JP2003268102A - Method for manufacturing polyketone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a high molecular weight polyketone useful as an industrial material in a high yield and for a short time and at a low cost. <P>SOLUTION: The method for manufacturing the polyketone from carbon monoxide and an ethylen unsaturated compound, comprises polymerization under a specific pressure and temperature, using a metal complex catalyst which is obtained from a palladium compound, a bidentate ligand having an atom of a group 15 element of the periodic table and an anion from an acid having a pKa of 4 or less, in a liquid medium which consists of a water soluble organic solvent and water and besides has such a water content of 1-50% as is expressed by equation (1): water content (%)=ä(a mass of water)/[a volume of whole water soluble organic solvents (ml) + a volume of water (ml)]}&times;100. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyketone having excellent mechanical properties and thermal properties. More specifically, it is suitable for use in industrial materials, has high strength, has a high elastic modulus, and has a polyketone having excellent thermal characteristics such as a high melting point and high heat resistance, which is high enough not to require a purification step such as polymer washing. It is an object of the present invention to provide a method for efficiently producing a catalyst using an active catalyst.

[0002]

BACKGROUND OF THE INVENTION Copolymer of carbon monoxide (CO) and an ethylenically unsaturated compound, particularly repeating units derived from carbon monoxide and repeating units derived from an ethylenically unsaturated compound are substantially alternately linked. The structurally structured polyketone has many excellent properties, and in particular, is excellent in mechanical properties and thermal properties, and is therefore suitable as an economically efficient engineering plastic material. Above all, from the high wear resistance,
It can be used for parts such as automobile gears and lightweight gasoline tanks because of its high chemical resistance and gas barrier properties.

Various methods are known as methods for producing such polyketones. For example, US Pat.
88, a method of copolymerizing CO and α-olefin in a solvent such as hexafluoroisopropanol using nickel cyanide or a nickel complex salt as a catalyst is disclosed in US Pat. No. 3,689,460. A method of using tetrakistriarylphosphine palladium as a catalyst in a solvent such as acetonitrile is disclosed in European Patent No. 4707.
No. 59 discloses a method of using a catalyst composed of a nickel compound and a bidentate ligand such as 2-mercaptobenzoic acid in a solvent such as toluene. However, these methods have a problem that the yield of polyketone per catalyst is extremely low.

In order to improve the low polymerization activity, European Patent No. 319083, US Pat. No. 4,925,917 and the like use phosphorus bidentate ligands to improve the yield of polyketone. According to these documents, a method of using a catalyst composed of a palladium compound, 1,3-bis {di (2-methoxyphenyl) phosphino} propane and an anion of an acid in a solvent such as methanol is disclosed. The yield of polyketone per unit is improved to a practical level. However, even in this method, the polymerization activity is still insufficient, and an expensive catalyst component remains in the polymer to a considerable extent.

If the catalyst component remains in the polymer, it causes deterioration of the polymer during molding, and cleaning of the polymer is essential.
Further, the polyketone obtained by this method is a low molecular weight substance,
It was not sufficient to develop the excellent mechanical and thermal properties of polyketone. Many techniques for increasing the yield have been reported, and, for example, Japanese Patent Application Laid-Open No. 2-1
No. 15223 gazette discloses that a catalyst composed of a palladium compound, 1,3-bis {di (2-methoxyphenyl) phosphino} propane and an anion of an acid is used, and high temperature and high pressure conditions of 90 ° C. and 8 MPa or more in methanol. Have been shown to carry out the polymerization of polyketones. In addition, JP-A-8
No. 2669192 discloses a boron compound such as cobalt carbonate, palladium and 1,3-bis {di (2-
A gas phase polymerization process with a catalyst comprising methoxyphenyl) phosphino} propane is disclosed. However,
Even with these methods, the amount of the catalyst residue in the polymer was not negligible and required a washing step. In particular, in the production method disclosed in JP-A-8-2669192, since a large amount of a large amount of quinone compound is added during the polymerization, a washing step is also essential.

Further, JP-A-4-216824 reports that the use of an acid having a higher acidity improves the yield of polyketone. However, even this method has a demerit that the polymerization activity is insufficient and the molecular weight of the obtained polyketone becomes low. It has been reported that the use of water as a polymerization solvent increases the polymerization activity. JP-A-2-180926 discloses that in a mixed solvent of an aprotic polar liquid and water,
When polymerization is carried out in a mixed medium of aprotic polar liquid and water using a catalyst composed of palladium, 1,3-bis {di (2-methoxyphenyl) phosphino} propane and anion, no water is used. It is sometimes disclosed that the yield of polyketone per catalyst is increased to a practical level. However, the polymerization activity was still insufficient even by this method.

