CN1098867C - Slurry process total density polyvinyl high-efficiency catalyst - Google Patents
Slurry process total density polyvinyl high-efficiency catalyst Download PDFInfo
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Abstract
The present invention relates to a high efficiency solid catalyst for producing theoretical density polyethylene by slurry polymerization. Commercial magnesium powder is used as initial raw material to prepare nascent state magnesium halide, and then the magnesium halide reacts with organic alcohol and alkylaluminium in sequence to obtain solid suspension. The obtained solid suspension reacts with transition metal halide to obtain the main component of the catalyst in the presence of electron donors and alkylaluminium, and the main component of the catalyst and an organic metal compound as a catalyst promoter together form the high efficiency solid catalyst. The catalyst has the advantages of simple preparing operation, high polymerization activity, sensitive hydrogen regulation, strong copolymerization capability, stable polymerization reaction, favorable particle shape of a polymerization product, etc.
Description
The present invention relates to a kind of low pressure slurry polymerization that is applicable to and produce the high-performance solid catalyzer of full density polythene and the method for preparing this catalyzer.
After the seventies, polyethylene high-efficiency catalyst was succeeded in developing, great change had taken place in world's polyethylene industry.Over 20 years, obtained significant progress especially as polyethylene catalysts research of tap, and formed three big systems: chromium is that effective catalyst, Ziegler-Natta type effective catalyst and metallocene are effective catalyst.Wherein Mg-Ti is that effective catalyst occupies critical role with its good performance in the polyethylene catalysts field.Also by being total to polishing, suspension pickling process etc. has developed into present advanced person's chemical reaction method to its preparation method.The Mg-Ti that the mentioned catalyzer of the present invention belongs to just with the chemical reaction method preparation is an effective catalyst, and is applied to slurry polymerization production full density polythene.About above-mentioned various catalyzer, existing many patents are delivered, but each is variant between the different patents of different company, and its relative merits are also respectively arranged.
For example, in the Chinese patent of Japanese publication (CN1085569A), be that Magnesium Chloride Anhydrous and organic alcohols compound such as 2-Ethylhexyl Alcohol are reacted, the final homogeneous solution that forms, add organo-aluminium compound again to separate out precipitation, with a large amount of titanium tetrachloride dippings, finally make catalyzer then.This catalyst activity is higher, and operation steps is simple, and the products obtained therefrom particle diameter is even, the bulk density height.But in the Preparation of catalysts process, the magnesium compound solubilizing reaction needs 120 ℃～140 ℃ high temperature, and uses in a large number as senior alkane such as decane as solvent, not only cost height but also have the solvent recuperation problem.In the process that is written into transition metal component titanium, use the titanium tetrachloride that is far longer than the amount of being written into to flood, cause the equipment corrosion problem.
In the Chinese patent (CN1092093A), be that magnesium chloride is dissolved in the mixture of organophosphate and alcohols, form homogeneous solution, join in the titanium compound in the presence of precipitation additive organic carboxyl acid acid anhydride, titaniferous catalyst component is separated out in reaction.The catalyst activity height that this kind method makes, the polymerization product excellent property, the solvent usage quantity is few, has improved throughput.But, the temperature requirement-5 of magnesium compound solution and titanium tetrachloride solution hybrid reaction ℃ in catalyst preparation process～10 ℃, the operating procedure condition is relatively harsher, is not easy to industrial production and application.
The purpose of this invention is to provide a kind of novel slurry polymerization and produce the effective catalyst of full density polythene, it is starting raw material that this catalyzer adopts commercially available magnesium powder, make the nascent state magnesium halide, again it is successively reacted with organic alcohols and aluminum alkyls, the solids suspension that obtains is reacted with transition metal halide in the presence of electron donor and aluminum alkyls and finally make the body of catalyst component; This body of catalyst component constitutes polyethylene high-efficiency catalyst of the present invention with the promotor organometallic compound.This Preparation of Catalyst is easy and simple to handle, and has polymerization activity height, hydrogen and transfer characteristics such as responsive, that copolymerized ability is strong, stable polymerization reaction, polymer beads form are good.
