Polyoxyalkylenes with pendant long-chain acyloxy groups and method for producing same using DMC catalysts

Abstract

The invention relates to polyoxyalkylenes having pendant long-chain acyloxy radicals and to a process for preparation thereof by an alkoxylation reaction using double metal cyanide (DMC) catalysts.

Claims

1. A polyoxyalkylene of formula (I)
A[—O—(CH.sub.2—CHR—O—).sub.n—(CH.sub.2—CH(CH.sub.2OZ)—O—).sub.m1—(CH.sub.2—CH(CH.sub.2Cl)—O—).sub.m3—(CH.sub.2—CH(CH.sub.3)—O—).sub.o—H].sub.a   (I) where A is hydrogen or an organic radical derived from an organic starter compound selected from the group consisting of monohydric monomeric alcohols, polyhydric monomeric alcohols, oligomeric alcohols, and polymeric alcohols, R is independently hydrogen, an alkyl group comprising 2-18 carbon atoms or a phenyl radical, Z is a radical of an organic acid of formula —C(═O)—Z.sub.E where Z.sub.E is an organic radical selected from the group consisting of linear or branched, saturated or unsaturated aliphatic hydrocarbyl radicals having 7 to 22 carbon atoms or aromatic hydrocarbyl radicals having 6 to 21 carbon atoms, m.sub.1 is a number of 1 to 50, m.sub.3 is 0, n is a number of 0 to 200, o is a number of 1 to 1000, and a is a number of 1 to 8; wherein the polyoxyalkylene does not comprise a terminal structural unit comprising an acyloxy radical; wherein the polyoxyalkylene does not include a methylidene group; where the polyoxyalkylene does not comprise a halogen atom.

2. The polyoxyalkylene according to claim 1, which has a weight-average molar mass of 400 to 50 000 g/mol.

3. An interface-active polymer, comprising the polyoxyalkylenes according to claim 1.

4. A surfactant, comprising the interface-active polymer according to claim 3.

5. The polyoxyalkylene according to claim 1, where Z.sub.E is an organic radical selected from the group consisting of linear or branched, saturated or unsaturated aliphatic hydrocarbyl radicals having 7 to 22 carbon atoms or aromatic hydrocarbyl radicals having 6 to 17 carbon atoms.

6. The polyoxyalkylene according to claim 1, where —C(═O)—Z is selected from the group consisting of carboxylates of 2-ethylhexanoic acid, isotridecylcarboxylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid, ricinoleic acid, undecylenoic acid and mixtures thereof.

7. The polyoxyalkylene according to claim 1, where —C(═O)—Z is selected from the group consisting of carboxylates of fatty acid mixtures obtained from palm oil, coconut oil, olive oil, rapeseed oil, soya oil, sunflower oil, safflower oil, linseed oil, peanut oil, castor oil, and tall oil.

8. The polyoxyalkylene according to claim 1, wherein A has a weight-average molar mass of 15 to 4983 g/mol.

Description

EXAMPLES

(1) GPC Measurements:

(2) GPC measurements for determining the polydispersity and mean molar masses Mw were conducted under the following measurement conditions: SDV 1000/10 000 A column combination (length 65 cm), temperature 30° C., THF as mobile phase, flow rate 1 ml/min, sample concentration 10 g/I, RI detector, evaluation against polypropylene glycol standard.

(3) Determination of the Content of Chlorine and Vinyl Groups:

(4) The determination of the content of chlorine and vinyl groups was conducted with the aid of .sup.13C NMR spectroscopy. An NMR spectrometer of the Bruker Avance 400 type was used. For this purpose, the samples were dissolved in CDCl.sub.3.

(5) Determination of OH Number:

(6) Hydroxyl numbers were determined according to the method DGF C-V 17 a (53) of the Deutsche Gesellschaft fur Fettwissenschaft [German Society for Fat Science]. This involved acetylating the samples with acetic anhydride in the presence of pyridine and determining the consumption of acetic anhydride by titration with 0.5 n potassium hydroxide solution in ethanol using phenolphthalein.

(7) The iodine numbers [g of iodine/100 g of sample] are determined by the method according to Hanus, known as method DGF C-V 11 a (53) of the Deutsche Gesellschaft fur Fette.

