A CN 102260360 A CN102260360 A CN 102260360A CN 2010101933949 A CN2010101933949 A CN 2010101933949A CN 201010193394 A CN201010193394 A CN 201010193394A CN 102260360 A CN102260360 A CN 102260360A
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Abstract
The invention relates to a catalyst for ethylene polymerization, its preparation and application. The catalyst comprises titanium-bearing active components and activator component, wherein, the titanium-bearing active components comprise at least one kind of magnesium halide, at least one kind of titanium halide, at least one kind of electron donor compound and at least one kind of modifier which are loaded on a silica carrier; The electron donor compound is selected from alcohol or ether, and the modifier is thiocyanate propyltriethoxysilane. The activator component shown as AlR'nX3-n is an organo-aluminum compound, wherein, R' represents hydrogen of C1-20 alkyl, X represents halogen, and n represents a number which is larger than 1 and no larger than 3. The molar ration of the titanium-bearing active components to the activator component is 1 to 200. The catalyst for ethylene gasphase polymerization or copolymerization has the advantages of high catalytic activity, high bulk density of polyethylene powder, little fine powder and the like.
Description
Technical field
The present invention relates to a kind of slurry type high activity silica gel carrier catalyst component and preparation thereof that is used for ethene gas-phase polymerization or copolymerization technology, and the application in the application of this catalyzer in ethene gas-phase polymerization or copolymerization, particularly ethene gas fluidised bed polymerisation frozen state or the super frozen state polymerization.
Background technology
Gas-phase polythene technology is a kind of advanced person's polyethylene production technology, has many covering devices using gas phase process to produce polyethylene in the world.The Ziegler-Natta catalyst that is applicable to gas-phase polythene technology will have good fluidity, and its form is sphere or class sphere.The catalyzer form is the form of replicating vector normally, so when the research carrier two kinds of thinkings are arranged, a kind of is with MgCl
2Or MgCl
2Complex compound dissolving after separate out again, control certain formation condition, preparation class sphere Ti-MgCl
2Catalyzer is as CN1463991.Its advantage of the catalyzer that makes like this is to have higher titanium content and polymerization activity, is applicable to vapor phase process, and shortcoming is that the Preparation of catalysts process is loaded down with trivial details, the condition harshness, and cost is higher relatively; Another kind is to be preparing carriers gas-phase polyethylene catalyzer Ti-MgCl with sphere or class spherical silica gel
2/ SiO
2, the good fluidity of this catalyzer, active suitable, polyethylene tap density height is highly suitable for gas fluidized-bed process.The catalyzer of Unipol gas fluidized-bed process is that active constituent loading prepares on macrobead silica gel with titanium magnesium exactly, catalyst form is decided by used silica-gel carrier particulate form fully, so the performance of catalyzer is also relevant with the size and the microvoid structure thereof of used silica gel.For example: the disclosed catalyzer that is used for gas-phase fluidized bed polymerization process of US4302565, the median size of its used silica gel is generally 40～80 microns.Linear low-density polyethylene film resinoid by this Catalyst Production has good processing properties and mechanical property.At the ethylene polymerization activity of this catalyzer on the industrialization gas phase fluidization bed apparatus generally about 3500g PE/g Cat, but then active significantly reduction when being used for gas-phase fluidized-bed condensation technology owing to the shortening of the catalyzer residence time, thereby cause polyvinyl ash rising and influenced polyvinyl performance, the catalytic activity that therefore improves this type of catalyzer is one of key factor that improves the vinyl polymerization amount.In addition, the form of polymer beads and size distribution are the principal elements that influences gas phase fluidization bed apparatus smooth operation, and therefore good polymer beads form and size distribution, fine powder content are the target that such catalyzer is pursued less.
In above-mentioned disclosed patent, because the catalyst activity component is carried on the carrier by the impregnating method, the uniform distribution of control catalyst active principle on support of the catalyst be difficulty relatively, repeated poor in the catalyst preparation process, so catalyst activity and resulting polymers particle form and size distribution are all unsatisfactory.Patent US 4376062 and patent CN 1493599A are on the basis of above-mentioned catalyst activity component, the silicon-dioxide of smoke-like is introduced catalyst particle, mix with parent by titanium compound, magnesium compound and electron donor compound, obtain catalyzer by spray-dired method, after this catalyzer is used for the ethene gas-phase fluidized bed polymerization process, the particle diameter of gained catalyzer and particle form are easy to control, and catalyst efficiency also improves.But the catalytic activity of catalyzer and the form of polymerisate are still unsatisfactory, and when this catalyzer is applied to the copolymerization of ethene and high alpha-olefin such as 1-hexene, the content of hexane extractable content is still higher in the resulting polymers, and this will reduce the final product performance of polyvinyl resin.
