KR20100050742A - Process for producing polyketone - Google Patents

Abstract

PURPOSE: A manufacturing method of polyketone is provided to improve the catalyst activation and the inherent viscosity by adding bis(2-hydroxyethyl) octhyl amine while manufacturing the polyketone out of a liquid medium. CONSTITUTION: A manufacturing method of polyketone comprises a step of forming the polyketone by copolymerizing an ethylenically unsaturated compound and carbon monoxide out of a liquid medium under the presence of an organo metallic complex catalyst, after adding bis(2-hydroxyethyl) octhyl amine during the polymerization. The organo metallic complex catalyst is composed of a transition metal oxide, a ligand, and a negative ion from acid with 4 pKa. The liquid medium is a mixed solvent formed with 70~90ol% of acetic acid and 30~10vol% of water.

Description

Process for producing Polyketone

The present invention relates to a method for producing a polyketone having improved catalytic activity and intrinsic viscosity, and more particularly, when preparing a polyketone by copolymerizing carbon monoxide and an ethylenically unsaturated compound in a liquid medium, bis (2- The present invention relates to a method for producing a polyketone having improved catalytic activity and intrinsic viscosity by adding hydroxyethyl) octylamine.

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 the ultra high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fibers, the fibers can be stretched at a high magnification and 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 palladium acetate, 1-3-bis (diphenylphosphino) propane and phosphorus tungstic acid were used in a methanol solvent containing 17% by volume of water, 85 ° C, 30 minutes at 4.8 MPa of ethylene and carbon monoxide mixed gas In 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 in 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 with high catalyst activity, even if the polymerization time is prolonged, there is a problem that it is impossible to obtain a polymer having an intrinsic viscosity of 2 or more necessary for 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 polymerizing at 5.2 ° C. with an input ratio of ethylene and carbon dioxide at 1: 2 at 50 ° C. and a pressure of 4 MPa. . According to the patent, it is possible to obtain polyketone under relatively low temperature and low pressure, but it is impossible to obtain polyketone having 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. A polyolefin having an intrinsic viscosity of 6.45 by polymerizing a Group 10 metal source such as palladium and 1,3-bis (diphenylphosphino) propane in a methanol solvent at 80 ° C. for 30 minutes at 5.5 MPa of ethylene and carbon monoxide equimolar mixed gas. A ketone 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, the object of the present invention is to produce the catalytic activity by adding bis (2-hydroxyethyl) octylamine during the polymerization of the polyketone in the liquid medium and An object of the present invention is to provide a method for producing polyketone having an improved intrinsic viscosity.

In order to solve the above problems, a preferred embodiment of the present invention is (a) a Group 9, 10 or 11 transition metal compound, (b) a ligand having an element of Group 15 and (c) pKa is 4 In the presence of an organometallic complex catalyst consisting of an anion of an acid of the following acid, carbon monoxide and an ethylenically unsaturated compound are copolymerized in a liquid medium to produce a polyketone, wherein bis (2-hydroxyethyl) octylamine is added during polymerization. Characterized in that.

According to another preferred embodiment of the present invention, the liquid medium is a mixed solvent consisting of 70 to 90 vol% acetic acid and 30 to 10 vol% water. According to another preferred embodiment of the present invention, the component (a) is palladium acetate and the component (b) is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis It is characterized by the above-mentioned (diphenyl phosphino) propane.

According to another preferred embodiment of the present invention, the component (c) is trifluoroacetic acid.

According to another preferred embodiment of the present invention, the molar ratio of the component (a): bis (2-hydroxyethyl) octylamine is 1: 0.1-5, and the input ratio of the carbon monoxide and the ethylenically unsaturated compound is 1: 1. Or 1: 2.

According to the present invention, when preparing a polyketone by copolymerizing carbon monoxide and an ethylenically unsaturated compound in a liquid medium in the presence of an organometallic complex catalyst, bis (2-hydroxyethyl) octylamine is added during polymerization. And it provides a method for producing a polyketone with an improved intrinsic viscosity.

Hereinafter, the present invention will be described in detail.

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 used mainly for 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 methanol or dichloromethane is used as a liquid medium, it may cause a stop reaction during the polymerization step, but when a mixed solvent of acetic acid and water is used as the liquid medium, it does not have the effect of stopping the catalytic activity. Play a role.

