JP2003504172A - Catalyst composition and use thereof - Google Patents

Abstract

  (57) [Summary] (A) a Group VIII metal compound, (b) an anion, and (c) a compound of formula R ¹R^TwoM¹-R^Five-M^TwoR^ThreeR^Four[Wherein, R¹, R^Two, R^ThreeAnd R^FourRepresents an optionally substituted homo- or heterohydrocarbyl group; M¹And M^TwoRepresents the same or different elements selected from arsenic, antimony, phosphorus and nitrogen;^FiveRepresents a divalent bridging group in which the bridge is composed of three atoms, two atoms outside the bridge are carbon atoms, and one atom (X) in the middle of the bridge is a group (I) Embedded image (X represents carbon or silicon, and Y may represent various groups and structures).]

Description

Detailed Description of the Invention

The present invention relates to catalyst compositions and their use as catalysts in the production of polyketone polymers.

Catalyst compositions for producing polyketone polymers are known in the art. Usually, this type of catalyst composition will contain a Group VIII metal compound, a bidentate ligand, and a p of 6 or less.
The base is an anion of an acid having Ka. Commonly used bidentate ligands are
Formula R ₂ MR′-MR ₂ (wherein each R independently represents an optionally substituted hydrocarbyl group, and each M represents a chelating atom selected from arsenic, antimony, phosphorus and nitrogen. , R'is usually a divalent bridging group containing 1 to 4 atoms in the bridge, which may or may not have a substituent) Is. The atoms forming the bridge are often carbon atoms and silicon atoms, while the substituents, if present, are usually composed of carbon and hydrogen, and optionally oxygen.

Such catalyst compositions have many variables that can affect the performance of the catalyst during the production of polyketones. Important variables in this regard are the type of Group VIII metal compound and the anion used, and, for bidentate ligands, the groups attached to the chelating atom and the bridging groups. The important parameters defining the performance of the catalyst are the bulk specific gravity of the polymer produced and the activity defined as the rate of polymerization. Furthermore, contamination of polyketone polymer chains with higher olefins (foo
Other effects of using a particular catalyst are also important, such as ringing and building in. A general object of the present invention is to provide a catalyst composition having excellent performance in that not only the bulk density and the polymerization rate of the resulting polymer but also the pollution is small and the economical efficiency associated with the catalyst composition is also advantageous. It is to provide things. Such economic efficiency means, for example, the number of steps required to synthesize a ligand and availability of various reactants,
In terms of cost, the synthesis of the ligand and the costs associated therewith are mentioned. In accordance with the present invention, it has been found that the above overall objectives are best achieved by using specific ligands with novel types of bridging groups.

Bidentate ligands with specific bridging groups have been described in various patent specifications, for example EP-A-0.
, 296, 687. EP-A-0,296,687 discloses a catalyst composition using a bidentate ligand containing a divalent bridging group in which the bridge is composed of three carbon atoms. An atom in the middle of the bridge has a part of a —CR ⁷ R ⁸ — group, wherein R ⁷ and R ⁸ are the same or different monovalent substituents consisting of carbon, hydrogen and optionally oxygen. Is forming. The most preferred bridging group is clearly the 2,2-dimethylpropylene group, which is EP-
It is used in all the examples of A-0,296,687 as a part of a phenyl group containing a bidentate ligand of phosphorus or a polar substituted phenyl group bonded to the phosphorus atom. The most preferred anions of the acid are said to be the p-toluenesulfonate anion and the trifluoroacetate anion. The catalyst composition disclosed in EP-A-0,296,687 gives very good polymerization rates. However, no information is given on the bulk density of the obtained polymer.

An object of the present invention is to provide a catalyst composition having a polyketone polymer having an excellent polymerization rate and having a high bulk density without causing significant contamination. Furthermore, the present invention aims at providing a catalyst composition which is attractive from an economic point of view and therefore is obtained at a relatively low cost.

That is, the present invention includes (a) a Group VIII metal compound, (b) an anion, and (c)
) Formula R ¹ R ² M ¹ -R ⁵ -M ² R ³ R ⁴ {wherein R ¹ , R ² , R ³ and R ⁴ represent the same or different hydrocarbyl groups which may be optionally substituted. M ¹ and M ² represent the same or different elements selected from arsenic, antimony, phosphorus and nitrogen; R ⁵ represents a divalent bridging group having 3 atoms in the bridge, and 2 outside the bridge. The atom is a carbon atom, and one atom (X) in the middle of the bridge is a group

[Chemical 5] [However, X represents a carbon or silicon, Y is ^{-C (R 6) (R 7} ) - or -
^{Si (R 6) (R 7} ) - ^{group, -P (R 8) -,} - P (O) (R 8) - or -
^{P (S) (R 8)} - group, -SO ₂ - or -SO- group, -Al (R ⁸⁾ - group,
Or base

[0007]

[Chemical 6] (Provided that X, M ¹ , M ² , R ¹ , R ² , R ³ and R ⁴ are as defined above, R ⁶ and R ⁷ are the same or different groups, and are carbon, hydrogen and Optionally represents an oligomeric or polymeric chain consisting of one or more heteroatoms, or R ⁶ and R ⁷ together with the carbon or silicon atom to which they are attached are carbon, hydrogen and optionally oxygen and / or Alternatively, an alicyclic structure composed of silicon is formed.
However, R ⁶ and R ⁷ are not methyl groups when X is a carbon atom and the acid derived from the anion is p-toluenesulfonic acid or trifluoroacetic acid. R ⁸ represents hydrogen or an alkyl group having 1 to 5 carbon atoms) and forms a part of the following]. The Group VIII metal compound used as component (a) may be a platinum compound, a cobalt compound, a nickel compound or a palladium compound, preferably a palladium compound. This compound may take the form of a salt of a carboxylic acid, preferably acetic acid. The most preferred Group VIII metal compound is palladium acetate.

