JPH07179598A - Catalyst composition and production of copolymer - Google Patents

Abstract

PURPOSE: To provide a catalyst composition comprising a group VIII metal of the periodic table and a specific anion which exhibits improved catalytic activity and is useful for the preparation of a copolymer of carbon monoxide with at least one compound containing an ethylenically unsaturated bond.

CONSTITUTION: There is provided a catalytic composition comprising (A) a group VIII metal of the periodic table (preferably palladium, rhodium and nickel) and (B) an anion containing an oxidant moiety in its molecular structure (e.g. an anion of a sulfonic acid or a carboxylic acid). This catalytic composition provides a polymer with better thermal stability compared with a polymer prepared using a large amount of an oxidizing agent to enhance the catalytic activity.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst composition for producing a copolymer of carbon monoxide and one or more compounds containing an ethylenically unsaturated bond, and a process for producing such a copolymer.

[0002]

2. Description of the Related Art A linear copolymer of carbon monoxide and one or more ethylenically unsaturated compounds, wherein the units derived from carbon monoxide alternate with or substantially alternate with units derived from ethylenically unsaturated compounds. It is known from many patent applications that polymers can be prepared by reacting monomers under polymerization conditions using a catalyst system consisting of a Group VIII metal and anions. Under the conditions of the polymerization, the anions mentioned above are not or only weakly coordinated with the Group VIII metal.

The preparation of these copolymers is carried out in the liquid phase, that is to say by continuous diluent with a liquid diluent which is a non-polymerizable liquid in which the catalyst is dissolved but the copolymer formed is substantially insoluble. Are formed. Recovery and purification of the product generally requires filtration and centrifugation steps, and further recovery of pure diluent generally requires a distillation step.

The production of the copolymer can also be carried out in the gas phase, in which case a continuous phase is formed with gaseous carbon monoxide gas, but one or more other monomers are polymerized. If present in the gas phase under conditions, a continuous phase may be formed with carbon monoxide and these monomers. The vapor phase production of the copolymer is considered to be advantageous because the product recovery is easier than the liquid phase method. On the industrial scale, which is typical of liquid phase processes, it is possible to dispense with costly separation and purification steps, which improves the economics of the manufacturing process.

Although considerable efforts have been made to increase the activity of the catalyst system, some improvement has been obtained, for example, by changing the reaction conditions or changing the components contained in the catalyst. European Patent Application Publication No. 23914
According to the specification 5, the catalytic activity is enhanced by adding an oxidant, eg quinone, to the catalyst system. The preferable addition amount is 1 to 10,0 per 1 gram atom of palladium.
It is said to be in the range of 00 mol, particularly in the range of 10 to 5,000 mol. In practice (according to the examples) the process is carried out in the liquid phase and the amount of quinone is in the range of 10 or 100 mol per gram atom of palladium. EP-A-272728 teaches that other oxidizing agents, such as organic nitrites and nitro compounds, are also suitable for enhancing the catalytic activity. These compounds are generally used in large amounts like quinones. This patent application mentions hydroxy-substituted nitrobenzenes such as 4-hydroxy-nitrobenzene among many nitro compounds as suitable oxidizing agents.

[0006]

Surprisingly, in particular in gas phase operation, the catalytic activity is improved by using a catalyst composition containing an anion containing an organic oxidant moiety in its molecular structure. It has been found that, compared with the improvement of the catalytic activity obtained by the use of a large amount of oxidizing agent, which has been conventionally performed, it is significantly increased, and the use of a large amount of oxidizing agent can be avoided. Polymers made with this catalyst composition have unexpectedly superior thermal stability compared to polymers made with large amounts of oxidizing agents to enhance catalytic activity.

Therefore, the present invention provides (a) the periodic table VIII.
It relates to a catalyst composition consisting of a group metal and (b) an anion containing an oxidant moiety in its molecular structure.

The present invention further relates to a process for preparing a copolymer which comprises copolymerizing carbon monoxide and one or more ethylenically unsaturated compounds in the presence of the catalyst composition of the present invention.

Those skilled in the art will expect that the anions of the catalyst composition of the present invention will not or only weakly coordinate with the Group VIII metal under the polymerization conditions.

