Catalytic composition for copolymerization of ethylene with butene-1

专利摘要:
A catalyst formed from selected organo aluminum compounds and precursor compositions formed from a magnesium compound, titanium compound and electron donor compound and impregnated in very fine particle sized porous silica; a process for preparing such catalyst; and a process for preparing film grade ethylene copolymers with such catalyst.
公开号:SU1295996A3
申请号:SU813338297
申请日:1981-06-28
公开日:1987-03-07
发明作者:Хи Ли Киу；Стэнли Киелосзик Гари
申请人:Юнион Карбид Корпорейшн (Фирма)；
IPC主号:

专利说明:

The invention relates to a catalytic composition for the copolymerization of ethylene with butene-1 to produce an ethylene copolymer used in the form of a film having high mechanical and optical properties.
The purpose of the invention is to improve the properties of the copolymer due to the content of silica, which has a certain particle size distribution, due to a certain ratio of the composition of the precursor substance and silica and the molar ratio of aluminum to titanium.
Preparation of the catalytic composition.
In a 12 liter flask, to prepare the precursor, equipped with a mechanical stirrer, 41.8 g (0.439 mol) of anhydrous magnesium chloride and 2.5 l of tetrahydrofuran (THF) are placed. To this mixture is added dropwise 27.7 g (0.146 mol) of TiCl over 1/2 hour. For complete
four
dissolving the material, the mixture is heated to within 1/2 h.
The composition of the precursor can be isolated from solution by crystallization or precipitation. On. At this stage, it can be analyzed for the content of magnesium and titanium, since some of the compounds of magnesium and / or titanium can be lost in the process of extracting the composition of the preceding substance. The amount of the electron donor compound is determined by chromatographic method.
500 g of silica carrier, dewatered at 600-800 ° C and treated with 1-8% by weight of triethylaminoia, are added to this solution and stirred for 1/4 hour. The mixture is dried in a stream of nitrogen at 60- approximately 3 -5 h, in order to obtain a dry, free-flowing powder, which has an average particle size equal to that of silica particles. The composition of the precursor obtained has the composition: TiMg. (THF)
Preparation of impregnated precursor from a previously prepared composition of the preceding substance.
B flask with a capacity of 12l equipped with a mechanical stirrer. Dissolve
five
0
five

