KR20090072440A - Process for producing polyketone used catalyst precursor - Google Patents

Abstract

A process for producing polyketone is provided to improve catalyst activation and inherent viscosity by using a mixed solvent of water and methanol as a liquid medium, and palladium acetate-[1,3-bis(diphenylphosphino)propane precursor as a catalyst, and adding oleic acid in the polymerization. A process for producing polyketone comprises a step of manufacturing polyketone by copolymerizing carbon monoxide and ethylenically unsaturated compound in a liquid medium in the presence of a catalyst. The catalyst is a catalyst precursor and an organometallic complex consisting of anions of acids with pKa of 4 or less and is added with oleic acids.

Description

Process for producing Polyketone using Catalyst Precursor

The present invention relates to a method for producing a polyketone with improved catalytic activity and intrinsic viscosity. Specifically, a mixed solvent composed of methanol and water is used as a liquid medium, and palladium acetate- [1,3-bis (diphenyl) is used as a catalyst component. Phosphino) propane] and relates to a method for producing polyketone having improved catalytic activity and intrinsic viscosity by adding oleic acid during polymerization.

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, since the wear resistance is high, the parts such as gears of automobiles and the chemical resistance are high, and the gas barrier properties, such as the lining material of the chemical transport pipe, are high, so that it can be used in a light gasoline tank. 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 of 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 low temperatures using a catalyst is disclosed. Japanese Patent Laid-Open No. 4-227726 discloses a method using a catalyst consisting of palladium, 2- (2,4,6-trimethylbenzene) -1,3-bis [di (2-methoxyphenyl) phosphino] propane and an anion. Japanese Patent Laid-Open No. 5-140301 discloses a method using a catalyst composed of palladium, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) phosphino] propane and an anion. However, according to these methods, there is a problem economically 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 reduced to 30 ° C. at 4.8 MPa at 85 ° C. 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 polymerizing 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 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 methanol and water as a liquid medium and as a catalyst component palladium acetate- [1,3-bis (diphenylphosphino) ) Propan] It is to provide a method for producing a polyketone with improved catalytic activity and intrinsic viscosity by using a precursor and adding oleic acid during polymerization.

In order to solve the above problems, a preferred embodiment of the present invention is a method for producing a polyketone by copolymerizing carbon monoxide and ethylenically unsaturated compounds in a liquid medium in the presence of a catalyst, wherein the catalyst is (a) Group 9 , A catalyst precursor synthesized with a ligand having a Group 10 or 11 transition metal compound and (b) a Group 15 element, and (c) an organometallic complex comprising an anion of an acid having a pKa of 4 or less, and the catalyst It provides a method for producing a polyketone, characterized in that it is added with oleic acid.

According to another preferred embodiment of the present invention, the component (a) is palladium acetate, and the component (b) is 1,3-bis (diphenylphosphino) propane.

According to another preferred embodiment of the present invention, the catalyst precursor is palladium acetate- [1,3-bis (diphenylphosphino) propane].

According to another preferred embodiment of the present invention, the molar ratio of the catalyst precursor: oleic acid prepared by synthesizing (a) and (b) is 1: 0.1-5.

According to the present invention, by using a mixed solvent consisting of methanol and water as a liquid medium, using a palladium acetate- [1,3-bis (diphenylphosphino) propane] precursor as a catalyst component and adding oleic acid during polymerization, catalytic activity and Provided is a method for producing polyketone having improved intrinsic viscosity.

Hereinafter, the present invention will be described in detail.

The method for producing a polyketone of the present invention comprises (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 A method for producing polyketone by copolymerizing carbon monoxide and ethylenically unsaturated compound in a liquid medium in the presence of an organometallic complex catalyst comprising a mixed solvent consisting of methanol and water as a liquid medium and palladium acetate- [1] as a catalyst component. , 3-bis (diphenylphosphino) propane] precursor and is characterized by adding oleic acid during polymerization.

