JP2006512446A - A transition method between Ziegler-Natta polymerization catalysts and alumoxane-based single-site polymerization catalysts - Google Patents

Abstract

Method of transition between polymerization catalyst systems, preferably between catalyst systems that are incompatible with each other. In particular, this method relates to the transition between olefin polymerization reactions using Ziegler-Natta catalyst systems, metallocene catalyst systems and other MAO-based single site catalyst systems.

Description

  The present invention relates to a process for migration between polymerization catalyst systems, preferably between catalyst systems that are incompatible with each other. Specifically, the present invention relates to an olefin polymerization reaction utilizing a Ziegler-Natta catalyst system and a metallocene or other MAO-based single site catalyst {a) as a cocatalyst (or activator) or scavenger or both. An alumoxane; and (b) including any olefin polymerization catalyst system comprising: a metal compound characterized by having substantially one active site for coordination polymerization (single active site)} The present invention relates to a transition method between olefin polymerization reactions.

  In the production of olefin polymers in commercial reactors, another type of polymer that has different chemical and / or physical attributes can be produced from one type of catalyst system that produces a polymer having certain properties and characteristics. It is often necessary to move to a catalyst system. For example, transitions between similar Ziegler-Natta catalyst systems or compatible catalyst systems are generally facilitated. However, the process is generally complicated when the catalyst system is incompatible or of a different type. For example, in the case of a transition between two incompatible catalyst systems, such as a Ziegler-Natta catalyst system and a metallocene catalyst system, some of the components of the Ziegler-Natta catalyst system are poisonous to the metallocene catalyst system. I know it works. Thus, these components of the Ziegler-Natta catalyst system prevent the metallocene catalyst system from promoting polymerization.

In the past, to achieve an efficient transition between incompatible catalysts, the olefin polymerization process using the first catalyst has been stopped by various techniques well known in the art. The reactor was then emptied and reloaded, and the second catalyst system was introduced into the reactor. Such a catalyst exchange is time consuming and expensive due to the need to shut down the reactor for a long time during the transition.
US Pat. No. 6,369,174

  Migrate between incompatible catalysts without having to stop the polymerization reaction, empty the reactor, remove the original catalyst system from the reactor, and restart the polymerization reaction with another catalyst system It would be very advantageous if there was a way to do it. In addition, it reduces the amount of off-grade material produced during the transition process, shortens the transition time, increases the robustness and stability of the transition process, and opens the reactor to load the seed bed. Any migration method that can be avoided would be advantageous.

SUMMARY OF THE INVENTION The present invention relates to a method for transferring between at least two catalysts and / or catalyst systems in a polymerization process. The inventors have surprisingly found that certain materials, referred to herein as non-volatile adsorbents, are efficient between incompatible Ziegler-Natta catalyst systems and MAO-based single-site catalyst systems. It has been found that it acts as an effective kill agent or catalyst deactivator (deactivator) to achieve the transition. According to a preferred embodiment of the invention, the polymerization process is carried out by passing the monomer gas essentially continuously through the polymerization zone of a gas phase fluidized bed reactor containing a fluidized bed of polymer particles. According to this specific example, when the first catalyst and the second catalyst are incompatible, the first polymerization reaction performed in the presence of the first catalyst is performed in the presence of the second catalyst. The method of transition to the polymerization reaction of 2 is as follows:
(A) stop introducing the first catalyst into the reactor (this first catalyst includes a Ziegler-Natta catalyst);
(B) introducing and dispersing an effective amount of a non-volatile adsorbent into the reactor to deactivate the first catalyst and substantially stop the first polymerization reaction;
(C) A second catalyst comprising a MAO-based single site catalyst is introduced into the reactor and dispersed:
Including that.

  According to another preferred embodiment of the invention, the Ziegler-Natta catalyst comprises a titanium-triethylaluminum catalyst. According to another preferred embodiment of the present invention, the MAO-based single site catalyst comprises a metallocene catalyst.

Detailed Description of the Invention The present invention relates to a catalyst and / or transition method between catalyst systems for switching a reactor from production of one type of product to production of another type of product with minimal reactor downtime.

  In particular, the preferred method relates to the transition between a Ziegler-Natta catalyst / catalyst system and a metallocene catalyst / catalyst system. In this specification and the appended claims, the terms “catalyst” and “catalyst system” can be used interchangeably and have the same meaning.

  In the present invention, the term “MAO-based single-site catalyst” means (a) an alumoxane as a cocatalyst (or activator) or scavenger or both; and (b) an active site (site) for coordination polymerization. Means any olefin polymerization catalyst system comprising: a metal compound characterized by having one.

  Nonvolatile adsorbents are solid polymers or compounds that are nonvolatile liquids under conditions in the reactor. The non-volatile liquid under the conditions in the reactor does not necessarily have to be in the liquid state under non-reactor conditions, and in fact may be solid under non-reactor conditions. In the present invention, the term “nonvolatile” means that the adsorbent has a vapor pressure of 1 Torr or less at reactor conditions. The non-volatile adsorbent is preferably a solid polymer comprising a long chain copolymer of ethylene and a substituted alkene containing at least one functional group capable of efficiently deactivating the Ziegler-Natta catalyst. In the present invention, the term “long chain” refers to a linear, molecular chain, or chain containing 12 or more carbon or non-H (ie, other than H) atoms as side chains to the polymer backbone. A cyclic compound is meant. Even more preferably, the non-volatile adsorbent is a functional group capable of reacting with ethylene and aluminum alkyl (eg acrylate, vinyl ester, vinyl alcohol, olefinic anhydride, olefinic carboxylic acid ester, olefinic carboxylic acid). Long chain copolymers or terpolymers with one or more comonomers having acid, olefinic ether, olefinic amine, olefinic alcohol, olefinic amide, olefinic imine and olefinic thiol). Even more preferably, the non-volatile adsorbent is poly (ethylene-co-vinyl acetate), poly (ethylene-co-methyl acrylate), poly (ethylene-co-acrylic acid), poly (ethylene-co-methacrylic acid). ), Poly (ethylene-co-ethyl acrylate-co-maleic anhydride), poly (ethylene-co-butyl acrylate-co-maleic anhydride), poly (ethylene oxide) and poly (ethyleneimine) Of long chain polymers. Particularly preferably, the non-volatile adsorbent polymer is poly (ethylene-co-acrylic acid), poly (ethylene-co-ethyl acrylate-co-maleic anhydride), poly (ethylene-co-butyl acrylate-co-maleic anhydride). Acid) or poly (ethylene-co-vinyl acetate).