Japanese Unexamined Patent Publication No. 8-283403 discloses a polymerization technique in which it is essential to carry out the polymerization in a mixed solvent of methanol and 1 to 50% by volume of water. In this method, a Group 10 metal source such as palladium and 1,3-
A catalyst composed of bis (diphenylphosphino) propane and an anion of an inorganic acid is used. Especially 17
In a methanol solvent containing vol%, palladium acetate, 1,
Polymerization is carried out with 3-bis (diphenylphosphino) propane and phosphotungstic acid under the conditions of 85 ° C. and a mixed gas of ethylene and carbon monoxide in a molar ratio of 4.8 MPa, but the polymerization activity is 5.7 kg / Only g-Pd · hr. The obtained polyketone was not sufficient for exhibiting excellent physical properties as well as the amount of catalyst residue and cost, and the intrinsic viscosity was as low as 1.36.

[0008] WO 00/68296 discloses a polymerization method in water or in a mixed solvent of water and an organic solvent with a water-soluble catalyst consisting of a water-soluble phosphorus bidentate ligand, palladium and an anion. It is disclosed. In addition, in WO 01/02463 pamphlet, palladium and 3,3-bis {bis- (2-methoxyphenyl)-
A method for producing phosphanylmethyl} -1,5-dioxa-spiro [5.5] undecane and an acid with an anion is disclosed. This method is a technology that gives the highest level of polymerization activity in the prior art, but the structure of the catalyst is complicated, the synthesis is multi-step and labor-intensive, and the polymerization activity is 50
It does not reach kg / g-Pd · hr.

As described above, a technique for economically and inexpensively producing a polyketone having a practically sufficient molecular weight with high polymerization activity has not been found yet.

[0010]

An object of the present invention is to provide a method for efficiently producing a polyketone having a practically sufficiently high molecular weight by such a high polymerization activity that a purification step such as washing of a polymer is not required. Is to provide.

[0011]

The inventors of the present invention have conducted extensive studies on a method for producing a polyketone in order to achieve the above object, and as a result, the liquid medium contains a specific amount of water under specific polymerization conditions. In this case, they found that the yield of polyketone increased remarkably so that the catalyst residue was negligible, and completed the present invention.

That is, according to the present invention, when a polyketone is produced by copolymerizing carbon monoxide and an ethylenically unsaturated compound, the polyketone comprises a water-soluble organic solvent and water, and the water content represented by the formula (1) is In a liquid medium that is 1-50%,
In the presence of a metal complex catalyst obtained from a palladium compound, a bidentate ligand having an atom of a Group 15 element of the periodic table, and an anion of an acid having a pKa of 4 or less, carbon monoxide and ethylenic non-existence are obtained. Saturated carbon is always supplied so that the ethylenically unsaturated carbon in the polymerization reaction system has a molar amount of 1 to 20 times that of carbon monoxide, the pressure is 7 MPa or more, and the temperature is 90 to 2
A method for producing a polyketone, which comprises polymerizing carbon monoxide and ethylenically unsaturated carbon under the condition of 00 ° C.

[0013]

[Equation 2]

The present invention will be described in detail below. There are many studies on high polymerization activity in the polymerization of polyketone, and various techniques have been reported. However,
All of them were insufficient for the purpose of the present invention of producing a polyketone with such a high polymerization activity that the catalyst residue can be ignored. The present invention, by using a liquid medium consisting of a water-soluble organic solvent and a specific amount of water as the liquid medium,
This is a solution to the above problem. The specific amount of water is 1 to 50% of water contained in the liquid medium. The specific amount of water is the volume fraction of water represented by the mathematical formula (1) as the water content (%) in the liquid medium. In the formula, the volume of the water-soluble organic solvent is a value at 25 ° C.

[0015]

[Equation 3]

In the polymerization, it is not clear why a high polymerization activity can be achieved by using a liquid medium having a water content of 1 to 50%, but due to some interaction between water molecules and palladium which is a catalyst component. It is considered that the catalytic reaction is promoted. The improvement of polymerization activity by water is
Too little water is ineffective. On the other hand, if the water content is too high, the solubility of the ethylenically unsaturated compound in the liquid medium will be low, or the dispersibility of the organometallic complex as the catalyst will be poor, so that the water content has an upper limit. Water content 1 ~
It becomes possible to obtain the polyketone with high polymerization activity for the first time when a 50% liquid medium is used. The water content is preferably 3 to 30%, more preferably 5 to 20%.
Furthermore, it is 10,000-100 with respect to a palladium compound.
000000 times molar amount, 100 to 5 with respect to the acid anion
When 0000 times the molar amount of water is contained, the effect of water is further improved.

