JPH08269192A - Process for vapor phase copolymerization of carbon monoxide and unsaturated ethylene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain copolymers in high molecular weights and at a high rate of polymerization which are useful as thermoplastic materials such as fibers, films, sheets of the like by the gas phase reaction of carbon monoxide with ethylenically unsaturated compounds in the presence of a specific catalyst.

SOLUTION: In the presence of (A) a catalyst system composed of, as the base, (A₁) a source of cations of a Group VIII metal of the periodic table such as palladium acetate, (A₂) a source of anions which comprise a plurality of boron atoms such as B₁₁CH₁₂ ^-, a source of organoboron-containing anions such as triphenyl boron or an aluminoxane, and (A₃) a source of ligands such as a compound of the formula: R¹R²P-R-R³R⁴ [wherein R¹-R⁴ are each a (polar substituted)aryl such as ortho-alkoxyphenyl; and R is a divalent organic 2-4C bridging group such as trimethylene], (B) carbon monoxide and (C) an ethylenically unsaturated compound such as ethene are reacted in gas phase to obtain a desired copolymer.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a gas phase process for copolymerizing carbon monoxide with an ethylenically unsaturated compound.

[0002]

A copolymer of carbon monoxide and an ethylenically unsaturated compound, wherein the units derived from carbon monoxide and the units derived from an ethylenically unsaturated compound are arranged alternately or substantially alternately. The production of ## STR1 ## is described in many published patent specifications, most of which relate to the production of copolymers in a liquid phase process. These copolymers can also be produced by a gas phase process. In this type of process, in the substantial absence of liquid diluent, i.e. under conditions such that the gas phase forms a continuous phase,
A monomer is contacted with a catalyst composition based on (a) a Group VIII metal compound of the Periodic Table, (b) an anion, and (c) a bidentate ligand. A specific example of a gas phase process of this kind is known from European Patent Application No. 244883.
One example of a suitable anion is the paratoluene sulfonate anion. A suitable source of this anion is the corresponding acid, in this case paratoluenesulfonic acid. The present invention has put a great deal of effort into research to improve the performance of catalyst compositions, for example by changing the type and source of anions used as catalyst component b). European Patent Application No. 5
08502 describes that the inclusion of certain Lewis acids as component b) makes it possible to obtain highly active catalysts for gas phase processes. European Patent Application No. 5015
In No. 76, Lewis acid / Bronsted (B
It is recommended to use a roentsted) acid mixture.

The present invention provides improved catalysts for gas phase processes. The catalyst has, as an anion, an anion containing a plurality of boron atoms, such as a carbolate.
anate) or an anion containing organic boron,
Examples include hydrocarbyl borate anions. These anions are bulky, with no or only weak coordination with the Group VIII metal. Surprisingly, these anions do not give an improvement when liquid-phase polymerizations are carried out under similar conditions, whereas they improve the catalytic activity in the gas-phase process and also the molecular weight of the resulting copolymers. More notably, neutral organoboranes, such as trihydrocarbylborane, can serve as a suitable anion source.
The use of aluminoxanes as anion sources also results in catalyst compositions that exhibit the desired activity in gas phase processes. DE 90012229 proposes to use a carbolate anion as a catalyst component in a group VIII metal catalyzed alternating copolymerization of carbon monoxide and an olefin. However, this prior patent specification does not provide details regarding the conditions of use of the carbolate anion and its advantages. This prior patent specification is concerned with liquid phase slurry polymerization and does not mention gas phase processes at all. Brookhart
Et al. (J. Am. Chem. Soc. 114 (199
2) p. 5894 and 116 (1994) p. 364
1), in liquid phase synthesis of stereoregular copolymer of carbon monoxide and styrene-related olefin, tetrakis [3,5-bis- (trifluoromethyl) phenyl] borate anion with specific palladium / nitrogen bidentate complex. Used in combination. European Patent Application No. 590942 discloses the use of certain aluminoxanes in liquid phase slurry polymerization of Group VIII metal catalysts with carbon monoxide and ethene. The favorable results of the present invention are not surprising from these patent specifications, but are truly surprising. Prior unpublished European patent application No. 619335 is directed to the study of the use of boron hydrocarbyl compounds as catalyst components in the liquid phase copolymerization of carbon monoxide with ethylenically unsaturated compounds.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides (a) a cation source of a Group VIII metal of the periodic table, (b) a source of anions containing a plurality of boron atoms, or an organic boron-containing anion. A source of ions or an aluminoxane, (c)
It relates to a gas phase process for the production of copolymers, which comprises reacting carbon monoxide with an ethylenically unsaturated compound in the presence of a catalyst system based on a source of ligands.

[0005] The present invention includes (a) a Group VIII metal cations of the Periodic Table, (b) an anion containing a plurality of boron atoms, and the general formula BZ ₄ ^- in [wherein each Z is independently Represents a substituted or unsubstituted hydrocarbyl group], or a boron-containing anion selected from the anions represented by the general formula BZ ¹ ₃ [wherein each Z ¹ independently represents a substituted or unsubstituted hydrocarbyl group] And borane or aluminoxane represented by (c) (1) the general formula R ¹ R ² M ¹ −
RM ² R ³ R ⁴ (I) [wherein, M ¹ and M ² independently represent a phosphorus, arsenic or antimony atom, and R ¹ ,
R ² , R ³ and R ⁴ each independently represent an unsubstituted or polar substituted hydrocarbyl group, and R represents a divalent bridging group containing 1 to 5 carbon atoms in the bridge] Order, (2) The following general formula

[Chemical 2][Where X is¹And X²Independently, each with 3 or more on the bridge
Contains four atoms, two or more of which are carbon atoms
Represents a certain organic cross-linking group], (3)
General formula R^FiveS-Q-SR⁶(III) [wherein R^Fiveas well as
R⁶Are independently unsubstituted or polar substituted hydrocarbyl
Represents a group, Q is a divalent bridge containing 2 to 4 carbon atoms in the bridge
Represents a group] and a (4) general formula
R⁷R⁸R ⁹M³(IV) [wherein M³Also phosphorus and arsenic
R represents an antimony atom⁷, R⁸And R⁹Is
Independently represents an unsubstituted or polar substituted hydrocarbyl group.
And a ligand selected from monodentate ligands
It also relates to a catalyst composition comprising.