In order to realize this purpose, polyethylene high-efficiency catalyst of the present invention adopts following method preparation.The catalyzer that the present invention is mentioned partly is made up of body of catalyst component and promotor two.The body of catalyst component mainly divides following step to be prepared:
(1) preparation of nascent state magnesium halide:
Under nitrogen protection, commercially available magnesium powder reacts with halogenated alkane (RX) in varsol, and the adding mode of haloalkane can be once to add or slowly dropping, adds the back and continues reaction 0.5～10 hour, preferably 1～8 hour.The entire reaction temperature is controlled at 10 ℃～100 ℃, preferably 20 ℃～80 ℃, finally forms the nascent state magnesium halide; This reaction also can be carried out in the presence of electron donor.The nascent state magnesium halide that generates, even particle size, and be near-spherical.The structural formula of this nascent state magnesium halide is (RMgX)
p(MgX
2)
q(ED)
t, wherein, p: q: t=(0～1.0): 1.0: (0～2.0) (mol ratio), preferably (0.05～0.8): 1.0: (0～1.0); R is the alkyl group that contains 3～12 carbon atoms; X is a halogen, preferably chlorine; Electron donor ED contains an oxygen, sulphur, nitrogen, silicon, phosphorus atom organic compound at least, can be to contain the aliphatics of 3～8 carbon atoms or aromatic ether, ester, amine, alcohol etc., as diethyl ether, tetrahydrofuran (THF), ethyl acetate, ethyl benzoate, tributyl phosphate, isopropylcarbinol, N, dinethylformamide etc.Varsol is aliphatic hydrocarbon, alicyclic hydrocarbon and arene etc., as Skellysolve A, iso-pentane, pentamethylene, hexanaphthene, benzene etc., preferably contains the aliphatic hydrocarbon of 5～10 carbon atoms.Halogenated alkane (RX) can be chloro-propane, n-propylcarbinyl chloride, chloro-iso-butane, chloro iso-pentane etc.
(2) processing again of nascent state magnesium halide:
Under nitrogen protection, the nascent state magnesium halide in the time of preferably 20 ℃～80 ℃, adds organic alcohols compound (R ' OH), stirring reaction under 10 ℃～100 ℃.The adding mode of organic alcohols can be once to add or slowly dropping, adds the back and continues reaction 0.5～8 hour, and the best is 1～6 hour.Obtain the heavy-gravity brown black suspension liquid after the reaction.Organic alcohols (R ' OH) be the fatty alcohol that contains 3～12 carbon atoms, as methyl alcohol, ethanol, 2-methyl amyl alcohol, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc.The amount of the organic alcohols that adds is R ' OH/Mg=0.2～6 (mol ratios), and the best is 0.5～6.0 (mol ratio).
Then, add aluminum alkyls in above-mentioned suspension, keep temperature of reaction at 20 ℃～100 ℃, preferably 30 ℃～90 ℃, the adding mode can be once to add or slowly dropping, adds the back and continues stirring reaction 0.5～8 hour, and the best is 1～6 hour.Along with aluminum alkyls ground adds and carries out corresponsively, thickness swollen suspension is thinning gradually, finally forms the splendid lead solids suspension of particle form.The complex compound carrier that gained lead solid is made up of magnesium, aluminium, halogen and alkoxyl group etc.Used aluminum alkyls can be triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-octylaluminium, three (2-ethyl) hexyl aluminium, aluminium diethyl monochloride, dichloro one aluminium triethyl, chlorination di-isopropyl aluminium, sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium etc. in the reaction.Usage quantity is controlled to be R ' OH/Al=0.2～7 (mol ratio), is preferably 0.5～5 (mol ratio).
(3) preparation of titanium-containing catalyst main body component:
This is a vital step in the whole Preparation of Catalyst.Under nitrogen protection, with the above-mentioned complex compound carrier suspension that makes, in the presence of electron donor and aluminum alkyls, add and contain titanium halide, containing the titanium halide mode that adds can be once to add or slowly dropping, adds the back and continues reaction 1～10 hour, is preferably 2～8 hours; Control reaction temperature is preferably 30 ℃～60 ℃ at 20 ℃～90 ℃; Electron donor ED, haloalkyl aluminium, contain and follow following mol ratio: ED: Al: Ti: Mg=(0.5～3.0) between the titanium halide: (0.5～5.0): 1: (2.0～10.0).Stirring reaction finally makes brownish black body of catalyst component suspension.The mole ratio of components of the polyethylene high-efficiency catalyst main body component that makes by the present invention is as follows: Ti
3+: Ti
Always: Mg: Cl=(0.7～1.0): 1.0: (2.0～10): (4.0～25).