Generally, the anion is an anion derived from an acid having a pKa of less than 6, especially an acid having a pKa of less than 2. The anion may contain one or more anionic groups, preferably one anionic group. The anion is preferably an anion derived from sulfonic acid or carboxylic acid. Phosphonic acids are other suitable sources of anions that are weakly or not coordinated at all. Other suitable anions include those containing boron as a negatively charged center such as the tetrakis (hydrocarbyloxy) borate anion or the tetraarylborate anion.

The oxidant moiety may comprise an aromatic or (cyclic) aliphatic group to which is bonded one or more oxo, nitro or nitroso groups. The oxidant moiety is a nitrophenyl group, 1,3-dinitrophenyl group, 4-isopropyl-
It is preferably selected from nitro group-containing groups such as 1-nitrophenyl groups and nitropropyl groups. Thus the corresponding anion is 1,2 substituted with a suitable anion group.
It is selected from 3-dinitrobenzene, 4-isopropyl-1-nitrobenzene and nitropropane.

The oxidant moiety is selected from groups containing two carbonyl groups conjugated with ethylenic and / or aromatic unsaturation to form quinones, especially 1,2- or 1,4-quinones. Is preferred. In such cases, the anion of the invention may be 1,2- or 1,4-benzoquinone substituted with a suitable anion group, 1,2- or 1,4-
Naphthoquinone or 1,2-, 1,4- or 9,10
-May be anthraquinone. A preferred anionic group is the anionic group of sulfonic acid.

In the present invention, 9,10-anthraquinone-2,6-disulfonic acid, especially 1,2-naphthoquinone-4-sulfonic acid, 1,4-naphthoquinone-2-sulfonic acid and 9,10-anthraquinone-2. Very good results have been obtained with anions derived from sulphonic acid.

Generally, the anions can be added to the catalyst composition of the present invention in the form of salts, such as the form of cobalt, nickel or silver salts, or in the form of acids. Thus, if desired, the anion may be added simultaneously with the Group VIII metal, for example as a complex containing the Group VIII metal and anion.
As one example, a complex that can be prepared by reacting palladium chloride with a silver salt of 1,2-naphthoquinone-4-sulfonic acid in acetonitrile as a solvent, Pd (CH ₃ CN)
₂ (1,2-naphthoquinone-4-sulfonate) ₂ .

Generally, the amount of anion present in the catalyst composition of the present invention is 0.5 per gram atom Group VIII metal.
-20 mol, preferably 1.0 to 10 mol per gram atom of Group VIII metal, and more preferably 1.5 to 5 mol per gram atom of Group VIII metal.

Group VIII metals include noble metals such as ruthenium, rhodium, palladium, osmium, iridium and platinum and iron group metals such as iron, cobalt and nickel. Mixtures of Group VIII metals may be used if desired. Among the Group VIII metals, palladium,
Rhodium and nickel are preferred, and palladium is particularly preferred.

To add the Group VIII metal into the catalyst system, a metal salt is generally used, preferably a metal salt of a carboxylic acid, such as acetic acid.

The catalyst composition of the present invention comprises a Group VIII metal and anion as well as a complex with a Group VIII metal via one or more atoms selected from phosphorus, arsenic, antimony, sulfur and nitrogen atoms. It is preferable to include a ligand that can be formed.

Suitable ligands include monodentate, bidentate and polydentate ligands. Preference is given to bidentate ligands, in particular bidentate ligands which are able to form complexes with Group VIII metals via two atoms selected from phosphorus, sulfur and nitrogen atoms.

A preferred nitrogen-containing bidentate ligand has the formula (I):

[0021]

[Chemical 1]

(Wherein X and Y represent an organic bridging group containing 3 or 4 bridging atoms, two of which are carbon atoms). Bridging groups X and Y
May be linked together by a third bridging group. Examples of the nitrogen-containing bidentate ligand of the formula (I) include 2,
There are 2'-bipyridine and 1,10-phenanthroline.

Preferred sulfur-containing bidentate ligands have the general formula R ¹
S-R-SR ² (wherein R represents a divalent organic bridging group containing two or more carbon atoms in the bridge, and R ¹ and R ² are each independently a hydrocarbon group which may be substituted). Which represents), such as 1,2-bis (ethylthio) ethane and cis-1,2-bis (benzylthio) ethane.