0
five
five
130 g of the previous composition in 2.5 liters of dry THF. The solution can be heated to 60 ° C in order to facilitate dissolution. 500 g of silica carrier, dehydrated at 600-800 ° C and treated with 1-8% by weight of triethylaluminum, is added to the solution and the mixture is stirred for 1/4 hour. The mixture is dried in a stream of nitrogen at about 3%. -5 h in order to obtain a dry, free flowing powder, which has a particle size equal to that of silica particles.
Activation is carried out according to the following procedure.
Into the mixing tank - toT the required amounts of the impregnated composition of the preceding substance and the activator compound in combination with a sufficient amount of a diluent - anhydrous aliphatic hydrocarbon, such as isopentane, in order to obtain a suspension system.
The combination of the activator and the precursor is used in such amounts as to obtain a partially activated composition of the precursor, in which the Al / Ti ratio is 5.
Then the contents of the suspension system are thoroughly mixed at room temperature and atmospheric pressure for approximately 1/4 - 1/2 hours. The resulting suspension is dried in a stream of dry, inert gas, such as nitrogen or argon, at atmospheric pressure and a temperature of approximately 65 ± 10 ° C, in order to remove the hydrocarbon diluent. The process continues for about 3-5 hours. The resulting catalyst exists in the form of a partially activated composition of a precursor that impregnates the pores of the silica. This material is a free flowing granular material that has the size and shape of silica particles. It is not pyrophoretic if the content of alkylaluminium does not exceed 10% by weight, and is stored in an atmosphere of dry inert gas, for example nitrogen or argon, until further use.
When an additional activator enters the polymerization reactor in order to complete the activation of the composition of the preceding substance, it is fed to the reactor as a dilute solution in a hydrocarbon solvent, such as isopentane. These diluted solutions contain approximately 2-30 wt.% Activator compound.
The activator compound is added to the polymerization reactor in order to maintain the AI / Ti ratio in the reactor at a level from about LO; up to 400: 1, preferably 15: 60: 1.
The copolymerization of ethylene with butane-1 is carried out as follows.
Examples 1-6
In each of Examples 1-6, the catalyst used is formed in order to obtain an impregnated silica catalyst containing at 1 wt.h. the composition of the preceding substance 3.8 wt.h. silica. Used in example I silica. is the raw silica MSID, grade 952.
Silica in Example 2 is a large fraction of Devison MSID Silica, Grade 952, which, after fractionation, is retained on 60, 80 and 120 mesh sieves (according to U.S. standards).
In Example 3, a Davison MSID silica fraction, grade 952, which passes through a 230 mesh screen, is used. Examples 4-6 use virgin silica, Crosfield Company Ltd., grade EP-10 from Akzo Hemi Ltd, Ketgeen grade F-7, and Polypore, U.S.A. Chemikl Co., respectively. Used in each of the examples, silica carriers, as well as the average particle size and particle size distribution for such carriers are given in table. 1 along with the content of titanium and THF in impregnated carriers.
In each example, the silica impregnated with the composition of the preceding substance is partially activated with tri-n-hexyl aluminum, as described in the methodology, in order to obtain a catalytic composition with a polar Al / Ti ratio of 5 ± 1. The activation of the composition of the preceding substance is completed in the polymerization reactor with a solution containing 5% by weight of triethylaluminum in isopentane in order to obtain a fully activated catalyst in a reactor with a molar ratio A / Ti 25 40.
Each polymerization reaction is carried out for 48 hours at 85 ° C under a pressure of 300 psi (gas) (21 psi), with a gas velocity of about 3-6 times more than the fluidization rate (Gmf) and catalyst bulk productivity of approximately 77-104 kg / h / m in a fluidized bed reactor system.
In tab. 2 shows the molar ratio of 1 butene-1 (ethylene and H), ethyl, and the volume productivity values of the catalyst used in each npiiMepe (in pounds per hour per cubic foot of the bed volume), as well as various properties of the polymers obtained in these examples , and various properties of film samples obtained from such polymers,
Example 7-9. In these examples, the procedures of examples 1-6 are repeated at a pressure of 28 atm, using silica particles of various sizes as a carrier for the preceding compound.
In 7, use Davison silica MSID, grade 952.
In Example 8, the Davison MSID silica mid-grade, grade 952, is used that passes through a 120 mesh standard sieve and is held on 170 and 230 mesh standard sieves.
In Example 9, the Devinson MSID silica fine fraction, grade 952, is passed through a standard 230 mesh sieve.
In tab. Figure 3 shows silica carriers used in each of the examples, as well as the average particle size and particle size distribution for such carriers, as well as the content of titanium and THF in the impregnated carriers.
In tab. Figure 4 shows the molar ratios of butene-1 (ethylene and hydrogen), ethylene, as well as the bulk capacity of the catalyst bed used in each example, in addition, different properties of the polymers obtained in these examples, and different properties of film samples obtained from such polymers.
Example YuiP.In both examples, the procedure of examples 1-6 is repeated in a large propane reactor at a pressure of 19 atm. Silica with a different particle size is used as a carrier of the precursor.
Example 10 uses raw Davison MSID grade 952.
In Example 1, a Davison MSID silica fraction, grade 952, was used that was isolated by airborne classification. This isolated fraction passes through a standard 230 mesh sieve.
In tab. 5 summarizes the silica carriers used in each of the examples, as well as the average particle size and particle size distribution for such carriers along with the titanium and THF content of the impregnated carriers.
In tab. 6 shows the molar ratios of butene-1 (ethylene and hydrogen), ethylene, as well as the values of the volumetric productivity of the catalyst used in each example, in addition, various properties of the polymers obtained by examples, and various of their silica carrier. Sieve analysis, wt.% when the size of the sieve mesh. (mkm)
60 (297)
80 (177) 120 (525) 170 (88) 230 (63) 325 (44)
screening 2 microns
Average particle size, Impregnated carrier, mmol / g
THF, wt.%
samples of films prepared from these polymers.
In tab. 1-6 according to examples 1-11, various grades of silica are given: Q - unsolved grade; fc- round fraction MSID, grade 952; c-fine fraction; d - unprocessed, grade EP-10; e-undirected Kedzhen F-I is an undisclosed polypore.