  The non-volatile adsorbent may also be selected from the group consisting of alkoxylated amines, alkoxylated amides, carboxylic acids, thiols and alcohols. Even more preferably, the non-volatile liquid under conditions in the reactor comprises long chain diethanolamine, and even more preferably the non-volatile liquid comprises N-octadecyl diethanolamine or N-hexadecyl diethanolamine.

  In the present invention, the non-volatile adsorbent is used in an amount effective to deactivate the first catalyst system. Effective amounts range from about 0.1 to about 10,000 mg per liter of reactor volume, preferably about 1 to about 7500 mg per liter of reactor volume, and even more preferably about 1 per liter of reactor volume. 10 to about 5000 mg.

  Nonvolatile adsorbents variably reduce catalyst activity and can also include complete deactivation.

  The non-volatile adsorbent preferably reduces the activity of the first catalyst system by at least 30% or more, more preferably by at least 70% or more, particularly by at least 90% or more. preferable.

  The method of the present invention is preferably used in gas phase, solution phase, slurry or bulk phase polymerization processes. Particularly preferably, the process of the invention is used for a gas phase polymerization process in a fluidized bed reactor.

  In a typical continuous gas fluidized bed polymerization process for producing a polymer from monomers, a gas stream containing the monomer is passed through a fluidized bed reactor under reactive conditions in the presence of a catalyst. The polymer product is removed from the fluid bed reactor. A circulating gas stream is also removed from the reactor, which is continuously circulated and usually cooled. The circulating gas stream is returned to the reactor along with sufficient additional monomer to replace the monomer consumed in the polymerization reaction. For a detailed description of the gas phase fluidized bed polymerization process, see U.S. Pat. Nos. 4,543,399 and 4,588,790, 5,028,670, 5,352,769, and 5,405,922. All of these disclosures are incorporated herein by reference.

  In order for a catalyst to produce a product with a given density and melt index, this generally depends on how well the catalyst incorporates the comonomer, so there is a given gas composition in the reactor. I have to let it.

  In general, this gas contains at least one α-olefin having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, such as ethylene, propylene, butene-1, pentene-1, 4 -Cyclic olefins such as methylpentene-1, hexene-1, octene-1, decene-1 alpha-olefins and styrene are included. Other monomers can include polar vinyl, diene, norbornene, acetylene, and aldehyde monomers. In a preferred embodiment of the invention, the gas composition contains ethylene and at least one α-olefin having 3 to 15 carbon atoms.

  In general, the gas composition also contains a predetermined amount of hydrogen to control the melt index of the polymer produced. In a typical environment, the gas also contains a predetermined amount of dew point raising component, and the remaining portion of the gas composition consists of a non-condensable inert gas such as nitrogen.

  Depending on the second catalyst introduced into the reactor, the gas concentrations of the various components of the gas composition can be varied, for example, the comonomer and hydrogen gas concentrations can be increased or decreased.

  Generally, there is only a slight difference in their performance for hydrogen and comonomers when migrating between compatible catalysts, but when migrating between incompatible catalysts. Is not so easy. For example, Ziegler-Natta and metallocene catalysts have very different responses to molecular weight regulators such as hydrogen and comonomers, which make these catalysts incompatible. If trace amounts of active Ziegler-Natta catalyst are present under metallocene catalytic reactor conditions, very high molecular weight products are produced. Furthermore, particularly in the continuous transfer process, small particles (referred to as microparticles) of less than about 100 μm may be produced at high levels (amounts) due to the interaction between the two incompatible catalysts. These particulates can cause operational problems in the reactor such as contamination and sheeting.

  It is reasonable to predict that the interaction or contact of the two catalysts will occur during the transition from the first catalyst to the second catalyst, especially in a continuous process. For compatible catalysts, the transition is usually performed by stopping the supply of the first catalyst and starting the supply of the second catalyst. In general, it takes a long time until the first catalyst is completely consumed. Therefore, for a relatively long time, the resin produced is a mixture of one produced from the first catalyst and one produced from the second catalyst.

  Compatible catalysts are those that have similar monomer and comonomer insertion and termination rates and / or that do not adversely interact with each other.

In this specification and the appended claims, the term “incompatible catalyst” refers to a catalyst that meets one or more of the following:
(1) A catalyst in which the activity of at least one catalyst is reduced by 50% or more when they are present together.
(2) A catalyst in which the molecular weight of the polymer produced by one catalyst is at least twice the molecular weight of the polymer produced by the other catalyst under the same reaction conditions.
(3) Catalysts that differ in comonomer uptake or reactivity ratio by about 30% or more under the same conditions.

  As noted above, the preferred method of the present invention is applicable to the transition between Ziegler-Natta catalysts and metallocene catalysts. According to this method, in steady-state operation using a Ziegler-Natta catalyst, the introduction of the Ziegler-Natta catalyst into the reactor is first stopped, and then the Ziegler-Natta catalyst is deactivated to carry out the first polymerization reaction. The first polymerization reaction is stopped by introducing and dispersing an effective amount of non-volatile adsorbent into the reactor to substantially stop it. In the present invention, the term “nonvolatile” means that the adsorbent has a vapor pressure of 1 Torr or less at reactor conditions. After the first polymerization reaction has stopped, the process continues to introduce and disperse the MAO-based single site catalyst into the reactor to initiate and achieve the second polymerization reaction at steady state conditions. In the present invention, a MAO-based single site catalyst means (a) an alumoxane as a cocatalyst (or activator) or scavenger or both; and (b) having substantially one active site for coordination polymerization. Is meant to include any olefin polymerization catalyst system comprising: The present invention envisions various non-limiting examples of the methods recited in the claims. Preferably, the polymerization process is a continuous phase polymerization process carried out in a fluidized bed reactor.

  Preferably, the Ziegler-Natta catalyst comprises a titanium-triethylaluminum catalyst and the MAO based single site catalyst comprises a metallocene catalyst.