A particularly preferred bidentate ligand is of the formula: R ¹ R ² P—R—PR ³ R ⁴ (II) where R is as defined above and R ¹ , R ² and R ³
And R ⁴ each independently represent a substituted or unsubstituted hydrocarbon group).

R ¹ , R ² , R ³ and R ⁴ may represent the same or different and optionally substituted aliphatic, cycloaliphatic or aromatic groups. Aromatic groups substituted with one or more polar groups are preferred. Particularly preferred is the formula (II), wherein each of R ¹ , R ² , R ³ and R ⁴ is attached at one or both ortho positions relative to the phosphorus atom to which the phenyl group is generally attached. Represents a phenyl group containing an alkoxy group containing up to 4 carbon atoms).

Examples of suitable phosphorus-containing bidentate ligands include
1,2-bis (diphenylphosphino) ethane, 1,3
-Bis (diphenylphosphino) propane, 1,3-bis [bis (2-methoxyphenyl) phosphino] propane and 1,3-bis [bis (2,6-dimethoxyphenyl) phosphino] propane.

The amount of bidentate ligand in the catalyst system is advantageously in the range 0.5 to 100 mol per gram atom Group VIII metal, 1 to 50 m / gram atom Group VIII metal.
The range of ol is preferable. When the catalyst system comprises a phosphorus-containing bidentate ligand of formula (II), its amount is preferably in the range 0.5 to 2.0 mol per gram atom Group VIII metal,
More preferably, it is in the range of 0.75 to 1.5 mol.

When the method of the present invention is carried out as a gas phase method, it is preferable to use a supported catalyst, that is, a catalyst in which the catalyst composition is supported on a support or carrier material. The support may be an inorganic material such as silica, alumina, talc or activated carbon, or an organic material such as a gel of cellulose, dextrose or dextran. Preference is given to supports which are porous carrier materials, in particular carrier materials having a pore volume of 0.01 cm ³ or more per gram as determined by mercury porosimetry.

Highly suitable supports are polymeric substances such as polyethylene, polypropylene, polyoxymethylene and polystyrene. If desired, a mixed material such as a polymer including silica may be used.

Preferred carrier materials are linear alternating copolymers of carbon monoxide and one or more ethylenically unsaturated compounds, especially those copolymers whose structure and composition are to be prepared by the process of the present invention. Are the same copolymers.

The preparation of the catalyst system is carried out in a separate step prior to the process according to the invention, for example by mixing the catalyst components or, if appropriate, the carrier material with a solution or suspension of the catalyst components or their precursors. It is convenient to do this by impregnating. Various catalyst components may be added with or without the support material.

The ethylenically unsaturated compound preferably used as a starting material in the copolymerization method of the present invention includes a compound composed only of carbon and hydrogen, and one or more heteroatoms in addition to carbon and hydrogen. Compounds such as unsaturated esters having are included.

Unsaturated hydrocarbons are the preferred ethylenically unsaturated compounds. Suitable examples are lower olefins such as ethene, propene and 1-butene, cyclic compounds such as cyclopentene and aromatic compounds such as styrene and α-methylstyrene. Preference is given to using ethene or a mixture containing ethene and propene or ethene and 1-butene.

The molar ratio of the monomer, ie carbon monoxide, to the ethylenically unsaturated compound is generally chosen in the range from 5: 1 to 1: 5. The molar ratio is preferably 2: 1 to
It is preferably selected in the range of 1: 2, for example the monomers are preferably used in substantially equimolar amounts.

When the process according to the invention is carried out as a gas phase process, a small amount of volatile protic liquids such as lower aliphatic alcohols, ie alcohols generally having up to 4 carbon atoms and / or hydrogen are added. Preferably. The amount of this liquid is chosen such that the liquid becomes substantially gaseous under the polymerization conditions. A suitable amount is 40 to 60% by weight, based on the amount sufficient to saturate the gas phase under the polymerization conditions. In particular, when the Group VIII metal is contained in the catalyst composition as a compound containing a hydrocarbon group or an acyl group bonded to the Group VIII metal via a covalent bond, a non-polar group such as toluene is used. A liquid may be used. Generally, such hydrocarbon or acyl groups are aliphatic and preferably contain up to 8 carbon atoms.