Electron donor (ED) is the organic compound that contains an oxygen, sulphur, nitrogen, silicon, phosphorus atom at least, can be to contain the aliphatics of 3～8 carbon atoms or aromatic ether, ester, amine, alcohol etc., as diethyl ether, tetrahydrofuran (THF), ethyl acetate, ethyl benzoate, tributyl phosphate, isopropylcarbinol, N, dinethylformamide etc.Above electron donor can be used alone or as a mixture.
Aluminum alkyls is triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-octylaluminium, three (2-ethyl) hexyl aluminium, aluminium diethyl monochloride, dichloro one aluminium triethyl, chlorination di-isopropyl aluminium, sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium etc.
Contain titanium halide and be general molecular formula Ti (OR ")
mCl
4-mCompound, R in the formula " be the alkyl group that contains 3～4 carbon atoms, m=0～4.As titanium tetrachloride, tetrabutyl titanate, methoxyl group titanous chloride, butoxy titanous chloride etc.
The body of catalyst component that makes by the present invention becomes polyethylene high-efficiency catalyst of the present invention with the promotor mutual group.Promotor can be selected one or more organometallic compounds for use, as organic zinc, organic-magnesium, organo-aluminium compound.Can be triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium, three hexyl aluminium, zinc ethyl etc.; Be preferably organo-aluminium compound.The proportioning of promotor and body of catalyst component is Al/Ti=20～400 (mol ratios), preferably 30～300 (mol ratios).
Effective catalyst of the present invention can be directly used in the slurry polymerization explained hereafter full density polythene of ethene.Polymerization temperature remains on 50 ℃～100 ℃, is the best with 60 ℃～90 ℃; Stagnation pressure is 0.7～1.5MPa during polymerization.If new LDPE (film grade) in producing can add comonomer and carry out polyreaction with telomerized polymer density.Common employed comonomer is the aliphatics alpha-olefin that contains 3～8 carbon atoms.Suitable alpha-olefin has propylene, butene-1, amylene-1, hexene-1,4-methyl-amylene-1, heptene-1 and octene-1, is preferably butene-1 and hexene-1.The polymerization product density that makes is 0.910～0.960 gram per centimeter
3
Be the melting index of telomerized polymer, can use chain-transfer agent usually.The most frequently used chain-transfer agent is a hydrogen, also can adopt zinc ethyl etc.The amounts of hydrogen of using can be adjustable between 0.10～0.95 (volume ratio) of total gas volume, thereby can make melting index MI
2.16Polyethylene product between 0-300 gram/10 minutes.Polyethylene high-efficiency catalyst polymerization activity height of the present invention, polymerization is 4 hours under 80 ℃, 0.8MPa pressure, can reach 30～90 myriagrams polyethylene/gram titanium, and have higher bulk density (＞0.30 gram per centimeter
3).
Polyethylene high-efficiency catalyst of the present invention has the following advantages:
1, catalyst preparation process is simple and easy to do, and operational condition requires not harsh, is applicable to industrial production and application.
2, the nascent state magnesium halide that adopts in the Preparation of Catalyst, after the processing through organic alcohols and aluminum alkyls, obtain having more polycrystalline phase defective, and uniform particles is the solid complex carrier of near-spherical, when making the catalyzer of final gained be used for polyreaction, the polymer beads that makes is even, does not almost have less than 200 purpose fine powders to produce, and bulk density is higher.
3, owing to adopted above-mentioned solid complex carrier, in the presence of electron donor, only need to reach higher year titanium efficient with containing titanium halide on a small quantity, not only solved in the actual production and flooded the equipment corrosion problem that causes, and alleviated the difficulty of aftertreatment work owing to a large amount of employings contain titanium halide.This catalyzer has very high catalytic activity.
4, use this catalyzer to carry out polymerization, reacting balance, polymerization temperature is easy to control, does not have sticking still phenomenon.
5, catalyst performance is good, and hydrogen is transferred responsive, and copolymerized ability is strong.
Further specify the present invention with embodiment below, but and do not mean that restriction the present invention.