权利要求:
Claims (1)
[1]
The Catalytic Composition for the Co-Polymerization of Ethylene with Butene-1, containing the composition of the precursor substance comprising titanium, magnesium, chlorine and tetrahydrofuran and having the composition: (ED), (Where ED is tetrahydrofuran, porous silica, and tri-n -hexylalkmium, characterized in that, in order to improve the properties of the copolymer, the catalytic composition contains silica, having a particle size distribution from 2 to 44 microns and a cut-off particle size of 22 or 35 microns, with the following content of components: 1 wt. composition n edshestvuyuschego substance 3.8 May h. of silica, and the molar ratio Al / Ti, equal to 5.
Table 1
table 2
Silica carrier Sieve and analysis, wt.%, With the size of the sieve mesh. (mkm)
catalyst volume capacity, kg / h / m fluidized bed volume
Polymer properties
melt index flow rate
101
2.40
13 Table 5
1295996
Options
Example 10 I 11
Silica carrier
Sieve size, mesh (mkm)
0.215 0.217 10.09.6
Table 6
Example 10 I 11
I
Working conditions
molar ratio
C / Cj And / C
volume catalyst productivity, kg / h / m volume
VNIIPI Order 629/63
Circulation 511 Subscription Pro-polygr. pr-tie, Uzhgorod, st. Project, 4
14 Continued table. 6
fluid bed 96
Polymer properties melt index 1.7
melt flow rate 26.5 density, g / cm
Ti, ppm ash,%
Granulometric properties
bulk density, kg / m
0,920
3
0.031
408
96
2.2
26.0 0.920 2 0.020
424
-J. sieve analysis, wt.%, LINE; sieve size, mesh (mkm)
50
average particle size, microns
Film properties
55
film type evaluation O
+40

类似技术:

---

公开号 | 公开日 | 专利标题

---

SU1295996A3|1987-03-07|Catalytic composition for copolymerization of ethylene with butene-1

---

CA1272348A|1990-07-31|Process for polymerising ethylene using a chromiumoxide catalyst

---

CA1265646A|1990-02-06|PROCESS FOR THE START UP OF POLYMERISATION ORCOPOLYMERISATION IN THE GAS PHASE OF .alpha.-OLEFINS INTHE PRESENCE OF A ZIEGLER-NATTA CATALYST SYSTEM

---

USRE35346E|1996-10-01|Process for the polymerisation of ethylene or the copolymerisation of ethylene and alpha-olefins in a fluidised bed in the presence of a chromium based catalyst

---

EP0584626A2|1994-03-02|Process for producing ethylene polymers having reduced hexane extractable content

---

AU622062B2|1992-03-26|Preparation of very low molecular weight polyethylene in a fluidized bed

---

US4767823A|1988-08-30|Halogenated ethylene polymers with improved resistance to agglomeration

---

US4542198A|1985-09-17|Polymerization catalysts

---

JPH0791330B2|1995-10-04|Method for producing solid catalyst component for olefin polymerization

---

US4228260A|1980-10-14|Supported chromium-oxide polymerization catalyst having a porous silica support used in the polymerization of olefins

---

US4097409A|1978-06-27|Preparation of titanium containing catalyst on magnesium support material

---

AU619138B2|1992-01-16|Preparation of very low molecular weight polyethylene in a fluidized bed

---

KR100520010B1|2005-12-21|Catalyst Systems of the Ziegler-Natta Type

---

US4251388A|1981-02-17|Titanium trichloride catalytic component and method for homo- or co-polymerization of α-olefin