As the water-soluble organic solvent used for the liquid medium in the present invention, various water-soluble organic solvents can be used, and there is no limitation as long as it can dissolve the ethylenically unsaturated compound and carbon monoxide. Absent. In the present invention, the water-soluble organic solvent means an organic solvent that dissolves water in an amount of 10 vol% or more, and examples thereof include alcohols such as methanol, ethanol, propanol, butanol, hexafluoroisopropanol, and ethylene glycol; m
-Phenols such as cresol; amines such as aniline; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, tetrahydrofuran, diglyme; nitriles such as acetonitrile; esters such as acetic acid and methyl acetate. Among these, a single solvent or a mixed solvent of a plurality of types is used. Water-soluble organic solvents that are preferable from the viewpoints of economic efficiency and handling safety are alcohols and esters, and more preferably methanol and ethanol.

In the present invention, the metal complex catalyst used for the polymerization of polyketone has a periodic table (inorganic chemical nomenclature (1
993) A catalyst comprising a compound containing palladium of Group 10 element of Tokyo Kagaku Dojin), a bidentate ligand having an atom of Group 15 element, and a metal complex obtained from an anion of an acid having a pKa of 4 or less. Is. Examples of palladium compounds include carboxylates, phosphates, carbamates, sulfonates, and the like, and specific examples thereof include palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, palladium chloride. , Screw (N,
Examples include N-diethylcarbamate) bis (diethylamino) palladium and palladium sulfate. These may be used alone or in combination of several kinds.

In the present invention, a ligand is a chemical dictionary 7
Pressed edition 16th edition (1974) Kyoritsu Publishing p. As defined in 4, it refers to an atomic group containing an atom directly bonded to a central atom in a complex. In the present invention,
It is necessary to use a bidentate ligand having an atom of Group 15 of the Periodic Table. Examples thereof include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,
Nitrogen bidentate ligands such as 2'-bi-4-picoline and 2,2'-biquinoline; 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) phosphino} propane, 1 , 3-bis {sodium di (2-methoxy-4-sulfonate-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 [{sodium 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,
Examples thereof include phosphorus bidentate ligands such as 3-bis {di (2-methoxyphenyl) phosphino} propane.

Of these, a particularly preferred ligand is a phosphorus bidentate ligand. Particularly preferred linnidentate ligands from the viewpoint of polyketone yield are 1,3-bis {di (2-methoxyphenyl) phosphino} propane and 1,2-bis [{di (2-methoxyphenyl) phosphino} methyl. ] Benzene, and in terms of the molecular weight of polyketone, 2-hydroxy-1,3-bis {di (2-methoxyphenyl) phosphino} propane and 2,2-dimethyl-1,3-bis {di (2 -Methoxyphenyl) phosphino} propane. From the viewpoint of being safe without requiring an organic solvent, water-soluble 1,3-bis {di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino} propane and 1,2-bis [{di ( 2-Methoxy-4-sulfonate sodium-phenyl) phosphino}
Methyl] benzene is preferred. 1,3-, which is easy to synthesize, available in large quantities, and economically preferable
Bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane.

Examples of the acid anion in the present invention include pK such as trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid.
a is an anion of an organic acid having 4 or less; an anion of an inorganic acid having a pKa of 4 or less, such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrofluoroboric acid, hexafluorophosphoric acid, fluorosilicic acid; Examples thereof include anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylanilium tetrakis (pentafluorophenyl) borate. These may be used alone or in combination of two or more.

Of these, the preferred acid anion is p
It is an anion of an inorganic acid or an organic acid having a Ka of 4 or less. From the standpoint of both polymer yield and molecular weight, the anions of sulfuric acid, methanesulfonic acid and trifluoromethanesulfonic acid are preferred. pKa is a numerical value defined by pKa = -log10Ka, where Ka is the dissociation constant of the acid, and the smaller the value, the stronger the acid. The amount of the palladium compound used as a catalyst, since its preferred value varies depending on the type of ethylenically unsaturated compound selected and other polymerization conditions, the range cannot be unconditionally determined,
Preferably, the volume of the reaction zone is 0.01 to
10,000 micromol, more preferably 0.1-10
It is 00 micromol. The capacity of the reaction zone refers to the capacity of the liquid phase of the reactor.

The amount of the ligand used is not limited, but is preferably 0.1 per 1 mol of the palladium compound.
It is -10 mol, more preferably 1-3 mol. The amount of the acid anion used is preferably 0.1 to 10000 mol, and more preferably 1 to 1 mol, per 1 mol of the palladium compound.
It is 1000 mol.