Palladium, a bidentate ligand of general formula (II) and tetrakis [3,5-bis (trifluoromethyl) phenyl], as used by Brookhart et al.
An unsupported catalyst composition based on borate anions,
And VIII metal, a bidentate ligand of the general formula (I) and an alkylaluminoxane [wherein the alkyl group contains 2-3 carbon atoms and a β-hydrogen atom, as used in European Patent Application No. 590942]. Of unsupported catalyst compositions based on and are excluded from the scope of patent protection. As used herein in the text and in the claims, the term "Group VIII metal of the Periodic Table" refers to the noble metals ruthenium, rhodium, palladium, osmium, iridium and platinum and the iron metals iron. , Cobalt and nickel.

[0007]

The catalyst system suitable for use in the process of the present invention is based on a cation source of the above metals. Sources of Group VIII metal cations include salts of inorganic acid salts such as sulfuric acid, nitric acid and phosphoric acid, and salts of sulfonic acids such as methane sulfone and paratoluene sulfonic acid. Preferred sources are salts of carboxylic acids such as acetic acid, propionic acid and trifluoroacetic acid. If desired, the metal is used as a cation source in elemental form or in the zero-valence state, eg in complex form, such as a complex in which a Group VIII metal is covalently bonded to one or two hydrocarbyl groups. You can These covalently bonded hydrocarbyl groups can be aliphatic or aromatic and typically contain up to 12 carbon atoms. Preferred covalently bonded hydrocarbyl groups are aliphatic groups, especially n-alkyl groups such as methyl and n-butyl groups. VI
Catalyst systems based on Group II noble metals are preferred, and those based on palladium are most preferred. The preferred source of these cations is palladium (II) acetate.

The catalyst composition of the present invention may be based on component (b) based on an anion containing a plurality of boron atoms. The number of boron atoms is typically 4-20, more typically 8-16. These anions may be unsubstituted or substituted, eg halogenated. Di-negatively charged polyhedral borate salts, such as the anions of the formulas B ₁₀ H ₁₀ ²⁻ and B ₁₂ H ₁₂ ²⁻ , and their halogenated analogues can be used. However, preferably carborate anions, such as 1,2-dicarbaundecaborate and 7,8-dicarbaundecaborate, especially of the formula B ₁₁ CH ₁₂
^- Use anion represented by. Carborates of this type are known and are described by K. The method of Shelly et al.
m. Chem. Soc. 197 (1985) 5955).
Can be manufactured by the following method.

The catalyst composition of the present invention may also be based on an organoboron-containing anion with respect to component (b). Very suitable anion of this kind, formula BZ ₄ ^- [in the formula,
Each Z independently represents a substituted or unsubstituted hydrocarbyl group, such as an aliphatic group or an aromatic group, which groups typically have up to 12 carbon atoms. Preferred groups Z are aryl groups which may be substituted or unsubstituted. Preferred substituents are electron withdrawing groups or atoms such as halogen atoms, trihalomethyl groups and nitro groups. The group Z is in particular a phenyl group, more particularly perfluorophenyl or 3,5
It is a-(trifluoromethyl) -phenyl group. The four groups Z are typically the same. Preferred anions of the general formula BZ ₄ ⁻ are tetraphenylborate, tetrakis (perfluorophenyl) borate and tetrakis [3,5-bis (trifluoromethyl) phenyl] borate anions. Specific examples of suitable aliphatic groups Z include methyl, n-butyl and isobutyl groups.

Another organoboron-containing anion that can be used in the catalyst system of the present invention is the following general formula

Embedded image [In the formula, the divalent group A is independently an alkylene group typically having 2 to 6 carbon atoms, an orthophenylene or an orthobiphenylene group, or a general formula -φ-CO- (wherein, φ is Selected from the group represented by orthophenylene group), and is tetra (hydrocarbyloxy) borate. The group A may be substituted by alkyl groups or halogen atoms, which are suitable, for example having up to 6 carbon atoms. Anions of this kind are known from European patent applications 314309 and 391579. Preferred anions of this kind are those based on unsubstituted orthophenylene radicals A, especially salicylic acid or 5
-Chloro-, 5-methyl-, 4-methyl- or 5-
It is an anion that can be considered to be derived from bromosalicylic acid.

The boron-containing anions of this invention may be incorporated into the catalyst composition in the form of salts such as metal salts or dialkyloxonium salts. Preferred metal salts are cobalt, nickel and silver salts. A preferred dialkyloxonium salt is diethyloxonium salt. For example, Co
[B ₁₁ CH ₁₂ ] ₂ , Ni [B ₁₁ CH ₁₂ ] ₂ and Ag [B
Very good results can be obtained with ₁₁ CH ₁₂ ]. If the anion is introduced in the form of an alkali (alkaline earth) metal, ie a metal that is also present in the polymerization process, then an ether, such as a linear or cyclic polyalkylene polyether, such as tetraethylene glycol or a crown ether, can be added to the polymerization process. It is desirable to exist as a separate catalyst component.