Summary of the invention
The purpose of this invention is to provide a kind of improved catalyzer that is used for ethene gas-phase polymerization or copolymerization, by in the preparation process of catalyst activity component parent, adding thiocyanate groups propyl-triethoxysilicane properties-correcting agent, when making the catalyst component of gained and organoaluminum promotor one be used from vinyl polymerization or copolymerization, the catalytic activity of catalyzer obviously improves, and poly particle form of product and size distribution have also obtained improving significantly.
The catalyst component that is used for ethene gas-phase polymerization or copolymerization provided by the invention, it comprises the product of following reaction:
A. titaniferous active ingredient
Load has at least a magnesium dihalide, a kind of titanium-containing compound, a kind of electron donor compound and thiocyanate groups propyl-triethoxysilicane properties-correcting agent on silica supports, described electron donor compound is selected from a kind of of alcohol or ether, or their mixture.
B. activator component
General formula is AlR '
nX
3-nOrgano-aluminium compound, R ' is 1～20 alkyl for hydrogen or carbonatoms in the formula, X is a halogen, n is the number of 1＜n≤3.
Above-mentioned titaniferous active ingredient can adopt following method preparation:
(1) parent preparation
In the electron donor compound, magnesium dihalide compound, titanium-containing compound, thiocyanate groups propyl-triethoxysilicane are carried out the prepared in reaction parent;
Described electron donor compound is selected from a kind of of alcohol or ether, or their mixture, concrete as: C
1～C
4Alcohol, C
2～C
6Aliphatic ether, C
3～C
4Cyclic ethers in a kind of or their mixture, particular methanol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, ether, hexyl ether and tetrahydrofuran (THF) etc., most preferably tetrahydrofuran (THF).These electron donors can use separately, also can be used in combination.
Described titanium-containing compound is titanium chloride and titanium bromide, is preferably TiCl
3Or TiCl
4
The preferred magnesium dichloride of described magnesium compound.
In the parent of preparation, the molar ratio of each component preferably is controlled at and makes 1＜Mg/Ti＜20,0＜properties-correcting agent/Ti＜5, and wherein the preferable range of properties-correcting agent/Ti is 0.1～1.0.The add-on of electron donor generally is controlled at every mole of titanium and is approximately 5 moles to 300 moles, is preferably 10 moles to 100 moles.
(2) preparation of complex carrier
The parent and the blending of smoke-like silica supports of step (1) gained are obtained suspension:
Wherein the silica supports particle diameter is generally 0.01～1 μ m, preferred 0.01～0.1 μ m, and the silica supports of selecting for use is a hydrophobic type, promptly its surface does not have the water of absorption.The carrier of sufficient amount should be mixed with mother liquor, formation is suitable for spray-dired suspension, and promptly the weight content of this carrier is 10～60% in suspension, is preferably 20～40%.
(3) spray shaping
The suspension that step (2) is obtained carries out spraying drying and obtains ingredient of solid catalyst, and its average diameter of particles is at 10～50 μ m.
(4) prereduction
In order to make the titanium-containing catalyst component that obtains after the spraying drying be applicable to the production ethene polymers, also must adopt organo-aluminium compound that titanium atom in the described catalyst component is reduced into and to make the effective polymeric valence state of ethene.Generally in varsol, ingredient of solid catalyst and activator component that step (3) obtains are reacted, obtain catalyzer.
Described activator component is general formula AlR '
nX
3-nOrgano-aluminium compound, R ' is 1～20 alkyl for hydrogen or carbonatoms in the formula, X is a halogen, n is the number of 1＜n≤3.Can select AlEt for use
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2A kind of among the Cl or their mixture.Wherein the mol ratio of organo-aluminium compound and titanium is 10～500.
Described varsol such as iso-pentane, hexane, heptane, toluene, dimethylbenzene, petroleum naphtha and mineral wet goods.
The catalyzer that obtains after reduction can add in the polymerization reactor dry back, also can directly join this suspension that contains catalyst component and activator in the reactor, activate fully with additional activator in reactor, activator can be selected AlEt for use again
3, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2A kind of among the Cl or their mixture.
