Process for preparing 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, in which as a catalyst component, an organometallic complex comprising palladium acetate, 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane, and an anion of an acid with pKa of 4 or lower, as a liquid medium, a mixed solvent of methanol and 1000 to 10000 ppm of water, and upon polymerization, benzothiazole or benzophenone is added.

Description

EXAMPLES

Example 1

0.0140 g of palladium acetate, 0.0398 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane (BIBMAPP), 0.0499 g of trifluoroacetic acid and 0.4225 g of benzothiazole were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2497.5 ml of methanol and 1000 ppm 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 800 rpm. When the internal temperature reached 70° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:1.8) was added until the internal pressure of the autoclave became 100 bar. The contents were stirred for 2 hours while the internal temperature and the internal pressure were maintained at 70° C. and 100 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 51.2 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 3.8 kg/g-Pd·hr, and the intrinsic viscosity was 16.8 dl/g.

The results are summarized in Table 1.

Example 2

0.0140 g of palladium acetate, 0.0398 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane, 0.0499 g of trifluoroacetic acid and 0.4225 g of benzothiazole were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2497.5 ml of methanol and 1000 ppm 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 800 rpm. When the internal temperature reached 80° 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 2 hours while the internal temperature and the internal pressure were maintained at 80° 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 72.8 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 5.4 kg/g-Pd·hr, and the intrinsic viscosity was 15.7 dl/g.

The results are summarized in Table 1.

Example 3

0.0140 g of palladium acetate, 0.0398 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane, 0.0249 g of trifluoroacetic acid, 0.0215 g of sulfuric acid and 0.4225 g of benzothiazole were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2497.5 ml of methanol and 1000 ppm 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 800 rpm. When the internal temperature reached 70° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:1.8) was added until the internal pressure of the autoclave became 70 bar. The contents were stirred for 2 hours while the internal temperature and the internal pressure were maintained at 70° 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 90.3 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 6.7 kg/g-Pd·hr, and the intrinsic viscosity was 13.5 dl/g.

The results are summarized in Table 1.

Example 4

0.0140 g of palladium acetate, 0.0398 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane and 0.1226 g of sulfuric acid were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2475 ml of methanol and 25 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 800 rpm. When the internal temperature reached 70° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:1.8) was added until the internal pressure of the autoclave became 85 bar. The contents were stirred for 2 hours while the internal temperature and the internal pressure were maintained at 70° C. and 85 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 440.8 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 32.7 kg/g-Pd·hr, and the intrinsic viscosity was 4.5 dl/g.

The results are summarized in Table 1.

Example 5

0.0140 g of palladium acetate, 0.0398 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane and 0.0429 g of sulfuric acid were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2200 ml of methanol and 300 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 800 rpm. When the internal temperature reached 70° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:1) was added until the internal pressure of the autoclave became 90 bar. The contents were stirred for 2 hours while the internal temperature and the internal pressure were maintained at 70° C. and 90 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 489.3 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 36.3 kg/g-Pd·hr, and the intrinsic viscosity was 4.3 dl/g.

The results are summarized in Table 1.

Example 6

0.0140 g of palladium acetate, 0.0398 g of 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane, and 0.0499 g of trifluoroacetic acid were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2497.5 ml of methanol and 2.5 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 800 rpm. When the internal temperature reached 80° 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 3 hours while the internal temperature and the internal pressure were maintained at 80° 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 368.1 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 27.3 kg/g-Pd·hr, and the intrinsic viscosity was 5.7 dl/g.