The boron-containing anion is suitably a VI group.
Anionic group VIII complexes by reacting a neutral complex of a group II metal, such as a dialkyl compound, with a salt of a boron-containing anion and a cation capable of removing the anion from the complex of group VIII. Can be introduced into the catalyst composition by forming and neutralizing itself. As a non-limiting example, L ₂ Pd (CH ₃ ) ₂ +2
_{^{Cat + + 2B (C 6 F}} 5) 4 - → [L 2 Pd 2+]
_{[B (C 6 F 5)} 4 -] 2 + CH 3 -Cat, or L
_{2 Pd (CH 3) 2 +} Cat + + B (C 6 F 5) 4 - →
^{_{[L 2 PdCH 3 +] [}} B (C 6 F 5) 4 -] + CH
₃ ^- Cat can be used. In the above formula, [Cat ⁺ ] is, for example, diphenylmethylammonium (C ₆ H ₅ ) ₂ CH
₃ NH ⁺ ) and thus [CH ₃ -Cat] becomes methane and diphenylmethylamine, and L is a complexing site (coordinating group (d
entate group)). In this regard, reference may be made to the chemistry of the Group IV metals titanium, zirconium and hafnium, reactions of this kind being known to those skilled in the art.

In the catalyst composition, a compound of the general formula BZ ¹ ₃ [wherein Z ¹ is independently a substituted or unsubstituted hydrocarbyl group,
For example, an aliphatic group or an aromatic group is represented, and these groups typically contain up to 12 carbon atoms] by introducing a borane represented by
It can also be produced, for example, during polymerization. Preferred groups Z ¹ are aryl groups which may be substituted or unsubstituted. Preferred substituents are electron withdrawing groups or atoms such as halogen atoms, trihalomethyl groups and nitro groups. The group Z ¹ is in particular a phenyl group, more particularly a perfluorophenyl or a 3,5-bis (trifluoromethyl) phenyl group. The three Z ¹ groups are typically the same. Preferred compounds of the formula BZ ¹ ₃ is a triphenyl borane, tris (perfluorophenyl) borane and tris [3,5-bis (trifluoromethyl) phenyl] borane. Specific examples of suitable aliphatic groups Z ¹ include methyl and n-butyl.

[0014] type of boron-containing anions that are generated when using the formula BZ ¹ ₃ borane as a catalyst component is dependent chosen reaction conditions, for example of the type of the other catalyst components. This can be explained with three concrete examples. (1) When a Group VIII metal, such as palladium, is present as a complex containing a covalently bound hydrocarbyl group, such as a methyl group, a boron-containing anion can be produced, for example, as follows: L ₂ Pd (CH ₃ ) ⁺ ＋ BZ
¹ ₃ → [L ₂ Pd ²⁺ ] [BZ ¹ ₃ (CH ₃ ) ^- ] or L ₂ Pd (CH ₃ ) ₂ + BZ ¹ ₃ → [L ₂ Pd (C
_{^{H 3) +] [BZ 1}} 3 (CH 3) -], or L ₂ Pd
(CH ₃ ) ₂ + 2BZ ¹ ₃ → [L ₂ Pd ²⁺ ] [BZ ¹
₃ (CH ₃ ) ^- ] ₂ . In the formula, L represents a complexing sites of the ligand (coordinating _{^{group), BZ 1 3 (CH 3}} ) - represents a boron-containing anions.

(2) The Group VIII metal is present as a complex compound containing a covalently bound hydrocarbyl group as in the case of (1) above, and further, it has the general formula YXH [wherein X:
Represents oxygen or sulfur, and Y represents the following meaning], for example, in the case where methanol is present, the boron-containing anion is converted into the neutral borane complex BZ ¹ ₃ ( YXH) _q , where q is 1, 2 or 3, especially ^1.
₃ + CH ₃ OH → [BZ ¹ ₃ + (CH ₃ OH)] and L ₂ Pd (CH ₃ ) ⁺ + [BZ ¹ ₃ + (CH ₃ O
H)] → [L ₂ Pd ²⁺ ] [BZ ¹ ₃ (OC
H ₃ ) ^- ] + CH ₄ or BZ ¹ ₃ + 2CH ₃ OH →
[BZ ¹ ₃ + (CH ₃ OH) ₂ ] and L ₂ Pd (CH
₃ ) ⁺ + [BZ ¹ ₃ + (CH ₃ OH) ₂ ] → [L _{2
^{Pd 2+] [BZ 1 3 (}} OCH 3) -] + CH 4 + CH 3
OH. In the _{^{formula, BZ 1 3 (OCH 3)}} - is a boron-containing anions. Compound YXH may suitably be water (X is oxygen, Y is hydrogen) or alcohol, silanol, oxime or mercaptan, in which case the typical structure of YXH may be: When YOH is an alcohol, Y typically represents an optionally substituted aliphatic or aromatic hydrocarbyl group. These groups may be substituted or unsubstituted and are typically 1
It contains not more than 2, especially not more than 6, carbon atoms. Suitable alcohols YOH are eg 2-methoxyethanol, 4-t
-Butyl-cyclohexanol, isopropanol, benzyl alcohol, perfluorohexanol and hexafluoroisopropanol. The preferred alcohol YOH is methanol. When YOH is silanol, the group Y contains a silicon atom bonded to the hydroxy group of YOH. The silicon atom may carry a phenyl group, or a straight or branched chain alkyl group typically containing up to 12 carbon atoms, more typically up to 6 carbon atoms. The alkyl group further includes a silicon atom or -Si.
It may include O-groups. Specific examples of silanol YOH include (phenyl) (CH ₃ ) ₂ SiOH and (t-C ₄ H
₉ ) (CH ₃ ) ₂ SiOH and ((CH ₃ ) ₃ SiO)
₃ SiOH is mentioned. YOH, when referring to an oxime, is the condensation product of an aldehyde (which in this case can be a cis or trans oxime) or ketone with a hydroxyamine rather than formaldehyde. Aldehydes and ketones of this kind may be aliphatic or aromatic and typically contain up to 12 carbon atoms, more typically up to 6 carbon atoms. Very suitable are, for example, cyclohexanone oxime and acetone oxime. YS
When H represents mercaptan, the group Y is typically defined as an optionally substituted aliphatic or aromatic hydrocarbyl group. These groups may be substituted,
Typically, in view of the odor of mercaptan, 6 carbon atoms
Includes more than one, especially up to 25. Suitable mercaptan YS
H is for example 4-t-butylcyclohexyl mercaptan, para-octylbenzyl mercaptan and octadecyl mercaptan.