The person skilled in the art should, in order to obtain a high polymerization rate, that the anion used as component (b) should not be coordinated with the Group VIII metal or, if coordinated, be very weak. It will be understood that it must be done. Examples of suitable anions include anions of protonic acids such as acids obtained by combining a Lewis acid and a protic acid, and acids consisting of an adduct of boric acid and 1,2-diol, catechol or salicylic acid. . Preferred acids have a pKa of less than 6 measured at 18 ° C. in aqueous solution,
Particularly less than 4, more especially less than 2. Examples of suitable acids are known in the art and include sulfuric acid, perchloric acid, methanesulfonic acid, sulfonic acids such as p-toluenesulfonic acid, and 2,6-dihydroxybenzoic acid, maleic acid, trichloroacetic acid, Examples thereof include carboxylic acids such as difluoroacetic acid and trifluoroacetic acid. An example of an acid composed of a combination of a Lewis acid (BF ₃ ) and a protonic acid (HF) is tetrafluoroboric acid (HBF ₄ ). Other suitable anions are borate anions consisting of boron with the same or different hydrocarbyl groups attached, such as tetraarylborate and carborate.
Hydrocarbylborane, such as triphenylborane, or aluminoxane (a
Luminoxane), such as methyl aluminoxane and t-butyl aluminoxane, can also be applied as the compound functioning as an anion source. Other examples of suitable anions are described in EP-A-0,743,336. Most preferably for the purposes of the present invention, the anion is derived from a protic acid selected from p-toluene sulfone, trifluoroacetic acid, maleic acid and mixtures of two or more thereof.

In this connection, it was also found that maleic acid in particular has a beneficial effect on various properties such as oxidative stability and the whiteness of the polyketone polymers produced. It has been found that this beneficial effect is not limited to the particular ligands that are the subject of the present invention, but extends beyond these ligands to other ligands as well. Therefore, it was concluded that the beneficial effect was due to the use of maleic acid as the anion source. The amount of anion source is suitably selected such that the anion is provided in the range of 0.1 to 50 equivalents, preferably 0.5 to 25 equivalents, per mole of Group VIII metal. However, aluminoxane has a molar ratio of alumina to Group VIII metal of 40.
00: 1 to 10: 1, preferably 2000: 1 to 100: 1, most preferably 5
It may be used in an amount such that it ranges from 00: 1 to 200: 1.

In the ligand forming component (c) of the catalyst composition, the R ¹ , R ² , R ³ and R ⁴ groups are preferably one or more substantially non-polar groups and / or Represents a same or different aryl group optionally substituted with one or more polar groups. In a further preferred embodiment, R ¹ , R ² , R ³ and R ⁴ independently represent a phenyl group or a substituted phenyl group, in the latter case a C1-C4 alkoxy group, most preferably a methoxy group, an aryloxy group, Most preferably a phenyloxy group, and C1
There are one or more substituents selected from ~ C4 alkyl groups, most preferably methyl groups. Examples of suitable substituted groups are 2-methoxyphenyl, 2,4-dimethoxyphenyl, 4-methoxyphenyl, 2,6-dimethoxyphenyl, 2-methoxy-5-methylphenyl and 2,4,6-triphenyl. It is methoxyphenyl. R ¹ ,
Most preferably, the R ² , R ³ and R ⁴ groups are all the same and are selected from phenyl, 2-methoxyphenyl and 2-methoxy-5-methylphenyl.

The central atom X of the ligand bridge may be a carbon atom or a silicon atom, but is preferably a carbon atom. The chelating atoms M ¹ and M ² are preferably both phosphorus atoms. The central atom X of the bridging group forms part of the cyclic structure shown in formula (I). This cyclic structure ends with a Y group. The Y group present in the ligand represents a variety of different groups capable of forming two stable bonds with oxygen atoms both shown in formula (I) and consequently forming a stable cyclic structure. . Thus, the Y group can represent the groups described above. Among them, Y is ^{-C (R 6) (R 7} ) - group, or ^{-Si (R 6) (R 7} ) -
Can represent a group. Wherein R ⁶ and R ⁷ are the same or different groups or chains and represent an oligomeric or polymeric chain consisting of carbon, hydrogen and optionally one or more heteroatoms, or R ⁶ and R 7 ⁷ together with the carbon atom to which they are attached form an alicyclic structure consisting of carbon, hydrogen and optionally oxygen,
However, R ⁶ and R ⁷ are not methyl groups when X is a carbon atom and the acid derived from the anion (component (b)) is p-toluenesulfonic acid or trifluoroacetic acid.

In a preferred embodiment, R ⁶ and R ⁷ independently represent an alkyl group or a polymer chain consisting of carbon, hydrogen and optionally one or more heteroatoms such as oxygen, nitrogen, sulfur and phosphorus. . Among these, C1-C4 alkyl groups such as methyl or ethyl, or polyketone polymer chains, that is, having one or more carbonyl groups alternating with olefin monomers, or in a random distribution that intersects the polymer chains. A polymer chain having a carbonyl group. The length of these polymer chains can vary within wide limits and includes both oligomers and polymers. If R ⁶ and R ⁷ are polyketone polymer chains, these chains can serve as carriers to which the ligands are covalently attached. In this way, a catalyst supported on a carrier is obtained. This kind of catalyst
It may also be useful in liquid phase (or slurry) polymerization processes for making linear alternating polyketone polymers, but is of particular interest to gas phase polymerization processes. Furthermore, if R ⁶ and R ⁷ are polyketone polymer chains, more than one ligand may be attached to the single polymer chain. Thus, in a preferred aspect of the invention, one polymeric chain can serve as a "backbone" pendant to two or more ligands of formula (I). In fact, these ligands are attached to the polyketone backbone polymer via the keto group. That is, Y in formula (I) is the carbon atom of the original keto group in the polymer chain.