The results are summarized in Table 1

	TABLE 1
			Catalyst system		Input
	Catalytic	Amount	Amount of catalyst		ratio
	I.V.	Activity	produced	input (g)	Solvent	Ligand/	Acid/
	(dl/g)	(Kg/gPd · hr)	(g)	Pd	Ligand	Acid	(ml)	Pd	Pd
Ex. 1	16.8	3.8	51.2	Pd(OAc)2	BIBMAPP	TFA	MeOH	1.2	7
				0.0140	0.0398	0.0499	2497.5
Ex. 2	15.7	5.4	72.8	Pd(OAc)2	BIBMAPP	TFA	MeOH	1.2	7
				0.0140	0.0398	0.0499	2497.5
Ex. 3	13.5	6.7	90.3	Pd(OAc)2	BIBMAPP	TFA/	MeOH	1.2	7
						H2SO4
				0.0140	0.0398	0.0249/	2497.5
						0.0215
Ex. 4	4.5	32.7	440.8	Pd(OAc)2	BIBMAPP	H2SO4	MeOH	1.2	20
				0.0140	0.0398	0.1226	2475
Ex. 5	4.3	36.3	489.3	Pd(OAc)2	BIBMAPP	H2SO4	MeOH	1.2	7
				0.0140	0.0398	0.0429	2200
Ex. 6	5.7	27.3	368.1	Pd(OAc)2	BIBMAPP	TFA	MeOH	1.2	7
				0.0140	0.0398	0.0499	2497.5
							Partial
							pressure
				Rx	Rx	Polymerization	of
		Material	Amount	Temp	Pressure	Time	gas
		added	added	(° C.)	(bar)	(hr)	(CO:Et)
	Ex. 1	Water	1000 ppm	70	100	2	1:1.8
		Benzothiazole	0.4225 g
	Ex. 2	Water	1000 ppm	80	70	2	1:2
		Benzothiazole	0.4225 g
	Ex. 3	Water	1000 ppm	70	70	2	1:1.8
		Benzothiazole	0.4225 g
	Ex. 4	Water	1000 ppm	70	85	2	1:1.8
			25 ml
	Ex. 5	Water	120,000 ppm	70	90	2	1:1
			300 ml
	Ex. 6	Water	1000 ppm	80	70	3	1:2
			2.5 ml
	Pd(OAc)2: Palladium acetate
	BIBMAPP: 1,3-Bis[bis(2-methoxy-5-methylphenyl)phosphino]propane
	TFA: Trifluoroacetic acid

Comparative Example 1

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane, 0.0499 g of trifluoroacetic acid and 0.4225 g of benzothiazole were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2497.5 ml of methanol and 1000 ppm 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 800 rpm. When the internal temperature reached 70° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:1.8) was added until the internal pressure of the autoclave became 100 bar. The contents were stirred for 2 hours while the internal temperature and the internal pressure were maintained at 70° C. and 100 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 51.0 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 3.9 kg/g-Pd·hr, and the intrinsic viscosity was 9.7 dl/g.

The results are summarized in Table 2.

Comparative Example 2

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane, 0.0499 g of trifluoroacetic acid and 0.4225 g of benzothiazole were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2497.5 ml of methanol and 1000 ppm 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 800 rpm. When the internal temperature reached 80° 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 2 hours while the internal temperature and the internal pressure were maintained at 70° 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 69.5 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 5.2 kg/g-Pd·hr, and the intrinsic viscosity was 8.9 dl/g.

The results are summarized in Table 2.

Comparative Example 3

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane, 0.0249 g of trifluoroacetic acid, 0.0215 g of sulfuric acid and 0.4225 g of benzothiazole were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2497.5 ml of methanol and 1000 ppm 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 800 rpm. When the internal temperature reached 70° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:1.8) was added until the internal pressure of the autoclave became 70 bar. The contents were stirred for 2 hours while the internal temperature and the internal pressure were maintained at 70° 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 91.7 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 6.9 kg/g-Pd·hr, and the intrinsic viscosity was 7.5 dl/g.

The results are summarized in Table 2.

Comparative Example 4

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane and 0.1226 g of sulfuric acid were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2475 ml of methanol and 25 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 800 rpm. When the internal temperature reached 70° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:1.8) was added until the internal pressure of the autoclave became 85 bar. The contents were stirred for 2 hours while the internal temperature and the internal pressure were maintained at 70° C. and 85 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 128.7 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 7.2 dl/g.

The results are summarized in Table 2.

Comparative Example 5

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane and 0.0429 g of sulfuric acid were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2200 ml of methanol and 300 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 800 rpm. When the internal temperature reached 70° C., a mixed gas of carbon monoxide and ethylene (the molar ratio of 1:1) was added until the internal pressure of the autoclave became 90 bar. The contents were stirred for 2 hours while the internal temperature and the internal pressure were maintained at 70° C. and 90 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 132 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 9.8 kg/g-Pd·hr, and the intrinsic viscosity was 7.0 dl/g.