(3) General formula YX defined as described above
When a compound of H, such as methanol, is present and a base is further present, the boron-containing anion is converted to the neutral borane complex BZ as described above, for example, according to the following reaction formula
Can be generated via ¹ ₃ (YXH) _q : BZ ¹ ₃ + C
_{^{H 3 OH → [BZ 1 3}} (CH 3 OH)] and [BZ
_{^{1 3 (CH 3 OH)]}} + base → [base -H ^+] + B
Z ¹ ₃ (OCH ₃ ) ^- , or BZ ¹ ₃ + 2CH ₃ OH
_{^{→ [BZ 1 3 (CH 3}} OH) 2] and [BZ ¹ ₃ (C
H ₃ OH) _2] + base → [base -H ^{+] +} BZ ¹ _{3
^{(OCH 3) - + CH 3}} OH.

[0017] In the above ^{_{formula, BZ 1 3 (OCH 3)}} - is a boron-containing anions. Suitable bases capable of removing a proton from the complex BZ ¹ ₃ (YXH) _q are tertiary amines or tertiary phosphines, eg hydrocarbyl groups, which typically contain up to 12 carbon atoms and are preferably aliphatic. The groups are trihydrocarbylamine and trihydrocarbylphosphine. These hydrocarbyl groups are preferably the same as each other. Suitable tertiary amines and phosphines are, for example, triethylamine, N, N-dimethylaniline and tri-n-butylphosphine. Another suitable base comprises a carboxylate anion, typically a carboxylate anion with a pKa of 2 or more, preferably 4-10 (measured in water at 18 ° C.), especially up to 12 carbon atoms, It is an anion of an acid that is aromatic or aliphatic. The carboxylate anion is typically a fatty acid anion. Specific examples of suitable carboxylate anions include acetate, propionate, pivaloate and para-methylbenzoate anions. Another suitable base is an inorganic base such as a phosphate anion, such as dihydrogen phosphate (dihydr).
and an anion of phosphate. The amounts of compound YXH and base that can be used in the catalyst composition of the present invention can vary within wide limits. However, compounds YXH and the molar ratio of borane BZ ¹ ₃ 1: 10 to 1
0: 1, especially 1: 5 to 5: 1, more particularly 1: 2 to 2
2: 1 is preferred. The amount of the base relative to the amount of borane BZ ¹ ₃ (mol) (eq) is from 1:10 to 10: 1, in particular 1: 5 to 5: 1, and more particularly 1: 2 to 2: 1 is there.

The amount of boron-containing anions present in the catalyst composition of the present invention is not critical. Typically, 0.5 to 2 per gram atom of Group VIII metal.
00, preferably 1.0 to 50, more preferably 1.0
Used in an amount of -10 equivalents. The catalyst composition can be isolated, for example, as a metal cation-free complex compound introduced with a boron-containing anion, and the separated complex can be used in the process of the present invention. However, V
When the group III metal is a noble metal, cobalt, nickel, manganese, lead, zinc, magnesium,
The presence of iron (II), copper (II), lanthanum or neodymium cations may have a beneficial effect on catalytic activity in addition to the effect of the presence of boron-containing anions. Therefore, in the process of the present invention, as further components, cobalt, nickel, manganese, lead, zinc, magnesium,
A cation source selected from iron (II), copper (II), lanthanum or neodymium, preferably cobalt, nickel, manganese, lead, zinc, magnesium and iron (I
It is advantageous to use a catalyst composition based on a cation source selected among I), most preferably a cation source selected among cobalt, nickel and manganese. The metal cation is 1.0 to 50 gram atom per gram atom of Group VIII metal, especially 1.0 to 1 gram atom.
It is preferably included in an amount of 0 gram atom.

The catalyst composition of the present invention may contain an aluminoxane as component (b). Aluminoxanes or alumoxanes are well known to those skilled in the art. These materials are typically prepared by the controlled hydrolysis of aluminum alkyls. Preference is given to using aluminoxanes containing an average of 2 to 10, in particular 3 to 5 aluminum atoms per molecule. The use of methylaluminoxane can give advantageous results in the gas phase copolymerization process. Another preferred aluminoxane is an alkylaluminoxane in which the alkyl group is a group containing 2 to 6 carbon atoms and carrying a β-hydrogen atom, in particular a t-butyl group. Especially the latter is M. R. Mason et al. (J. Am. Che
m. Soc. 115 (1993) 4971). The amount of aluminoxane that can be used can vary within wide limits. Preferably, it is used in an amount containing from 10 to 4000 grams of aluminum per gram atom of Group VIII metal, more preferably from 100 to 2000 grams of aluminum.