Example 1

Synthesis Examples

Example A

Preparation of Epichlorohydrin Alkoxylation Products

Example A1

Precursor 1

(8) A 3 liter autoclave was initially charged with 339.6 g of poly(oxypropylene) monobutyl ether as starter (mass-average molar mass M.sub.w=382 g/mol) and 2.25 g of zinc hexacyanocobaltate DMC catalyst and heated to 130° C. while stirring. The reactor was evacuated down to an internal pressure of 30 mbar in order to remove any volatile ingredients present by distillation. To activate the DMC catalyst, a portion of 80 g of propylene oxide was fed in. After the reaction had commenced and the internal pressure had dropped, firstly a further 179 g of propylene oxide were metered in while cooling. Subsequently, under the same conditions, 1645 g of propylene oxide and 494 g of epichlorohydrin in a mixture were metered in at 130° C. and a maximum internal reactor pressure of 1.5 bar within 2 h. This was followed by further reaction at 130° C. for 30 minutes, in the course of which the internal reactor pressure dropped to 0.5 bar. Finally, as end block, a further 259 g of propylene oxide were added on at 130° C. Another period of continued reaction under the same conditions was followed by a degassing stage. In the course of this, volatile components such as residual propylene oxide and epichlorohydrin were distilled off under reduced pressure at 130° C. The virtually colourless chlorinated alkoxylation product of low viscosity was cooled to below 90° C. and discharged from the reactor. By GPC the product had a weight-average molar mass of 2700 g/mol and a polydispersity M.sub.w/M.sub.n of 1.37, and by .sup.13C NMR analysis contained 5.7 mol of Cl per molecule.

Example A2

Precursor 2

(9) A 3 liter autoclave was initially charged with 615.6 g of poly(oxypropylene-co-oxyethylene) monoallyl ether as starter (mass-average molar mass M.sub.w=780 g/mol, 20% by weight of oxyethylene units, 80% by weight of oxypropylene units) and 2.05 g of zinc hexacyanocobaltate DMC catalyst and heated to 130° C. while stirring. The reactor was evacuated down to an internal pressure of 30 mbar in order to remove any volatile ingredients present by distillation. To activate the DMC catalyst, a portion of 75 g of propylene oxide was fed in. After the reaction had commenced and the internal pressure had dropped, firstly a further 155 g of propylene oxide were metered in while cooling. Subsequently, under the same conditions, 1469 g of propylene oxide and 439 g of epichlorohydrin in a mixture were metered in at 130° C. and a maximum internal reactor pressure of 1.5 bar within 135 min. This was followed by further reaction at 130° C. for 30 minutes. Finally, as end block, a further 230 g of propylene oxide were added on at 130° C. Another period of continued reaction was followed by a degassing stage under reduced pressure at 130° C. The virtually colourless chlorinated alkoxylation product of low viscosity was cooled to below 90° C. and discharged from the reactor. By GPC the product had a weight-average molar mass of 2754 g/mol and a polydispersity M.sub.w/M.sub.n of 1.28, and by .sup.13C NMR analysis contained 6.0 mol of Cl per molecule. The iodine number was 6.9 g of iodine/100 g.

Example A3

Precursor 3

(10) A 3 liter autoclave was initially charged with 425.1 g of poly(oxypropylene-co-oxyethylene) monobutyl ether as starter (mass-average molar mass M.sub.w=540 g/mol, 60% by weight of oxyethylene units, 40% by weight of oxypropylene units) and 2.15 g of zinc hexacyanocobaltate DMC catalyst and heated to 130° C. while stirring. The reactor was evacuated down to an internal pressure of 30 mbar in order to remove any volatile ingredients present by distillation. To activate the DMC catalyst, a portion of 93 g of propylene oxide was fed in. After the reaction had commenced and the internal pressure had dropped, while cooling and at internal temperature 130° C., 930 g of propylene oxide, 1059 g of ethylene oxide and 222 g of epichlorohydrin in a mixture were metered in at a maximum internal reactor pressure of 1.3 bar within 3.5 h. A 30-minute post-reaction at 130° C. followed. Finally, as end block, a further 353 g of ethylene oxide were added at 130° C. Another period of continued reaction was followed by a degassing stage under reduced pressure at 130° C. The virtually colourless chlorinated alkoxylation product of low viscosity was cooled to below 90° C. and discharged from the reactor. By .sup.13C NMR analysis, the product contained 3.0 mol of Cl per molecule.