  The non-volatile adsorbent is preferably a solid polymer or a non-volatile liquid under conditions in the reactor.

  Even more preferably, the non-volatile adsorbent is a solid polymer comprising a long chain copolymer of ethylene and a substituted alkene containing at least one functional group capable of efficiently deactivating the first catalyst. In the present invention, the term “long chain” means a linear or molecular chain containing 12 or more carbon or non-hydrogen atoms (atoms other than hydrogen atoms) as a side chain with respect to the polymer main chain. Or a cyclic compound is meant. Even more preferably, the non-volatile adsorbent is a functional group capable of reacting with ethylene and aluminum alkyl (eg acrylate, vinyl ester, vinyl alcohol, olefinic anhydride, olefinic carboxylic acid ester, olefinic carboxylic acid). Long chain copolymers or terpolymers with one or more comonomers having acid, olefinic ether, olefinic amine, olefinic alcohol, olefinic amide, olefinic imine and olefinic thiol). Even more preferably, the non-volatile adsorbent is poly (ethylene-co-vinyl acetate) (provided by DuPont Chemical Company, also referred to as an ethylene / vinyl acetate copolymer, where the vinyl acetate concentration is ethylene Higher than concentration, which is vinyl acetate / ethylene interpolymer), poly (ethylene-co-methyl acrylate), poly (ethylene-co-acrylic acid) (also referred to as ethylene / acrylic acid copolymer, eg, The Dow Chemical Company The acrylic acid concentration is higher than the ethylene concentration and is an acrylic acid / ethylene interpolymer), poly (ethylene-co-methacrylic acid) (also referred to as an ethylene / methacrylic acid copolymer, for example, Dupont Chemical Company), poly (ethylene) One or more long chain polymers such as poly (ethylene-co-butylacrylate-co-maleic anhydride), poly (ethylene oxide) and poly (ethyleneimine) including. Particularly preferably, the non-volatile adsorbent polymer is poly (ethylene-co-acrylic acid), poly (ethylene-co-ethyl acrylate-co-maleic anhydride), poly (ethylene-co-butyl acrylate-co-maleic anhydride). ) Or poly (ethylene-co-vinyl acetate). One skilled in the art will recognize that other suitable solid polymer non-volatile adsorbents may be used.

  If the non-volatile adsorbent is a non-volatile liquid under the conditions in the reactor, it can be selected from the group consisting of alkoxylated amines, alkoxylated amides, carboxylic acids, thiols and alcohols. Even more preferably, the non-volatile liquid comprises long chain diethanolamine. Even more preferably, the non-volatile liquid comprises N-octadecyl diethanolamine or N-hexadecyl diethanolamine. One skilled in the art will recognize that other suitable compounds can be used that are non-volatile liquids under conditions in the reactor. For other suitable non-limiting examples of compounds that can be non-volatile liquids under conditions in the reactor, see US Pat. No. 6,369,174. The entire contents of this patent specification are incorporated herein by reference.

  All polymerization catalysts, including conventional types of transition metal catalysts and bulky ligand metallocene type catalysts, are suitable for use in the process of the present invention. The following is a non-limiting description of various polymerization catalysts useful in the present invention.

Conventional Type Transition Metal Catalysts Conventional types of transition metal catalysts are conventional Ziegler-Natta catalysts that are well known in the art. Examples of conventional types of transition metal catalysts are described in U.S. Pat. Nos. 4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741. The disclosures of which are incorporated herein by reference in their entirety. Conventional types of transition metal catalyst compounds that can be used in the present invention include transition metal compounds from Groups 3-17, preferably Groups 4-12, and more preferably Groups 4-6 of the Periodic Table of Elements. Is included.

These conventional-type transition metal catalysts may be represented by the formula MR _x. Wherein M is a metal from group 3-17, preferably group 4-6, even more preferably a metal from group 4, particularly preferably titanium, R is a halogen or hydrocarbyloxy group, x is the valence of the metal M. Non-limiting examples of R include alkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examples of conventional type transition metal catalysts where M is titanium include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₄ H ₉ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , TiCl ₃ · 1 / 3AlCl ₃ and Ti (OC ₁₂ H ₂₅ ) Cl ₃ Is included.

Conventional types of transition metal catalyst compounds based on magnesium / titanium electron donor complexes useful in the present invention are described, for example, in U.S. Pat. Nos. 4,302,565 and 4,302,566. All disclosures are incorporated herein by reference. Catalysts derived from Mg / Ti / Cl / THF are particularly preferred and are well known to those skilled in the art. One non-limiting example of a general method for preparing such a catalyst includes dissolving TiCl ₄ in THF, reducing the compound to MgCl ₃ with Mg, adding MgCl ₂ , and solvent Is included. See also Example 1b of US Pat. No. 5,290,745. The disclosure of which is incorporated herein by reference.

British Patent No. 2,105,355 and US Pat. No. 5,315,036, the disclosures of which are incorporated herein by reference, describe various conventional types of vanadium catalyst compounds. Non-limiting examples of conventional types of vanadium catalyst compounds include vanadyl trihalides, alkoxy halides and alkoxides such as VOCl ₃ , VOCl ₂ (OBu) (where Bu is butyl) and VO (OC ₂ H ₅ ) ₃ ; vanadium tetrahalide and vanadium alkoxy halide, eg VCl ₄ and VCl ₃ (OBu); vanadium and vanadyl acetylacetonate and chloroacetylacetonate, eg V (AcAc) ₃ and VOCl ₂ (AcAc), where (AcAc) is acetylacetonate). Preferred conventional types of vanadium catalyst compounds are VOCl ₃ , VCl ₄ and VOCl ₂ —OR, where R is a hydrocarbon group, preferably a C ₁ -C ₁₀ aliphatic or aromatic hydrocarbon group such as ethyl, phenyl. , Isopropyl, butyl, propyl, n-butyl, isobutyl, t-butyl, hexyl, cyclohexyl, naphthyl and the like) and vanadium acetylacetonate.

  Still other conventional types of transition metal catalyst compounds and catalyst systems suitable for use in the present invention are disclosed in U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062, 4,379,758, Disclosure in each specification of US Pat. The disclosures of which are incorporated herein by reference in their entirety.