The catalyst of the present invention comprises a palladium compound, a bidentate ligand having an atom of Group 15 element of the periodic table, and pKa.
Is produced by contacting with an anion of an acid of 4 or less. Any method is used for contact. For example, it may be used as a solution in which the three components are mixed in advance in an appropriate solvent, or the three components may be separately supplied to the polymerization system and contacted in the polymerization system. Further, the complex obtained by previously reacting the palladium compound with the ligand may be brought into contact with the acid anion. Further, an oxidizing agent such as benzoquinone or naphthoquinone may be added to the catalyst composed of the above three components.

This catalyst is diluted with a liquid medium composed of water and a water-soluble organic solvent described above, and the ethylenically unsaturated compound and carbon monoxide are polymerized in a reaction vessel such as an autoclave to obtain a polyketone. To manufacture. During the polymerization, the supply of carbon monoxide and the ethylenically unsaturated compound into the polymerization system is always (ethylenically unsaturated compound) /
It is supplied so that the molar ratio of (carbon monoxide) is 1 to 20, and the pressure is maintained at 7 MPa or more. If the pressure is less than 7 MPa, the polymerization activity per unit mass of palladium is insufficient. The reason for this is not clear, but it is considered that the solubility of carbon monoxide and the ethylenically unsaturated compound in the liquid medium is involved.

The method of introducing carbon monoxide and the ethylenically unsaturated compound into the polymerization reaction system is not limited, and gaseous compounds are pressurized and charged, and liquid compounds are charged into a liquid medium. For example, in the polymerization of an ethylenically unsaturated compound and carbon monoxide, a gas mixed in any ratio in advance may be introduced into the reaction system under pressure, or after introducing ethylene to a predetermined pressure, carbon monoxide is introduced. May be charged under pressure, or may be charged in reverse order. The ethylenically unsaturated carbon in the polymerization reaction system supplies the ethylenically unsaturated carbon and the carbon monoxide in a molar amount of 1 to 20 times that of carbon monoxide. If the molar ratio of (ethylenically unsaturated compound) / (carbon monoxide) is less than 1, carbon monoxide will be excessive and ethylene will be insufficient in the liquid solvent diluting the catalyst, resulting in insufficient polymerization activity. However, if this molar ratio exceeds 20, the ethylenic compound will be in excess, and carbon monoxide will be insufficient, so that high polymerization activity cannot be exhibited. Therefore, the molar ratio of (ethylenically unsaturated compound) / (carbon monoxide) in the reaction system is 1 to 2
0, preferably 2.5 to 17, more preferably 4 to 13
At that time, high polymerization activity is exhibited.

Examples of ethylenically unsaturated compounds used in the present invention are ethylene, propylene, 1-butene, 1
Α-olefins such as hexene, 1-octene and 1-decene; alkenyl aromatic compounds such as styrene and α-methylstyrene; cyclopentene, norbornene, 5-methylnorbornene, tetracyclododecene, tricyclodecene, pentacyclopenta Examples thereof include cyclic olefins such as decene and pentacyclohexadecene; vinyl halides such as vinyl chloride; acrylic acid esters such as ethyl acrylate and methyl methacrylate. Among these, preferred ethylenically unsaturated compounds are α-olefins, and more preferred ethylenically unsaturated compounds are α-olefins having 2 to 4 carbon atoms. The most preferred ethylenically unsaturated compound is ethylene. These ethylenically unsaturated compounds can be used alone or as a mixture of plural kinds.

Of these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, and most preferably ethylene. When using plural kinds of ethylenically unsaturated compounds, it is preferable to select ethylene as one of the components from the viewpoint of thermal stability as a material of the obtained polyketone, and more preferably, the ethylenically unsaturated compound to be used. It is to contain 95% or more of ethylene in the total molar amount of the compound.

The polymerization temperature used in the present invention is 90 to 20.
It is 0 ° C. When the polymerization temperature is lower than 90 ° C, the polymerization activity is low and a large amount of catalyst component remains in the polymer. Also, 20
When the temperature exceeds 0 ° C, the polymer formation rate is high, but the molecular weight of the obtained polyketone is too low, resulting in insufficient mechanical strength and thermal properties. When the polyketone is produced under the above conditions, a polymer having a high polymerization activity, which cannot be obtained by the conventional production methods, can be obtained.

