KR20060057719A - Method of manufacturing polyketone - Google Patents

Abstract

The present invention relates to a method for producing a polyketone with improved catalytic activity and intrinsic viscosity, and more particularly, using a mixed solvent composed of 70 to 90 vol% acetic acid and 30 to 10 vol% water as a liquid medium. 1,3-bis [di (2-methoxyphenyl) phosphino] propane is used as a ligand of the component, and the poly-improvement improves catalytic activity and intrinsic viscosity by controlling the input ratio of carbon monoxide and ethylenically unsaturated compound to 1: 2. It relates to a method for producing a ketone.

Polyketone, catalytic activity, intrinsic viscosity, acetic acid, water, ligand

Description

Process for producing Polyketone

The present invention relates to a method for producing a polyketone with improved catalytic activity and intrinsic viscosity, and more particularly, using a mixed solvent composed of 70 to 90 vol% acetic acid and 30 to 10 vol% water as a liquid medium. 1,3-bis [di (2-methoxyphenyl) phosphino] propane is used as a ligand of the component, and the poly-improvement improves catalytic activity and intrinsic viscosity by controlling the input ratio of carbon monoxide and ethylenically unsaturated compound to 1: 2. It relates to a method for producing a ketone.

Copolymers of carbon monoxide with ethylenically unsaturated compounds, in particular polyketones having a structure in which a repeating unit derived from carbon monoxide and a repeating unit derived from an ethylenically unsaturated compound are alternately connected, have excellent mechanical and thermal properties, and are excellent in wear resistance and chemical resistance. It has high gas barrier properties and is a useful material for various applications. The high molecular weight of this fully alternating copolymerized polyketone is considered to be useful as an engineering plastic material having higher mechanical and thermal properties and excellent economical efficiency. In particular, the wear resistance is high, and parts such as automobile gears and chemical resistance are high, and the gas barrier property, such as lining material of chemical transport pipe, is high, so that it can be used for light gasoline tanks and the like. In addition, when an ultra high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fibers, it is possible to stretch at high magnification and to have a high strength and a high modulus of elasticity oriented in the stretching direction. It is very suitable for building materials and industrial materials.

As a method for obtaining a high molecular weight polyketone exhibiting high mechanical and thermal properties, European Patent No. 319083 discloses palladium, 1,3-bis [di (2-methoxyphenyl] phosphino] propane and an anion. A method of polymerizing at a low temperature using a catalyst is disclosed in Japanese Patent Laid-Open No. 4-227726, which discloses palladium and 2- (2,4,6-trimethylbenzene) -1,3-bis [di (2- Japanese Unexamined Patent Publication No. 5-140301 discloses a method of using a catalyst composed of methoxyphenyl) phosphino] propane and an anion, with palladium and 2-hydroxy-1,3-bis [di (2-methoxyphenyl) force. A method using a catalyst consisting of pino] propane and an anion has been disclosed, however, these methods have been economically problematic because the yield of polyketone per catalyst is low and the method of synthesizing the phosphorus ligand is difficult and expensive. .

As a method of obtaining a high molecular weight polyketone using a cheap catalyst, Japanese Patent Laid-Open No. 6-510552 uses a catalyst consisting of palladium, 1,3-bis (diphenylphosphino) propane and an anion of boron fluoride. To disclose polymerization in a tert-butanol solvent. According to this method, although a high molecular weight polyketone is obtained, there is a problem that the yield of polyketone per catalyst is very low, resulting in a high cost of polyketone.

As a method of economically obtaining high molecular weight polyketone at a high yield, Japanese Patent Laid-Open No. 8-283403 discloses a method of polymerization in a mixed solvent of methanol and 1 to 50% by volume of water. In this method, a catalyst consisting of a Group 10 metal source such as palladium, 1,3-bis (diphenylphosphino) propane and an anion of an inorganic acid is used. Particularly, when using palladium acetate, 1-3-bis (diphenylphosphino) propane and phosphorus tungstic acid in a methanol solvent containing 17% by volume of water, the temperature was 30 at 85 ° C and 4.8 MPa in a molar mixed gas such as ethylene and carbon monoxide. By the time of the polymerization reaction, a polymer having an intrinsic viscosity of 1.36 was obtained, and the catalytic activity at that time was 5.7 kg / g-Pd · hr. When sulfuric acid is used instead of phosphorus tungstic acid as the mixed solvent, the catalytic activity is 9.5 kg / g-Pd · hr. According to this method, although a high molecular weight polyketone is obtained by high catalyst activity, even if lengthening superposition | polymerization time is long, there existed a problem that it was impossible to obtain the polymer with intrinsic viscosity 2 or more required in order to make a high performance material.