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) ) consists of anions of acids 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 copper or silver complexes, carbonates, phosphates, carbamates, sulfonates, and the like, and specific examples thereof include copper acetate, trifluoro copper acetate, 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-py Nitrogen ligands such as choline, 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-methoxy Phenyl) phosphino] 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 focused on improving the intrinsic viscosity and catalytic activity of polyketones, unlike the prior art, a Group 9, Group 10 or Group 11 transition metal compound (a) is used under a mixed solvent of methanol and water as a liquid medium. ) And a method of synthesizing an organometallic complex catalyst consisting of a ligand (b) having an element of Group 15 as a precursor. This is because the use of palladium acetate- [1,3-bis (diphenylphosphino) propane] precursor not only has high catalytic activity but also enables the production of polyketones having high intrinsic viscosity suitable for tire cords.

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.

Among the acids having the above-described pKa of 4 or less, trifluoroacetic acid and p-toluene sulfonic acid or sulfuric acid are most preferably used in terms of improving intrinsic viscosity.

In this invention, it is preferable that the molar ratios of the said (a), (b) component: (c) component are 1: 7. Generally, in the prior art, the molar ratio of (a), (b) component: (c) component is 1:20, but the amount of acid addition is large. However, in the present invention, when the ratio is 1: 7, it is most satisfactory. It has been found that polyketones with sufficient catalytic activity and intrinsic viscosity can be obtained. In the present invention, the molar ratio of the components (a) and (b) to (c) is adjusted to 1: 7 to improve the catalytic activity and intrinsic viscosity of the polyketone, and to achieve economic benefits.

The present invention is another feature of the addition of oleic acid during the polymerization of polyketone. In the present invention, it is possible to achieve the effect of improving the intrinsic viscosity of the polyketone by adding oleic acid during the polymerization of the polyketone. The molar ratio of the (a) Group 9, 10 or 11 transition metal compound and oleic acid is 1: 0.1-20, preferably 1: 0.1-10, most preferably 1: 0.1-5. If the molar ratio of transition metal and oleic acid is less than 1: 0.1, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of transition metal and oleic acid is greater than 1:20, the polyketone catalytic activity is rather decreased. It is not desirable because it tends to.

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 further characterized by using a mixed solvent comprising a water-soluble organic solvent and 500 to 5000 ppm water as the liquid medium.

Specific examples of the water-soluble organic solvent that can be used in the present invention include alcohols such as methanol, ethanol, propanol, butanol, hexafluoroisopropanol and ethylene glycol; phenols such as m-cresol; Amines such as aniline; Ketones such as acetone and methyl ethyl ketone; Ethers such as diethyl ether, tetrahydrofuran and diglyme; Nitriles such as acetonitrile; Ester, such as acetic acid and methyl acetate, etc. are mentioned, These are used individually or as mixed solvent of multiple types. From the viewpoint of economy and safety of handling, preferred water-soluble organic solvents are alcohols, and more preferably methanol.

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 on the pressure at the time of polymerization, but it is generally atmospheric pressure to 20 MPa, preferably 4 to 15 MPa.

Hereinafter, the structure and effect of the present invention will be described in more detail with specific catalyst precursor preparation methods, examples and comparative examples, but these examples are only intended to make the present invention more clearly understood, and limit the scope of the present invention. It is not intended to be. 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 ° C. thermostat, the viscosity is measured at 30 ° C. using an Ubelode viscometer. 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.

(Catalyst precursor production method)

Palladium acetate (100mg, 0.446mmol) and equimolar 1,3-bis (diphenylphosphino) propane are stirred at room temperature and dissolved in acetone (10ml). After a few minutes, it turns into a yellow solution, and after 10 minutes, n-hexane is dropped dropwise to precipitate palladium acetate- [1,3-bis (diphenylphosphino) propane] in the form of yellow microcrystals. It is washed with diethyl ether and filtered through filter paper and dried under vacuum.