In carrying out the present invention, a known polymerization method / manufacturing process can be used. For example, as the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method,
Alternatively, a gas phase polymerization method in which a small amount of a polymer is impregnated with a high-concentration catalyst solution is used, and the manufacturing process may be either batch type or continuous type. According to the production method of the present invention, a polyketone can be produced with a polymerization activity of 50 kg / g-Pd · hr or more, and even if special polymer washing is not performed, the obtained polyketone has a bad influence on polymer physical properties such as heat deterioration. It contains almost no catalyst component that gives The catalyst residue in the polyketone is preferably 5 ppm or less, more preferably 3 ppm or less, most preferably 1 ppm or less. Therefore, the higher the polymerization activity is, the more the amount of the catalyst residue in the polymer can be reduced, and the higher the productivity is. Therefore, the polymerization activity is preferably 50% or less.
kg / g-Pd · hr or more, more preferably 60 kg /
g-Pd · hr or more, most preferably 70 kg or more / g
-Pd · hr.

The polyketone obtained in the present invention has a practically sufficient molecular weight. Especially, the intrinsic viscosity is 1.4dl / g
If it is above, it becomes possible to exhibit the outstanding thermal property and mechanical property. In order to exhibit higher mechanical properties, the intrinsic viscosity is more preferably 1.5 dl / g or more, and further preferably 1.7 dl / g or more because the dimensional stability after molding is excellent. Heretofore, the terminal structure and the influence on the physical properties of the polyketone have not been related to each other at all, but the terminal structure is important even for a high molecular weight polyketone. Generally, the terminal structure (RO-CO-structure, where R is an organic group) present in the polyketone is susceptible to deterioration, and is modified by overheating during molding and the like,
This leads to deterioration of heat resistance and physical properties of the fiber. Therefore, the R-O-CO-terminal structure in the polyketone is 10 meq / kg.
It is important to make the following, but the polyketone according to the present invention has few terminal R—O—CO— structures and has good thermal stability.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described with reference to Examples and the like, but these do not limit the scope of the present invention. As the organic solvent in the examples, a completely dried solvent obtained by further dehydrating dehydrated one for organic synthesis with magnesium sulfate under a dry nitrogen stream before polymerization was used. As the water, distilled water containing no impurities such as metals was used. As sulfuric acid, special grade 96% sulfuric acid was used. This sulfuric acid contained 4% water, and in consideration of this, the sulfuric acid was prepared and polymerized so as to have the same amount of sulfuric acid and water content as described in the examples.

The measuring method of each measured value used in the present invention is as follows. (1) Represents the amount of palladium in catalytic activity unit and the yield of polyketone per unit time. Polymerization activity (kg / g-Pd · hr) = polyketone yield (kg) / [molar amount of Pd (mol)
X atomic weight of Pd (g / mol) x polymerization time (hr)]

(2) Catalyst residue The polyketone produced is subjected to elemental analysis by high-frequency plasma emission spectrometry, and the residual amount of palladium atoms used as a catalyst in the produced polymer is shown. Catalyst residue (ppm) = amount of palladium (μg) / mass of polyketone (g)

(3) Intrinsic viscosity Intrinsic viscosity [η] is a value obtained based on the following defining equation. In the formula, t and T are flow times of a viscous tube at 25 ° C. of a dilute solution of hexafluoroisopropanol having a purity of 98% or more and a polyketone dissolved in hexafluoroisopropanol, and C is a solute mass in grams of 100 ml of the above solution. It is a value.

[0036]

Example 1 Palladium acetate 1.0 micromol, 1,
3-bis {di (2-methoxyphenyl) phosphino} propane 1.2 μmol and sulfuric acid 50 μmol, methanol water mixed solvent 100 ml containing 18% of water 100 ml
Dissolved in water, and this solution was replaced with nitrogen.
It was charged into a ml autoclave. Then 1,4-
After adding 1 mg of benzoquinone and sealing the autoclave, the contents were heated with stirring, and when the internal temperature reached 90 ° C, ethylene was added until the internal pressure of the reactor reached 5.0 MPa. Subsequently, carbon monoxide was added until the pressure reached 8.0 MPa. When the gas input flow rate at this time was measured, the molar ratio of (ethylene) / (carbon monoxide) was 3.4. Stirring was continued for 4 hours while maintaining the internal temperature and internal pressure in this state. After cooling, purge the gas in the autoclave,
The contents were taken out.

The reaction solution was filtered, washed once with methanol and then dried under reduced pressure to obtain 21.3 g of a polymer. At this time, the polymerization activity was 50.2 kg / g-Pd · hr, [η] was 3.4, and the catalyst residue was 5 ppm. ^{From the} results of ¹³ C-NMR and IR measurements, it was confirmed that this polymer was a polyketone that substantially consisted of repeating units derived from carbon monoxide and repeating units derived from ethylene.