---

CA1312068C|1992-12-29|Ethylene polymerization catalyst

---

US7141636B1|2006-11-28|Method for producing a polymer

---

CA1276384C|1990-11-13|Preparation of homopolymers and copolymers of ethylene by means of a ziegler catalyst system

---

AU621777B2|1992-03-19|High activity vanadium-based catalyst

---

EP0661301A1|1995-07-05|Process for producing ethylene polymers having reduced hexane extractable content

---

KR20000023620A|2000-04-25|High activity catalysts for the preparation of polyethylene with an intermediate molecular weight distribution

---

US4415713A|1983-11-15|High activity supported catalytic components and method for homo- or co-polymerization of α-olefin

---

EP0324835B1|1992-12-02|Propylene polymerization catalyst and method

---

JPH06316606A|1994-11-15|Homopolymerization and copolymerization of 1-olefin

---

US4284525A|1981-08-18|Titanium trichloride catalytic component and method for homo- of co-polymerization of α-olefin

---

JP3215691B2|2001-10-09|Method for producing olefin polymer

同族专利:

---

公开号 | 公开日

---

US4521573A|1985-06-04|

---

DD210459A5|1984-06-13|

---

MX158563A|1989-02-15|

---

KR830006340A|1983-09-24|

---

ES503478A0|1982-11-01|

---

CS228511B2|1984-05-14|

---

EG15793A|1987-03-30|

---

MA19185A1|1981-12-31|

---

GR75713B|1984-08-02|

---

NO160714C|1989-05-24|

---

KR840001786B1|1984-10-20|

---

JPS5744611A|1982-03-13|

---

IN154420B|1984-10-27|

---

IL63155A|1984-10-31|

---

AT18769T|1986-04-15|

---

DE3174173D1|1986-04-30|

---

DK288081A|1981-12-31|

---

AU540181B2|1984-11-08|

---

EP0043220A1|1982-01-06|

---

NO812155L|1982-01-04|

---

ES8303457A1|1983-03-01|

---

AU7218381A|1982-01-07|

---

ES8300118A1|1982-11-01|

---

IL63155D0|1981-09-13|

---

PH19877A|1986-08-13|

---

DD160520A5|1983-08-17|

---

KR840001785B1|1984-10-20|

---

NZ197460A|1984-03-16|

---

FI812029L|1981-12-31|

---

JPS6050367B2|1985-11-08|

---

IN156046B|1985-05-04|

---

ZA814068B|1982-07-28|

---

BR8104037A|1982-03-16|

---

CS232723B2|1985-02-14|

---

IE52782B1|1988-03-02|

---

IE811456L|1981-12-30|

---

CA1171844A|1984-07-31|

---

CS325182A2|1984-02-13|

---

US4405495A|1983-09-20|

---

EP0043220B1|1986-03-26|

---

NO160714B|1989-02-13|

---

FI70417B|1986-03-27|

---

TR21555A|1984-09-26|

---

ES513361A0|1983-03-01|

---

FI70417C|1986-09-19|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

RU2725609C1|2017-05-18|2020-07-03|Базелл Полиолефин Италия С.Р.Л.|Catalyst components for olefin polymerization|US3094568A|1959-12-01|1963-06-18|Gulf Research Development Co|Process for alkylating aromatics in the presence of a heavy metal halide, an organic halide and an organo aluminum halide|

---

GB1111758A|1965-09-03|1968-05-01|Du Pont|Production of cyclododecatrienes|

---

FR1550186A|1967-08-31|1968-12-20|

---

IE35231B1|1970-03-26|1975-12-24|Solvay|Process for the preparation of a ziegler-natta type catalyst|

---

NL7113778A|1970-10-13|1972-04-17|

---

US4098979A|1970-12-29|1978-07-04|Sumitomo Chemical Company, Limited|Method for preparing easily processable polyolefin granule|

---

DE2343361A1|1972-08-30|1974-03-14|Stamicarbon|POLYALKYLENE|

---

US3953414A|1972-09-13|1976-04-27|Montecatini Edison S.P.A.,|Catalysts for the polymerization of olefins to spherically shaped polymers|