When carrying out the copolymerization process as a liquid phase process, it is preferred to use a diluent in which the catalyst composition is soluble and the copolymer product formed is substantially insoluble. A preferred diluent is a volatile protic liquid consisting of a lower alcohol, ie an alcohol generally having 4 or less carbon atoms, especially methanol. The diluent may be a non-polar agent such as toluene, especially when a Group VIII metal is included in the catalyst composition as described above.

The copolymer is preferably produced at a temperature in the range of 20 to 200 ° C., but a reaction temperature outside this range may be used. The reaction temperature is preferably selected in the range of 25 to 150 ° C. Suitable pressure is generally 1 to
Within the range of 200 bar, but preferably from 2 to 15
It is in the range of 0 bar. The amount of catalyst used in the process of the invention may be varied within wide limits. 10 ^-7 -10 ^-3 per mol of the ethylenically unsaturated compound to be polymerized,
In particular, it is preferable to use a catalytic amount containing a Group VIII metal of 10 ⁻⁶ −10 ⁻⁴ gram atom.

The copolymer obtained by the present invention can be processed into molded products, films, sheets, fibers and the like. They have excellent mechanical properties, which make them suitable for a variety of commercially interesting applications, such as the automobile industry, the manufacture of packaging for food and beverages and various applications in the home.

[0039]

The present invention will be described in detail with reference to the following examples.

Example 1 (Comparative) A carbon monoxide / ethene copolymer was prepared as follows.

A catalyst solution containing tetrahydrofuran 0.25 ml, methanol 3.75 ml, palladium acetate 0.01 mmol 1,3-bis [bis (2-methoxyphenyl) phosphino] propane 0.011 mmol p-toluenesulfonic acid 0.05 mmol was added. A catalyst was prepared by adsorbing carbon monoxide on a linear alternating terpolymer of ethene and propene (8 g). The catalyst thus prepared was introduced into a 500 ml autoclave equipped with a mechanical stirrer. After closing the autoclave, the air inside was replaced with 1 bar carbon monoxide, 20 bar carbon monoxide and then 20 bar.
I pushed in the bar ethen. The temperature of the contents of the autoclave was set to 90 ° C., and carbon monoxide / ethene 1: 1 (v
/ V) The mixture was pushed in to maintain the pressure. 5 hours later
The pressure was released and the reaction mixture was cooled to room temperature to terminate the polymerization.

Carbon monoxide used to maintain pressure /
The polymerization rate was calculated from the consumption of the ethene mixture. The polymerization rate measured after 1 hour of polymerization time (an approximate value of the initial polymerization rate), the polymerization rate measured after 4 hours and the average polymerization rate over the entire 5 hours are shown in Table 1. The amount of copolymer obtained corresponded to the average polymerization rate.

Examples 2-7 A carbon monoxide / ethene copolymer was prepared in a manner substantially similar to Example 1, except that p-toluenesulfonic acid was replaced by the sulfonic acids or cobalt sulfonates listed in Table 1. One type was used at 0.05 mmol.

The polymerization rate was as shown in Table 1. The amount of copolymer obtained corresponded to the average polymerization rate.

Examples 8 and 9 (for comparison) A carbon monoxide / ethene copolymer was prepared in much the same way as in Example 1, but 1,4 as an additional compound was added to the catalyst solution.
Naphthoquinone was added. The amount of 1,4-naphthoquinone was 0.05 mmol in Example 8 and 0.
It was 5 mmol.

The polymerization rate was as shown in Table 1. The amount of copolymer obtained corresponded to the average polymerization rate.

[0047]

[Table 1]

1) For comparison, not according to the invention.

2) 0.05 mmol of naphthoquinone was present.

3) 0.5 mmol of naphthoquinone was present.

Example 10 (Comparative) A carbon monoxide / ethene copolymer was prepared as follows.
In a 300 ml autoclave equipped with a mechanical stirrer, methanol (130 ml) and a linear alternating terpolymer of carbon monoxide with ethene and propene (2.7 g).
Was filled.