The catalyzer that the present invention relates to be applicable to ethene homopolymerization or with the copolymerization of other high alpha-olefin, wherein alpha-olefin adopts a kind of in propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, the 4-methyl-1-pentene during copolymerization.Polymerization technique adopts vapor phase process, slurry process and solution method, is more suitable in gas fluidised bed polymerisation particularly gas-phase fluidized-bed frozen state or super condensation mode.Temperature of reaction: 85～90 ℃; Reaction pressure: 2.0MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.17～0.22; 1-butylene/ethene=0.38～0.42.Simultaneously, because catalyst particle size of the present invention is thinner, so can adopt inert diluent with catalyst dilution, for example the mineral wet goods is realized the even charging of catalyzer, stable operation by the transferpump feeding manner.
Embodiment
Embodiment 1
1. Preparation of Catalyst
To process N
2Fully add 3.0g TiCl in the metathetical 250mL there-necked flask
4, 6.9 the gram MgCl
2With the 170mL tetrahydrofuran (THF), to stir down and be warming up to 65 ℃, isothermal reaction 2 hours is 1: 0.2 a ratio adding thiocyanate groups propyl-triethoxysilicane in Ti and alkoxyl group mol ratio, isothermal reaction 2 hours is cooled to 30 ℃.
To a process N
2Fully add 10.4 gram silica gel (CabotCorporationTS-610 in the metathetical 250mL there-necked flask, particle diameter is 0.02～0.1 μ m) after, mother liquor after the cooling is added, keep 30 ℃ of temperature, stirred 2 hours, the mother liquor after stirring is carried out spraying drying with the spraying drying instrument to mother liquor, spray condition: 160 ℃ of inlet temperatures, 80 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein Ti content is 2.05%, Mg content is 6.33%, THF content is 29.7%.In the ingredient of solid catalyst that obtains, add mineral oil, be made into the mineral oil solution that contains solids 30%, press THF according to the content of THF: AlEt
2Cl: Al (C
6H
13)
3=1: 0.45: 0.2 mol ratio adds AlEt
2The Cl reaction adds Al (C after 20 minutes again
6H
13)
3
2. the slurry polymerization of ethene
The 2L reactor is heated to about 80 ℃, vacuumizes 1h,, blow row with hydrogen then with the drying nitrogen displacement.In polymeric kettle, add the 1L hexane, the triethyl aluminum and the above-mentioned catalyzer 50mg that add 1mmol simultaneously, be warming up to 75 ℃ subsequently, add hydrogen 0.18MPa, the hydrogenation back that finishes adds ethene and makes the still internal pressure reach 1.03MPa, be warming up to 85 ℃ after, react after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
3. the gas phase copolymerization of ethene and butylene
Be aggregated on the φ 150 fluidized-bed ethene gas-phase polymerization devices and carry out, catalyst levels is 0.2g, AlEt
3: 5mmol, 600g polyethylene powder are as dispersion agent, and polymerizing condition is: temperature of reaction: 88 ℃; Reaction pressure: 2.0MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.18; 1-butylene/ethene=0.38.Polymerization 2 hours, polymerization result sees Table 2.
Embodiment 2
1. Preparation of Catalyst
To process N
2Fully add 3.0g TiCl in the metathetical 250mL there-necked flask
4, 6.9 the gram MgCl
2With the 170mL tetrahydrofuran (THF), to stir down and be warming up to 65 ℃, isothermal reaction 2 hours is 1: 0.4 a ratio adding thiocyanate groups propyl-triethoxysilicane in Ti and alkoxyl group mol ratio, isothermal reaction 2 hours is cooled to 30 ℃.