---

US3925338A|1973-03-16|1975-12-09|Monsanto Co|Control of polymer particle size in olefin polymerization|

---

NL7502153A|1974-02-27|1975-08-29|Monsanto Co|PROCEDURE FOR PARTICLE SIZE CONTROL IN THE POLYMERIZATION OF ALKINES.|

---

DE2553179A1|1975-11-27|1977-06-08|Hoechst Ag|METHOD OF MANUFACTURING A CATALYST|

---

GB1562200A|1975-12-04|1980-03-05|British Petroleum Co|Process for the production of a supported ziegler catalystcomponent|

---

NL7702323A|1977-03-04|1978-09-06|Stamicarbon|CATALYST FOR THE PREPARATION OF POLYALKENES.|

---

GB2010870B|1977-12-21|1982-05-26|Bp Chem Int Ltd|Polymerisaton catalyst|

---

US4302566A|1978-03-31|1981-11-24|Union Carbide Corporation|Preparation of ethylene copolymers in fluid bed reactor|

---

US4302565A|1978-03-31|1981-11-24|Union Carbide Corporation|Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization|JPH0324485B2|1982-04-30|1991-04-03|Japan Synthetic Rubber Co Ltd|

---

EP0099774B2|1982-06-24|1995-03-22|BP Chimie Société Anonyme|Process for the polymerization and copolymerization of alpha-olefins in a fluidized bed|

---

JPH0629287B2|1984-03-14|1994-04-20|三菱油化株式会社|Olefin polymerization catalyst component|

---

IT1178466B|1984-03-20|1987-09-09|Montedison Spa|CATALYSTS FOR THE HOMO AND COPOLYMERISATION OF ETHYLENE AND POLYMERS OBTAINED|

---

JPS61110981U|1984-12-21|1986-07-14|

---

US4760121A|1986-01-03|1988-07-26|Mobil Oil Corporation|Preparation of alpha-olefin polymers of relatively narrow molecular weight distrbution|

---

DE3634915A1|1986-10-14|1988-04-28|Basf Ag|METHOD FOR PRODUCING HOMO- AND COPOLYMERISATES OF ETHYLENE BY MEANS OF A ZIEGLER CATALYST SYSTEM|

---

JPS63122710A|1986-11-12|1988-05-26|Nippon Petrochem Co Ltd|Production of polyolefin|

---

US5617707A|1987-04-17|1997-04-08|Mobil Oil Corporation|Stretch wrap film inherently exhibiting a significant cling property|

---

US5273809A|1987-04-17|1993-12-28|Mobil Oil Corporation|Multilayer stretch wrap film inherently exhibiting a significant cling property|

---

DE3815486A1|1988-05-06|1989-11-16|Basf Ag|CATALYST FOR THE POLYMERIZATION OF ETHYLENE, METHOD FOR THE PRODUCTION THEREOF AND USE OF THE OBTAINED ETHYLENE POLYMERISATE FOR THE PRODUCTION OF FILMS WITH LOW BLOCK PROPERTIES|

---

WO1989010942A1|1988-05-13|1989-11-16|Mitsui Petrochemical Industries, Ltd.|Titanium catalyst component, process for its preparation, catalyst for producing ethylenic polymer containing said titanium catalyst component, and process for producing ethylenic polymer|

---

US5192731A|1988-05-13|1993-03-09|Mitsui Petrochemical Industries, Ltd.|Titanium catalyst components, process for preparing same, catalysts containing same for preparing ethylene polymers and process for preparing said ethylene polymers|

---

US4876229A|1988-05-31|1989-10-24|Mobil Oil Corporation|Catalyst composition for polymerizing olefins of narrow molecular weight distribution and polymerization therewith|

---

US4983694A|1988-05-31|1991-01-08|Mobil Oil Corporation|Process for polymerizing olefins to form polymers of narrow molecular weight distribution|

---

EP0380241B1|1989-01-21|1996-03-20|Mitsubishi Chemical Corporation|Process for preparing ethylene copolymers|

