Process for producing polyketone

Abstract

The present invention relates to a process for preparing polyketone with improved catalytic activity and intrinsic viscosity, and specifically a process for preparing polyketone wherein an organometallic complex comprising acetate-palladium and 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane is used as a catalyst component, and a mixed solvent of 70 to 90 vol % of acetic acid and 10 to 30 vol % of water is used as a liquid medium.

Description

EXAMPLES

Example 1

0.0129 g of palladium acetate, and 0.0366 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane (BIBMAPP) were dissolved in the mixture of 2249 ml of acetic acid and 417 ml of water. After removing the air from the solution under vacuum, the obtained solution was charged into a stainless-steel autoclave which had been purged with nitrogen. After sealing the autoclave, the contents were heated under stirring at a speed of 700 rpm. When the internal temperature reached 90° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:2) was added until the internal pressure of the autoclave became 65 bar. The contents were stirred for 1 hour while the internal temperature and the internal pressure were maintained at 90° C. and 65 bar, respectively. After cooling, the contents were taken out from the autoclave which had been degassed. The solution was filtered and then washed with methanol several times. The solution was dried under reduced pressure at room temperature to 80° C., to obtain 73 g of a polymer.

The results of ¹³C-NMR and IR confirmed that the polymer was polyketone which substantially consists of repeating units each derived from carbon monoxide and ethylene. The catalytic activity was equal to 11.8 kg/g-Pd·hr, and the intrinsic viscosity was 3.1 dl/g.

The results are summarized in Table 1.

Example 2

0.0129 g of palladium acetate, and 0.0366 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane (BIBMAPP) were dissolved in the mixture of 2249 ml of acetic acid and 417 ml of water. After removing the air from the solution under vacuum, the obtained solution was charged into a stainless-steel autoclave which had been purged with nitrogen. After sealing the autoclave, the contents were heated under stirring at a speed of 700 rpm. When the internal temperature reached 90° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:2) was added until the internal pressure of the autoclave became 70 bar. The contents were stirred for 15 hours while the internal temperature and the internal pressure were maintained at 90° C. and 70 bar, respectively. After cooling, the contents were taken out from the autoclave which had been degassed. The solution was filtered and then washed with methanol several times. The solution was dried under reduced pressure at room temperature to 80° C., to obtain 890.3 g of a polymer.

The results of ¹³C-NMR and IR confirmed that the polymer was polyketone which substantially consists of repeating units each derived from carbon monoxide and ethylene. The catalytic activity was equal to 9.5 kg/g-Pd·hr, and the intrinsic viscosity was 5.0 dl/g.

The results are summarized in Table 1.

Example 3

0.0236 g of palladium acetate, and 0.0674 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane (BIBMAPP) were dissolved in the mixture of 1350 ml of acetic acid and 250 ml of water. After removing the air from the solution under vacuum, the obtained solution was charged into a stainless-steel autoclave which had been purged with nitrogen. After sealing the autoclave, the contents were heated under stirring at a speed of 700 rpm. When the internal temperature reached 90° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:2) was added until the internal pressure of the autoclave became 45 bar. The contents were stirred for 1 hour while the internal temperature and the internal pressure were maintained at 90° C. and 45 bar, respectively. After cooling, the contents were taken out from the autoclave which had been degassed. The solution was filtered and then washed with methanol several times. The solution was dried under reduced pressure at room temperature to 80° C., to obtain 183.9 g of a polymer.

The results of ¹³C-NMR and IR confirmed that the polymer was polyketone which substantially consists of repeating units each derived from carbon monoxide and ethylene. The catalytic activity was equal to 16,24 kg/g-Pd·hr, and the intrinsic viscosity was 2.3 dl/g.

The results are summarized in Table 1.

Example 4

0.0129 g of palladium acetate, and 0.0366 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane (BIBMAPP) were dissolved in the mixture of 2249 ml of acetic acid and 417 ml of water. After removing the air from the solution under vacuum, the obtained solution was charged into a stainless-steel autoclave which had been purged with nitrogen. After sealing the autoclave, the contents were heated under stirring at a speed of 700 rpm. When the internal temperature reached 90° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:2) was added until the internal pressure of the autoclave became 70 bar. The contents were stirred for 1 hour while the internal temperature and the internal pressure were maintained at 90° C. and 70 bar, respectively. After cooling, the contents were taken out from the autoclave which had been degassed. The solution was filtered and then washed with methanol several times. The solution was dried under reduced pressure at room temperature to 80° C., to obtain 72.5 g of a polymer.