Embodiment 1:
(a) preparation of body of catalyst component:
Fully clean 500 milliliters of round bottom glass reactors that have agitator, condenser, dropping funnel of process drying treatment with nitrogen; and under nitrogen protection, add 300 ml n-hexanes and 6.5 gram magnesium powder, under 20 ℃, 70 milliliters of n-propylcarbinyl chlorides are under agitation slowly added in the reactor.After the adding, be warming up to 40 ℃ of following isothermal reactions 8 hours, obtain nascent state magnesium chloride solids suspension, structural formula is MgCl
2(MgBuCl)
0.45Conditioned reaction liquid temp to 60 ℃ under agitation slowly adds 45 milliliters of dehydrated alcohols, adds the back and continues reaction 2 hours.Reaction remains under this temperature after finishing, and one side stirs one side and slowly adds 37 milliliters of triethyl aluminums, adds the back and continues reaction 4 hours, obtains the lead solids suspension.In reaction solution, add 6 milliliters of tetrahydrofuran (THF)s and 4.1 milliliters of aluminium diethyl monochlorides, under agitation 6.3 gram titanium tetrachlorides are slowly added reaction solution down at 60 ℃, after the adding, isothermal reaction 4 hours.Be cooled to room temperature, clean three times with normal hexane.Altogether contain 250 milliliters of the slurry of body of catalyst component.Analyze the gained slurry, contain Ti
3+Be 108 Bos mole/milliliter, Ti
AlwaysBe 126 mmole/milliliters, Mg is 895 mmole/milliliters, and Cl is 1966 mmole/milliliters.Therefore, Ti
3+: Ti
Always: Mg: Cl=0.86: 1.0: 7.1: 15.6 (mol ratio), carry titanium rate (promptly analyzing total titanium amount of gained and the mol ratio that adds the titanium amount) and then reach 95%.
(b) polyreaction:
Fully clean 1 liter of stainless steel cauldron with high-purity nitrogen.Afterwards, in reactor, add the industrial hexane of 600 milliliters of dryings, the body of catalyst component that high purity hexene-1, the 3.0 mmole promotor triethyl aluminum of 15 milliliters of dryings and (a) set by step of 0.0097 mmole (in titanium) make.Feed hydrogen to gauge pressure 0.2MPa, feed ethene subsequently, the control stagnation pressure is 0.8MPa.Be warming up to 80 ℃, polyreaction 4 hours.Obtain the white polyethylene solid, weighing is 187 grams.Can get as calculated: catalytic efficiency is 50.4 myriagrams polyethylene/gram titanium, melting index MI
2.16Be 4.4 grams/10 minutes, density is 0.940 gram per centimeter
3, bulk density is 0.326 gram per centimeter
3
Embodiment 2:
(a) preparation of body of catalyst component:
Fully clean 500 milliliters of round bottom glass reactors that have agitator, condenser, dropping funnel of process drying treatment with nitrogen; and under nitrogen protection, add 300 ml n-hexanes; 6.5 gram magnesium powder and 7 milliliters of tetrahydrofuran (THF)s under agitation slowly add 56 milliliters of n-propylcarbinyl chlorides in the reactor under 20 ℃.After the adding, be warming up to 40 ℃ of following isothermal reactions 8 hours, obtain nascent state magnesium chloride solids suspension, structural formula is MgCl
2(MgBuCl)
0.50(THF)
0.48Conditioned reaction liquid temp to 60 ℃ under agitation slowly adds 45 milliliters of dehydrated alcohols, adds the back and continues reaction 2 hours.Reaction remains under this temperature after finishing, and one side stirs one side and slowly adds 37 milliliters of triethyl aluminums, adds the back and continues reaction 4 hours.Obtain the lead solids suspension.In reaction solution, add 6 milliliters of tetrahydrofuran (THF)s and 4.1 milliliters of aluminium diethyl monochlorides, under agitation 6.3 gram titanium tetrachlorides are slowly added reaction solution down at 60 ℃, after the adding, isothermal reaction 4 hours.Be cooled to room temperature, clean three times with normal hexane.Altogether contain 250 milliliters of the slurry of body of catalyst component.Analyze the gained slurry, the Ti that contains
3+Be 114 mmole/milliliters, Ti
AlwaysBe 126 mmole/milliliters, Mg is 903 mmole/milliliters, and Cl is 1931 mmole/milliliters.Therefore, Ti
3+: Ti
Always: Mg: Cl=0.90: 1.0: 7.2: 15.3 (mol ratio), carry titanium rate (promptly analyzing total titanium amount of gained and the mol ratio that adds the titanium amount) and then reach 95%.