Other catalysts can include cationic catalysts such as AlCl ₃ and other cobalt, iron, nickel and palladium catalysts well known in the art. For example, see U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and 4,689,437. All of these disclosures are incorporated herein by reference.

  For further details on the Ziegler-Natta catalyst, see, for example, U.S. Pat. Nos. 3,687,920, 4,086,408, 4,376,191, 5,019,633, 4,482,687, 4,101,445, 4,560,671, Nos. 4,719,193, 4,755,495 and 5070055 are referred to. The disclosures of which are incorporated herein by reference.

  Typically, these conventional types of transition metal catalyst compounds are activated by one or more conventional types of cocatalysts described below.

Conventional types of cocatalyst compounds for the transition metal catalyst compounds customary types of conventional type cocatalysts described above can be represented by the formula ^{_{M 3 M 4 v X 2 c}} R 3 bc. Here, M ³ is a metal from Groups 1 to 3 and 12 to 13 of the Periodic Table of Elements, M ⁴ is a Group 1 element of the Periodic Table of Elements, v is a number from 0 to 1, and each X ² is any halogen, c is a number from 0 to 3, each R ³ is a monovalent hydrocarbon group or hydrogen, b is a number from 1 to 4, and bc is at least 1. is there. Other conventional types of organometallic promoter compounds for the above conventional types of transition metal catalysts include those having the formula M ³ R ³ _k . Where M ³ is a Group IA, IIA, IIB or IIIA metal such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium and gallium, and k is 1 depending on the valence of M ^3. 2 or 3, the valence usually depends on the group to which M ³ belongs, and each R ³ can be any monovalent group, which is a hydrocarbon group and fluoride, aluminum or oxygen or their Includes hydrocarbon groups containing Group 13-16 elements such as combinations.

  Non-limiting examples of conventional types of organometallic cocatalyst compounds useful for the above conventional types of catalyst compounds include methyl lithium, butyl lithium, dihexyl mercury, butyl magnesium, diethyl cadmium, benzyl potassium, diethyl zinc Tri-n-butylaluminum, diisobutylethylboron, diethylcadmium, di-n-butylzinc and tri-n-amylboron, and especially aluminum alkyls such as trihexylaluminum, triethylaluminum, trimethylaluminum and triisobutylaluminum Is included. Other conventional types of cocatalyst compounds include Group 2 metal monoorganohalides and hydrides, and Group 3 and 13 metal mono- or diorganohalides and hydrides. Non-limiting examples of such conventional types of co-catalyst compounds include didiisobutyl aluminum bromide, isobutyl boron dichloride, methyl magnesium chloride, ethyl beryllium chloride, ethyl calcium bromide, diisobutyl aluminum hydride, methyl cadmium hydride, diethyl boron hydride, Hexyl beryllium hydride, dipropyl boron hydride, octyl magnesium hydride, butyl zinc hydride, dichloro boron hydride, dibromoaluminum hydride and bromocadmium hydride are included. Conventional types of organometallic cocatalyst compounds are well known to those skilled in the art, and a more complete discussion of these compounds can be found in the specifications of US Pat. Nos. 3,212,002 and 5,093,415. All of these disclosures are incorporated herein by reference.

Bulky Ligand Metallocene Type Catalyst Compounds In general, bulky ligand metallocene type catalyst compounds include half sandwich and full sandwich compounds having one or more bulky ligands bonded to at least one metal atom. Typical bulky ligand metallocene type compounds are generally described as containing one or more bulky ligands and one or more leaving groups bonded to at least one metal atom. In one preferred embodiment, binding eta at least one bulky ligand is a metal atom, particularly preferably is eta ⁵ bonded to the metal atom.

  A bulky ligand is generally represented by one or more open, acyclic or fused rings or ring systems or combinations thereof. These bulky ligands (preferably rings or ring systems) typically consist of atoms selected from Group 13-16 atoms of the Periodic Table of Elements, which atoms are carbon, nitrogen, oxygen, silicon, sulfur, phosphorus Preferably, it is selected from germanium, boron and aluminum or combinations thereof. The ring or ring system may be a cyclopentadienyl ligand or a cyclopentadienyl type ligand structure or other similar ligand structure (eg pentadiene, cyclooctatetraenediyl or imide ligand) (but is not limited thereto) It is particularly preferred that it consists of a plurality of carbon atoms. The metal atom is preferably selected from Groups 3 to 15 of the Periodic Table of Elements and a lanthanide or actinide series. Preferably, the metal is a transition metal from Groups 4-12, even more preferably a transition metal from Groups 4, 5, and 6, especially when the transition metal is Group 4. preferable.

In one embodiment, the bulky ligand metallocene-type catalyst compound of the present invention is represented by the following formula:
L ^A L ^B MQ _n (I)
Where M is a metal atom from the periodic table of elements and can be a Group 3-12 metal or lanthanide or actinide series of the Periodic Table of Elements, and M is a Group 4, 5 or 6 transition metal. More preferably, M is a Group 4 transition metal, and even more preferably M is zirconium, hafnium or titanium. L ^A and L ^B are bulky ligands, substituted with open, acyclic or fused rings or ring systems, eg unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl type ligands, or heteroatoms And / or a cyclopentadienyl type ligand containing heteroatoms. Non-limiting examples of bulky ligands include cyclopentadienyl ligand, cyclopentaphenanthrenyl ligand, indenyl ligand, benzoindenyl ligand, fluorenyl ligand, octahydrofluorenyl ligand, cyclooctatetraenedi Yl ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands, etc. (including their corresponding hydrides such as tetrahydroindenyl ligands) Is included. In one embodiment, L ^A and L ^B may be any other ligand structure capable of t bound to M, preferably capable of eta ³ bound to M, particularly preferably any other ligand structure capable of eta ⁵ bond Can be. In yet another embodiment, the atomic molecular weight (MW) of L ^A or L ^B is preferably greater than 60 a.mu and greater than 65 a.mu. In another embodiment, L ^A and L ^B include one or more heteroatoms such as nitrogen, silicon, boron, germanium, sulfur, oxygen and phosphorus in combination with carbon atoms, open, acyclic or preferred Can also form fused rings or ring systems, such as heterocyclopentadienyl auxiliary ligands. Other L ^A and L ^B bulky ligands include bulky amides, phosphides, alkoxides, aryl oxides, imides, carbolides, borolides, porphyrins, phthalocyanines, cholines and other polyazo macros. Cycles are included, but are not limited to these. Each L ^A and L ^B can independently be the same or different type of bulky ligand bound to M. In one embodiment of formula (I), only either L ^A or L ^B is present.