EP 0361584 discloses a process for polymerizing polyketones at low pressure by adding trifluoroacetic acid to palladium and 1,3-bis (diphenylphosphino) propane. According to the patent, a polyketone polymer having a catalytic activity of 1.3 kg / g-Pd · hr and an intrinsic viscosity of 1.8 can be obtained by polymerization reaction at 5.2 ° C. with an input ratio of ethylene and carbon dioxide at 1: 2 at 50 ° C. and 4 MPa. . According to the above patent, polyketone can be obtained under relatively low temperature and low pressure, but it is impossible to obtain polyketone having a high intrinsic viscosity required for high performance materials.

Japanese Patent Laid-Open No. 2002-317044 discloses a method of polymerizing polyketone by using sulfuric acid as an inorganic acid in a catalyst system similar to the prior art. The intrinsic viscosity was 6.45 by polymerizing a Group 10 metal source such as palladium and 1,3-bis (diphenylphosphino) propane in a methanol solvent for 30 minutes at 80 ° C and 5.5 MPa of ethylene and carbon monoxide equimolar mixed gas. A polyketone polymer was obtained, and the catalytic activity at that time was 6.0 kg / g-Pd · hr.

As described above, in the method for producing polyketone using carbon monoxide and ethylenically unsaturated compound as a raw material, not only has high catalytic activity but also has a high intrinsic viscosity suitable for use for tire cords. Development is desired.

The present invention is to solve the problems of the prior art as described above, an object of the present invention is to use a mixed solvent consisting of 70 to 90% by volume of acetic acid and 30 to 10% by volume of water as a liquid medium, the catalyst component Preparation of polyketone using 1,3-bis [di (2-methoxyphenyl) phosphino] propane as an agent and adjusting the input ratio of carbon monoxide and ethylenically unsaturated compound at 1: 2 to improve catalytic activity and intrinsic viscosity To provide a way.

The process for producing a polyketone of the present invention is a liquid medium in the presence of an organometallic complex catalyst consisting of a ligand having an element of Group (a) Group 9, Group 10 or Group 11 and (b) Group 15 The method for producing a polyketone by copolymerizing carbon monoxide and an ethylenically unsaturated compound in the above is characterized in that a mixed solvent composed of 70 to 90% by volume of acetic acid and 30 to 10% by volume of water is used as a liquid medium.

The present invention is characterized by using a mixed solvent consisting of acetic acid and water, without using methanol, dichloromethane or nitromethane, which have been mainly used in the production of polyketone as a liquid medium. This is because by using a mixed solvent of acetic acid and water as the liquid medium in the production of the polyketone it is possible to improve the catalytic activity while reducing the production cost of the polyketone.

When a mixed solvent of acetic acid and water is used as the liquid medium, when the concentration of water is less than 10% by volume, the catalytic activity is less affected. However, when the concentration is more than 10% by volume, the catalytic activity rapidly increases. On the other hand, when the concentration of water exceeds 30% by volume, catalytic activity tends to decrease. Therefore, in the present invention, it is preferable to use a mixed solvent composed of 70 to 90 vol% acetic acid and 30 to 10 vol% water as the liquid medium.

In the present invention, the catalyst is composed of a ligand having an element of Group (a) Group 9, Group 10 or Group 11 and Group (b) Group 15 of the Periodic Table (IUPAC Inorganic Chemistry Nomenclature, 1989) .

Examples of the Group 9 transition metal compound in the Group 9, 10 or 11 transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamate salts, sulfonates, and the like. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, and trifluoromethane sulfonic acid ruthenium.

Examples of the Group 10 transition metal compound include a complex of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, and palladium trifluoroacetate. , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium, palladium sulfate and the like.

Examples of the Group 11 transition metal compound include a complex of copper or silver, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include copper acetate, trifluoroacetate, copper acetylacetate, silver acetate, Trifluoro silver acetate, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferred transition metal compounds (a) are palladium compounds in terms of yield and molecular weight of polyketones, and in terms of improving catalytic activity and intrinsic viscosity. Most preferably, palladium acetate is used in the process.

Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picolin , Nitrogen ligands such as 2,2'-bikinolin, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Butane, 1,3-bis [di (2-methyl) phosphino] propane, 1,3-bis [di (2-isopropyl) phosphino] propane, 1,3-bis [di (2-methoxyphenyl ) Pinospino] propane, 1,3-bis [di (2-methoxy-4-sulfonic acid-phenyl) phosphino] propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (Diphenylphosphino) benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, 1,2- Bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino] methyl] benzene, 1,1'-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Spinosyns; there may be mentioned a ligand, such as propane.