[0013]   In another preferred embodiment, R⁶And R⁷Together with the carbon atom to which they are attached
Optionally substituted with one or more substantially non-polar groups or one or more polar groups.
To form a cycloalkyl group which may be optionally substituted. Substantially non-polar substituents include
Alkyl groups, preferably C1-C4 alkyl groups are mentioned, among which methyl and
And ethyl groups are most preferred. Suitable polar substituents are especially alkoxy groups (preferably
Suitably C1-C4 alkoxy groups such as methoxy and ethoxy), oxo groups,
Examples thereof include a hydroxy group and a carboxyl group. But R⁶And R⁷Haso
Together with the carbon atom to which they are attached, a cycloalkyl group, most preferably a
It is preferable to form a clopentyl group or a cyclohexyl group.   Generally, X is a carbon atom and Y is -C (R⁶) (R⁷) -Table
For example, (a) commercially available 2,2-bis (bromomethyl) -1,3-propane is used as the ligand.
Compound R with diol⁶-C (= O) -R⁷The step of reacting with
b) The compound thus obtained is treated with Li-M¹R¹R²And / or Li-M²R ³ R^FourTo recover the ligand by reacting with a chelating atom-containing compound such as
Can be manufactured by a method including   Hereinafter, this method is referred to as method I.

Step (a) can be performed by a method known in the art. For example US
Example 1 of -4,851,461 illustrates this reaction for cyclohexanone. Process conditions typically include temperatures of 10 to 160 ° C. and essentially zero to 10
Pressure to bar. The step (a) is preferably carried out at a temperature rise of at least 60 ° C. under atmospheric pressure. The step (b) is performed, for example, in European Patent Application No. 982
Effectively according to the method disclosed in 03587. This document is L
Disclosed is both the preparation of i-M ¹ R ¹ R ² type compounds and the reaction of halogen-containing compounds with these lithium compounds, thereby providing a dentate composition useful as a catalyst component of a catalyst composition for preparing polyketone polymers. Manufactures orders. Process (b)
Is preferably carried out at a temperature of 55 ° C. or lower, preferably 40 ° C. or lower, particularly 30 ° C. or lower. Suitably this step is carried out at least -50 ° C, preferably at least -15 ° C, most preferably at least 0 ° C. Such processes generally require cooling, which preferably brings the reaction mixture to 0-25 ° C. The pressure is not particularly critical and can vary from essentially zero to 10 bar. This process is
Preference is given to working at a pressure of 0.5 to 1.5 bar.

[0015]   Alternatively, X is a carbon atom and Y is -C (R⁶) (R⁷) -Table
For example, (a) commercially available 2,2-bis (bromomethyl) -1,3-propane is used as the ligand.
Reacting a diol with a protecting agent that reacts with the hydroxyl group, step (b)
The product of (a) was added to Li-M¹R¹R²And / or Li-M²R³R^FourAs
Reacting with a compound containing a chelating atom, (c) from the hydroxyl group
The product of the step of recovering the protecting agent, and (d) the step (c) is treated with a compound R⁶-C
(= O) -R⁷And a step of recovering the ligand (Method II)
Can be manufactured by   It is known in the art to protect the hydroxyl group of 1,3-diol by a chemical reaction.
Are known in the art. Suitable protectants include, for example, ketones (and thereby ketals).
And aldehydes (which form acetals).
It Examples of suitable protectants are propanone, formaldehyde and ethanal.
It The removal of the protective agent after step (b) is preferably carried out by adding an acid.
Such methods are also well known in the art. The steps (b) and (d) are as described above.
It can be performed under the same conditions as those outlined.   Similarly, Y is -Si (R⁶) (R⁷)-Group is represented by R ⁶ -C (= O) -R⁷Instead of (R⁶) (R⁷) SiCl₂Method I
Or method II. Commercially available compound (R⁶) (R⁷) SiCl₂Example
Is diethyl silicon dichloride.

[0016]   Furthermore, Y can also represent one of the following groups: (I) -P (R⁸)-, -P (O) (R⁸) -Or-P (S) (R⁸) -Group
(Ii) -SO₂-Or-SO- group, or (Iii) -Al (R⁸) -Group Where R⁸Is hydrogen or an alkyl group having 1 to 5 carbon atoms. Of these Y groups
Ligands having either one are also relatively simple and
It can be manufactured effectively. More specifically, Y is -P (R⁸) -Representing formula I
The ligand is R⁶-C (= O) -R⁷Instead of dihalophosphine (eg R⁸ -PCl₂Can be effectively produced by Method I or Method II. Y is-
P (O) (R⁸)-, -P (S) (R⁸)-,-SO₂-, -SO- or -A
l (R⁸) -The ligand of formula I is R⁶-C (= O) -R⁷Instead of it
Dihalophosphine oxide (for example, R⁸-POCl₂Or R⁸-POBr ₂ ), Dihalophosphine sulfides (eg R⁸-PSCl₂Or R⁸-PS
Br₂), Sulfuryl chloride (SO₂Cl₂), Thionyl chloride (SOCl₂)Also
Is ethyl aluminum dichloride (C₂H_FiveAlCl₂) By method II
Most preferably manufactured.

In a further aspect, Y may represent a group of formula (II). In this case, 4
A bidentate ligand is obtained. A compound of formula (II) is prepared according to Method I in 2 mol of 1,3-
It is preferably obtained by reacting dibromo-2,2-dihydroxymethylenepropane with 1 mol of 1,4-cyclohexanedione and then reacting with a compound containing a chelating atom. The amount of the ligand used in the catalyst composition is 0.5 to 2 per mol of the Group VIII metal,
Particularly, 0.75 to 1.5 mol is preferable. In order to improve the performance of the catalyst composition, an organic oxidant promoter may be added to the present catalyst composition. Suitable accelerators are quinones such as benzoquinone, naphthoquinone and anthraquinone. The amount of the promoter used is 1 to 250 per mol of the Group VIII metal.
The range of 1 to 100 is preferable. The catalyst composition of the present invention is preferably used in the form of a solution in a liquid. Suitable liquids include, for example, C ₁ -C ₄ alcohols such as methanol and ethanol,
Mention may be made of C ₂ -C ₈ ethers such as diethyl ether, tetrahydrofuran or dimethyl ether of diethylene glycol (diglyme), C ₂ -C ₆ ketones such as acetone and methyl ethyl ketone and polar solvents such as aromatic solvents such as toluene. For purposes of this invention, methanol and acetone are preferred.
The invention also relates to the catalyst composition solution described above.