Independently, each L ^A and L ^B may be unsubstituted or substituted with a combination of substituents R. Non-limiting examples of substituent R include hydrogen or a linear or branched alkyl or alkenyl group, alkynyl group, cycloalkyl group or aryl group, acyl group, aroyl group, alkoxy group, aryloxy Group, alkylthio group, dialkylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl- or dialkyl-carbamoyl group, acyloxy group, acylamino group, aroylamino group, linear, branched or cyclic alkylene group Or one or more groups selected from combinations thereof. In preferred embodiments, the substituent R has up to 50 non-hydrogen atoms (non-hydrogen atoms), preferably 1-30 carbon atoms, which are also substituted with halogens, heteroatoms, etc. be able to. Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and all isomers thereof, such as t-butyl, Including isopropyl and the like. Other hydrocarbyl groups include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid groups (including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, etc.); and halocarbyl substituted organo Metalloid groups (including tris (trifluoromethyl) silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like); and disubstituted boron groups (including dimethylboron, for example); and disubstituted pnictogen Groups (including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine), chalcogen groups (methoxy, ethoxy, propoxy, phenoxy, methyl sulfide) Including fine ethylsulfide) and the like. Non-hydrogen substituents R include carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium atoms, etc., and olefinically unsaturated substituents (including but not limited to vinyl-terminated ligands). Olefins such as 3-butenyl, 2-propenyl, 5-hexenyl and the like. 3-30 selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or combinations thereof, wherein at least two R groups (preferably two adjacent R groups) are taken together A ring structure having a number of atoms can also be formed. A substituent R group such as 1-butanyl can also form a carbon σ bond to the metal M.

  Other ligands such as at least one leaving group Q may be bound to the metal. In this specification and the appended claims, the term “leaving group” refers to a bulky ligand metallocene-type catalyst cation that can be extracted from a bulky ligand metallocene catalyst compound to polymerize one or more olefins. Any ligand that can. In one embodiment, Q is a monoanionic labile (mobile) ligand with a σ bond to M.

  Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl groups having 1 to 20 carbon atoms, hydrides or halogens, etc. Or combinations thereof. In another embodiment, two or more Qs form part of a fused ring or ring system. Other examples of Q ligands include those for substituents for R as described above, cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, Phenoxy, bis (N-methylanilide), dimethylamide, dimethylphosphide groups and the like are included. The value for n is 0, 1 or 2 depending on the oxidation state of the metal so that the above formula (I) represents a neutral bulky ligand metallocene type catalyst compound.

In one embodiment, the bulky ligand metallocene-type catalyst compound of the present invention is one in which L ^A and L ^B in formula (I) are cross-linked together by at least one bridging group A as represented by the following formula: Is included.
L ^A AL ^B MQ _n (II)

These bridged compounds of formula (II) are referred to as bridged bulky ligand metallocene type catalyst compounds. L ^A , L ^B , M, Q and n are as defined above. Non-limiting examples of bridging groups A are at least one group 13-16 atom (eg, at least one of carbon, oxygen, nitrogen, silicon, boron, germanium and tin atoms, or combinations thereof). Includes, but is not limited to, bridging groups, often referred to as divalent moieties. The bridging group A preferably contains carbon, silicon, iron or germanium atoms, and particularly preferably contains at least one silicon atom or at least one carbon atom. The bridging group A can also contain a substituent R (including halogen) as defined above. Non-limiting examples of bridging group A can be represented by R ′ ₂ C, R ′ ₂ Si, R ′ ₂ SiR ′ ₂ Si, R ′ ₂ Ge, R′P. Where R ′ is a group that is independently hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl substituted organometalloid, halocarbyl substituted organometalloid, disubstituted boron, disubstituted dictogen, substituted chalcogen or halogen; Also, two or more R ′ can be taken together to form a ring or ring system.

In one embodiment, bulky ligand metallocene-type catalyst compounds of the the formula (I) and substituted R substituents on the bulky ligands L ^A and L ^B is equal or different number on each bulky ligand (II) It is substituted with a group. In another embodiment, the bulky ligands L ^A and L ^B of formulas (I) and (II) are different from each other.

  Other bulky ligand metallocene type catalyst compounds and catalyst systems useful in the present invention include U.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208, No. 5296434, No. 5321106, No. 5329031, No. 5304614, No. 5676401, No. 5723398, No. 575578, No. 5854363, No. 5856547, No. 5858903, Nos. 5859158 and 5929266 and International Publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529 , WO98 / 46650, WO99 / 02540 and WO99 / 14221 pamphlets and European Patent Publication Nos. 0578838A, 0638595A, 0513380B, 0816372A1, 00839834A2, and 0632819B1 Nos. 074821B1 and 0757996B1 are included. All of which are incorporated herein by reference.

  In one embodiment, the bulky ligand metallocene type catalyst compounds useful in the present invention include bridged heteroatom-monobulky ligand metallocene type compounds. These types of catalysts and catalyst systems are described in, for example, International Publications WO92 / 00333, WO94 / 07928, WO91 / 04257, WO94 / 03506, WO96 / 00244, and WO97 / 15602. U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405, and European Patent Publication No. 0420436A. All of which are incorporated herein by reference.