Among them, the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly, in view of the yield of polyketone, a phosphorus ligand is preferably 1,3-bis [di (2- Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, and 2-hydroxy-1,3-bis [in terms of molecular weight of the polyketone. Di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane, and do not require an organic solvent in terms of safety Water-soluble 1,3-bis [di (2-methoxy-4-sulfonate-phenyl) phosphino] propane, 1,2-bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino ] Methyl] benzene, the synthesis | combination is easy, it is available in large quantities, and economically preferable is 1, 3-bis (diphenyl phosphino) propane and 1, 4-bis (diphenyl phosphino) butane.

Particularly preferred ligand (b) having group 15 atom in the present invention is 1,3-bis [di (2-methoxyphenyl) phosphino] propane, which uses a mixed solvent of acetic acid and water as a liquid medium. In the present invention, when 1,3-bis [di (2-methoxyphenyl) phosphino] propane is used as a ligand instead of 1,3-bis (diphenylphosphino) propane, which is a conventionally used ligand, This is because it is possible not only to have catalytic activity but also to manufacture polyketone having a high intrinsic viscosity suitable for a tire cord.

The amount of the Group 9, 10 or 11 transition metal compound (a) to be used may be limited, since the appropriate value varies depending on the type of ethylenically unsaturated compound selected or other polymerization conditions. Although it is not possible, it is usually 0.01-100 mmol, preferably 0.01-10 mmol, per liter of the capacity of the reaction zone. The capacity of the reaction zone means the capacity of the liquid phase of the reactor. The amount of the ligand (b) is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol per mol of the transition metal compound (a).

In the present invention, examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1 Α-olefins such as tetradecene, 1-hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. These ethylenically unsaturated compounds are used individually or in mixture of multiple types. Preferred ethylenically unsaturated compounds among these are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, and most preferably ethylene.

The present invention is also characterized by adjusting the input ratio of carbon monoxide and ethylenically unsaturated compound to 1: 2. In the production of polyketone, it is common to set the input ratio of carbon monoxide and ethylenically unsaturated compound to 1: 1, but in the present invention, by adjusting the input ratio to 1: 2, it was possible to simultaneously achieve improvement in catalytic activity and intrinsic viscosity.

In the present invention, the copolymerization of carbon monoxide and the ethylenically unsaturated compound comprises an organometallic consisting of the Group 9, Group 10 or Group 11 transition metal compound (a) and the ligand (b) having an element of Group 15 Occurred by a complex catalyst, the catalyst is produced by contacting the two components. Arbitrary methods can be employ | adopted as a method of making it contact. That is, you may make and use the solution which mixed two components previously in a suitable solvent, and may respectively supply two components separately to a polymerization system, and may contact them in a polymerization system.

In carrying out the present invention, as the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a gas phase polymerization method in which a small amount of polymer is impregnated with a high concentration of a catalyst solution are used. The polymerization may be either batchwise or continuous. The reactor used for superposition | polymerization can use a well-known thing as it is or processing it. There is no restriction | limiting in particular about polymerization temperature, Generally 40-180 degreeC, Preferably 50-120 degreeC is employ | adopted. There is no restriction | limiting also in the pressure at the time of superposition | polymerization, Usually, it is normal pressure-20 MPa, Preferably it is 4-15 MPa.

Hereinafter, the structure and effect of the present invention will be described in more detail with specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention, and are not intended to limit the scope of the present invention. Intrinsic viscosity and catalytic activity of polyketone in Examples and Comparative Examples were evaluated by the following method.

(1) intrinsic viscosity

After dissolving the polymerized resin at a concentration of 0.01 g / 100 ml to 1 g / 100 ml (m-cresol) for about 1 to 5 hours in a 60 ^o C incubator, the viscosity was measured at 30 ^o C using an Ubelode viscometer. do. Plot the viscosity according to the concentration and extrapolate to find the intrinsic viscosity.

(2) catalytic activity

It calculates | requires by the weight and time (kg / g-Pd * hr) of the weight of polymerized resin / palladium.