To a process N
2Add 10.4 gram silica gel (CabotCorporationTS-610 in the metathetical 250mL there-necked flask, particle diameter is 0.02～0.1 μ m) after, mother liquor after the cooling is added, keep 30 ℃ of temperature, stirred 2 hours, the mother liquor after stirring is carried out spraying drying with the spraying drying instrument to mother liquor, spray condition: 160 ℃ of inlet temperatures, 80 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein Ti content is 2.17%, Mg content is 6.03%, THF content is 29.5%.In the ingredient of solid catalyst that obtains, add mineral oil, be made into the mineral oil solution that contains solids 30%, press THF according to the content of THF: AlEt
2Cl: Al (C
6H
13)
3=1: 0.45: 0.2 mol ratio adds AlEt
2The Cl reaction adds Al (C after 20 minutes again
6H
13)
3
2. the slurry polymerization of ethene
The 2L reactor is heated to about 80 ℃, vacuumizes 1h,, blow row with hydrogen then with the drying nitrogen displacement.In polymeric kettle, add the 1L hexane, the triethyl aluminum and the above-mentioned catalyzer 50mg that add 1mmol simultaneously, be warming up to 75 ℃ subsequently, add hydrogen 0.18MPa, the hydrogenation back that finishes adds ethene and makes the still internal pressure reach 1.03MPa, be warming up to 85 ℃ after, react after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
3. the gas phase copolymerization of ethene and butylene
Be aggregated on the φ 150 fluidized-bed ethene gas-phase polymerization devices and carry out, catalyst levels is 0.2g, AlEt
3: 5mmol, 600g polyethylene powder are as dispersion agent, and polymerizing condition is: temperature of reaction: 88 ℃; Reaction pressure: 1.8MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.20; 1-butylene/ethene=0.40.Polymerization 2 hours, polymerization result sees Table 2.
Embodiment 3
1. Preparation of Catalyst
To process N
2Fully add 3.0g TiCl in the metathetical 250mL there-necked flask
4, 6.9 the gram MgCl
2With the 170mL tetrahydrofuran (THF), to stir down and be warming up to 65 ℃, isothermal reaction 2 hours is 1: 0.6 a ratio adding thiocyanate groups propyl-triethoxysilicane in Ti and alkoxyl group mol ratio, isothermal reaction 2 hours is cooled to 30 ℃.
To a process N
2Add 10.4 gram silica gel (CabotCorporationTS-610 in the metathetical 250mL there-necked flask, particle diameter is 0.02～0.1 μ m) after, mother liquor after the cooling is added, keep 30 ℃ of temperature, stirred 2 hours, the mother liquor after stirring is carried out spraying drying with the spraying drying instrument to mother liquor, spray condition: 160 ℃ of inlet temperatures, 80 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein Ti content is 2.38%, Mg content is 6.25%, THF content is 28.9%.In the ingredient of solid catalyst that obtains, add mineral oil, be made into the mineral oil solution that contains solids 30%, press THF according to the content of THF: AlEt
2Cl: Al (C
6H
13)
3=1: 0.45: 0.2 mol ratio adds AlEt
2The Cl reaction adds Al (C after 20 minutes again
6H
13)
3
2. the slurry polymerization of ethene
The 2L reactor is heated to about 80 ℃, vacuumizes 1h,, blow row with hydrogen then with the drying nitrogen displacement.In polymeric kettle, add the 1L hexane, the triethyl aluminum and the above-mentioned catalyzer 50mg that add 1mmol simultaneously, be warming up to 75 ℃ subsequently, add hydrogen 0.18MPa, the hydrogenation back that finishes adds ethene and makes the still internal pressure reach 1.03MPa, be warming up to 85 ℃ after, react after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
3. the gas phase copolymerization of ethene and butylene
Be aggregated on the φ 150 fluidized-bed ethene gas-phase polymerization devices and carry out, catalyst levels is 0.2g, AlEt
3: 5mmol, 600g polyethylene powder are as dispersion agent, and polymerizing condition is: temperature of reaction: 88 ℃; Reaction pressure: 2.0MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.18; 1-butylene/ethene=0.38.Polymerization 2 hours, polymerization result sees Table 2.
Embodiment 4
1. Preparation of Catalyst
To process N
2Fully add 3.0g TiCl in the metathetical 250mL there-necked flask
4, 6.9 the gram MgCl
2With the 170mL tetrahydrofuran (THF), to stir down and be warming up to 65 ℃, isothermal reaction 2 hours is 1: 1 a ratio adding thiocyanate groups propyl-triethoxysilicane in Ti and alkoxyl group mol ratio, isothermal reaction 2 hours is cooled to 30 ℃.
