KR20090069381A - Process for producing polyketone - Google Patents

Abstract

A process for producing polyketone is provided to improve catalyst activity while reducing manufacturing costs of polyketone by using a mixed solvent of water and acetic acid as a liquid medium. A polyketone is obtained by copolymerizing carbon monoxide and ethylenically unsaturated compound in a liquid medium in the presence of an organometallic complex catalyst. The organometallic complex catalyst comprises (a) a transition metal compound of Group 9, 10 or 11; (b) a ligand having elements of Group 15; and (c) negative ion of acid with pKa of 4 or less. The liquid medium uses the mixed solvent consisting of acetic acid of 70-90 volume % and water of 30-10 volume %. Sodium 2,2-methylene-bis-(4,6-di-tert-butylphenyl)phosphate is added in the polymerization.

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. Sodium 2,2-methylene-bis- (4,6-di-tert-butylphenyl) phosphate (sodium 2,2-methylene-bis- (4,6-di-tert-butylphenyl) phosphate (hereinafter referred to as BSP) The present invention relates to a method for producing a polyketone having improved catalytic activity and intrinsic viscosity.

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 with 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-Pdhr. When sulfuric acid is used instead of phosphorus tungstic acid as the mixed solvent, the catalytic activity is 9.5 kg / g-Pdhr. 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 above patent, a polyketone polymer having a catalytic activity of 1.3 kg / g-Pdhr and an intrinsic viscosity of 1.8 can be obtained by subjecting the polymerization ratio of ethylene and carbon dioxide to a ratio of 1: 2 at a pressure of 50 MPa and 4 MPa for 5.2 hours. According to this 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-Pdhr.

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, BSP during polymerization It is an object of the present invention to provide a method for producing polyketone having improved catalytic activity and intrinsic viscosity.

The process for producing the 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 an ethylenically unsaturated compound in a liquid medium in the presence of an organometallic complex catalyst comprising: a mixture consisting of 70 to 90% by volume acetic acid and 30 to 10% by volume water It is characterized by using a solvent and adding BSP during the polymerization.

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 increases rapidly. 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 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) ) pKa is made up of an anion of an acid 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-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-methoxy) Phosphorus ligands, such as ciphenyl) phosphino] propane, etc. are mentioned.

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 organic solvents and are safe 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 not number, it is usually from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per liter of 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) having an element of Group 15 is 1 to 10 times (molar ratio) of the amount of the Group 9, Group 10 or Group 11 transition metal compound (a), and an anion of an acid having a pKa of 4 or less. The use amount of (c) is 10 to 100 times (molar ratio) of the use amount of the Group 9, 10 or 11 transition metal compound (a).

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.

In particular, the anion (c) of an acid having a preferred pKa of 4 or less in the present invention is trifluoroacetic acid, which is an acid having a conventional pKa of 4 or less in the present invention using a mixed solvent of acetic acid and water as a liquid medium. This is because when trifluoroacetic acid is used, it is possible not only to have a high catalytic activity but also to manufacture a polyketone having a high intrinsic viscosity suitable for a tire cord.

The invention is further characterized by the addition of BSP during the polymerization of polyketones. In the present invention, it is possible to achieve the effect of improving the intrinsic viscosity of the polyketone by adding BSP during the polymerization of the polyketone. The molar ratio of the (9) Group 9, Group 10 or Group 11 transition metal compound and BSP is 1: 5 to 100, preferably 1:10 to 100, and more preferably 1:10 to 50. If the molar ratio of transition metal and BSP is less than 1: 5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of transition metal and BSP is greater than 1: 100, 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.

In this invention, it is preferable to adjust the injection ratio (partial-pressure ratio) of carbon monoxide and an ethylenically unsaturated compound to 1: 1 or 1: 2. In the production of polyketone, it is common to set the ratio of carbon monoxide and ethylenically unsaturated compound to 1: 1, but in the present invention in which a mixed solvent of acetic acid and water is used as a liquid medium and BSP is added during polymerization, carbon monoxide and ethylenically unsaturated compounds are used. It was found that the addition of the compound to the ratio of 1: 1 and the improvement of the catalytic activity and the intrinsic viscosity at the same time can be achieved even when the ratio is 1: 2.