(Example 1)

0.0129 g of palladium acetate and 0.0307 g of 1,3-bis [di (2-methoxyphenyl] phosphino] propane were dissolved in a mixed solvent of 2249 ml of acetic acid and 417 ml of water, and the solution was evacuated by vacuum. After the autoclave was sealed, the contents were heated with stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 2 mixed gas of carbon monoxide and ethylene was autoclave pressured. Stirring was continued for 1 hour, keeping the internal temperature at 90 ° C. and internal pressure at 65 bar After cooling, the gas in the autoclave was purged and the contents were taken out The reaction solution was filtrated with methanol After washing several times, it dried under reduced pressure at room temperature to 80 degreeC and obtained 58.4 g of polymers.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was equivalent to 9.4 kg / gPd · hr and the intrinsic viscosity was as high as 3.1 dl / g.

Table 1 summarizes these results.

(Example 2)

0.0129 g of palladium acetate and 0.0307 g of 1,3-bis [di (2-methoxyphenyl] phosphino] propane were dissolved in a mixed solvent of 2249 ml of acetic acid and 417 ml of water, and the solution was evacuated by vacuum. After the autoclave was sealed, the contents were heated with stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 2 mixed gas of carbon monoxide and ethylene was autoclave pressured. Stirring was continued for 15 hours while maintaining the internal temperature at 90 ° C. and the internal pressure at 70 bar After cooling, the gas in the autoclave was purged and the contents were taken out. After washing several times, it dried under reduced pressure at room temperature to 80 degreeC and obtained 690.2 g of polymers.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was equivalent to 7.4 kg / gPd · hr, and the inherent viscosity was a high value of 4.9 dl / g.

Table 1 summarizes these results.

(Example 3)

0.0236 g of palladium acetate and 0.0559 g of 1,3-bis [di (2-methoxyphenyl] phosphino] propane were dissolved in a mixed solvent of 1350 ml of acetic acid and 250 ml of water, and the solution was evacuated by vacuum. After the autoclave was sealed, the contents were heated with stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 2 mixed gas of carbon monoxide and ethylene was autoclave pressured. Stirring was continued for 1 hour while maintaining the internal temperature at 90 ° C. and the internal pressure at 45 bar After cooling, the gas in the autoclave was purged and the contents were taken out. After washing several times, it dried under reduced pressure at room temperature to 80 degreeC and obtained 164.2g of polymers.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 14.5 kg / gPd · hr, and the intrinsic viscosity was a high value of 2.1 dl / g.

Table 1 summarizes these results.

(Example 4)

0.0129 g of palladium acetate and 0.0307 g of 1,3-bis [di (2-methoxyphenyl] phosphino] propane were dissolved in a mixed solvent of 2249 ml of acetic acid and 417 ml of water, and the solution was evacuated by vacuum. After the autoclave was sealed, the contents were heated with stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 2 mixed gas of carbon monoxide and ethylene was autoclave pressured. Stirring was continued for 1 hour while maintaining the internal temperature at 90 ° C. and internal pressure at 70 bar After cooling, the gas in the autoclave was purged and the contents were taken out. After washing several times, it dried under reduced pressure at room temperature to 80 degreeC and obtained 57.3g of polymers.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 9.2 kg / gPd · hr and the intrinsic viscosity was a high value of 4.1 dl / g.

Table 1 summarizes these results.

(Example 5)

0.0129 g of palladium acetate and 0.0307 g of 1,3-bis [di (2-methoxyphenyl] phosphino] propane were dissolved in a mixed solvent of 2249 ml of acetic acid and 417 ml of water, and the solution was evacuated by vacuum. After the autoclave was sealed, the contents were heated with stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 2 mixed gas of carbon monoxide and ethylene was autoclave pressured. Stirring was continued for 15 hours while maintaining the internal temperature at 90 ° C. and the internal pressure at 70 bar After cooling, the gas in the autoclave was purged and the contents were taken out. After washing several times, it dried under reduced pressure at room temperature to 80 degreeC and obtained 609.5g of polymers.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 6.5 kg / gPd · hr and the intrinsic viscosity was high value of 5.3 dl / g.

Table 1 summarizes these results.

(Comparative Example 1)

0.0129 g of palladium acetate and 0.0238 g of 1,3-bis (diphenylphosphino) propane were dissolved in a mixed solvent of 2249 ml of acetic acid and 417 ml of water, and this solution was removed by air, followed by nitrogen-substituted stainless steel. Charged to the Clive. After the autoclave was sealed, the contents were heated while stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 1 mixed gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 60.8 bar. Stirring was continued for 1 hour while maintaining the internal temperature at 90 ° C. and the internal pressure at 60.8 bar. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed several times with methanol, and dried under reduced pressure at room temperature to 80 占 폚 to obtain 51.4 g of a polymer.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 8.3 kg / gPd · hr and the intrinsic viscosity was 0.6 dl / g.