To a process N
2Add 10.4 gram silica gel (CabotCorporationTS-610 in the metathetical 250mL there-necked flask, particle diameter is 0.02～0.1 μ m) after, mother liquor after the cooling is added, keep 30 ℃ of temperature, stirred 2 hours, the mother liquor after stirring is carried out spraying drying with the spraying drying instrument to mother liquor, spray condition: 160 ℃ of inlet temperatures, 80 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein Ti content is 2.30%, Mg content is 6.12%, THF content is 31.7%.In the ingredient of solid catalyst that obtains, add mineral oil, be made into the mineral oil solution that contains solids 30%, press THF according to the content of THF: AlEt
2Cl: Al (C
6H
13)
3=1: 0.45: 0.2 mol ratio adds AlEt
2The Cl reaction adds Al (C after 20 minutes again
6H
13)
3
2. the slurry polymerization of ethene
The 2L reactor is heated to about 80 ℃, vacuumizes 1h,, blow row with hydrogen then with the drying nitrogen displacement.In polymeric kettle, add the 1L hexane, the triethyl aluminum and the above-mentioned catalyzer 50mg that add 1mmol simultaneously, be warming up to 75 ℃ subsequently, add hydrogen 0.18MPa, the hydrogenation back that finishes adds ethene and makes the still internal pressure reach 1.03MPa, be warming up to 85 ℃ after, react after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
3. the gas phase copolymerization of ethene and butylene
Be aggregated on the φ 150 fluidized-bed ethene gas-phase polymerization devices and carry out, catalyst levels is 0.2g, AlEt
3: 5mmol, 600g polyethylene powder are as dispersion agent, and polymerizing condition is: temperature of reaction: 88 ℃; Reaction pressure: 2.0MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.18; 1-butylene/ethene=0.38.Polymerization 2 hours, polymerization result sees Table 2.
Embodiment 5
1. Preparation of Catalyst
To process N
2Fully add 3.0g TiCl in the metathetical 250mL there-necked flask
4, 6.9 the gram MgCl
2With the 170mL tetrahydrofuran (THF), to stir down and be warming up to 65 ℃, isothermal reaction 2 hours is 1: 1.5 a ratio adding thiocyanate groups propyl-triethoxysilicane in Ti and alkoxyl group mol ratio, isothermal reaction 2 hours is cooled to 30 ℃.
To a process N
2Add 10.4 gram silica gel (CabotCorporationTS-610 in the metathetical 250mL there-necked flask, particle diameter is 0.02～0.1 μ m) after, mother liquor after the cooling is added, keep 30 ℃ of temperature, stirred 2 hours, the mother liquor after stirring is carried out spraying drying with the spraying drying instrument to mother liquor, spray condition: 160 ℃ of inlet temperatures, 80 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein Ti content is 2.31%, Mg content is 6.10%, THF content is 30.19%.In the ingredient of solid catalyst that obtains, add mineral oil, be made into the mineral oil solution that contains solids 30%, press THF according to the content of THF: AlEt
2Cl: Al (C
6H
13)
3=1: 0.45: 0.2 mol ratio adds AlEt
2The Cl reaction adds Al (C after 20 minutes again
6H
13)
3
2. the slurry polymerization of ethene
The 2L reactor is heated to about 80 ℃, vacuumizes 1h,, blow row with hydrogen then with the drying nitrogen displacement.In polymeric kettle, add the 1L hexane, the triethyl aluminum and the above-mentioned catalyzer 50mg that add 1mmol simultaneously, be warming up to 75 ℃ subsequently, add hydrogen 0.18MPa, the hydrogenation back that finishes adds ethene and makes the still internal pressure reach 1.03MPa, be warming up to 85 ℃ after, react after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
3. the gas phase copolymerization of ethene and butylene
Be aggregated on the φ 150 fluidized-bed ethene gas-phase polymerization devices and carry out, catalyst levels is 0.2g, AlEt
3: 5mmol, 600g polyethylene powder are as dispersion agent, and polymerizing condition is: temperature of reaction: 88 ℃; Reaction pressure: 2.0MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.18; 1-butylene/ethene=0.38.Polymerization 2 hours, polymerization result sees Table 2.
Comparative Examples 1
1. Preparation of Catalyst
To process N
2Fully add 3.0g TiCl in the metathetical 250mL there-necked flask
4, 6.9 the gram MgCl
2With the 170mL tetrahydrofuran (THF), be warming up to 65 ℃ under stirring, isothermal reaction 2 hours is cooled to 30 ℃.