[0018]   In a further aspect, the invention also provides the formula R¹R²M¹-R^Five-M²R³R^Four(In the formula,
R¹, R², R³, R^Four, M¹, M²And R^FiveIs R when X is a carbon atom ⁶ And R⁷Has the same meaning as above, except that is not a methyl group)
Of compounds. In a highly preferred embodiment, R⁶And R⁷Are the same or different
C₁~ C_FourAlkyl group, preferably methyl or ethyl or polyketone
Represents a coalesced chain, or R⁶And R⁷Together with the carbon atom to which they are attached
To form a cyclopentyl group or a cyclohexyl group.   The invention also relates to a mixture of carbon monoxide and one or more olefinically unsaturated compounds.
Relates to a method for producing a polymer, wherein the polymerization is performed in the presence of a catalyst as defined above.

Olefinically unsaturated compounds which can be used as monomers in the above process include compounds consisting of carbon and hydrogen, and compounds which further contain heteroatoms such as unsaturated esters, ethers and amides. Unsaturated hydrocarbons are preferred. Examples of suitable olefinic monomers are olefins such as ethene, propene, butene-1, octene-1, decene-1 and dodecene-1, cyclic olefins such as cyclopentene, fragrances such as styrene and α-methylstyrene. Group compounds and vinyl esters such as vinyl acetate and vinyl propionate. Most preferred are ethene, and ethene and other olefinically unsaturated compounds, especially propene, butene-1, octene-1, decene-1 and dodecene-1.
A mixture with α-olefins such as In general, the molar ratio of one carbon monoxide to the other unsaturated compound used as a monomer is chosen in the range from 1: 5 to 5: 1. This molar ratio is 1: 2 to 2: 1.
Is preferred, and an approximately equimolar ratio is most preferred. The process according to the invention is preferably carried out at a total pressure of 20 to 150 bar. However, for economic reasons, a total pressure of 20-75 bar is usually preferred. Polymerization is usually 20 to 2
It is carried out at a temperature in the range of 00 ° C, preferably 40-150 ° C.

The present invention provides a supercritical phase as a gas phase polymerization.
case) polymerization, and also as liquid phase or slurry polymerization. When carried out as a gas phase method, the catalyst composition is preferably supported on a carrier. Suitable support materials and methods and methods of impregnating the support with a catalyst solution are well known in the art. Suitable diluents when operating in the supercritical phase are ethene or carbon dioxide. The diluent used when working as a slurry process must not be a liquid such that the polyketone polymer formed is essentially insoluble and in suspension. Suitable diluents are ketones (eg acetone), chlorinated hydrocarbons (eg chloroform or dichloromethane), aromatics (eg toluene, benzene, chlorobenzene) and proton diluents, C1-C4 alcohols (eg methanol and ethanol). . Among these diluents, C1 to C4 alcohols, particularly methanol, are preferable. The amount of catalyst composition used in the process of the present invention is such that there are 10 ^-7 to 10 ^-3 , especially 10 ^-6 to 10 ^-4 Group VIII metal per mole of olefinically unsaturated compound to be copolymerized. Is the amount. The method of the present invention may be carried out batchwise or continuously.

[0021]

【Example】

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these specific modes. In these examples, the polymer's limited viscosity number (LV)
N). The concept of LVN is well known in the art, eg EP-A-
0,246,674 and EP-A-0,319,083. The LVN referred to in the present invention is the LVN described in EP-A-0,319,083,
That is, it is the LVN based on the viscosity measured at 60 ° C. for four polymer solutions prepared by dissolving the polymer in m-cresol at 60 ° C. at four different concentrations.

Example 1 (for comparison) 2,2-Dimethyl-1,3-bis (bis (o-anisyl) phosphino) propane was prepared according to the following method via the following intermediate. a) 2,2-Dimethyl-1,3-propanediol dimesylate In a 1 liter reactor equipped with a mechanical stirrer and a dropping funnel, 2,2-dimethyl-1,
3-Propanediol 33.3 g (0.32 mol), triethylamine 72.7
g (0.72 mol) and 250 ml of dichloromethane were charged. The mixture was cooled to 0 ° C. and 82.4 g (0.72 mol) of methanesulfonyl chloride was added at such a rate as to maintain the temperature at 0-10 ° C. The resulting mixture was stirred at room temperature for another hour. Then 200 ml of water was added. The organic phase was separated and washed twice with 200 ml of water. The organic phase was dried over anhydrous MgSO ₄ , filtered through a P3 glass filter and then evaporated to dryness. Finally, the residue was slurried with 500 ml of hexane, and 2,2-dimethyl-1,3-propanediol dimesylate was mixed with 7 ml.
4.1 g (0.285 mol, 89%) was obtained.

B) 1,3-Dibromo-2,2-dimethylpropane 74.1 g (0.285) of 2,2-dimethyl-1,3-propanediol dimesylate in a 1 liter reactor equipped with a mechanical stirrer. Mol), anhydrous lithium bromide 50 g (0
． 57 mol) and 500 ml of N, N-diethylacetamide. The mixture was stirred at 120 ° C. for 6 hours. After cooling, transfer the reaction mixture to a separating funnel,
1 liter of water and 500 ml of hexane were added. Separate the hexane phase and add 5 more water.
It was washed twice with 00 ml. Then, the hexane phase was dried over anhydrous MgSO ₄ ,
After filtering with a glass filter, it was evaporated and dried. The residue obtained is vacuum distilled to 1
, 3-Dibromo-2,2-dimethylpropane 56.1 g (0.244 mol, 86
%) Was obtained.