It was confirmed that the polymers obtained in the following Examples and Comparative Examples were all polyketones which substantially consisted of repeating units derived from carbon monoxide and repeating units derived from ethylene.

[0039]

COMPARATIVE EXAMPLE 1 The procedure of Example 1 was repeated except that the mixed solvent in Example 1 was changed to methanol and the sulfuric acid was changed to methanesulfonic acid, to obtain 8.8 g of polyketone. Polymerization activity is 20.8kg / g-Pd
The hr and [η] were 2.9, and the catalyst residue was 12 ppm in the elemental analysis after further washing with methanol several times.

[0040]

Comparative Example 2 The water content of the mixed solvent in Example 1 was 70%.
The same procedure as in Example 1 was carried out except that the amount was changed to 10% to obtain 10.9 g of polyketone. Polymerization activity is 2
At 5.8 kg / g-Pd · hr, [η] was a low value of 0.5, and the catalyst residue was 10 ppm in the elemental analysis after further washing with methanol several times.

[0041]

Comparative Example 3 Palladium acetate in Example 1 was changed to nickel acetate, and the phosphorus ligand was changed to 1,2-bis {di (2-
The procedure of Example 1 was repeated except that it was changed to methoxyphenyl) phosphino} ethane, and only a trace amount of polyketone was obtained.

[0042]

[Example 2] The water content of the mixed solvent in Example 1 was 1%.
The same operation as in Example 1 was carried out except that the above procedure was changed to, to obtain 12.9 g of a polyketone. Polymerization activity is 3
0.5 kg / g-Pd · hr, [η] was 6.2, and the catalyst residue was 7 ppm.

[0043]

Example 3 The water content of the mixed solvent in Example 1 was set to 40.
The same procedure as in Example 1 was carried out except that the amount was changed to 10% to obtain 20.5 g of polyketone. Polymerization activity is 4
8.3 kg / g-Pd · hr, [η] was 2.2, and the catalyst residue was 5 ppm.

[0044]

[Example 4] The same operation as in Example 1 was carried out except that the sulfuric acid in Example 1 was changed to methanesulfonic acid, to obtain 19.2 g of polyketone. Polymerization activity is 4
5.4 kg / g-Pd · hr, [η] was 3.5, and the catalyst residue was 5 ppm.

[0045]

[Example 5] The same operation as in Example 1 was carried out except that the sulfuric acid in Example 1 was changed to trifluoromethanesulfonic acid, to obtain 19.8 g of a polyketone. Polymerization activity was 46.3 kg / g-Pd · hr, and [η] was 3.
5, the catalyst residue was 4 ppm.

[0046]

Comparative Example 4 The procedure of Example 1 was repeated except that the sulfuric acid in Example 1 was changed to acetic acid.
g of polyketone was obtained. Polymerization activity is 7.6kg / g-P
d · hr, which was insufficient. [Η] was a low value of 1.2, and the catalyst residue was a large amount of 30 ppm in elemental analysis after further washing with methanol several times.

[0047]

Example 6 With the method of charging carbon monoxide and ethylene in Example 1, ethylene was added until the internal pressure of the reactor reached 7.0 MPa when the internal temperature reached 90 ° C. Subsequently, carbon monoxide was added until the pressure reached 8.0 MPa. When the gas input flow rate at this time was measured, the molar ratio of (ethylene) / (carbon monoxide) was 14.3. Then, the same operation as in Example 1 was carried out to obtain 18.9 g of a polyketone. Polymerization activity is 44.5 kg / g-Pd · hr,
[Η] was 2.2 dl / g, and the catalyst residue was 5 ppm.

[0048]

Example 7 With the method of charging carbon monoxide and ethylene in Example 1, ethylene was added until the internal temperature reached 90 MPa when the internal temperature reached 90 ° C. Subsequently, carbon monoxide was added until the pressure reached 8.0 MPa. When the gas input flow rate at this time was measured, the molar ratio of (ethylene) / (carbon monoxide) was 1.2. Then, the same operation as in Example 1 was carried out to obtain 14.3 g of a polyketone. Polymerization activity is 33.7 kg / g-Pd · hr,
[Η] was 2.6 and the catalyst residue was 6 ppm.