In this specific example, the bulky ligand metallocene-type catalyst compound is represented by the following formula:
L ^C AJMQ _n (III)
{Where M is a group 3-16 metal atom of the periodic table or a metal selected from the actinide and lanthanide groups, preferably M is a group 4-12 transition metal, and more preferably M is A Group 4, 5 or 6 transition metal, particularly preferably M is a Group 4 transition metal (of any oxidation state), in particular titanium,
L ^C is a substituted or unsubstituted bulky ligand bound to M;
J binds to M,
A binds to M and J;
J is a heteroatom assisted ligand;
A is a crosslinking group,
Q is a monovalent anionic ligand,
n is an integer 0, 1 or 2. }
In the above formula (III), L ^C , A and J form a condensed ring system. In one embodiment, L ^C in formula (III) is as defined above for L ^A and A, M and Q in formula (III) are as defined above in formula (I). In the formula (III), J is a heteroatom-containing ligand, where J is an element having a coordination number of 3 from group 15 of the periodic table or an element having a coordination number of 2 from group 16. Preferably J contains a nitrogen, phosphorus, oxygen or sulfur atom, with nitrogen being particularly preferred.

  In another embodiment, the bulky ligand-type metallocene-type catalyst compound comprises a complex of a metal (preferably a transition metal), a bulky ligand (preferably a substituted or unsubstituted π-bonded ligand) and one or more heteroallyl moieties, such as the United States It is described in both specifications of Japanese Patent Nos. 5527752 and 5747406 and European Patent Publication No. 0735057B1. All of which are incorporated herein by reference.

In one embodiment, the bulky ligand metallocene type catalyst compound is represented by the following formula:
L ^D MQ ₂ (YZ) X _n (IV)
(Where M is a Group 3-16 metal of the periodic table, preferably a Group 4-12 transition metal, particularly preferably a Group 4, 5 or 6 transition metal,
L ^D is a bulky ligand bonded to M;
Each Q independently binds to M; Q ₂ (YZ) forms a mono-charged multidentate ligand;
A or Q is also a monovalent anionic ligand bound to M;
X is a monovalent anionic group when n is 2, and is a divalent anionic group when n is 1,
n is 1 or 2. )

In formula (IV), L ^D and M are as defined above for formula (I). Q is as defined above for formula (I), preferably Q is selected from the group consisting of —O—, —NR—, —CR ₂ — and —S—, and Y is C or S; Z is selected from the group consisting of —OR, —NR ₂ , —CR ₃ , —SR, —SiR ₃ , —PR ₂ , —H and a substituted or unsubstituted aryl group, provided that Q is —NR—. Is selected from the group consisting of —OR, —NR ₂ , —SR, —SiR ₃ , —PR ₂ and —H, R is a group containing carbon, silicon, nitrogen, oxygen and / or phosphorus; Preferably R is a hydrocarbon group having 1 to 20 carbon atoms, particularly preferably an alkyl, cycloalkyl or aryl group, n is an integer of 1 to 4, and preferably 1 or 2. , X is a monovalent anionic group when n is 2, and n is 1 The case is a divalent anionic group, preferably X is a carbamate, other heteroaryl moieties described by a combination of carboxylate or Q, Y and Z.

  In another embodiment of the invention, the bulky ligand metallocene-type catalyst compound is a heterocyclic ligand complex in which the bulky ligand, ring or ring system contains one or more heteroatoms or combinations thereof. Non-limiting examples of heteroatoms include Group 13-16 elements, with nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus and tin being preferred. Examples of these bulky ligand metallocene-type catalyst compounds include WO96 / 33220, WO96 / 34021, WO97 / 17379, and WO98 / 22486, as well as European Patent Publication No. 0874405A1 and US Patents. No. 5,637,660, No. 5,539,124, No. 5,554,775, No. 5,756,611, No. 5,330,049, No. 5,744,417 and No. 5,856,258. The disclosures of which are incorporated herein by reference.

  In another embodiment, bulky ligand metallocene-type catalyst compounds such as those described in both US Pat. Nos. 6,103,357 and 6,103,620, the disclosures of which are incorporated herein by reference. , A complex known as a transition metal catalyst based on a bidentate ligand containing a pyridine or quinoline moiety. In another embodiment, the bulky ligand metallocene-type catalyst compound is that described in both pamphlets of International Publication Nos. WO99 / 01481 and WO98 / 42664. All of these disclosures are incorporated herein by reference.

In one embodiment, the bulky ligand metallocene type catalyst compound is represented by the following formula:
((Z) XA _t (YJ)) _q MQ _n (V)
(Where M is a metal selected from Groups 3-13 of the Periodic Table of Elements or from the lanthanide and actinide series;
Q binds to M and each Q is a monovalent, divalent or trivalent anion,
X and Y are bonded to M, and one or more of X and Y are heteroatoms, preferably both X and Y are heteroatoms;
Y is contained in the heterocycle J, where J has 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms,
Z is bonded to X, where Z has 1-50 non-hydrogen atoms, preferably 1-50 carbon atoms, preferably Z is 3-50 atoms, preferably 3-30. A cyclic group having the following carbon atoms:
t is 0 or 1,
when t is 1, A is a bridging group bonded to at least one of X, Y or J (preferably X and J);
q is 1 or 2,
n is an integer of 1 to 4 depending on the oxidation state of M. )
In one embodiment, Z is optional when X is oxygen or sulfur. In another embodiment, Z is present when X is nitrogen or phosphorus. In one embodiment, Z is preferably an aryl group, and more preferably a substituted aryl group.

It is also within the scope of the present invention that in one embodiment of the other bulky ligand metallocene-type catalyst compound , the bulky ligand metallocene-type catalyst compound comprises Ni ²⁺ and Pd ²⁺ complexes described in the following references: Johnson et al. `` New Pd (II)-and Ni (II) -Based Catalysts for Polymerization of Ethylene and a-Olefins '', J. Am. Chem. Soc., 1995, 117, 6414-6415 and Johnson et al., `` Copolymerization of Ethylene. and Propylene with Functionalized Vinyl Monomers by Palladium (II) Catalysts ”, J. Am. Chem. Soc., 1996, 118, 267-268, and International Publication WO 96/23010, published on August 1, 1996, WO 99 / 02472 pamphlet, US Pat. Nos. 5,852,145, 5,866,663 and 5,880,241. All of these disclosures are incorporated herein by reference. These complexes can be either alkylation reaction products or dialkyl ether adducts of the described dihalide complexes, which are activated to a cationic state by the activators of the invention described below. be able to.

  Also, diimine-based ligands of Group 8-10 metal compounds disclosed in International Publication No. WO96 / 23010, WO97 / 48735, and Gibson et al., Chem. Comm., Pages 849-850 (1998), Included as a bulky ligand metallocene type catalyst. The disclosures of which are incorporated herein by reference.