[0024] c) 2,2-dimethyl-1,3-bis (bis (o-anisyl) phosphino) 40 ml of THF in propane mechanical stirrer and a reflux condenser 100ml reactor under an argon atmosphere equipped with, N, N -Diethylamino-bis (2-anisyl) phosphine 3
． 17 g (10 mmol) and 486 mg (21 mmol) of 30% lithium dispersion were charged at 0 ° C. under argon atmosphere. The reaction mixture was stirred for 16 hours. After stirring, precipitation occurred. ³¹ P NMR showed complete conversion of the starting phosphine. Then, after adding 5 ml of DMSO, 1.15 g (5 mmol) of 1,3-dibromo-2,2-dimethylpropane was slowly added. After stirring for another 2 hours,
20 ml of methanol were added and the solvent was removed under vacuum. 50 ml of dichloromethane and 50 ml of water were added to this residue. Next, the dichloromethane phase is mixed with anhydrous Mg
It was dried over SO ₄ , filtered through a P3 glass filter, and then evaporated and dried at 20 ° C. under vacuum. The residue was refluxed in 10 ml of methanol to obtain a white precipitate. After filtration and drying, the desired diphosphine was obtained as a white solid in a yield of 1.73 g (3.1 mmol, corresponding to a yield of 62%). The solid was pure by ¹ H, ¹³ C and ³¹ P NMR.

Example 2 3,3-Bis- [bis- (2-methoxyphenyl) -phosphanylmethyl] -1,5-dioxa-spiro [5.5] undecane was prepared via the following intermediate according to the following method. . a) 3,3-bis - bromomethyl-1,5-dioxa - following reaction spiro [5.5] undec cans the compound (wherein, "MsOH" was prepared according represents methanesulfonic acid).

[Chemical 7] 5,2-bis (bromomethyl) -1,3-propanediol 52.4 g (0.
2 mol), 19.6 g (0.2 mol) of cyclohexanone, 200 ml of toluene and 0.5 ml of methanesulfonic acid were refluxed for 2 hours using a Dean Stark apparatus. During this time the theoretical amount of water (3.6 ml; 0.2 mol) was collected. After cooling, the mixture is diluted with 200 ml of sodium bicarbonate and 2 x 200 ml of water.
It was extracted with. The organic phase was dried over anhydrous MgSO ₄ , filtered through a P3 glass filter and then concentrated. The yield was almost quantitative. According to gas chromatographic analysis, the purity was 98% (in toluene as a solvent).

B) 3,3-Bis- [bis- (2-methoxyphenyl) -phosphanylmethyl] -1,5-dioxa-spiro [5.5] undecane The following reaction (“An” is (Representing anisyl which is a 2-methoxyphenyl group).

[Chemical 8] 40 ml THF in a 100 ml reactor equipped with mechanical stirrer and reflux condenser,
3.17 g (10 mmol) of N, N-diethylamino-bis (2-anisyl) phosphine and 486 mg (21 mmol) of 30% lithium dispersion were charged at 0 ° C. under an argon atmosphere. The reaction mixture was stirred for 16 hours. After stirring, a thick precipitate formed. ³¹ P NMR showed complete conversion of the starting phosphine. The lithium diethylamide was quenched by the addition of 535 mg (10 mmol) ammonium chloride, which raised the temperature to 6 ° C. The mixture was cooled to 0 ° C. again and after stirring for a further 30 minutes 1.71 g (5 mmol) of compound (a) in 5 ml of THF was added over 10 minutes. The mixture was stirred for an additional 2 hours while slowly raising the temperature to 20 ° C. Then 10 ml of methanol were added, the solvent was removed under vacuum and 40 ml of toluene and 40 ml of water were added. The organic phase was separated and washed with 20 ml of water. The toluene phase is concentrated to 10 ml and methanol 30 ml
Was added and the mixture was refluxed until a white precipitate formed. The mixture was allowed to crystallize overnight. It was then filtered through a P3 glass filter, rinsed with methanol and dried. The desired diphosphine was obtained as a white solid in a yield of 2.54 g (76% yield). The solid was pure by ¹ H, ¹³ C and ³¹ P NMR.

Example 3 Preparation of Catalyst Solution I Palladium acetate (16.9 mg, 0.0752 mmol) in 20 ml of acetone.
Was added. After 5 minutes all solids had dissolved resulting in an orange solution. Subsequently, 53.1 mg (0.0789 mmol) of the ligand prepared in Example 2 was added. A clear yellow solution was obtained within minutes. After 1 hour, trifluoroacetic acid (51.4 mg
, 34.8 ml, 0.451 mmol) was added. The solution was stirred for 1 hour to give a clear pale yellow solution. When kept at room temperature, this solution was found to be stable for at least 4 weeks.

Example 4 Preparation of Catalyst Solution II Example 3 was repeated except that maleic acid was added instead of trifluoroacetic acid. Therefore, a catalyst solution was prepared based on 16.9 mg (0.0752 mmol) of palladium acetate, 53.1 mg (0.0789 mmol) of the ligand of Example 2, 175 mg (1.50 mmol) of maleic acid and 20 ml of acetone as a base material. did. When kept at room temperature, this solution was also found to be stable for at least 4 weeks.

Example 5 Polymerization Seed powder (5.4 g, ethene / propene / CO terpolymer, 2 wt% propene)
) Was weighed and placed directly in a 0.5 l autoclave, then 270 g of methanol
(334 ml) was added. Catalyst Solution I was introduced from a polyethylene injector. The autoclave was closed, the stirrer was turned and the system was pressurized to 50 bar nitrogen pressure to test the reactor for leaks and remove most of the oxygen. After 5 minutes, the pressure was carefully released. The furnace was switched on and when a temperature of 88 ° C. was reached, ethene was added and then 24 bar carbon monoxide was introduced. As a result, the total pressure was 50 bar (self pressure of methanol was 2 bar). A 1: 1 (mol / mol) CO / ethene gas mixture was introduced during the operation in order to maintain the pressure during the polymerization at 50 bar. Polymerization is CO
It is considered that it started (t = 0) at the time of introducing. The polymerization proceeded at 90 ° C. for 1 hour. The heating was then stopped, the reactor started to cool, and the pressure was carefully released. The polymer was filtered off using a Buchner funnel, washed with methanol and then dried overnight in an oven. The mass of the resulting CO / ethene (CO / E) copolymer was measured, corrected for the seed powder, and the bulk density and LVN were measured. The results are shown in Table I.