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. 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 a ligand having an element of (a) Group 9, Group 10 or Group 11 transition metal compound of the Periodic Table (IUPAC Inorganic Chemical Nomenclature, 1989), (b) Group 15 and (c) ) is composed of an anion of an acid having a pKa of 4 or less.

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 acetyl acetate, 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.

In the present invention, which focuses on the intrinsic viscosity and catalytic activity of the polyketone, the ligand (b) having a group 15 atom is preferably 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) propane, most preferably 1,3-bis [di (2-methoxyphenyl) phosphino] propane.

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.

Examples of the anion (c) of an acid having a pKa of 4 or less include anions of an organic acid having a pKa of 4 or less, such as trifluoroacetic acid, trifluoromethane sulfonic acid, and p-toluene sulfonic acid; Anions of inorganic acids having a pKa of 4 or less, such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate.

Particularly preferred anion (c) of acids having a pKa of 4 or less in the present invention is trifluoroacetic acid, which is suitable for tire cords as well as having high catalytic activity when a mixed solvent of acetic acid and water is used as the liquid medium. It is possible to produce polyketones having a high intrinsic viscosity.

The present invention is characterized in that bis (2-hydroxyethyl) octylamine is added during the polymerization of polyketone. In the present invention, by adding bis (2-hydroxyethyl) octylamine during the polymerization of the polyketone, the effect of improving the intrinsic viscosity of the polyketone can be achieved. The use of bis (2-hydroxyethyl) octylamine in the polymerization can fundamentally prevent fouling of polymer particles produced during the reaction. In general, fouling occurs when the concentration is high during polymerization, and polymerization is performed by adding bis (2-hydroxyethyl) octylamine, an antifouling agent, to prevent fouling of the inner wall of the reactor. Operation of the polymerization reaction can be performed without the result, and as a result, the resulting product can have the effect of improving the intrinsic viscosity and increasing the activity of the polyketone.

The molar ratio of the (a) Group 9, 10 or 11 transition metal compound and bis (2-hydroxyethyl) octylamine is 1: 0.1 to 20, preferably 1: 0.1 to 10, more preferably Is 1: 0.1-5. If the molar ratio of the transition metal and bis (2-hydroxyethyl) octylamine is less than 1: 0.1, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory, and the transition metal and bis (2-hydroxyethyl) octylamine If the molar ratio exceeds 1:20, the produced polyketone catalytic activity tends to decrease, which is not preferable.

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.

In the present invention, it is preferable to adjust the input ratio of carbon monoxide and ethylenically unsaturated compound to 1: 1 or 1: 2. In the preparation of polyketones, the ratio of carbon monoxide and ethylenically unsaturated compounds is usually 1: 1, but a mixed solvent of acetic acid and water is used as a liquid medium, and bis (2-hydroxyethyl) octylamine is added during polymerization. In the present invention, it was found that not only the input ratio of carbon monoxide and ethylenically unsaturated compound is 1: 1, but also the catalyst activity and intrinsic viscosity improvement can be simultaneously achieved even when adjusted to 1: 2.

In the present invention, a mixed solvent of acetic acid and water is used as a liquid medium, and bis (2-hydroxyethyl) octylamine is added during polymerization to improve the catalytic activity and intrinsic viscosity of the polyketone. Unlike at least 10 hours of polymerization time for improvement, polyketones with high intrinsic viscosity could be produced with only 2 hours of polymerization time.

In the present invention, the copolymerization of carbon monoxide and the ethylenically unsaturated compound includes the Group 9, Group 10 or Group 11 transition metal compound (a), the ligand (b) having an element of Group 15 and pKa of 4 It occurs by the organometallic complex catalyst which consists of the anion (c) of the following acids, and this catalyst is produced by contacting the said three 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 three components previously in a suitable solvent, and may respectively supply three 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, and 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)

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis [di (2-methoxyphenyl] phosphino] propane and 0.0249 g of trifluoroacetic acid were added together with 0.5649 g of bis (2-hydroxyethyl) octylamine in 100 ml of acetone. The mixed solution was dissolved in a mixed solvent of 1350 ml of acetic acid and 250 ml of water, and the solution was evacuated by vacuum, and then charged into a nitrogen-substituted stainless autoclave. The mixture was warmed with stirring at a speed of 800 rpm, and when the internal temperature reached 70 ° C., a 1: 2 mixture of carbon monoxide and ethylene was added until the autoclave internal pressure became 75 bar, while maintaining the internal temperature at 70 ° C. and internal pressure at 75 bar Stirring was continued for 2 hours 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 ° C. to obtain 253.2 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 18.8 kg / gPd · hr and the inherent viscosity was a high value of 5.2 dl / g.