The results of ¹³C-NMR and IR confirmed that the polymer was polyketone which substantially consists of repeating units each derived from carbon monoxide and ethylene. The catalytic activity was equal to 11.6 kg/g-Pd·hr, and the intrinsic viscosity was 4.2 dl/g.

The results are summarized in Table 1.

	TABLE 1
									Partial
			Catalyst system	Solvent	Input				pressure
	Catalytic	Amount	[Amount of	(ml)	ratio	Rx	Rx	Polymerization	of
	I.V.	Activity	produced	catalyst input(g)]	Acetic		Ligand/	Temp	Pressure	Time	gas
	(dl/g)	(Kg/gPd · hr)	(g)	Pd	Ligand	acid	water	Pd	(° C.)	(bar)	(hr)	(CO:Et)
Ex. 1	3.1	11.8	73	Pd(OAc)2	BIBMAPP	2249	417	1.2	90	65	1	1:2
				0.0129	0.0366
Ex. 2	5.0	9.5	890.3	Pd(OAc)2	BIBMAPP	2249	417	1.2	90	70	15	1:2
				0.0129	0.0366
Ex. 3	2.3	16.24	183.9	Pd(OAc)2	BIBMAPP	1350	250	1.2	90	45	1	1:2
				0.0236	0.0674
Ex. 4	4.2	11.6	72.5	Pd(OAc)2	BIBMAPP	2249	417	1.2	90	70	1	1:2
				0.0129	0.0366
Pd(OAc)2: Palladium acetate
BIBMAPP: 1,3-Bis[bis(2-methoxy-5-methylphenyl)phosphino]propane

Comparative Example 1

0.0129 g of palladium acetate, and 0.0307 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane were dissolved in the mixture of 2249 ml of acetic acid and 417 ml of water. After removing the air from the solution under vacuum, the obtained solution was charged into a stainless-steel autoclave which had been purged with nitrogen. After sealing the autoclave, the contents were heated under stirring at a speed of 700 rpm. When the internal temperature reached 90° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:2) was added until the internal pressure of the autoclave became 65 bar. The contents were stirred for 1 hour while the internal temperature and the internal pressure were maintained at 90° C. and 65 bar, respectively. After cooling, the contents were taken out from the autoclave which had been degassed. The solution was filtered and then washed with methanol several times. The solution was dried under reduced pressure at room temperature to 80° C., to obtain 58.4 g of a polymer.

The results of ¹³C-NMR and IR confirmed that the polymer was polyketone which substantially consists of repeating units each derived from carbon monoxide and ethylene. The catalytic activity was equal to 9.4 kg/g-Pd·hr, and the intrinsic viscosity was 3.1 dl/g.

The results are summarized in Table 2.

Comparative Example 2

0.0129 g of palladium acetate, and 0.0307 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane were dissolved in the mixture of 2249 ml of acetic acid and 417 ml of water. After removing the air from the solution under vacuum, the obtained solution was charged into a stainless-steel autoclave which had been purged with nitrogen. After sealing the autoclave, the contents were heated under stirring at a speed of 700 rpm. When the internal temperature reached 90° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:2) was added until the internal pressure of the autoclave became 70 bar. The contents were stirred for 15 hours while the internal temperature and the internal pressure were maintained at 90° C. and 70 bar, respectively. After cooling, the contents were taken out from the autoclave which had been degassed. The solution was filtered and then washed with methanol several times. The solution was dried under reduced pressure at room temperature to 80° C., to obtain 690.2 g of a polymer.

The results of ¹³C-NMR and IR confirmed that the polymer was polyketone which substantially consists of repeating units each derived from carbon monoxide and ethylene. The catalytic activity was equal to 7.4 kg/g-Pd·hr, and the intrinsic viscosity was 4.9 dl/g.

The results are summarized in Table 2.