Example 6 Example 5 was repeated except that catalyst solution II was used instead of catalyst solution I. The results are shown in Table I.

Example 7 (for comparison) Instead of the catalyst solution I, 0.0752 mmol of palladium acetate, 0.0789 mmol of the ligand prepared in Example 1, 0.451 mmol of trifluoroacetic acid and 20 ml of acetone were used as the base materials. Example 5 was repeated except that the catalyst solution was added. The mass of the obtained polymer was measured, corrected for the seed powder, and the bulk density and LVN (in m-cresol at 60 ° C.) were measured. The results are shown in Table I.

Example 8 Polymerization Seed powder (33.6 g, ethene / propene / CO terpolymer, propene 6w)
t%) and weighed directly into an autoclave of 1.25 l, then methanol 5
60 g (693 ml) and 11.2 g of water were added. Catalyst Solution I was introduced from a polyethylene injector. The autoclave was closed, the stirrer was turned and the system was pressurized to 50 bar nitrogen pressure in order to test the reactor for leaks and remove most of the oxygen present. After 5 minutes, the pressure was carefully released and the reactor was flushed with CO 3 times. 72 g of liquid propene were added and an additional 10 bar of CO was introduced. The furnace was switched on and when a temperature of 76 ° C. was reached, ethene was added until the final pressure reached 46 bar. As a result, the CO / olefin molar ratio was 0.7 and the ethene / propene molar ratio was 0.4 (the self-pressure of methanol was 2 bar). Pressure during polymerization is 4
During the polymerization, a 1: 1 (mol / mol) CO / ethene gas mixture was introduced in order to maintain 6 bar. The polymerization is considered to have started when CO was introduced. The polymerization proceeded at 76 ° C. for 6 hours. The heating was then stopped, the reactor started to cool, and the pressure was carefully released. The polymer was filtered off using a Buchner funnel, washed with methanol, and then dried in a vacuum oven overnight. The mass of the resulting CO / ethene / propene (CO / E / P) terpolymer was measured, corrected for seed powder, and the bulk density and LVN (in m-cresol at 60 ° C) were measured. . The results are shown in Table I.

Example 9 Example 8 was repeated except that catalyst solution II was used instead of catalyst solution I. The results are shown in Table I.

Example 10 (for comparison) Instead of the catalyst solution I, 0.0752 mmol of palladium acetate, 0.0789 mmol of the ligand prepared in Example 1, 0.451 mmol of trifluoroacetic acid and 20 ml of acetone were used as base materials. Example 6 was repeated except that the catalyst solution was added. The mass of the resulting polymer was measured, corrected for the seed powder, and the bulk density and LVN were measured. The melting point (mp) was also measured. The results are shown in Table I.

[0035]

[Table 1] Table I Polymerization results ┌───┬──────┬─────┬─────┬────┐ │ Example │ Polymer │ Speed │ LVN │ m. p. │ │ │ │ (kg / gh) │ (dl / g) │ (℃) │ ├───┼──────┼─────┼─────┼────┤ │ 5 │ CO / E │ 44 │ 1.20 │ Not measured │ ├───┼──────┼─────┼─────┼────┤ │ 6 │ CO / E │ 33 │ 1.27 │ Not measured │ ├───┼──────┼─────┼─────┼────┤ │ 7 ^* │ CO / E │ 25 │ 1.35 │ Not measured │ ├───┼──────┼─────┼─────┼────┤ │ 8 │CO / E / P│11.5 │1.33 │221 │ ├───┼──────┼─────┼─────┼────┤ │ 9 │CO / E / P│10.9 │1 ^{.20 │225 │ ├───┼──────┼─────┼─────┼────┤ │10 * │CO /} E / P│10 5 │1.44 │228 │ └───┴──────┴─────┴─────┴────┘ * for comparison

From the results in Table I it can be seen that the catalyst composition of the present invention provides high molecular weight (expressed as LVN) polyketone polymers at high speeds.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] July 2, 2001 (2001.7.2)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Contents of correction]

[Chemical 1] [However, X represents a carbon or silicon, Y is ^{-C (R 6) (R 7} ) - or -
^{Si (R 6) (R 7} ) - ^{group, -P (R 8) -,} - P (O) (R 8) - or -
^{P (S) (R 8)} - group, -SO ₂ - or -SO- group, -Al (R ⁸⁾ - group,
Or base

[Chemical 2] (Provided that X, M ¹ , M ² , R ¹ , R ² , R ³ and R ⁴ are as defined above, R ⁶ and R ⁷ are the same or different groups, and are carbon, hydrogen and Optionally represents an oligomeric or polymeric chain consisting of one or more heteroatoms, or R ⁶ and R ⁷ together with the carbon or silicon atom to which they are attached are carbon, hydrogen and optionally oxygen and / or Alternatively, an alicyclic structure composed of silicon is formed.
However, R ⁶ and R ⁷ are not simultaneously a methyl group. R ⁸ represents hydrogen or an alkyl group having 1 to 5 carbon atoms) and forms a part of the above}.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Contents of correction]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Contents of correction]

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 4

[Correction method] Change

[Contents of correction]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 5

[Correction method] Change

[Contents of correction]

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Contents of correction]

Such catalyst compositions have many variables that can affect the performance of the catalyst during the production of polyketones. Important variables in this regard are the type of Group VIII metal compound and the anion used, and, for bidentate ligands, the groups attached to the chelating atom and the bridging groups. The important parameters defining the performance of the catalyst are the bulk specific gravity of the polymer produced and the activity defined as the rate of polymerization. Furthermore, contamination of polyketone polymer chains with higher olefins (foo
Other effects of using a particular catalyst are also important, such as ringing and building in. A general object of the present invention is to provide a catalyst composition having excellent performance in that not only the bulk density and the polymerization rate of the resulting polymer but also the pollution is small and the economical efficiency associated with the catalyst composition is also advantageous. It is to provide things. Such economic efficiency means, for example, the number of steps required to synthesize a ligand and availability of various reactants,
In terms of cost, the synthesis of the ligand and the costs associated therewith are mentioned. In accordance with the present invention, it has been found that the above overall objectives are best achieved by using specific ligands with novel types of bridging groups.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Contents of correction]