  Other bulky ligand metallocene type catalysts include Group 5 and 6 metal imide complexes described in EP 0816384A2 and US Pat. No. 5,851,945. The disclosures of which are incorporated herein by reference. Bulky ligand metallocene-type catalysts further include bridged bis (arylamide) Group 4 compounds described by D. H. McConville et al. In Organometallics, 1195, 14, 5478-5480. The disclosure of which is incorporated herein by reference. Other bulky ligand metallocene type catalysts are described in US Pat. No. 5,852,146 as bis (hydroxy aromatic nitrogen ligands). The disclosure of which is incorporated herein by reference. Other metallocene type catalysts containing one or more Group 15 atoms include those described in International Publication No. WO 98/46651. The disclosure of which is incorporated herein by reference.

  In one embodiment, the above-described bulky ligand metallocene-type catalyst of the present invention is a structural isomer, optical isomer, enantiomer {meso and racemic isomers (eg, US Pat. No. 5,852,143). It is also envisaged that the disclosure is incorporated herein by reference))} and mixtures thereof.

  In order to better understand the present invention, the following examples are provided as relating to actual tests conducted in the practice of the present invention.

  In order to better understand the present invention, the following non-limiting examples are provided as relating to actual tests conducted in the practice of the present invention.

General conditions for Examples 1-10 All materials were purchased as commercial products and used as they were. The catalyst used was spray-dried 5: 1 MgCl ₂ / prepared as described in Example 1b of US Pat. No. 5,290,745, the entire contents of which are incorporated herein by reference. TiCl ₃ / THF catalyst. A computer controlled 1 liter 316 stainless steel reactor equipped with an air driven two-blade paddle stirrer and an internal steam heating shell and an external water cooling shell at 35 ° C. while purging with 500 sccm of nitrogen. Dry by heating for minutes. After cooling to 50 ° C., 600 ml of hexane was charged under inert conditions. A catalyst loading vessel containing catalyst and cocatalyst was then attached to the reactor, resisting nitrogen purge. The reservoir at the top of the injection tube was pressurized with nitrogen to about 1620 kPa (235 psi). The reactor was sealed, heated to 85 ° C. and pressurized with ethylene (ethylene partial pressure of about 930 kPa (135 psi)). Slurry polymerization with Mg / Ti / Cl / THF catalyst system (15 mmol Ti) and Et ₃ Al cocatalyst (0.5 mmol Al, Al / Ti ca. 33: 1) was initiated in the reactor and this reaction Stabilized. After 20 minutes, a non-volatile adsorbent was added as slurry in 50 ml of hexane from a cylinder attached to the reactor (according to the table below), pressurized with ethylene and sent into the reactor, and the remainder in the cylinder was further hexane Was poured into the reactor. The polymerization was then continued for an additional 20 minutes, and the reaction was terminated by venting the polymerization gas and opening the reactor. The reactor pressure during the polymerization was maintained by computer controlled adjustment of the mass flow controller, and the instantaneous rate of the polymerization reaction was followed by the gas flow through the mass flow controller.

Example 11: Transition from Ziegler Natta to metallocene in a fluidized bed Active Ziegler using MgCl ₂ / TiCl ₃ / THF catalyst supported on TEA-treated 955 silica with TEA (triethylaluminum) cocatalyst Natta polymerization was carried out in a continuous gas phase fluidized bed reactor having a nominal diameter of about 36 cm (about 14 inches) and a bed weight of about 54 kg (about 120 pounds). The reactor temperature was 85 ° C. The total pressure is about 2413 kPa (gauge pressure) (about 350 psig), the ethylene monomer partial pressure is about 827 kPa (about 120 psi), and hydrogen and hexene have an MI of about 1 dg / min and a density of 0.918 g / cc. It was present in proportions for producing the polymer. The circulating gas velocity was about 60 cm / second (about 2 feet / second) and the resin production rate was about 16 kg / hour (about 35 pounds / hour). The TEA concentration in the bed was about 200 ppmw and was added directly to the fluidized bed as a dilute solution in isopentane. In order to initiate the transition from Ziegler-Natta catalyzed polymerization to metallocene catalyzed polymerization, the MgCl ₂ / TiCl ₃ / THF catalyst feed and TEA co-catalyst feed were stopped.

  Next, long chain diethanolamine commercially available from ICI Specialty Chemicals under the trade name ATMER-163 was added to the reactor fluidized bed to a concentration of 1000 ppmw based on the polymer bed weight. This was almost four times the calculated amount required to react with the aluminum alkyl, but also with a low ATMER-163: TEA molar ratio such as 2: 1 or 1: 1, or less than 1: 1. It was also possible to adopt. ATMER-163 completely stopped the polymerization activity within a few minutes based on the heat balance around the fluidized bed and the automatic stopping of the monomer feed by the control system. The reactor was held constant for 12 hours with other conditions without a polymerization reaction and then purged with high purity nitrogen to remove hydrogen and monomer in preparation for establishing conditions for metallocene polymerization. . The retention time of 12 hours after addition of ATMER-163 could be reduced to 1 hour, 2 or a few minutes and could be removed in some cases. ATMER-163 was added almost immediately after the supply of Ti-based catalyst was stopped, but it is also possible to attenuate the polymerization reaction over a period of time to remove some of the catalyst and cocatalyst from the bed before the start of the transition. Let's go.

  To produce a polymer having an MI of about 1 dg / min and a density of 0.918 g / cc after the above nitrogen purge, ATMER-163 addition and 12 hours hold, 85 ° C., about 2413 kP (gauge pressure) ( Reactor conditions of 350 psig) total pressure, about 1379 kPa (200 psi) ethylene partial pressure and about 150 ppmv hydrogen and hexane were established. The bed weight remained about 54 kg (about 120 pounds) and the circulating gas velocity was maintained at about 60 cm / sec (about 2.0 ft / sec). A metallocene catalyst system containing bis (1,3-methylbutylcyclopentadienyl) zirconium dichloride and methylalumoxane was then added to the reactor. This metallocene catalyst system is well known to those skilled in the art and a non-limiting example of its general method of preparation is described in US Pat. No. 5,776,612, the entire contents of which are incorporated by reference. After introducing the metallocene catalyst system into the reactor, the polymerization resumed very quickly and when the experiment was over the reactor was operating well for about 40 hours (MI of about 1 dg / min and 0.918 g / cc of A polymer with a density was produced). There was no high molecular weight gel in the polymer product, indicating that only the metallocene catalyst system was active during the polymerization.