---

US6025448A|1989-08-31|2000-02-15|The Dow Chemical Company|Gas phase polymerization of olefins|

---

US6538080B1|1990-07-03|2003-03-25|Bp Chemicals Limited|Gas phase polymerization of olefins|

---

IT1240613B|1990-03-26|1993-12-17|Enichem Anic Spa|SUPPORTED CATALYST FOR THE POLYMERIZATION AND COPOLYMERIZATION OF OLEFINICALLY UNSATURATED COMPOUNDS, AND PROCEDURE OFPOLYMERIZATION USING THE SAME|

---

FI86989C|1990-12-19|1992-11-10|Neste Oy|Process for producing a polymerization catalyst component for olefins, a polymerization catalyst component prepared by the process, and its use|

---

CS25992A3|1991-01-30|1992-08-12|Union Carbide Chem Plastic|Process for reducing hexane obtained from ethylene co-polymers|

---

US5763547A|1992-10-02|1998-06-09|The Dow Chemical Company|Supported catalyst complexes for olefin in polymerization|

---

FI92405C|1992-12-22|1994-11-10|Borealis Holding As|New olefin polymerization catalyst, process for its preparation and its use for polymerization of olefins|

---

US5264506A|1992-12-30|1993-11-23|Union Carbide Chemicals & Plastics Technology Corporation|Process for producing sticky polymers|

---

KR100291452B1|1993-12-08|2001-09-17|리챠드 지. 워터맨|Elongated Kling Films and Manufacturing Method Thereof|

---

US5461123A|1994-07-14|1995-10-24|Union Carbide Chemicals & Plastics Technology Corporation|Gas phase fluidized bed polyolefin polymerization process using sound waves|

---

US5428118A|1994-07-15|1995-06-27|Union Carbide Chemicals & Plastics Technology Corporation|Gas phase fluidized bed polyolefin polymerization process using gas or gas-solids tangential flow|

---

US5661097A|1994-08-12|1997-08-26|The Dow Chemical Company|Supported olefin polymerization catalyst|

---

US5589539A|1994-11-23|1996-12-31|Union Carbide Chemicals & Plastics Technology Corporation|Process for preparing an in situ polyethylene blend|

---

CA2163465A1|1994-11-23|1996-05-24|Arkalgud Venkatapathia Ramamurthy|In situ polyethylene blend|

---

US5521264A|1995-03-03|1996-05-28|Advanced Extraction Technologies, Inc.|Gas phase olefin polymerization process with recovery of monomers from reactor vent gas by absorption|

---

US5681908A|1995-03-03|1997-10-28|Advanced Extraction Technologies, Inc.|Absorption process for rejection of reactor byproducts and recovery of monomers from waste gas streams in olefin polymerization processes|

---

KR970015606A|1995-09-01|1997-04-28|윤덕용|Method for preparing metallocene supported catalyst for polyolefin polymerization|

---

EP0771820A1|1995-11-03|1997-05-07|Union Carbide Chemicals & Plastics Technology Corporation|Supported ziegler-natta catalysts for polyolefin production|

---

US6187883B1|1996-08-23|2001-02-13|Sumitomo Chemical Company, Limited|Solid catalyst component for α-olefin polymerization, catalyst for α-olefin polymerization, and process for producing α-olefin polymer|

---

US6242545B1|1997-12-08|2001-06-05|Univation Technologies|Polymerization catalyst systems comprising substituted hafinocenes|

---

US8497330B2|1997-12-08|2013-07-30|Univation Technologies, Llc|Methods for polymerization using spray dried and slurried catalyst|

---

US6140264A|1998-05-12|2000-10-31|Nova Chemicals Ltd.|Split aluminum addition process for making catalyst|

---

JP2002265507A|2001-03-09|2002-09-18|Sumitomo Chem Co Ltd|Prevention of sheeting in fluidized bed vapor phase olefin polymerization reaction|

---

EP1611169B1|2003-03-21|2010-06-02|Dow Global Technologies Inc.|Morphology controlled olefin polymerization process|