Bidentate ligands with specific bridging groups have been described in various patent specifications, for example EP-A-0.
, 296, 687. EP-A-0,296,687 discloses a catalyst composition using a bidentate ligand containing a divalent bridging group in which the bridge is composed of three carbon atoms. An atom in the middle of the bridge has a part of a —CR ⁷ R ⁸ — group, wherein R ⁷ and R ⁸ are the same or different monovalent substituents consisting of carbon, hydrogen and optionally oxygen. Is forming. The serial placement, R ⁶ and R ⁷ together _{-CH 2 -O-C (CH 3} ) 2 -O-CH 2 - includes forming a ring structure by a group. The most preferred bridging group is clearly the 2,2-dimethylpropylene group, which is EP-A-0,
In all examples of 296, 687, it is used as part of a phosphorus bidentate phenyl-containing phenyl group or a polar substituted phenyl group attached to the phosphorus atom. The most preferred anions of the acid are said to be the p-toluenesulfonate anion and the trifluoroacetate anion. The catalyst composition disclosed in EP-A-0,296,687 gives very good polymerization rates. However, no information is given on the bulk density of the obtained polymer. Sila Suitable catalyst compositions for the production of the polyketone in EP-A-0,300,583 and EP-A-0,743,336 (sila) - having a ring structure such as a ring structure on propane crosslinking The use of different crosslinks is described. None of these filing does not refer to bulk density.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Contents of correction]

An object of the present invention is to provide a catalyst composition having a polyketone polymer having an excellent polymerization rate and having a high bulk density without causing significant contamination. Furthermore, the present invention aims at providing a catalyst composition which is attractive from an economic point of view and therefore is obtained at a relatively low cost.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Contents of correction]

[0007]

[Chemical 6] (Provided that X, M ¹ , M ² , R ¹ , R ² , R ³ and R ⁴ are as defined above, R ⁶ and R ⁷ are the same or different groups, and are carbon, hydrogen and Optionally represents an oligomeric or polymeric chain consisting of one or more heteroatoms, or R ⁶ and R ⁷ together with the carbon or silicon atom to which they are attached are carbon, hydrogen and optionally oxygen and / or Alternatively, an alicyclic structure composed of silicon is formed.
However, R ⁶ and R ⁷ are not simultaneously (bot) methyl group. R ⁸ represents hydrogen or an alkyl group having 1 to 5 carbon atoms) and forms a part of the following]. The Group VIII metal compound used as component (a) may be a platinum compound, a cobalt compound, a nickel compound or a palladium compound, preferably a palladium compound. This compound may take the form of a salt of a carboxylic acid, preferably acetic acid. The most preferred Group VIII metal compound is palladium acetate.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Contents of correction]

[0035]

[Table 1] Table I Polymerization results ┌───┬──────┬─────┬─────┬────┬─────┐ │ Example │ Polymer │ Speed │ LVN │ m. p. │ Bulk density │ │ │ │ (kg / gh) │ (dl / g) │ (℃) │ (g / L) │ ├───┼──────┼─────┼─── ──┼────┼─────┤ │ 5 │ CO / E │ 44 │ 1.20 │ Not measured │ 186 │ ├───┼──────┼───── ┼─────┼────┼─────┤ │ 6 │ CO / E │ 33 │ 1.27 │ Not measured │ 182 │ ├─── ┼──────┼─ ────┼─────┼────┼─────┤ │ 7 ^* │ CO / E │ 25 │ 1.35 │ Not measured │ 157 │ ├─── ┼─── ───┼─────┼─────┼────┼─────┤ │ 8 │CO / E / P│11.5 │1.33 │221 │ 227 │ ├─ ──┼──────┼─────┼─────┼────┼─────┤ │ 9 │CO / E / P│ 0.9 │1.20 │225 │ 177 │ ├───┼──────┼─────┼─────┼────┼─────┤ │10 * │CO / E / P│10.5 │1.44 │228 │ 122 │ └───┴──────┴─────┴─────┴────┴── ───┘ * For comparison

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Alexander Willem Vander               Made             Netherlands Nuel-1031 CM             Amsterdam Bathoeusuehi 3 F-term (reference) 4G069 AA06 BA27A BA27B BA36A                       BC65A BC69A BC72A BC72B                       BE05A BE05B BE08A BE13A                       BE22A BE25A BE26B BE31A                       BE34A BE36A BE36B BE37A                       CB46 DA02                 4H050 AA01 AB40 WB11 WB22                 4J005 AB01 BB02

Claims (20)