(Example 1)

0.0398 g of palladium acetate- [1,3-bis (diphenylphosphino) propane] precursor and 0.0832 g of p-toluene sulfonic acid were dissolved in 100 ml of acetone together with 0.5649 g of oleic acid. This solution was dissolved in a mixed solvent of 2497.5 ml of methanol and 2.5 ml of water, and the solution was evacuated by 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 캜 to obtain 152.6 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 11.3 kg / gPd · hr and the intrinsic viscosity was a high value of 4.0 dl / g.

Table 1 summarizes these results.

(Example 2)

0.0398 g of palladium acetate- [1,3-bis (diphenylphosphino) propane] precursor and 0.0249 g of sulfuric acid were dissolved together with 0.5649 g of oleic acid in a mixed solvent of 2490 ml of methanol and 10 ml of water. After removal, it was charged into a nitrogen-substituted stainless autoclave. After the autoclave was sealed, the contents were warmed with stirring at 800 rpm, and when the internal temperature reached 70 ° C, a 1: 1 gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 70 bar. Stirring was continued for 8 hours while maintaining the internal temperature at 70 ° 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 ° C. to obtain 705.2 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 13.0 kg / gPd · hr and the intrinsic viscosity was a high value of 3.9 dl / g.

Table 1 summarizes these results.

(Comparative Example 1)

0.0281 g of palladium acetate, 0.0619 g of 1,3-bis (diphenylphosphino) propane, and 0.0832 g of p-toluene sulfonic acid were dissolved in a mixed solvent of 2497.5 ml of methanol and 2.5 ml of water, and the solution was evacuated by vacuum. Then, it charged to the stainless autoclave substituted by nitrogen. 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 57.3 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 2.1 kg / gPd · hr and the intrinsic viscosity was 1.6 dl / g.

Table 1 summarizes these results.

(Comparative Example 2)

0.0281 g of palladium acetate, 0.0619 g of 1,3-bis (diphenylphosphino) propane and 0.0249 g of sulfuric acid were dissolved in a mixed solvent of 2490 ml of methanol and 10 ml of water, and this solution was removed by air under vacuum, followed by nitrogen substitution. It loaded into the stainless autoclave. After the autoclave was sealed, the contents were warmed with stirring at 800 rpm, and when the internal temperature reached 70 ° C, a 1: 1 gas of carbon monoxide and ethylene was added until the autoclave internal pressure became 70 bar. Stirring was continued for 8 hours while maintaining the internal temperature at 70 ° 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 ° C. to obtain 230.7 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 2.1 kg / gPd · hr and the intrinsic viscosity was 2.3 dl / g.

Table 1 summarizes these results.

Claims (8)

In the method for producing a polyketone by copolymerizing carbon monoxide and ethylenically unsaturated compounds in a liquid medium in the presence of a catalyst, The catalyst comprises (a) a catalyst precursor synthesized with a ligand having a Group 9, 10 or 11 transition metal compound and (b) a Group 15 element, and (c) an anion of an acid having a pKa of 4 or less. Organometallic complex, And the catalyst is added with oleic acid. 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 (diphenylphosphino) propane. The method of claim 1, wherein the catalyst precursor is palladium acetate- [1,3-bis (diphenylphosphino) propane]. The method for producing polyketone according to claim 1, wherein the molar ratio of the catalyst precursor: oleic acid prepared by synthesizing (a) and (b) is from 1: 0.1 to 5. The method of producing a polyketone according to claim 1, wherein the molar ratio of the catalyst precursor prepared by synthesizing the above (a) and (b): (c) component is 1: 7. The method of claim 1, wherein the input ratio of carbon monoxide and ethylenically unsaturated compound is 1: 1. The method for producing polyketone according to claim 1, wherein a mixed solvent comprising methanol and water of 500 to 5000 ppm is used as the liquid medium.