The results are summarized in Table 2.

Comparative Example 6

0.0140 g of palladium acetate, 0.0399 g of 1,3-bis[di(2-methoxyphenyl)phosphino]propane and 0.0499 g of trifluoroacetic acid were dissolved in 100 ml of acetone. The solution was dissolved in the mixture of 2497.5 ml of methanol and 2.5 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 800 rpm. When the internal temperature reached 80° 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 3 hours while the internal temperature and the internal pressure were maintained at 80° 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 138.9 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 10.3 kg/g-Pd·hr, and the intrinsic viscosity was 5.3 dl/g.

The results are summarized in Table 2.

	TABLE 2
			Catalyst system		Input
	Catalytic	Amount	Amount of catalyst		ratio
	I.V.	Activity	produced	input (g)	Solvent	Ligand/	Acid/
	(dl/g)	(Kg/gPd · hr)	(g)	Pd	Ligand	Acid	(ml)	Pd	Pd
Comp.	9.7	3.9	51.0	Pd(OAc)2	BDOMPP	TFA	MeOH	1.2	7
Ex. 1				0.0140	0.0399	0.0499	2497.5
Comp.	8.9	5.2	69.5	Pd(OAc)2	BDOMPP	TFA	MeOH	1.2	7
Ex. 2				0.0140	0.0399	0.0499	2497.5
Comp.	7.5	6.9	91.7	Pd(OAc)2	BDOMPP	TFA/	MeOH	1.2	7
Ex. 3						H2SO4
				0.0140	0.0399	0.0249/	2497.5
						0.0215
Comp.	7.2	9.4	128.7	Pd(OAc)2	BDOMPP	H2SO4	MeOH	1.2	20
Ex. 4				0.0140	0.0399	0.1226	2475
Comp.	7.0	9.8	132	Pd(OAc)2	BDOMPP	H2SO4	MeOH	1.2	7
Ex. 5				0.0140	0.0399	0.0429	2200
Comp.	5.3	10.3	138.9	Pd(OAc)2	BDOMPP	TFA	MeOH	1.2	7
Ex. 6				0.0140	0.0399	0.0499	2497.5
							Partial
							pressure
				Rx	Rx	Polymerization	of
		Material	Amount	Temp	Pressure	Time	gas
		added	added	(° C.)	(bar)	(hr)	(CO:Et)
	Comp.	Water	1000 ppm	70	100	2	1:1.8
	Ex. 1	Benzothiazole	0.4225 g
	Comp.	Water	1000 ppm	80	70	2	1:2
	Ex. 2	Benzothiazole	0.4225 g
	Comp.	Water	1000 ppm	70	70	2	1:1.8
	Ex. 3
		Benzothiazole	0.4225 g
	Comp.	Water	10000 ppm	70	85	2	1:1.8
	Ex. 4		25 ml
	Comp.	Water	120,000 ppm	70	90	2	1:1
	Ex. 5		300 ml
	Comp.	Water	1000 ppm	80	70	3	1:2
	Ex. 6		2.5 ml
	Pd(OAc)2: Palladium acetate
	BDOMPP: 1,3-Bis[di(methoxyphenyl)phosphino]propane
	TFA: Trifluoroacetic acid

Effects of the Invention

According to the present invention, a process for preparing polyketone is provided, wherein palladium acetate and 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane are used as the catalyst components, and whether upon polymerization, benzothiazole is added or not, the catalytic activity and the intrinsic viscosity can be adjusted.

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, (b) a ligand containing a Group 15 element, and (c) an anion of an acid with pKa of 4 or lower, 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 methanol and 1,000 to 10,000 ppm of water.

3. The process for preparing polyketone according to claim 1, wherein upon polymerization, benzothiazole or benzophenone is added.

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

5. The process for preparing polyketone according to claim 1, wherein as the (c) component, trifluoroacetic acid or sulfuric acid is used singly or in a mixture thereof.

6. The process for preparing polyketone according to claim 1, wherein the molar ratio of the (a) component:the (b) component:the (c) component is 1:1.2:7.