[Claims] 1. (a) Group VIII metal compound, (b) anion, and (c)
) Formula R ¹ R ² M ¹ -R ⁵ -M ² R ³ R ⁴ {wherein R ¹ , R ² , R ³ and R ⁴ represent the same or different hydrocarbyl groups which may be optionally substituted. M ¹ and M ² represent the same or different elements selected from arsenic, antimony, phosphorus and nitrogen; R ⁵ represents a divalent bridging group having 3 atoms in the bridge, and 2 outside the bridge. The atom is a carbon atom, and one atom (X) in the middle of the bridge is a group [However, X represents a carbon or silicon, Y is ^{-C (R 6) (R 7} ) - or -
^{Si (R 6) (R 7} ) - ^{group, -P (R 8) -,} - P (O) (R 8) - or -
^{P (S) (R 8)} - group, -SO ₂ - or -SO- group, -Al (R ⁸⁾ - group,
Or group (Provided that X, M ¹ , M ² , R ¹ , R ² , R ³ and R ⁴ are as defined above, R ⁶ and R ⁷ are the same or different groups, and are carbon, hydrogen and Optionally represents an oligomeric or polymeric chain consisting of one or more heteroatoms, or R ⁶ and R ⁷ together with the carbon or silicon atom to which they are attached are carbon, hydrogen and optionally oxygen and / or Alternatively, an alicyclic structure composed of silicon is formed.
However, R ⁶ and R ⁷ are not methyl groups when X is a carbon atom and the acid derived from the anion is p-toluenesulfonic acid or trifluoroacetic acid. R ⁸ represents hydrogen or an alkyl group having 1 to 5 carbon atoms) and forms a part of the above}. 2. The catalyst composition according to claim 1, wherein the Group VIII metal compound is a palladium compound. 3. A catalyst composition according to claim 1 or 2, wherein component (b) is an anion of an acid having a pKa of less than 6, preferably less than 4. 4. The catalyst composition according to claim 3, wherein the acid is selected from p-toluenesulfonic acid, trifluoroacetic acid, maleic acid and a mixture of two or more thereof. 5. The R ¹ , R ² , R ³ and R ⁴ groups in the bidentate ligand are
A catalyst according to any one of claims 1 to 4 which represents an aryl group of the same or different type which may optionally be substituted with one or more substantially non-polar groups and / or one or more polar groups. Composition. 6. The R ¹ , R ² , R ³ and R ⁴ groups are C1 to C4 alkyl groups, preferably methyl, aryloxy groups, preferably phenyloxy, and C.
A catalyst composition according to claim 5 which represents a phenyl group optionally substituted with a substituent selected from 1 to C4 alkoxy groups, preferably methoxy. 7. The method according to claim 6, wherein the R ¹ , R ² , R ³ and R ⁴ groups are the same and are selected from a phenyl group, a 2-methoxyphenyl group and a 2-methoxy-5-methylphenyl group. Catalyst composition. 8. The catalyst composition according to claim 1, wherein X represents a carbon atom. 9. The catalyst composition according to claim 1, wherein Y represents a —C (R ⁶ ) (R ⁷ ) — group. 10. The catalyst composition according to claim 9, wherein R ⁶ and R ⁷ independently represent an alkyl group or a polymer chain consisting of carbon, hydrogen and optionally oxygen. 11. A catalyst composition according to claim 10 wherein R ⁶ and R ⁷ represent methyl or ethyl or polyketone polymer chains. 12. R ⁶ and R ⁷ together with the carbon atom to which they are attached are cycloalkyl groups which may be optionally substituted with one or more substantially non-polar groups or polar groups. The catalyst composition of claim 9, which forms. 13. The catalyst composition according to claim 12, wherein R ⁶ and R ⁷ together with the carbon atom to which they are attached form a cyclopentyl group or a cyclohexyl group. 14. A catalyst solution prepared by dissolving the catalyst composition according to claim 1 in a suitable liquid. 15. The catalyst solution according to claim 14, wherein the liquid is methanol or acetone. 16. A compound represented by the formula R ¹ R ² M ¹ -R ⁵ -M ² R ³ R ⁴ (wherein R ¹ , R ² , R ³ , R ⁴ , M ¹ , M ² and R ⁵ are as defined in claim 1). (As defined in). 17. Y is ^{-C (R 6) (R 7} ) - a expressed; R ⁶ and R ⁷ C1~C4 alkyl groups the same or different, preferably methyl or ethyl, or polyketone polymer chain, Alternatively, R ⁶ and R ⁷ together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl group. 18. The general formula R¹R²M¹-R^Five-M²R³R^Four {In the formula, R¹, R², R³, R^Four, M¹And M²As defined in claim 1
And R^FiveRepresents a divalent bridging group in which the bridge is composed of three atoms, and the outside of the bridge
2 atoms are carbon atoms, and one atom (X) in the middle of the bridge is a group [Chemical 3] [However, X is a carbon atom, and Y is -C (R⁶) (R⁷)-, -Si (R⁶) (
R⁷)-, Or -P (R⁸) − (However, R⁶, R⁷And R⁸Has the meaning as defined in claim 1) Represents] Form part of (A) 2,2-bis (bromomethyl) -1,3-
Compound R with propanediol⁶-C (= O) -R⁷, Compound (R⁶) (R⁷) S
iCl₂Or a step of reacting with dihalophosphine, and subsequently (b)
The compound thus obtained is a chelating atom-containing compound, preferably Li-M¹R¹R ² And / or Li-M²R³R^FourTo recover the ligand by reacting with
The manufacturing method including. 19. The general formula R¹R²M¹-R^Five-M²R³R^Four {In the formula, R¹, R², R³, R^Four, M¹And M²As defined in claim 1
And R^FiveRepresents a divalent bridging group in which the bridge is composed of three atoms, and the outside of the bridge
2 atoms are carbon atoms, and one atom (X) in the middle of the bridge is a group [Chemical 4] [However, X is a carbon atom, and Y is (i) -P (O) (R⁸) -Or-P (
S) (R⁸) -Group, (ii) -SO₂-Or-SO- group, or (iii)
-Al (R⁸) -Group (However, R⁸Has the meaning as defined in claim 1) Represents one type of] Form part of (A) 2,2-bis (bromomethyl) -1,3-
Reacting propanediol with a protecting agent that reacts with the hydroxyl groups,
b) The product of step (a) is a chelating atom containing compound, preferably Li-M.¹R ¹ R²And / or Li-M²R³R^FourReacting with (c) said hydro
Removing the protecting agent from the xyl group, and (d) the product of step (c)
Halophosphine oxide (R⁸-POCl₂Or R⁸-POBr₂), Dihalo
Phosphine sulfide (R⁸-PSCl₂Or R⁸-PSBr₂), Sulfur chloride
Ruffle (SO₂Cl₂), Thionyl chloride (SOCl₂) Or ethyl dichloride
Minium (C₂H_FiveAlCl₂) And recovering the ligand.
The manufacturing method. 20. A method for producing a polymer, wherein a mixture of carbon monoxide and one or more olefinically unsaturated compounds is polymerized in the presence of the catalyst composition according to any one of claims 1 to 13.