To a process N
2Add 10.4 gram silica gel (CabotCorporationTS-610 in the metathetical 250mL there-necked flask, particle diameter is 0.02～0.1 μ m) after, mother liquor after the cooling is added, keep 30 ℃ of temperature, stirred 2 hours, the mother liquor after stirring is carried out spraying drying with the spraying drying instrument to mother liquor, spray condition: 160 ℃ of inlet temperatures, 80 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein Ti content is 2.44%, Mg content is 6.22%, THF content is 31.3%.In the ingredient of solid catalyst that obtains, add mineral oil, be made into the mineral oil solution that contains solids 30%, press THF according to the content of THF: AlEt
2Cl: Al (C
6H
13)
3=1: 0.45: 0.2 mol ratio adds AlEt
2The Cl reaction adds Al (C after 20 minutes again
6H
13)
3
2. the slurry polymerization of ethene
The 2L reactor is heated to about 80 ℃, vacuumizes 1h,, blow row with hydrogen then with the drying nitrogen displacement.In polymeric kettle, add the 1L hexane, the triethyl aluminum and the above-mentioned catalyzer 50mg that add 1mmol simultaneously, be warming up to 75 ℃ subsequently, add hydrogen 0.18MPa, the hydrogenation back that finishes adds ethene and makes the still internal pressure reach 1.03MPa, be warming up to 85 ℃ after, react after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
3. the gas phase copolymerization of ethene and butylene
Be aggregated on the φ 150 fluidized-bed ethene gas-phase polymerization devices and carry out, catalyst levels is 0.2g, AlEt
3: 5mmol, 600g polyethylene powder are as dispersion agent, and polymerizing condition is: temperature of reaction: 88 ℃; Reaction pressure: 2.0MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.18; 1-butylene/ethene=0.38.Polymerization 2 hours, polymerization result sees Table 2.
Comparative Examples 2
1. Preparation of Catalyst
To process N
2Fully add 3.0g TiCl in the metathetical 250mL there-necked flask
4, 6.9 the gram MgCl
2With the 170mL tetrahydrofuran (THF), to stir down and be warming up to 65 ℃, isothermal reaction 2 hours is 1: 0.3 ratio adding Si (OEt) in Ti and alkoxyl group mol ratio
4, isothermal reaction 2 hours is cooled to 30 ℃.。
To a process N
2Add 10.4 gram silica gel (CabotCorporationTS-610 in the metathetical 250mL there-necked flask, particle diameter is 0.02～0.1 μ m) after, mother liquor after the cooling is added, keep 30 ℃ of temperature, stirred 2 hours, the mother liquor after stirring is carried out spraying drying with the spraying drying instrument to mother liquor, spray condition: 160 ℃ of inlet temperatures, 80 ℃ of temperature outs obtain ingredient of solid catalyst, and wherein Ti content is 2.27%, Mg content is 6.23%, THF content is 32.4%.In the ingredient of solid catalyst that obtains, add mineral oil, be made into the mineral oil solution that contains solids 30%, press THF according to the content of THF: AlEt
2Cl: Al (C
6H
13)
3=1: 0.45: 0.2 mol ratio adds AlEt
2The Cl reaction adds Al (C after 20 minutes again
6H
13)
3
2. the slurry polymerization of ethene
The 2L reactor is heated to about 80 ℃, vacuumizes 1h,, blow row with hydrogen then with the drying nitrogen displacement.In polymeric kettle, add the 1L hexane, the triethyl aluminum and the above-mentioned catalyzer 50mg that add 1mmol simultaneously, be warming up to 75 ℃ subsequently, add hydrogen 0.18MPa, the hydrogenation back that finishes adds ethene and makes the still internal pressure reach 1.03MPa, be warming up to 85 ℃ after, react after 2 hours, cooling discharge, slurry polymerization the results are shown in Table 1.
3. the gas phase copolymerization of ethene and butylene
Be aggregated on the φ 150 fluidized-bed ethene gas-phase polymerization devices and carry out, catalyst levels is 0.2g, AlEt
3: 5mmol, 600g polyethylene powder are as dispersion agent, and polymerizing condition is: temperature of reaction: 88 ℃; Reaction pressure: 2.0MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.18; 1-butylene/ethene=0.38.Polymerization 2 hours, polymerization result sees Table 2.
Claims (8)
1. ethylene rolymerization catalyst, it is characterized in that: it is made up of titaniferous active ingredient and activator component; The titaniferous active ingredient is that load has at least a magnesium dihalide, at least a halogenated titanium, the component of at least a electron donor compound and a kind of properties-correcting agent on silica supports; The electron donor compound is selected from alcohol or ether, and properties-correcting agent is the thiocyanate groups propyl-triethoxysilicane;
Activator component is an organo-aluminium compound, and its general formula is AlR '
nX
3-n, R ' is that hydrogen or carbonatoms are 1～20 alkyl in the formula, and X is a halogen, and n is the number of 1＜n≤3; The mol ratio of titaniferous active ingredient and activator component is 1～200.