The catalyst system of the present invention is based on a ligand source for component (C). It will be clear that the presence of two complexing sites on one ligand molecule contributes significantly to the formation of a stable catalyst. Therefore, it is preferable to use a ligand containing two or more coordinating groups capable of complexing with the Group VIII metal. Although less preferred, it is also possible to use monodentate ligands, ie compounds which contain only one coordinating group capable of complexing with the Group VIII metal. It is suitable to use bidentate ligands containing two phosphorus-containing, nitrogen-containing or sulfur-containing coordination groups. Also, 1-
It is also possible to use bidentate mixed ligands such as diphenylphosphino-3-ethylthiopropane. Preferred bidentate ligands have the general formula R ¹ R ² M ¹ -RM ² R ³
It can be represented by R ⁴ (I). In the above formula, M ¹ and M
² independently represents a phosphorus, arsenic or antimony atom, R ¹ , R ² , R ³ and R ⁴ independently represent an unsubstituted or polar substituted hydrocarbyl group, especially one having 10 or less carbon atoms, R represents a divalent organic bridging group containing 1 to 5 carbon atoms in the bridge.

In the ligand of formula (I), M ¹ and M ² preferably represent phosphorus atoms. R ¹ , R ² , R ³ and R ⁴
May independently represent an optionally polar substituted alkyl, aryl, alkaryl, aralkyl or cycloalkyl group. Preferably, one or more of R ¹ , R ² , R ³ and R ⁴ represents an aromatic group, especially an aromatic group substituted with a polar group. Suitable polar groups include halogen atoms such as fluorine and chlorine, alkoxy groups such as methoxy and ethoxy groups, and alkylamino groups such as methylamino, dimethylamino and diethylamino groups. Alkoxy and alkylamino groups contain in particular up to 5 carbon atoms in each alkyl group. R ¹ , R ² , R ³
And when one or more of R ⁴ represents a substituted aryl group, phenyl substituted with an alkoxy group, preferably a methoxy group, at one or both ortho positions relative to M ¹ or M ² is preferred. In the ligand of formula (I), R is 2-4
It is preferred to represent a divalent organic bridging group containing one bridging atom, two or more of which are carbon atoms. Specific examples of the suitable group R include —CH ₂ —CH ₂ —CH ₂ — and —CH _{2
-Si (CH 3) 2 -CH 2} -, - CH 2 -C (C
H _{3) 2} -CH ₂ - and, -CH ₂ -CH ₂ -CH ₂ -
CH ₂ -. R is preferably a trimethylene group.

Another suitable bidentate ligand has the general formula:

[Chemical 4] [Wherein X ¹ and X ² are each independently 3 or 4 on the bridge.
A nitrogen-containing compound represented by an organic bridging group containing two atoms, two or more of which are carbon atoms.].
There may be another bridging group connecting the bridging groups X ¹ and X ² . Specific examples of this type of compound include 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine,
4,4'-dimethoxy-2,2'-bipyridine, 1,1
0-phenanthroline, 4,7-diphenyl-1,10
-Phenanthroline and 4,7-dimethyl-1,10-
Examples include phenanthroline. Preferred compounds are 2,
2'-bipyridine and 1,10-phenanthroline.

Still another suitable bidentate ligand is of the general formula R ⁵
S-Q-SR ⁶ (III) [wherein R ⁵ and R ⁶ independently represent an unsubstituted or polar substituted hydrocarbyl group, and Q represents a divalent bridging group containing 2 to 4 carbon atoms in the bridge. ] It is a sulfur containing compound shown by these. The radicals R ⁵ and R ⁶ are preferably alkyl radicals, each having in particular up to 10 carbon atoms. Very suitable bisthio compounds are 1,2-bis (ethylthio) ethane and 1,2-bis (propylthio) ethene. As a monodentate ligand, a general formula R ⁷ R
⁸ R ⁹ M ³ (IV) [wherein M ³ represents a phosphorus, arsenic or antimony atom, and R ⁷ , R ⁸ and R ⁹ are each independently an unsubstituted or polar substituted hydrocarbyl group such as n-
It represents an alkyl group and an aryl group, especially a phenyl group]. Substituents which can be used are in particular alkoxy groups having up to 5 carbon atoms, such as methoxy and ethoxy groups. A preferred monodentate ligand is
Tris (o-tolyl) phosphine, tolyl (o-methoxyphenyl) phosphine, trinaphthylphosphine and tris (n-butyl) phosphine. The amount of bidentate ligand used can vary widely, but will usually depend on the amount of Group VIII metal present in the catalyst composition. The preferred amount of bidentate ligand is 0.5 to 0.8, preferably 0.5 to 2 moles per gram atom of Group VIII metal with the exception that the bidentate ligand is a nitrogen bidentate. In the case of a ligand, 0.5 to 20 per gram atom of Group VIII metal.
It is preferably used in an amount of 0, especially 1 to 50 mol. The monodentate ligand is 0. 0 per gram atom of Group VIII metal.
It is preferably included in an amount of 5 to 50, especially 1 to 25 mol.

The stability of the catalyst system can be increased by incorporating promoters. It is suitable to use an organic oxidation promoter such as quinone. Preferred accelerators are selected among benzoquinone, naphthoquinone and anthraquinone. Advantageously, the amount of promoter is in the range of 1 to 50, preferably 1 to 10 moles per gram atom of Group VIII metal. Catalytic activity can also be maintained at high levels during polymerization by (additional) constant or variable flow of organic oxidant, or intermittently. In the process of the invention,
Preference is given to using a catalyst system which is supported on a solid support. This is usually to facilitate the introduction of the catalyst system into the reactor. The invention also relates to a supported catalyst composition of this kind. Suitable support materials can be inorganic materials such as silica, alumina or charcoal, or organic materials such as cellulose or dextrose. Also, polymeric materials such as polyethene, polypropene, or copolymers of carbon monoxide and ethylenically unsaturated compounds, such as linear alternating copolymers of carbon monoxide and ethene, or carbon monoxide and ethene and propane or butene-1. Copolymers such as may be used. When an aluminoxane is used as the component (b), a commercially available supported aluminoxane, for example, methylaluminoxane supported on silica may be used.