In the present invention, a mixed solvent of acetic acid and water is used as the liquid medium, and the addition of BSP during the polymerization not only improves the catalytic activity and intrinsic viscosity of the polyketone, but also in the prior art, the polymerization time is at least 10 hours for the intrinsic viscosity. Contrary to the above, it was confirmed that the polyketone having a high intrinsic viscosity was possible even with the polymerization time of about 2 hours.

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, 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. Although there is no restriction | limiting also about the pressure at the time of superposition | polymerization, Usually, it is normal pressure-20 MPa, Preferably it is 4-15 MPa.

According to the present invention, a polyketone having improved catalytic activity and intrinsic viscosity by using a mixed solvent composed of 70 to 90% by volume acetic acid and 30 to 10% by volume water as a catalyst medium and adding BSP during the polymerization. A manufacturing method is provided.

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 1-5 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

The weight time of the polymerized resin / weight time of palladium (kg / g-Pdhr) is obtained.

(Example 1)

0.0142 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 together with 5.750 g of BSP in 100 ml of Acetone. Dissolved in 250 ml of a solvent and water, and the solution was evacuated by vacuum, and charged into a nitrogen-substituted stainless autoclave, after the autoclave was sealed, the contents were heated with stirring at a speed of 800 rpm, When the internal temperature reached 70 ° C., a 1: 2 mixed gas of carbon monoxide and ethylene was added until the autoclave internal pressure reached 75 bar, and stirring was continued for 2 hours while maintaining the internal temperature at 70 ° C. and the internal pressure at 75 bar. 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 170.2 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 12.6 kg / gPdhr and the intrinsic viscosity was high value of 5.6 dl / g.

Table 1 summarizes these results.

(Example 2)

0.0142 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 together with 5.750 g of BSP in 100 ml of Acetone. Dissolved in 250 ml of a mixed solvent of water, and the solution was evacuated by vacuum, and charged into a nitrogen-substituted stainless autoclave. When the internal temperature reached 90 ° C., a 1: 1 gas mixture of carbon monoxide and ethylene was added until the autoclave internal pressure reached 60 bar, while stirring was continued for 2 hours while maintaining the internal temperature at 90 ° C. and the internal pressure at 60 bar. 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 DEG C to obtain 195.5 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 14.3 kg / gPdhr and the intrinsic viscosity was high value of 4.8 dl / g.

Table 1 summarizes these results.

(Comparative Example 1)

0.0142 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 charged into a nitrogen-substituted stainless autoclave After sealing the autoclave, the contents were heated with stirring at a speed of 700 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 95.6 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 7.01 kg / gPdhr and the intrinsic viscosity was 3.2 dl / g.

Table 1 summarizes these results.

(Comparative Example 2)

0.0129 g of palladium acetate, 0.0238 g of 1,3-bis (diphenylphosphino) propane and 0.0249 g of trifluoroacetic acid were dissolved in 100 ml of Acetone. This 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 steel autoclave. 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 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 77.5 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 5.7 kg / gPdhr and the intrinsic viscosity was 2.2 dl / g.

Table 1 summarizes these results.

Table 1.

Claims (6)

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 polyketone by copolymerizing carbon monoxide and ethylenically unsaturated compound in a liquid medium, a mixed solvent comprising 70 to 90% by volume acetic acid and 30 to 10% by volume water is used as a liquid medium, A method for producing a polyketone, comprising adding, 2-methylene-bis- (4,6-di-tert-butylphenyl) phosphate. The method for producing polyketone according to 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 polyketone according to claim 1, wherein the molar ratio of component (a): sodium 2,2-methylene-bis- (4,6-di-tert-butylphenyl) phosphate is 1: 5 to 100. Manufacturing method. The method for producing a polyketone according to claim 1, wherein the input ratio (partial pressure ratio) of the carbon monoxide and the ethylenically unsaturated compound is 1: 1 or 1: 2.