Example A4

Precursor 4

(11) A 3 liter autoclave was initially charged with 392.4 g of poly(oxypropylene-co-oxyethylene) monobutyl ether as starter (mass-average molar mass M.sub.w=540 g/mol, 60% by weight of oxyethylene units, 40% by weight of oxypropylene units) and 2.23 g of zinc hexacyanocobaltate DMC catalyst and heated to 130° C. while stirring. The reactor was evacuated down to an internal pressure of 30 mbar in order to remove any volatile ingredients present by distillation. To activate the DMC catalyst, a portion of 90 g of propylene oxide was fed in. After the reaction had commenced and the internal pressure had dropped, while cooling and at internal temperature 130° C., 837 g of propylene oxide, 953 g of ethylene oxide and 400 g of epichlorohydrin in a mixture were metered in at a maximum internal reactor pressure of 1.3 bar within 3.5 h. A 30-minute post-reaction at 130° C. followed. Finally, as end block, a further 318 g of ethylene oxide were added at 130° C. Another period of continued reaction was followed by a degassing stage under reduced pressure at 130° C. The virtually colourless chlorinated alkoxylation product of low viscosity was cooled to below 90° C. and discharged from the reactor. By .sup.13C NMR analysis, the product contained 6.0 mol of Cl per molecule.

Example B

Preparation of the Inventive Ester-Modified Alkoxylation Products

Example B1

(12) A glass flask equipped with a stirrer and distillation apparatus was inertized with nitrogen, then initially charged with 300.0 g of precursor 1 and heated to 80° C. Within 20 min, 143.0 g of solid potassium laurate were added in portions while stirring. The resultant suspension was heated up to 120° C. and stirred at 120° C. and about 20 mbar with distillative removal of volatiles for 3 h. The reaction product was cooled down to 80° C. and salts were removed by filtration. The liquid reaction product was yellowish and slightly cloudy and, according to the .sup.13C NMR spectrum, had an average of 1.05 pendant lauric ester groups per molecule and still had 4.7 mol of organically bound chlorine.

Example B2

(13) The experiment described in B1 was repeated, except that, after a reaction time of 3 h at 120° C., the reaction temperature was increased to 180° C. After 1 further hour of reaction time, the reaction mixture was cooled as described above and filtered. The liquid reaction product was yellowish and slightly cloudy and, according to the .sup.13C NMR spectrum, had an average of 2.9 pendant lauric ester groups per molecule and still had 2.8 mol of organically bound chlorine.

Example B3

(14) A glass flask equipped with a stirrer and distillation apparatus was inertized with nitrogen, then initially charged with 300.0 g of precursor 1 and heated to 80° C. Within 15 min, 176.7 g of solid potassium palmitate were added in portions while stirring. The resultant suspension was heated up to 180° C. and stirred at 180° C. and about 20 mbar with distillative removal of volatiles for 4 h. The reaction product was cooled down to 80° C. and salts were removed by filtration. The liquid reaction product was yellowish and slightly cloudy and, according to the .sup.13C NMR spectrum, had an average of 3.0 pendant palmitic ester groups per molecule and still had 2.7 mol of organically bound chlorine.

Example B4

(15) A glass flask equipped with a stirrer and distillation apparatus was inertized with nitrogen, then initially charged with 300.0 g of precursor 1 and heated to 80° C. Within 15 min, 192.2 g of solid potassium oleate were added in portions while stirring. The resultant mixture was heated up to 200° C. and stirred at 200° C. and about 20 mbar with distillative removal of volatiles for 4 h. The reaction product was cooled down to 80° C. and salts were removed by filtration. The liquid reaction product was brownish and slightly cloudy and, according to the .sup.13C NMR spectrum, had an average of 4.9 pendant oleic ester groups per molecule and still had 0.8 mol of organically bound chlorine.