The amount of catalyst composition relative to the support can be varied within wide limits. A preferred supported catalyst is a support material 1k.
VI of 0.0002 to 0.001 gram atom per gram
Group II metals, especially 0.0000 / kg support material
5-0.005 gram atom Group VIII metal, more particularly 0.00001-0.
It contains 010 gram atoms of a Group VIII metal. It is convenient to impregnate the support with a solution of the catalyst system in a suitable solvent or liquid diluent. The amount of solvent or liquid diluent used is relatively low so that the excess can be easily removed before or during the first step of the copolymerization process. On the other hand, the presence of a small amount of liquid during the process was observed to slow down the deactivation rate of the catalyst system. The gas phase is a continuous phase during the polymerization because the amount of liquid is very small. The amount of liquid is, in particular, 20 to 80, which is sufficient to saturate the gas phase under the conditions of the polymerization.
%, More particularly 40-60% by weight. Preferred are polar solvents such as lower alcohols, for example methanol and ethanol, ethers such as diethyl ether or dimethyl ether (diglyme) of diethylene glycol, and ketones such as acetone and methyl ethyl ketone. Nonpolar solvents to be used to obtain such as toluene, or, in particular catalyst composition, for example, ^{_{[L 2 PdCH 3 +] [}} B (C 6 F 5) 4 -] or ^{_{[L 2 PdCOH 3 +] [}} B ( ^{_{C 6 F 5) 4 -]}} ( as is the case in the formula, L is represents a coordinating group), if it contains a group VIII metal covalently bound to a single hydrocarbyl or acyl group, the solvent The copolymerization may advantageously be carried out in the absence of

The amount of catalyst used in the process of the present invention can vary within wide limits. This amount is VIII per mole of ethylenically unsaturated compound to be copolymerized with carbon monoxide.
Calculated as gram atoms of a group metal, it may be 10 ⁻⁸ to 10 ⁻² . The preferable amount is 10 ⁻⁷ to 10 in the above calculation.
^-3 . Suitable ethylenically unsaturated compounds for use as monomers in the copolymerization process of the present invention include compounds consisting solely of carbon and hydrogen, as well as compounds containing heteroatoms, such as unsaturated esters. Preferred are unsaturated hydrocarbons. Specific examples of suitable monomers include lower α-olefins, that is, 2 to 6 carbon atoms.
Olefins, such as ethene, propene and butene-1, cyclic olefins such as cyclopentene, aromatic compounds such as styrene and α-methylstyrene, and vinyl esters such as vinyl acetate and vinyl propionate. Preferred is ethene, and mixtures of ethene with other α-olefins such as propene or butene-1. Generally, the molar ratio between carbon monoxide and the ethylenically unsaturated compound is 1: 5 to 5: 1.
Select within the range. This molar ratio is preferably 1.5: 1
˜1: 1.5, most preferred is a substantially equimolar ratio.

The copolymerization process of the present invention typically comprises 20 to 2
It is carried out at a temperature of 00 ° C, preferably at a temperature of 30 to 150 ° C. The reaction is advantageously carried out at a pressure of 2-200 bar, preferably at a pressure of 20-100 bar. The copolymers produced by the process of the present invention are suitable as thermoplastics for fibers, films or sheets, or for use in injection molding, compression molding and blow molding. These copolymers may be used in the automotive industry, in the manufacture of food and beverage packaging materials, and in various household applications.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below with reference to Examples.

[0029]

Example 1 A gas phase copolymerization catalyst solution of carbon monoxide and ethene was prepared as follows: 57.4 mg (0.1
1 mmole of 1,3-bis [bis (ortho-methoxy-phenyl) phosphino] propane was dissolved in 2.5 ml of tetrahydrofuran. After complete dissolution, the resulting solution was added to 22.0 mg (0.10 mmole) of palladium (II) acetate. Then 17.5 ml of methanol was added and the mixture was stirred for 1 hour to form a clear light brown solution. Then 84.5 mg (0.25 m
Mole) commercially available cobalt carborate (Co [B ₁₁
CH ₁₂ ] ₂ ) and 33.4 mg (0.22 mmole) of naphthoquinone (33.4 mg) were dissolved. 0.2 ml was taken from this solution and diluted with 2.0 ml of methanol. 1 m of the obtained 4.0 ml diluted catalyst solution
1 was introduced into a 0.5 liter autoclave together with 8 g of a previously prepared dry terpolymer of carbon monoxide, ethene and propene. The autoclave was equipped with a fixed stirrer and automatic pressure release means. The reactor was then closed and pressurized with nitrogen at 50 bar. The pressure is released and the autoclave is scavenged twice with carbon monoxide (6 bar), then carbon monoxide (24 bar) and ethene (2 bar).
Pressurized at 4 bar). The contents of the reactor were heated to 90 ° C. The carbon monoxide / ethene feedstock (molar ratio 1: 1) was started to maintain the pressure at 50 absolute bar. A solution of 111.3 mg of naphthoquinone in 100 ml of methanol was started 0.5 hours after the start of the reaction (defined as when the temperature of the reaction mixture reached 60 ° C.),
Added at a rate of 2.0 ml / mg palladium / hour. After a reaction time of 5 hours, the copolymerization reaction was stopped by automatic pressure release. The product was collected, dried overnight in a vacuum oven at 50 ° C. under a nitrogen purge and weighed. The average polymerization rate is 18.
It was 3 kg copolymer / (g palladium / hour). The intrinsic viscosity (Limiting V
The Iscosity Number, LVN) was 2.2 dl / g, calculated from the viscosity values measured at 60 ° C. at various copolymer concentrations in m-cresol.