Prepared by combining tetrahydrofuran 0.13 ml, methanol 0.88 ml, palladium acetate 0.005 mmol, 1,3-bis [bis (2-methoxyphenyl) phosphino] propane 0.0055 mmol p-toluenesulfonic acid 0.025 mmol. The catalyst solution was added. After closing the autoclave, the air inside was replaced with 1 bar carbon monoxide and 25 bar carbon monoxide and then 25 bar ethene were forced in. Set the temperature of the contents of the autoclave to 85
C. and maintained at pressure by pushing in a 1: 1 (v / v) mixture of carbon monoxide / ethene. After two and a half hours, the pressure was released and the reaction mixture was cooled to room temperature to terminate the polymerization. The copolymer was filtered, washed with methanol and dried at 70 ° C.

A copolymer (11 g) was obtained, and the average polymerization rate was calculated from the copolymer. As a result, 6 kg copolymer / (g P
d / hour).

Example 11 A carbon monoxide / ethene copolymer was prepared in substantially the same manner as in Example 10, except that p-toluenesulfonic acid was replaced by 1,2-naphthoquinone-4-sulfonic acid 0.025.
mmol was used.

A copolymer (20 g) was obtained. The average polymerization rate was 13 kg copolymer (g Pd / hour).

Examples 1-11 by C ¹³ -NMR analysis
It was confirmed that the carbon monoxide / ethene copolymer produced by (1) has a linear chain in which carbon monoxide-derived units alternate with ethene-derived units.

Claims (14)

[Claims] 1. A catalyst composition comprising a) a Group VIII metal of the periodic table, and b) an anion containing an oxidant moiety in its molecular structure. 2. Composition according to claim 1, characterized in that the anion is the anion of an acid having a pKa of less than 2, in particular a sulfonic acid or a carboxylic acid. 3. Anionic oxidant moieties are selected from groups containing two carbonyl groups conjugated to ethylenic and / or aromatic unsaturation, especially 1,2- or 1,4-quinones. The composition according to claim 1 or 2, characterized in that 4. The anion is 9,10-anthraquinone-2,6-disulfonic acid, 1,2-naphthoquinone-4-.
The composition according to claim 2 or 3, which is an anion derived from sulfonic acid, 1,4-naphthoquinone-2-sulfonic acid or 9,10-anthraquinone-2-sulfonic acid. 5. The composition according to claim 1, wherein the amount of anion present is in the range of 1.0 to 10 mol per gram atom of Group VIII metal. 6. Composition according to claim 5, characterized in that the amount of anions present is in the range from 1.5 to 5 mol per gram atom Group VIII metal. 7. A ligand capable of forming a complex with a Group VIII metal, the catalyst composition as an additional component c) via one or more atoms selected from phosphorus, arsenic, antimony, sulfur and nitrogen atoms. The composition according to any one of claims 1 to 6, comprising: 8. The ligand has the general formula R ¹ R ² P—R—PR ³
R ⁴ [Formula (II)] (In the formula, each of R ¹ , R ² , R ³ and R ⁴ independently represents a substituted or unsubstituted hydrocarbon group, and R is a divalent group containing two or more carbon atoms. (Representing an organic bridging group of), and the composition according to claim 7. 9. In the ligand of formula (II), R ¹ , R ² ,
The composition according to claim 8, wherein each of R ³ and R ⁴ represents a phenyl group having an alkoxy group at one or both ortho positions with respect to the phosphorus atom to which it is attached. 10. The composition according to claim 1, wherein the composition is supported on a support. 11. The composition of claim 10 wherein the support is a substantially porous carrier material which is a copolymer of carbon monoxide and one or more ethylenically unsaturated compounds. object. 12. A copolymer comprising copolymerizing carbon monoxide with one or more ethylenically unsaturated compounds in the presence of a catalyst composition according to any one of claims 1 to 11. Manufacturing method. 13. The method according to claim 12, wherein the copolymerization of carbon monoxide and one or more ethylenically unsaturated compounds is carried out in the gas phase. 14. Ethene or a mixture of ethene and propene or ethene and 1-butene is used as the ethylenically unsaturated compound, and the temperature is in the range of 25 to 150 ° C.
Copolymerization is carried out at a pressure in the range of 150 bar to 150 bar with a molar ratio of ethylenically unsaturated compound to carbon monoxide in the range of 5: 1 to 1: 5, and 1 mole of ethylenically unsaturated compound to be polymerized A catalyst comprising an amount of 10 ^-6 to 10 ^-4 gram atom Group VIII metal per catalyst is used.
The method according to 2 or 13.