Comparative Example 3

0.0236 g of palladium acetate, and 0.0559 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane were dissolved in the mixture of 1350 ml of acetic acid and 250 ml of water. After removing the air from the solution under vacuum, the obtained solution was charged into a stainless-steel autoclave which had been purged with nitrogen. After sealing the autoclave, the contents were heated under stirring at a speed of 700 rpm. When the internal temperature reached 90° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:2) was added until the internal pressure of the autoclave became 45 bar. The contents were stirred for 1 hour while the internal temperature and the internal pressure were maintained at 90° C. and 45 bar, respectively. After cooling, the contents were taken out from the autoclave which had been degassed. The solution was filtered and then washed with methanol several times. The solution was dried under reduced pressure at room temperature to 80° C., to obtain 164.2 g of a polymer.

The results of ¹³C-NMR and IR confirmed that the polymer was polyketone which substantially consists of repeating units each derived from carbon monoxide and ethylene. The catalytic activity was equal to 14.5 kg/g-Pd·hr, and the intrinsic viscosity was 2.1 dl/g.

The results are summarized in Table 2.

Comparative Example 4

0.0129 g of palladium acetate, and 0.0307 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane were dissolved in the mixture of 2249 ml of acetic acid and 417 ml of water. After removing the air from the solution under vacuum, the obtained solution was charged into a stainless-steel autoclave which had been purged with nitrogen. After sealing the autoclave, the contents were heated under stirring at a speed of 700 rpm. When the internal temperature reached 90° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:2) was added until the internal pressure of the autoclave became 70 bar. The contents were stirred for 1 hour while the internal temperature and the internal pressure were maintained at 90° C. and 70 bar, respectively. After cooling, the contents were taken out from the autoclave which had been degassed. The solution was filtered and then washed with methanol several times. The solution was dried under reduced pressure at room temperature to 80° C., to obtain 57.3 g of a polymer.

The results of ¹³C-NMR and IR confirmed that the polymer was polyketone which substantially consists of repeating units each derived from carbon monoxide and ethylene. The catalytic activity was equal to 9.2 kg/g-Pd·hr, and the intrinsic viscosity was 4.1 dl/g.

The results are summarized in Table 2.

	TABLE 2
									Partial
			Catalyst system	Solvent	Input				pressure
	Catalytic	Amount	[Amount of	(ml)	ratio	Rx	Rx	Polymerization	of
	I.V.	Activity	produced	catalyst input(g)]	Acetic		Ligand/	Temp	Pressure	Time	gas
	(dl/g)	(Kg/gPd · hr)	(g)	Pd	Ligand	acid	water	Pd	(° C.)	(bar)	(hr)	(CO:Et)
Ex. 1	3.1	9.4	58.4	Pd(OAc)2	BDOMPP	2249	417	1.2	90	65	1	1.2
				0.0129	0.0307
Ex. 2	4.9	7.4	690.2	Pd(OAc)2	BDOMPP	2249	417	1.2	90	70	15	1.2
				0.0129	0.0307
Ex. 3	2.1	14.5	164.2	Pd(OAc)2	BDOMPP	1350	250	1.2	90	45	1	1.2
				0.0236	0.0559
Ex. 4	4.1	9.2	57.3	Pd(OAc)2	BDOMPP	2249	417	1.2	90	70	1	1.2
				0.0129	0.0307
Pd(OAc)2: Palladium acetate
BDOMPP: 1,3-Bis[di(methoxyphenyl)phosphino]propane

EFFECTS OF THE INVENTION

According to the present invention, a process for prep According to the present invention, by using 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane as the ligand of the catalyst component, a mixed solvent of 70 to 90 vol % of acetic acid and 10 to 30 vol % of water as a liquid medium, and palladium acetate as a transition metal complex, a process for preparing polyketone with the improved catalytic activity and the improved activity even with a shorter reaction time, is provided.

Claims

1. A process for preparing polyketone, comprising copolymerization of carbon monoxide and an ethylenically unsaturated compound in a liquid medium in the presence of a catalyst, wherein the catalyst is an organometallic complex comprising (a) a Group 9, Group 10 or Group 11 transition metal complex, and (b) a ligand containing a Group 15 element, andthe (b) component is 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane.

2. The process for preparing polyketone according to claim 1, wherein the liquid medium is a mixed solvent of 70 to 90 vol % of acetic acid and 10 to 30 vol % of water.

3. The process for preparing polyketone according to claim 1, wherein the (a) component is palladium acetate.

4. The process for preparing polyketone according to claim 1, wherein the molar ratio of the (a) component: the (b) component of the catalyst is 1:1.2.