(b) polyreaction:
Fully clean 1 liter of stainless steel cauldron with high-purity nitrogen.Afterwards, add 600 milliliters of the industrial hexane of drying in reactor, promotor triethyl aluminum 4.4 mmoles and 0.01455 mmole (in titanium) be (a) body of catalyst component of making set by step.Feed hydrogen to gauge pressure 0.2MPa, feed ethene subsequently, the control stagnation pressure is 0.8MPa, is warming up to 80 ℃, polyreaction 4 hours.Obtain the white polyethylene solid, weighing is 183 grams.Can get as calculated: catalytic efficiency is 31.2 myriagrams polyethylene/gram titanium, melting index MI
2.16Be 3.2 grams/10 minutes, density is 0.960 gram per centimeter
3, bulk density is 0.341 gram per centimeter
3
Embodiment 3:
The preparation of body of catalyst component and polymeric reaction condition are undertaken by the same procedure of embodiment 1, remove the nascent state magnesium halide again in the treating processes consumption of organic alcohols change 90 milliliters into from 45 milliliters.In the slurry of gained body of catalyst component, Ti
3+: Ti
Always: Mg: Cl=0.95: 1.0: 7.5: 16.0 (mol ratio).Polymerization results sees Table one.
Embodiment 4:
The preparation of body of catalyst component and polymeric reaction condition are undertaken by the same procedure of embodiment 1, remove the nascent state magnesium halide again in the treating processes consumption of triethyl aluminum change 30 milliliters into from 37 milliliters, add the afterreaction time to extend to 6 hours by 4 hours.In the slurry of gained body of catalyst component, Ti
3+: Ti
Always: Mg: Cl=0.80: 1.0: 7.3: 15.9 (mol ratio).Polymerization results sees Table one.
Embodiment 5:
The preparation of body of catalyst component and polymeric reaction condition are undertaken by the same procedure of embodiment 1, remove to contain the consumption that titanium halide is written into titanium tetrachloride in the process and change 5 grams into from 6.3 grams, and temperature of reaction rises to 80 ℃ by 60 ℃.In the slurry of gained body of catalyst component, Ti
3+: Ti
Always: Mg: Cl=0.91: 1.0: 9.3: 19.4 (mol ratio).Polymerization results sees Table one.
Embodiment 6:
The preparation of body of catalyst component and polymeric reaction condition are undertaken by the same procedure of embodiment 1, remove and to contain titanium halide and be written into that the kind of electron donor changes tributyl phosphate into by tetrahydrofuran (THF) in the process, consumption is 18 milliliters, in the slurry of gained body of catalyst component, and Ti
3+: Ti
Always: Mg: Cl=0.88: 1.0: 7.3: 15.7 (mol ratio).Polymerization results sees Table one.
Table one
| Embodiment | Hydrogen dosage MPa | Ethene add-on MPa | Catalytic efficiency myriagram polyethylene/gram titanium | The density gram per centimeter 3 | MI 2.16Restrain/10 minutes | The bulk density gram per centimeter 3 |
| 3 | 0.20 | 0.60 | 43.2 | 0.943 | 1.8 | 0.336 |
| 4 | 0.20 | 0.60 | 37.5 | 0.942 | 3.2 | 0.321 |
| 5 | 0.20 | 0.60 | 55.7 | 0.947 | 2.7 | 0.347 |
| 6 | 0.20 | 0.60 | 28.8 | 0.937 | 3.8 | 0.351 |
Embodiment 7:
The body of catalyst component that employing is made by embodiment 1, other polymeric reaction conditions keep identical with method with embodiment 1, change the hydrogen add-on and control corresponding ethene add-on to experimentize, and get result such as table two:
Table two
| Test number | Hydrogen dosage MPa | Ethene dosage MPa | Catalytic efficiency myriagram polyethylene/gram titanium | The density gram per centimeter 3 | MI 2.16Restrain/10 minutes | The bulk density gram per centimeter 3 |
| 7-1 | 0 | 0.80 | 87.1 | 0.941 | 0 | 0.346 |
| 7-2 | 0.10 | 0.70 | 65.9 | 0.938 | 0.40 | 0.346 |
| 7-3 | 0.38 | 0.42 | 29.2 | 0.945 | 15.72 | 0.315 |
| 7-4 | 0.48 | 0.32 | 19.6 | 0.943 | 24.30 | 0.318 |
| 7-5 | 0.60 | 0.20 | 8.9 | 0.944 | 241.20 | 0.310 |
Embodiment 8:
The preparation of body of catalyst component and polymeric reaction condition are undertaken by the same procedure of embodiment 2, remove and to contain titanium halide and be written into that the kind of electron donor changes ethyl benzoate into by tetrahydrofuran (THF) in the process, consumption is 12 milliliters, in the slurry of gained body of catalyst component, and Ti
3+Ti
Always: Mg: Cl=0.9: 1.0: 7.9: 16.2 (mol ratio).Polymerization results sees Table three.