Example 2 The same operation as in Example 1 was carried out using 0.25 mmole of commercially available silver carborate (Ag [B ₁₁ CH ₁₂ ]) instead of cobalt carborate. The average polymerization rate is 14.
It was 6 kg polymer / (g palladium / hour). The LVN of the obtained copolymer was 2.5 dl / g. Example 3 The same operation as in Example 1 was carried out by using 0.25 mmole of nickel carborate (Ni [B ₁₁ CH ₁₂ ] ₂ ) instead of cobalt carborate. The results were almost the same as in Example 1. Example 4 (for comparison) The same operation as in Example 1 was carried out using 0.5 mmole of paratoluenesulfonic acid instead of cobalt carborate. The average polymerization rate was 3-4 kg copolymer / (g palladium / hour). The LVN of the resulting copolymer was about 2 dl / g.

Example 5 (1) 0.10 mmole of cobalt carborate was used instead of 0.25 mmole, (2) 0.10 mmole of palladium chloride was used instead of palladium acetate, and (3) naphthoquinone was added. The solution was filtered before and operated as in Example 1. The average polymerization rate is 16.
It was 9 kg copolymer / (g palladium / hour). The LVN of the obtained copolymer was 2.8 dl / g. Example 6 The same operation as in Example 1 was carried out using 0.5 mmole of tris (perfluorophenyl) borane instead of cobalt carborate. The average polymerization rate was 8.4 kg copolymer / (g palladium / hour). The LVN of the obtained copolymer was 3.0 dl / g.

Example 7 (Comparative) A liquid phase copolymerization catalyst solution of carbon monoxide and ethene was prepared as follows: 57.4 mg (0.1
1 mmole of 1,3-bis [bis (ortho-methoxy-phenyl) phosphino] propane was dissolved in 2.5 ml of tetrahydrofuran. After complete dissolution, the resulting solution was added to 22.0 mg (0.10 mmole) of palladium (II) acetate. Then 17.5 ml of methanol was added and the mixture was stirred for 1 hour to form a clear light brown solution. Then 84.5 mg (0.25
mmole) of commercially available cobalt carborate (Co [B
₁₁ CH ₁₂ ] ₂ ) was dissolved in the solution. 1 ml of the obtained catalyst solution was introduced into a 0.3 liter autoclave together with 170 ml of methanol and 2.7 g of a dried terpolymer of carbon monoxide, ethene and propene prepared in advance. The reactor was then closed and pressurized with nitrogen at 50 bar. The pressure is released and the autoclave is scavenged twice with carbon monoxide (6 bar), then carbon monoxide (25 bar).
Pressurized with bar and ethene (25 bar). The contents of the reactor were heated to 90 ° C. The carbon monoxide / ethene feedstock (molar ratio 1: 1) was started to maintain the pressure at 50 absolute bar. After a reaction time of 5 hours, the pressure was released to stop the copolymerization reaction. The product was collected, dried overnight in a vacuum oven at 50 ° C. under a nitrogen purge and weighed. The average polymerization rate is 6.1 kg copolymer / (g palladium / hour)
Met. The LVN of the obtained copolymer is 1.4 dl /
g.

Example 8 (for comparison) The same operation as in Example 7 was carried out using 0.5 mmole of trifluoroacetic acid instead of cobalt carborate.
The average polymerization rate was 7.1 kg copolymer / (g palladium / hour). The resulting copolymer has an LVN of 1.5.
It was dl / g. Example 9 (for comparison) The same operation as in Example 7 was carried out using 0.5 mmole of paratoluenesulfonic acid instead of cobalt carborate. The average polymerization rate was about 6 kg copolymer / (g palladium / hour). The LVN of the resulting copolymer was about 1.5 dl / g.

Examples 1-3, 5 and 6 are the gas phase processes of the present invention, wherein the anion of the present invention is used to utilize the paratoluenesulfonate anion (Example 4). ), A faster average polymerization rate reflecting a higher molecular weight and a higher polymer LVN produced are obtained. In Examples 1 to 3, cations of cobalt, silver and nickel were also present. In Example 5, the cobalt cation was removed prior to carrying out the polymerization. Example 7 has the formula B ₁₁ C for slurry phase polymerization.
H ₁₂ ^- the carborate anion, when using p-toluenesulfonic acid salt and trifluoroacetic acid anions in comparison with (Examples 8 and 9), indicating that it did not improve the rate of polymerization and LVN There is. As a result of ¹³ C-NMR analysis, the polymers obtained in Examples 1 to 9 have a straight chain in which monomer units derived from carbon monoxide and monomer units derived from ethene are alternately arranged. found.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Andre Beuys, Netherlands 1031 C.M.Amsterdam, Bathouesuehi 3 (72) Inventor Andrew Devoted Houghton, A.D.