Table 1 summarizes these results.

(Comparative Example 2)

0.0129 g of palladium acetate and 0.0238 g of 1,3-bis (diphenylphosphino) propane were dissolved in a mixed solvent of 2249 ml of acetic acid and 417 ml of water, and this solution was removed by air, followed by nitrogen-substituted stainless steel. Charged to the Clive. After the autoclave was sealed, the contents were heated while stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 1 mixed gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 60.8 bar. Stirring was continued for 15 hours while maintaining the internal temperature at 90 ° C. and the internal pressure at 60.8 bar. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed several times with methanol, and dried under reduced pressure at room temperature to 80 占 폚 to obtain 575.5 g of a polymer.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 6.1 kg / gPd · hr and the intrinsic viscosity was 0.2 dl / g.

Table 1 summarizes these results.

(Comparative Example 3)

0.0236 g of palladium acetate and 0.0433 g of 1,3-bis (diphenylphosphino) propane were dissolved in a mixed solvent of 1350 ml of acetic acid and 250 ml of water, and the solution was evacuated by vacuum, followed by nitrogen-substituted stainless steel. Charged to the Clive. After the autoclave was sealed, the contents were heated while stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 1 mixed gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 45.6 bar. Stirring was continued for 1 hour while maintaining the internal temperature at 90 ° C. and the internal pressure at 45.6 bar. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed several times with methanol, and dried under reduced pressure at room temperature to 80 占 폚 to obtain 11.3 g of a polymer.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 1.0 kg / gPd · hr and the intrinsic viscosity was 0.4 dl / g.

Table 1 summarizes these results.

(Comparative Example 4)

0.0129 g of palladium acetate and 0.0238 g of 1,3-bis (diphenylphosphino) propane were dissolved in a mixed solvent of 2249 ml of acetic acid and 417 ml of water, and this solution was removed by air, followed by nitrogen-substituted stainless steel. Charged to the Clive. After the autoclave was sealed, the contents were heated while stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 1 mixed gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 70 bar. Stirring was continued for 1 hour while maintaining the internal temperature at 90 ° C. and the internal pressure at 70 bar. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed several times with methanol, and dried under reduced pressure at room temperature to 80 占 폚 to obtain 50.5 g of a polymer.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 8.1 kg / gPd · hr and the intrinsic viscosity was 1.2 dl / g.

Table 1 summarizes these results.

(Comparative Example 5)

0.0129 g of palladium acetate and 0.0238 g of 1,3-bis (diphenylphosphino) propane were dissolved in a mixed solvent of 2249 ml of acetic acid and 417 ml of water, and this solution was removed by air, followed by nitrogen-substituted stainless steel. Charged to the Clive. After the autoclave was sealed, the contents were heated while stirring at a speed of 700 rpm, and when the internal temperature reached 90 ° C., a 1: 1 mixed gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 70 bar. Stirring was continued for 15 hours while maintaining the internal temperature at 90 ° C. and the internal pressure at 70 bar. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed several times with methanol, and dried under reduced pressure at room temperature to 80 占 폚 to obtain 517.3 g of a polymer.

^{From 13} C-NMR and IR results, it was confirmed that this polymer was a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 5.5 kg / gPd · hr and the intrinsic viscosity was 0.2 dl / g.

Table 1 summarizes these results.

According to the present invention, a mixed solvent composed of 70 to 90 vol% acetic acid and 30 to 10 vol% water is used as the liquid medium, and 1,3-bis [di (2-methoxyphenyl) force is used as the ligand of the catalyst component. There is provided a method for producing polyketone using Pino] propane and improving the catalytic activity and intrinsic viscosity by controlling the input ratio of carbon monoxide and ethylenically unsaturated compound to 1: 2.

Claims (4)

Copolymerizing carbon monoxide and an ethylenically unsaturated compound in a liquid medium in the presence of an organometallic complex catalyst comprising a ligand of (a) a Group 9, 10 or 11 transition metal compound and (b) a Group 15 element. A method for producing a polyketone by using a mixed solvent comprising 70 to 90 vol% acetic acid and 30 to 10 vol% water as a liquid medium. The method for producing polyketone according to claim 1, wherein the component (a) is palladium acetate. The method for producing a polyketone according to claim 1, wherein the component (b) is 1,3-bis [di (2-methoxyphenyl) phosphino] propane. The method of claim 1, wherein the input ratio of the carbon monoxide and the ethylenically unsaturated compound is 1: 2.