Embodiment 9:
The preparation of body of catalyst component and polymeric reaction condition are undertaken by the same procedure of embodiment 2, remove and to contain the kind that titanium halide is written into electron donor in the process and change tributyl phosphate and N into by tetrahydrofuran (THF), dinethylformamide mixes use, consumption is respectively 9 milliliters and 3 milliliters, in the slurry of gained body of catalyst component, Ti
3+Ti
Always: Mg: Cl=0.92: 1.0: 7.6: 17.4 (mol ratio).Polymerization results sees Table three.
Table three
| Embodiment | Hydrogen dosage MPa | Ethene dosage MPa | Catalytic efficiency myriagram polyethylene/gram titanium | The density gram per centimeter 3 | MI 2.16Restrain/10 minutes | The bulk density gram per centimeter 3 |
| 8 | 0.2 | 0.6 | 27.1 | 0.960 | 1.4 | 0.327 |
| 9 | 0.2 | 0.6 | 36.5 | 0.961 | 0.9 | 0.330 |
Embodiment 10:
The body of catalyst component that employing is made by embodiment 2, other polymeric reaction conditions keep identical with method with embodiment 1, change the hydrogen add-on and control corresponding ethene add-on to experimentize, and get result such as table four:
Table four
| Test number | Hydrogen add-on MPa | Ethene add-on MPa | Catalytic efficiency myriagram polyethylene/gram titanium | The density gram per centimeter 3 | MI 2.16Restrain/10 minutes | The bulk density gram per centimeter 3 |
| 10-1 | 0 | 0.80 | 77.4 | 0.941 | 0 | 0.346 |
| 10-2 | 0.10 | 0.70 | 61.2 | 0.943 | 1.20 | 0.350 |
| 10-3 | 0.20 | 0.60 | 45.9 | 0.944 | 3.40 | 0.345 |
| 10-4 | 0.40 | 0.40 | 26.2 | 0.940 | 10.53 | 0.325 |
| 10-5 | 0.52 | 0.28 | 14.6 | 0.946 | 33.70 | 0.318 |
| 10-6 | 0.60 | 0.20 | 5.8 | 0.945 | 322.0 | 0.320 |
Claims (12)
1, a kind of high-performance solid catalyzer that is used for slurry polymerization production full density polythene, it is made up of body of catalyst component and promotor two portions, it is characterized in that:
(1) under nitrogen protection, commercially available magnesium powder and halogenated alkane RX are in varsol, and in the time of 10 ℃～100 ℃, stirring reaction 0.5～10 hour makes the nascent state magnesium halide, and this is reflected under the electron donor ED existence and carries out; The structural formula of nascent state magnesium halide is (RMgX)
p(MgX
2)
q(ED)
t, p: q: t=(0～1.0) wherein: 1.0: (0～2.0) (mol ratio), R is the alkyl group that contains 3～12 carbon atoms, and X is a halogen, and ED is an electron donor; Described varsol is aliphatic hydrocarbon, alicyclic hydrocarbon and arene; Described halogenated alkane RX is chloro-propane, n-propylcarbinyl chloride, chloro-iso-butane, chloro iso-pentane,
(2) the nascent state magnesium halide that will make by above-mentioned steps (1), under nitrogen protection, controlled temperature is at 10 ℃～100 ℃, add organic alcohols R ' OH, stirring reaction 0.5～8 hour, obtain the heavy-gravity brown black suspension liquid, added the aluminum alkyls stirring reaction 0.5～8 hour down at 20 ℃～100 ℃ then, the final lead complex compound solid carrier suspension that contains magnesium, aluminium, alkoxyl group and halogen that forms; Described organic alcohols R ' OH is the fatty alcohol that contains 3～12 carbon atoms, and add-on is R ' OH/Mg=0.2～6 (mol ratios); Described aluminum alkyls is triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-octylaluminium, three (2-ethyl) hexyl aluminium, aluminium diethyl monochloride, dichloro one aluminium triethyl, chlorination di-isopropyl aluminium, sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium, add-on is R ' OH/Al=0.2～7 (mol ratios)