Claims (13)

[Claims] 1. A source of a cation of a Group VIII metal of the periodic table, and a source of an anion containing a plurality of boron atoms, or a source of an anion containing an organic boron.
Or a gas phase process for the production of copolymers, which comprises reacting carbon monoxide with an ethylenically unsaturated compound in the presence of a catalyst system based on aluminoxane and (c) a ligand source. 2. The catalyst system comprises, for component (b), an anion containing a plurality of boron atoms, for example a carbolate anion, for example an anion of the formula B ₁₁ CH ₁₂ ^— , as well as the general formula BZ ₄ ^— [. Wherein each Z independently represents a substituted or unsubstituted hydrocarbyl group], for example, tetraphenylborate, tetrakis (perfluorophenyl) borate and tetrakis [3,5-bis (trifluoromethyl) phenyl] Boranes based on a boron-containing anion selected from borate anions, or of the general formula BZ ¹ ₃ [wherein each Z ¹ independently represents a substituted or unsubstituted hydrocarbyl group], for example tri Phenylborane, Tris (perfluorophenyl)
Borane and tris [3,5-bis (trifluoromethyl) phenyl] borane or an aluminoxane, for example an aluminoxane containing an average of 3 to 5 aluminum atoms per molecule is used as a base.
The process described in. 3. The catalyst system comprises, for component (a), salts of palladium and carboxylic acids such as palladium acetate (I
I) as a base, and for the component (c), the general formula R ¹
R ² M ¹ -R-M ² R ³ R ⁴ (I) [wherein, M ¹ and M ² represent a phosphorus atom, and R ¹ , R ² , R ³ and R ⁴ are each independently, Represents an unsubstituted or polar substituted aryl group,
R represents a divalent organic bridging group containing 2 to 4 carbon atoms in the bridge], wherein the process is based on a bidentate ligand. 4. In the bidentate ligand of formula (I), R ¹ ,
Process according to claim 3, characterized in that each of R ² , R ³ and R ⁴ represents an ortho-alkoxyphenyl group and R represents a trimethylene group. 5. The catalyst system comprises a V-group catalyst for component (b).
1.0 to 50 equivalents, preferably 1.0 to 10 equivalents, of boron-containing anions per gram atom of Group III metal, or 100 to 2,000 per gram atom of Group VIII metal.
Based on an amount of aluminoxane containing 0 gram atom of aluminum, with regard to component (c), based on 0.5 to 8 mol of bidentate ligand per gram atom of Group VIII metal. Process according to any one of claims 2-4. 6. The catalyst system is based on a Group VIII noble metal and further catalyst components include cobalt, nickel, manganese, lead, zinc, magnesium, iron (II), copper (I).
I), a cation source of one or more metals selected from lanthanum and neodymium, in particular one or more metals selected from cobalt, nickel and manganese. 6. The process according to any one of to 5. 7. One or more metals selected from cobalt, nickel, manganese, lead, zinc, magnesium, iron (II), copper (II), lanthanum and neodymium per gram atom of Group VIII metal. Process according to claim 6, characterized in that it is included in an amount of 1.0 to 10 gram atoms. 8. A process according to claim 1, wherein the Group VIII metal of the catalyst system is covalently bonded to a single hydrocarbyl or acyl group. 9. The catalyst system further comprises a promoter such as benzoquinone, naphthoquinone or anthraquinone, No. VIII.
Process according to any one of claims 1 to 8, characterized in that it comprises an amount of 1 to 50 mol per gram atom of group metal. 10. The catalyst system of claim 1, wherein the catalyst system is supported on a support such as a copolymer of carbon monoxide and one or more ethylenically unsaturated compounds. The process described in. 11. Ethene or a mixture of ethene and propene or a mixture of ethene and 1-butene is used as ethylenically unsaturated compound, the reaction being carried out at a temperature in the range 30 to 150 ° C. and in the range 20 to 100 bar. Process according to any one of claims 1 to 10, characterized in that it is carried out at pressure. 12. (a) a cation source of a Group VIII metal of the periodic table, and (b) a source of an anion containing a plurality of boron atoms, or a source of an organic boron-containing anion, or an aluminoxane. , (C) a ligand source,
(D) A catalyst system based on a solid support material. 13. (a) a Group VIII metal cations of the Periodic Table, (b) anionic and formula BZ ₄ comprising a plurality of boron atoms ^- where unsubstituted or each Z is independently Represents a substituted hydrocarbyl group], or a boron-containing anion selected from the anions represented by the general formula BZ ¹ ₃ [wherein each Z ¹ independently represents a substituted or unsubstituted hydrocarbyl group] Borane or aluminoxane, and (c) (1) the general formula R ¹ R ² M ¹ -RM ² R ³ R
⁴ (I) [wherein, M ¹ and M ² independently represent a phosphorus, arsenic or antimony atom, and R ¹ , R ² , R ³ and R ⁴ each independently represent an unsubstituted or polar substituted hydrocarbyl group. And R represents a divalent bridging group containing 1 to 5 carbon atoms in the bridge], (2) the following general formula: [In the formula, X ¹ and X ² each independently represent an organic bridging group in which 3 or 4 atoms are contained in the bridge, and 2 or more of them are carbon atoms.] Child, (3)
Formula ^{R 5 S-Q-SR 6} (III) [ wherein, R ⁵ and R ⁶ represent independently unsubstituted or polar substituted hydrocarbyl group, Q is containing 2-4 carbon atoms in the bridge two Represents a divalent bridging group], and (4) the general formula R ⁷ R ⁸ R ⁹ M ³ (IV) [wherein M ³ represents a phosphorus, arsenic or antimony atom, and R ⁷ , R ⁸ and R ⁹ independently represent an unsubstituted or polar-substituted hydrocarbyl group], with the proviso that the catalyst composition is a Group VIII metal. When the catalyst is based on palladium and the catalyst component (c) is based on the bidentate ligand of the general formula (II), the catalyst component (b) is tetrakis [3,5-bis (trifluoromethyl) phenyl]. Other than borate anions,
When the catalyst composition is based on the bidentate ligand of the general formula (I) as the catalyst component (c), the catalyst component (b) contains an alkyl group containing 2 to 6 carbon atoms and β- A catalyst composition other than an alkylaluminoxane carrying hydrogen atoms.