  The addition of ATMER-163 to the Ziegler-Natta Ti catalyzed polymerization is a concise, at electrostatic voltage from approximately neutral to approximately 600 volts positive as measured by a high capacitance-high resistance probe in a fluidized bed. Brought a spike. This quickly returned to neutrality with very little fluctuations in the neutral electrostatic voltage around zero compared to before the ATMER-163 addition. The electrostatic voltage band rises slowly from approximately 0 to +50 or −50 volts during the 12 hour ATMER-163 holding period. When the EX-371 catalyst was added, the electrostatic voltage rose to more than -1000 volts, but it was almost 4 hours after it returned to neutrality. This electrostatic voltage eventually stabilized at about -150 volts in a band of about +200 or -200 volts for operation with metallocene catalysts.

  Thermocouples placed near the reactor wall at various locations in the fluidized bed show a decrease in the range of −10 to −25 ° C. compared to the fluid bed core temperature several hours after the metallocene catalyst feed is started. It was. This shows a collection of insulating layers of polymer particles along the reactor wall. The skin thermocouple reading returned to normal within about 10 hours. This was about 5-10 ° C. below the core temperature. One of the skin thermocouples spiked at approximately 3 hour intervals and was approximately 5 ° C. above the bed temperature for only a few minutes. No agglomerated molten resin sheet or mass was found in the granular polymer product discharged from the reactor during the metallocene polymerization. It would have been possible to continue or resume ATMMER-163 addition during that time when the metallocene addition was started or in response to electrostatic or skin thermocouple activity. The ATMER-163 was purged with nitrogen before use, but in this case no measurements were taken to remove possible water contamination. Since water is known to cause operational problems such as electrostatic and wall skin thermocouple activity when used in this particular transition, the use of dry ATMER-163 improves the transition I was guessed.

  While the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will recognize that the invention is useful in variations not necessarily illustrated herein. For example, the transition from one or more mixed catalysts to one or more incompatible mixed catalysts and vice versa is not beyond the scope of the present invention. For this reason, then, reference should be made solely to the appended claims in order to determine the true scope of the present invention.

Claims (18)

Transition from a first polymerization reaction carried out in the presence of the first catalyst to a second polymerization reaction carried out in the presence of the second catalyst when the first catalyst and the second catalyst are incompatible A way to
(A) stop introducing the first catalyst containing the Ziegler-Natta catalyst into the reactor;
(B) introducing and dispersing an effective amount of non-volatile adsorbent into the reactor to deactivate the first catalyst and substantially stop the first polymerization reaction; and (c) MAO based single site A second catalyst containing catalyst is introduced into the reactor and dispersed:
The transition method.   The method of claim 1, wherein the first polymerization reaction and the second polymerization reaction comprise a gas phase process.   The method of claim 1, wherein the first polymerization reaction and the second polymerization reaction are carried out in a fluidized bed reactor.   The method of claim 1, wherein the process is continuous.   The method of claim 1, wherein the Ziegler-Natta catalyst comprises a titanium-triethylaluminum catalyst.   The method of claim 1, wherein the MAO-based single site catalyst comprises a metallocene catalyst.   The method of claim 1, wherein the non-volatile adsorbent is selected from the group consisting of a solid polymer and a compound that is a non-volatile liquid under conditions in the reactor.   The method according to claim 7, wherein the non-volatile adsorbent is a solid polymer and includes at least one functional group capable of efficiently deactivating the first catalyst.   The method of claim 7, wherein the non-volatile adsorbent is a solid polymer and includes at least one functional group capable of reacting with an aluminum alkyl.   The method of claim 7, wherein the non-volatile adsorbent is a solid polymer and comprises a long chain copolymer and a substituted alkene.   The non-volatile adsorbent is ethylene and acrylate, vinyl ester, olefinic anhydride, olefinic carboxylic acid ester, olefinic carboxylic acid, olefinic ether, olefinic amine, olefinic alcohol, olefinic amide, olefinic imine and 8. The method of claim 7, comprising a long chain copolymer or terpolymer with one or more comonomers selected from the group consisting of olefinic thiols.   The nonvolatile adsorbent is poly (ethylene-co-vinyl acetate), poly (ethylene-co-methyl acrylate), poly (ethylene-co-acrylic acid), poly (ethylene-co-methacrylic acid), poly (ethylene- One or more selected from the group consisting of (co-ethyl acrylate-co-maleic anhydride), poly (ethylene-co-butyl acrylate-co-maleic anhydride), poly (ethylene oxide) and poly (ethyleneimine) 8. The method of claim 7, comprising a number of long chain polymers.   The non-volatile adsorbent is poly (ethylene-co-acrylic acid), poly (ethylene-co-ethyl acrylate-co-maleic anhydride), poly (ethylene-co-butyl acrylate-co-maleic anhydride) and poly ( 13. The method of claim 12, comprising one or more long chain polymers selected from the group consisting of (ethylene-co-vinyl acetate).   The non-volatile adsorbent is poly (ethylene-co-acrylic acid), poly (ethylene-co-ethyl acrylate-co-maleic anhydride), poly (ethylene-co-butyl acrylate-co-maleic anhydride) and poly ( 13. The method of claim 12, comprising one or more long chain polymers selected from the group consisting of (ethylene-co-vinyl acetate).   8. The method of claim 7, wherein the non-volatile liquid under conditions in the reactor comprises a compound selected from the group consisting of alkoxylated amines, alkoxylated amides, carboxylic acids, thiols and alcohols.   15. The method of claim 14, wherein the non-volatile liquid under conditions in the reactor comprises long chain diethanolamine.   16. The method of claim 15, wherein the non-volatile liquid under conditions in the reactor comprises N-octadecyl diethanolamine.   16. The method of claim 15, wherein the non-volatile liquid under conditions in the reactor comprises N-hexadecyl diethanolamine.