Table 1 summarizes these results.

(Example 2)

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis [di (2-methoxyphenyl] phosphino] propane and 0.0249 g of trifluoroacetic acid were mixed with 0.5649 g of bis (2-hydroxyethyl) octylamine in 100 ml of Acetone. The mixed solution was dissolved in a mixed solvent of 1350 ml of acetic acid and 250 ml of water, and the solution was evacuated by vacuum, and then charged into a nitrogen-substituted stainless autoclave. The mixture was warmed with stirring at a speed of 800 rpm, and when the internal temperature reached 90 ° C., a 1: 1 gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 60 bar, while maintaining the internal temperature at 90 ° C. and internal pressure at 60 bar, Stirring was continued for 2 hours 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 ° C. to obtain 237.6 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 17.7 kg / gPd · hr, and the intrinsic viscosity was a high value of 4.1 dl / g.

Table 1 summarizes these results.

(Comparative Example 1)

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis [di (2-methoxyphenyl] phosphino] propane and 0.0249 g of trifluoroacetic acid were dissolved in 100 ml of Acetone, a mixed solution of 1350 ml of acetic acid and 250 ml of water. After dissolving in a solvent and removing the air by vacuum, the solution was put in a stainless steel autoclave substituted with nitrogen After sealing the autoclave, the contents were heated with stirring at a speed of 800 rpm, and the internal temperature was raised to 70 ° C. At the point of arrival, a 1: 2 mixed gas of carbon monoxide and ethylene was added until the autoclave internal pressure reached 75 bar, stirring was continued for 2 hours while maintaining the internal temperature at 70 ° C. and the internal pressure 75 bar. The reaction solution was filtered, washed several times with methanol, and dried under reduced pressure at room temperature to 80 ° C. to obtain 74.0 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 5.5 dl / g.

Table 1 summarizes these results.

(Comparative Example 2)

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis (diphenylphosphino) propane and 0.0249 g of trifluoro acetate were dissolved in 100 ml of Acetone. The mixed solution was dissolved in a mixed solvent of 1350 ml of acetic acid and 250 ml of water. The solution was removed by air under vacuum, and then charged into a nitrogen-substituted stainless autoclave. After the autoclave was sealed, the contents were warmed with stirring at a speed of 800 rpm, and when the internal temperature reached 90 ° C., a 1: 1 gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 60 bar. Stirring was continued for 2 hours while maintaining the internal temperature at 90 ° C. and the internal pressure at 60 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 85.3 g of a polymer.

^{From 13} C-NMR and IR results, it was confirmed that this polymer is a polyketone consisting essentially of a repeating unit derived from carbon monoxide and a repeating unit derived from ethylene. The catalytic activity was 6.3 kg / gPd · hr and the intrinsic viscosity was 3.6 dl / g.

Table 1 summarizes these results.

According to the present invention, when preparing a polyketone by copolymerizing carbon monoxide and an ethylenically unsaturated compound in a liquid medium, the addition of bis (2-hydroxyethyl) octylamine during the polymerization of the polyketone improved catalytic activity and intrinsic viscosity A manufacturing method is provided.

Claims (7)

in the presence of an organometallic complex catalyst consisting of (a) a Group 9, 10 or 11 transition metal compound, (b) a ligand having an element of Group 15 and (c) an anion of an acid having a pKa of 4 or less, In the method for producing a polyketone by copolymerizing carbon monoxide and ethylenically unsaturated compound in a liquid medium, Bis (2-hydroxyethyl) octylamine is added at the time of superposition | polymerization, The manufacturing method of the polyketone characterized by the above-mentioned. The method for producing polyketone according to claim 1, wherein the liquid medium is a mixed solvent composed of 70 to 90 vol% acetic acid and 30 to 10 vol% water. The method of claim 1, wherein the component (a) is palladium acetate. The polyketone according to claim 1, wherein the component (b) is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) propane Manufacturing method. The method for producing polyketone according to claim 1, wherein the component (c) is trifluoroacetic acid. The method for producing polyketone according to claim 1, wherein the molar ratio of the component (a): bis (2-hydroxyethyl) octylamine is 1: 0.1-5. The method of claim 1, wherein the input ratio of the carbon monoxide and the ethylenically unsaturated compound is 1: 1 or 1: 2.