[0049]

Comparative Example 5 The method of charging carbon monoxide and ethylene in Example 1 was added until the internal temperature reached 90 ° C. and ethylene was added until the reactor internal pressure reached 2.0 MPa. Subsequently, carbon monoxide was added until the pressure reached 4.0 MPa. When the gas input flow rate at this time was measured, the molar ratio of (ethylene) / (carbon monoxide) was 2.0. Then, the same procedure as in Example 1 was carried out to obtain 4.1 g of polyketone. Polymerization activity was 9.6 kg / g-Pd · hr, and [η] was 1.
8. The catalyst residue was 25 ppm in the elemental analysis after further washing with methanol several times.

[0050]

Example 8 As a method of adding carbon monoxide and ethylene in Example 1, ethylene was added until the internal pressure of the reactor reached 4.5 MPa when the internal temperature reached 90 ° C., and then,
Carbon monoxide was added until the pressure reached 7.0 MPa. When the flow rate of gas input at this time was measured, (ethylene) /
The molar ratio of (carbon monoxide) was 3.7. Then, the same operation as in Example 1 was carried out to obtain 17.9 g of a polyketone. Polymerization activity is 42.1 kg / g-Pd · hr,
[Η] was 3.4, and the catalyst residue was 5 ppm.

[0051]

Example 9 As a method for adding carbon monoxide and ethylene in Example 1, ethylene was added until the internal pressure of the reactor reached 5.0 MPa when the internal temperature reached 90 ° C., and then,
Carbon monoxide was added until it reached 9.5 MPa. When the flow rate of gas input at this time was measured, (ethylene) /
The molar ratio of (carbon monoxide) was 2.3. Then, the same operation as in Example 1 was carried out to obtain 25.4 g of a polyketone. Polymerization activity is 59.8 kg / g-Pd · hr,
[Η] was 3.4 and the catalyst residue was 4 ppm.

[0052]

Comparative Example 6 As a method for adding carbon monoxide and ethylene in Example 1, ethylene was added until the internal pressure of the reactor reached 7.5 MPa when the internal temperature reached 90 ° C., and then,
Carbon monoxide was added to reach 8.0 MPa. When the flow rate of gas input at this time was measured, (ethylene) /
The molar ratio of (carbon monoxide) was 30.6. After this,
When operated in the same manner as in Example 1, 9.5 g of polyketone was obtained. Polymerization activity is 22.4 kg / g-Pd · hr,
[Η] was 2.2, and the catalyst residue was 11 ppm in the elemental analysis after further washing with methanol several times.

[0053]

Comparative Example 7 As a method of adding carbon monoxide and ethylene in Example 1, ethylene was added until the internal pressure of the reactor reached 2.0 MPa when the internal temperature reached 90 ° C., and then,
Carbon monoxide was added to reach 8.0 MPa. When the flow rate of gas input at this time was measured, (ethylene) /
The molar ratio of (carbon monoxide) was 0.7. Then, the same operation as in Example 1 was carried out to obtain 6.1 g of a polyketone. Polymerization activity is 14.5 kg / g-Pd · hr,
[Η] was 1.9, and the catalyst residue was also 17 ppm in elemental analysis after further washing with methanol several times.

[0054]

Example 10 As a method of introducing carbon monoxide and ethylene in Example 1, ethylene was added until the internal pressure of the reactor reached 5.0 MPa when the internal temperature reached 120 ° C., and then carbon monoxide was added. Add until 9.5 MPa. When the input flow rate of gas at this time was measured, (ethylene)
The molar ratio of / (carbon monoxide) was 2.4. After this,
When operated in the same manner as in Example 1, 30.7 g of polyketone was obtained. Polymerization activity is 72.5 kg / g-Pd · hr
And [η] was 1.5, and the catalyst residue was 3 ppm.

[0055]

Example 11 As a method for adding carbon monoxide and ethylene in Example 1, ethylene was added until the internal pressure of the reactor reached 6.0 MPa when the internal temperature reached 120 ° C., and then carbon monoxide was added. Added until 12.0 MPa. When the gas input flow rate at this time was measured, the molar ratio of (ethylene) / (carbon monoxide) was 2.1. Then, the same operation as in Example 1 was carried out to obtain 35.4 g of a polyketone. Polymerization activity is 83.4 kg / g-Pd.
It was as high as hr, [η] was 1.6, and the catalyst residue was 2 ppm, which was a very small amount. This example was repeated again, and the polyketone obtained without performing any special washing operation was subjected to elemental analysis. As a result, the catalyst residue was 2 ppm, which was a very small amount.