2. ethylene rolymerization catalyst preparation method according to claim 1 is characterized in that:
(1) preparation of parent: in the electron donor compound, magnesium dihalide compound, halogenated titanium, thiocyanate groups propyl-triethoxysilicane are carried out the prepared in reaction parent; The mol ratio of properties-correcting agent/Ti is 0.1～1.0; The add-on of electron donor is that every mole of titanium is 5 moles～300 moles; The mol ratio of magnesium dihalide/Ti is 10～1.0;
(2) preparation of complex carrier: with the parent and the particle diameter of step (1) gained is that 0.01～1 μ m silica supports particle blending obtains suspension; Silica supports particle blending weight is 10～60% of suspension;
(3) spray shaping: the suspension that step (2) is obtained carries out spraying drying and obtains solid titaniferous active ingredient;
(4) prereduction: the solid titaniferous active ingredient, the activator component that in varsol step (3) are obtained are reacted, and obtain catalyzer; The mol ratio of aluminium and titanium is 10～500.
3. ethylene rolymerization catalyst preparation method according to claim 2 is characterized in that:
Described halogenated titanium is selected from TiCl
3Or TiCl
4
4. ethylene rolymerization catalyst preparation method according to claim 2 is characterized in that: described electron donor compound is selected from C
1～C
4Alcohol, C
2～C
6Aliphatic ether, C
3～C
4Cyclic ethers in one or more mixture.
5. ethylene rolymerization catalyst preparation method according to claim 2 is characterized in that: wherein the particle diameter of nanometer grade silica particle is 0.01～0.1 μ m.
6. ethylene rolymerization catalyst preparation method according to claim 2 is characterized in that: wherein said electron donor is a tetrahydrofuran (THF).
7. ethylene rolymerization catalyst preparation method according to claim 2 is characterized in that: described magnesium dihalide is a magnesium dichloride.
8. the application of an ethylene rolymerization catalyst according to claim 1 is characterized in that: the catalyzer that is used for ethene gas fluidised bed polymerisation frozen state or super frozen state polymerization; Temperature of reaction: 85～90 ℃; Reaction pressure: 2.0MPa; Ethylene partial pressure: 0.66MPa; Hydrogen/ethene=0.17～0.22; 1-butylene/ethene=0.38～0.42.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010193394A CN102260360B (en) | 2010-05-27 | 2010-05-27 | Catalyst for ethylene polymerization, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010193394A CN102260360B (en) | 2010-05-27 | 2010-05-27 | Catalyst for ethylene polymerization, preparation and application thereof |
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| CN102260360B CN102260360B (en) | 2012-10-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759718A (en) * | 2016-08-22 | 2018-03-06 | 辽宁鼎际得石化股份有限公司 | It is a kind of to be used for ethylene homo or the catalyst of copolymerization and preparation method thereof |
| CN112279950A (en) * | 2019-07-25 | 2021-01-29 | 中国石油天然气股份有限公司 | Catalyst for ethylene gas phase polymerization or copolymerization process, catalyst component and preparation method |
| CN113563496A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization or copolymerization and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235110A (en) * | 2008-01-14 | 2008-08-06 | 中国石油天然气股份有限公司大庆化工研究中心 | Ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101235110A (en) * | 2008-01-14 | 2008-08-06 | 中国石油天然气股份有限公司大庆化工研究中心 | Ethene gas-phase polymerization or copolymerization catalyst composition and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759718A (en) * | 2016-08-22 | 2018-03-06 | 辽宁鼎际得石化股份有限公司 | It is a kind of to be used for ethylene homo or the catalyst of copolymerization and preparation method thereof |
| CN112279950A (en) * | 2019-07-25 | 2021-01-29 | 中国石油天然气股份有限公司 | Catalyst for ethylene gas phase polymerization or copolymerization process, catalyst component and preparation method |
| CN112279950B (en) * | 2019-07-25 | 2022-12-02 | 中国石油天然气股份有限公司 | Catalyst for ethylene gas phase polymerization process, catalyst component and preparation method |
| CN113563496A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization or copolymerization and preparation method and application thereof |
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