(3) under nitrogen protection; the complex compound carrier that will make by above-mentioned steps (2); in the presence of electron donor ED and aluminum alkyls; add and contain titanium halide; 20 ℃～90 ℃ following stirring reactions 1～10 hour; finally make the body of catalyst component, the proportion of composing of principal element is in the body of catalyst component: Ti
3+: Ti
Always: Mg: Cl=(0.7～1.0): 1.0: (2.0～10): (4.0～25); Described aluminum alkyls is triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-octylaluminium, three (2-ethyl) hexyl aluminium, aluminium diethyl monochloride, dichloro one aluminium triethyl, chlorination di-isopropyl aluminium, sesquialter ethylaluminium chloride, sesquialter chlorinated butyl aluminium; The described titanium halide that contains is Ti (OR ")
mCl
4-m, R " and be the alkyl group that contains 3～4 carbon atoms, m=0～4; Electron donor ED, aluminum alkyls, contain and follow following mol ratio: ED: Al: Ti: Mg=(0.5～3.0) between the titanium halide: (0.5～5.0): 1: (2.0～10.0),
(4) body of catalyst component and promotor are formed polyethylene high-efficiency catalyst, are directly used in the ethene slurry polymerization, and the proportioning of promotor and body of catalyst component is Al/Ti=20～400 (mol ratios); Described promotor is an organo-aluminium compound.
2, polyethylene high-efficiency catalyst according to claim 1 is characterized in that: described electron donor ED is the organic compound that contains an oxygen, sulphur, nitrogen, silicon, phosphorus atom at least.
3, polyethylene high-efficiency catalyst according to claim 1 is characterized in that: described electron donor ED contains the aliphatics of 3～8 carbon atoms or aromatic ether, ester, amine, alcohol.
4, polyethylene high-efficiency catalyst according to claim 1 is characterized in that: the structural formula of described nascent state magnesium halide is (RMgX)
p(MgX
2)
q(ED)
t, p: q: t=(0.05～0.8) wherein: 1.0: (0～1.0) (mol ratio), X is a chlorine, ED is an electron donor.
5, polyethylene high-efficiency catalyst according to claim 1 is characterized in that: described varsol is Skellysolve A, iso-pentane, pentamethylene, hexanaphthene, benzene.
6, polyethylene high-efficiency catalyst according to claim 1 is characterized in that: described electron donor ED is diethyl ether, tetrahydrofuran (THF), ethyl acetate, ethyl benzoate, tributyl phosphate, isopropylcarbinol, N, dinethylformamide.
7, polyethylene high-efficiency catalyst according to claim 1, the consumption that it is characterized in that organic alcohols R ' OH are R ' OH/Mg=0.5～6 (mol ratios).
8, polyethylene high-efficiency catalyst according to claim 1 is characterized in that: described organic alcohol is methyl alcohol, ethanol, 2-methyl amyl alcohol, 2-ethyl butanol, 2-Ethylhexyl Alcohol.
9, polyethylene high-efficiency catalyst according to claim 1, the consumption that it is characterized in that aluminum alkyls are organic alcohols R ' OH/Al=0.5～5 (mol ratios).
10, polyethylene high-efficiency catalyst according to claim 1 is characterized in that: promotor is an organo-aluminium compound, can be one or more the mixture in triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, the three hexyl aluminium.
11, polyethylene high-efficiency catalyst according to claim 1 is characterized in that it is Al/Ti=30～300 (mol ratios) that promotor and body of catalyst component are formed the proportioning of effective catalyst.