[0056]

Example 12 As a method of adding carbon monoxide and ethylene in Example 1, ethylene was added until the internal pressure of the reactor reached 8.0 MPa when the internal temperature reached 120 ° C., and then carbon monoxide was added. Added until 12.0 MPa. When the gas input flow rate at this time was measured, the molar ratio of (ethylene) / (carbon monoxide) was 4.2. Then, the same operation as in Example 1 was carried out to obtain 35.4 g of a polyketone. Polymerization activity is 92.3 kg / g-Pd.
It was as high as hr, [η] was 1.5, and the catalyst residue was 1 ppm, which was a very small amount. This example was repeated again, and the polyketone obtained without performing any special washing operation was subjected to elemental analysis. As a result, the catalyst residue was a very small amount of 1 ppm.

[0057]

[Comparative Example 8] The same operation as in Example 1 was carried out except that the temperature in Example 1 was changed to 75 ° C. As a result, the molar ratio of (ethylene) / (carbon monoxide) was 3.3. .
Then, the same operation as in Example 1 was carried out to obtain 4.7 g of a polyketone. Polymerization activity is 11.1 kg / g-Pd
-Hr, [η] was 5.2, and the catalyst residue was 21 ppm in the elemental analysis after further washing with methanol several times.

[0058]

Example 13 1,3-bis [di (2
1,3-methoxyphenyl) phosphino] propane
The procedure of Example 9 was repeated except that the bis (diphenylphosphino) propane was changed to 26.6.
g of polyketone was obtained. Polymerization activity is 62.8 kg / g-
Pd · hr is high, [η] is 1.4, catalyst residue is 4 pp
It was m.

[0059]

Example 14 The same procedure as in Example 9 was repeated except that methanol was changed to ethanol in Example 9, to obtain 26.2 g of polyketone. Polymerization activity is 6
High as 1.7 kg / g-Pd · hr, [η] is 3.6,
The catalyst residue was 4 ppm.

[0060]

Example 15 The same procedure as in Example 9 was carried out except that the methanol in Example 9 was changed to isopropanol, to obtain 22.4 g of polyketone. The polymerization activity was as high as 52.8 kg / g-Pd · hr, the [η] was 4.0, and the catalyst residue was 4 ppm.

[0061]

Example 16 The same procedure as in Example 9 was carried out except that the methanol in Example 9 was changed to acetic acid, to obtain 26.2 g of polyketone. The polymerization activity is 49.
8 kg / g-Pd · hr, [η] was 3.3, and the catalyst residue was 5 ppm. Table 1 shows a summary of these results.
And 2 are shown.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

EFFECTS OF THE INVENTION According to the present invention, a high molecular weight polyketone capable of exhibiting excellent mechanical and thermal properties, which is extremely useful as an industrial material, is produced from inexpensive raw materials of carbon monoxide and olefins in a high yield. It can be efficiently manufactured in a short time.

Claims (8)

[Claims] 1. When a polyketone is produced by copolymerizing carbon monoxide and an ethylenically unsaturated compound, the polyketone is composed of a water-soluble organic solvent and water and has a water content of 1 in the formula (1).
-50% in a liquid medium, a palladium compound, a bidentate ligand having an atom of Group 15 element of the periodic table, and pK
a in the presence of a metal complex catalyst obtained from an anion of an acid of 4 or less, carbon monoxide and ethylenically unsaturated carbon,
The ethylenically unsaturated carbon in the polymerization reaction system is always supplied in a molar amount of 1 to 20 times that of carbon monoxide, and the pressure is 7MP.
A method for producing a polyketone, which comprises polymerizing carbon monoxide and ethylenically unsaturated carbon under a condition of a or higher and a temperature of 90 to 200 ° C. [Equation 1] 2. The anion of an acid having a pKa of 4 or less is an anion of an acid consisting of at least one selected from sulfuric acid, methanesulfonic acid and trifluoromethanesulfonic acid. Method for producing polyketone. 3. The bidentate ligand having an atom of Group 15 element of the periodic table is 1,3-bis {di (2-methoxyphenyl) phosphino} propane or 1,3-bis (diphenylphosphino). The method for producing a polyketone according to claim 1, which is propane. 4. The method for producing a polyketone according to claim 1, wherein the water-soluble organic solvent used in the liquid medium is methanol or ethanol. 5. The polymerization activity of the metal complex catalyst is 50 kg-
Polyketone / g-Pd · hr or more, The method for producing a polyketone according to any one of claims 1 to 4, wherein: 6. The polymerization activity of the metal complex catalyst is 60 kg-
Polyketone / g-Pd · hr or more, The method for producing a polyketone according to any one of claims 1 to 4, wherein: 7. The polymerization activity of the metal complex catalyst is 70 kg-
Polyketone / g-Pd · hr or more, The method for producing a polyketone according to any one of claims 1 to 4, wherein: 8. A polyketone obtained by the method according to any one of claims 1 to 7.