---

US6953764B2|2003-05-02|2005-10-11|Dow Global Technologies Inc.|High activity olefin polymerization catalyst and process|

---

AU2004242899A1|2003-05-29|2004-12-09|Basell Poliolefine Italia S.R.L|Process for the preparation of a catalyst component and components therefrom obtained|

---

US7683140B2|2004-05-20|2010-03-23|Univation Technologies, Llc|Method for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring|

---

US7754830B2|2004-05-20|2010-07-13|Univation Technologies, Llc|Polymerization reaction monitoring with determination of induced condensing agent concentration for preventing discontinuity events|

---

US7071137B2|2004-08-25|2006-07-04|Novolen Technology Holdings, C.V.|Method of making a ziegler-natta catalyst|

---

US20060281879A1|2005-06-13|2006-12-14|Univation Technologies, Llc|Catalyst compositions comprising small silica support materials and methods of use in polymerization reactions|

---

US20060293470A1|2005-06-28|2006-12-28|Cao Phuong A|Polymerization process using spray-dried catalyst|

---

US20070049711A1|2005-09-01|2007-03-01|Chi-I Kuo|Catalyst compositions comprising support materials having an improved particle-size distribution|

---

EP1803747A1|2005-12-30|2007-07-04|Borealis Technology Oy|Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films|

---

WO2007130305A2|2006-05-05|2007-11-15|Dow Global Technologies Inc.|Hafnium complexes of carbazolyl substituted imidazole ligands|

---

ES2405556T3|2006-09-07|2013-05-31|Univation Technologies, Llc|Methods for online determination of the degree of stickiness of a resin using a model for depression of the melting initiation temperature|

---

US8273834B2|2006-09-07|2012-09-25|Univation Technologies, Llc|Methods for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring|

---

ES2526975T3|2010-04-05|2015-01-19|Dow Global Technologies Llc|Process for polymerizing olefin-based polymers containing high molecular weight fractions in condensed and super-condensed modes|

---

JP6621845B2|2015-05-08|2019-12-18|エクソンモービル ケミカル パテンツ インコーポレイテッド|Polymerization method|

---

JP6743463B2|2016-04-12|2020-08-19|住友化学株式会社|Method for producing polyolefin|

---

WO2018063765A1|2016-09-27|2018-04-05|Exxonmobil Chemical Patents Inc.|Polymerization process|

---

WO2018063764A1|2016-09-27|2018-04-05|Exxonmobil Chemical Patents Inc.|Polymerization process|

---

WO2018063767A1|2016-09-27|2018-04-05|Exxonmobil Chemical Patents Inc.|Polymerization process|

---

US11014998B2|2016-11-28|2021-05-25|Univation Technologies, Llc|Producing a polyethylene polymer|

---

WO2018118155A1|2016-12-20|2018-06-28|Exxonmobil Chemical Patents Inc.|Polymerization process|

---

US20200270375A1|2017-12-13|2020-08-27|Exxonmobil Chemical Patents Inc.|Deactivation Methods for Active Components from Gas Phase Polyolefin Polymerization Processes|

---

WO2019173030A1|2018-03-08|2019-09-12|Exxonmobil Chemical Patents Inc.|Methods of preparing and monitoring a seed bed for polymerization reactor startup|

---

EP3788081A1|2018-05-02|2021-03-10|ExxonMobil Chemical Patents Inc.|Methods for scale-up from a pilot plant to a larger production facility|

---

WO2019217173A1|2018-05-02|2019-11-14|Exxonmobil Chemical Patents Inc.|Methods for scale-up from a pilot plant to a larger production facility|

---

WO2021099123A1|2019-11-20|2021-05-27|Basell Poliolefine Italia S.R.L.|Process for the preparation of a catalyst component and components therefrom obtained|

---

US11124586B1|2020-11-09|2021-09-21|Chevron Phillips Chemical Company Lp|Particle size control of metallocene catalyst systems in loop slurry polymerization reactors|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

US06/163,959|US4405495A|1980-06-30|1980-06-30|Catalyst impregnated on fine silica, process for preparing, and use for ethylene polymerization|

---