12, polyethylene high-efficiency catalyst according to claim 1, it is characterized in that containing titanium halide is titanium tetrachloride, tetrabutyl titanate, methoxyl group titanous chloride, butoxy titanous chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110609A CN1098867C (en) | 1998-01-14 | 1998-01-14 | Slurry process total density polyvinyl high-efficiency catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110609A CN1098867C (en) | 1998-01-14 | 1998-01-14 | Slurry process total density polyvinyl high-efficiency catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1223268A CN1223268A (en) | 1999-07-21 |
| CN1098867C true CN1098867C (en) | 2003-01-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110609A Expired - Lifetime CN1098867C (en) | 1998-01-14 | 1998-01-14 | Slurry process total density polyvinyl high-efficiency catalyst |
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| Country | Link |
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| CN (1) | CN1098867C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7354981B2 (en) | 2003-12-03 | 2008-04-08 | China Petroleum & Chemical Corporation | Polyethylene catalyst and a process for preparing the same |
| CN110016096A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | Catalyst carrier for olefinic polymerization and preparation method thereof and ingredient of solid catalyst and catalyst system and olefine polymerizing process |
| CN110016095A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | Ingredient of solid catalyst for olefinic polymerization and preparation method thereof and catalyst and its application |
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| US6780808B2 (en) * | 2002-07-15 | 2004-08-24 | Univation Technologies, Llc | Enhanced solubility of magnesium halides and catalysts and polymerization process using same |
| AU2003280919A1 (en) | 2002-11-04 | 2004-06-23 | China Petroleum And Chemical Corporation | A catalyst for polymerization of ethylene, preparation thereof and use of the same |
| MY136156A (en) * | 2003-04-29 | 2008-08-29 | China Petroleum & Chemical | A solid main catalyst component for ethylene polymerization, a process for preparing the same and a catalyst containing the same. |
| CN100417670C (en) * | 2006-03-07 | 2008-09-10 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, its production and use |
| CN101161690B (en) * | 2006-10-10 | 2010-06-02 | 上海化工研究院 | Catalyst for preparing super-high molecular weight polyethylene and preparation method thereof |
| CN102432726A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Polyethylene resin for preparing chlorinated polyethylene and preparation method thereof |
| CN102432713B (en) * | 2010-09-29 | 2013-07-03 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method and application thereof |
| EP2742000A1 (en) * | 2011-08-08 | 2014-06-18 | Basf Se | Method for producing ultrapure magnesium hydroxide and magnesium oxide |
| CN103571026A (en) * | 2012-07-20 | 2014-02-12 | 中国石油化工股份有限公司 | Aging-resistant polyethylene resin specially used for rotational moulding, and preparation method thereof |
| CN104292595B (en) * | 2013-07-18 | 2016-08-24 | 中国石油化工股份有限公司 | High rigid linear low density polyethylene (LDPE) casting resin |
| SG11201807182YA (en) * | 2016-03-01 | 2018-09-27 | Univation Tech Llc | Method for improving ziegler-natta catalyst activity |
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| EP0055605A2 (en) * | 1980-12-24 | 1982-07-07 | Union Carbide Corporation | Improved catalyst composition for polymerizing ethylene, preparative method and polymerization process |
| CN1085569A (en) * | 1992-10-05 | 1994-04-20 | 三井石油化学工业株式会社 | The titanium catalyst component that is used for ethylene polymerization, the ethylene polymerization catalyzer, and it is used in method in the ethylene polymerization |
| CN1092081A (en) * | 1993-01-19 | 1994-09-14 | 英国石油化学品有限公司 | Catalyst composition and preparation of polyolefins method |
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| EP0055605A2 (en) * | 1980-12-24 | 1982-07-07 | Union Carbide Corporation | Improved catalyst composition for polymerizing ethylene, preparative method and polymerization process |
| CN1085569A (en) * | 1992-10-05 | 1994-04-20 | 三井石油化学工业株式会社 | The titanium catalyst component that is used for ethylene polymerization, the ethylene polymerization catalyzer, and it is used in method in the ethylene polymerization |
| CN1092081A (en) * | 1993-01-19 | 1994-09-14 | 英国石油化学品有限公司 | Catalyst composition and preparation of polyolefins method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7354981B2 (en) | 2003-12-03 | 2008-04-08 | China Petroleum & Chemical Corporation | Polyethylene catalyst and a process for preparing the same |
| CN110016096A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | Catalyst carrier for olefinic polymerization and preparation method thereof and ingredient of solid catalyst and catalyst system and olefine polymerizing process |
| CN110016095A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | Ingredient of solid catalyst for olefinic polymerization and preparation method thereof and catalyst and its application |
| CN110016096B (en) * | 2018-01-10 | 2021-05-11 | 中国石油化工股份有限公司 | Catalyst carrier for olefin polymerization and preparation method thereof, solid catalyst component, catalyst system and olefin polymerization method |
| CN110016095B (en) * | 2018-01-10 | 2021-07-02 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, preparation method thereof, catalyst and application thereof |
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