Example B5

(16) A glass flask equipped with a stirrer and distillation apparatus was inertized with nitrogen, then initially charged with 211.1 g of oleic acid. 308 g of a 20% by weight ethanolic KOH solution were added while stirring. At 50° C., 300.0 g of precursor 1 were metered in within 10 min and the mixture was heated to 200° C. with distillative removal of ethanol. With further distillative removal of volatiles at about 20 mbar, the mixture was stirred at 200° C. for 4 h. The reaction product was cooled down to 80° C. and salts were removed by filtration. The liquid reaction product was brownish and slightly cloudy and, according to the .sup.13C NMR spectrum, had an average of 5.7 pendant oleic ester groups per molecule and no longer had any organically bound chlorine.

Example B6

(17) A glass flask equipped with a stirrer and distillation apparatus was inertized with nitrogen, then initially charged with 85.0 g of oleic acid. 84.4 g of a 20% by weight ethanolic KOH solution were added while stirring. At 50° C., 308.4 g of precursor 3 were metered in within 10 min and the mixture was heated to 200° C. with distillative removal of ethanol. With further distillative removal of volatiles at about 20 mbar, the mixture was stirred at 200° C. for 4 h. The reaction product was cooled down to 80° C. and salts were removed by filtration. The waxy reaction product was brownish and slightly cloudy and, according to the .sup.13C NMR spectrum, had an average of 3 pendant oleic ester groups per molecule and no longer had any organically bound chlorine.

Example B7

(18) A glass flask equipped with a stirrer and distillation apparatus was inertized with nitrogen, then initially charged with 169.7 g of oleic acid. 186.3 g of a 20% by weight ethanolic KOH solution were added while stirring. At 50° C., 300.0 g of precursor 4 were metered in within 10 min and the mixture was heated to 200° C. with distillative removal of ethanol. With further distillative removal of volatiles at about 20 mbar, the mixture was stirred at 200° C. for 4 h. The reaction product was cooled down to 80° C. and salts were removed by filtration. The liquid reaction product was brownish and slightly cloudy and, according to the .sup.13C NMR spectrum, had an average of 6 pendant oleic ester groups per molecule and no longer had any organically bound chlorine.

Example B8

(19) A glass flask equipped with a stirrer and distillation apparatus was inertized with nitrogen, then initially charged with 169.5 g of oleic acid. 186.2 g of a 20% by weight ethanolic KOH solution were added while stirring. At 50° C., 298.5 g of precursor 2 were metered in within 10 min and the mixture was heated to 200° C. with distillative removal of ethanol. With further distillative removal of volatiles at about 20 mbar, the mixture was stirred at 200° C. for 4 h. The reaction product was cooled down to 80° C. and salts were removed by filtration. The liquid reaction product was brownish and slightly cloudy and, according to the .sup.13C NMR spectrum, had an average of 5.7 pendant oleic ester groups per molecule and had 0.3 mol of organically bound chlorine.

Example B9

(Non-Inventive)

(20) A glass flask equipped with a stirrer and distillation apparatus was inertized with nitrogen, then initially charged with 300.0 g of precursor 1 and heated to 80° C. Within 15 min, 49.3 g of solid sodium acetate were added in portions while stirring. The resultant suspension was heated up to 180° C. and stirred at 180° C. and about 20 mbar with distillative removal of volatiles for 4 h. The reaction mixture was cooled down to 80° C. and comparatively large amounts of salt were removed by filtration. The liquid reaction product was yellowish and, according to the .sup.13C NMR spectrum, did not have any pendant ester groups, and instead still had 6 mol of organically bound chlorine. No reaction in the sense of the invention took place.

Example C

Hydrosilylating Linkage of Unsaturated Polyethers Bearing Inventive Acyloxy Radicals to SiH Siloxanes

Example C1

(21) A linear polydimethylsiloxane having an average of 32 Si units and terminal SiH functionalization and the precursor from Example B8 were heated to 50° C. while stirring in a four-neck flask equipped with a precision glass stirrer, an internal thermometer and a reflux condenser. The excess of allyl groups in the polyether over SiH groups in the siloxane here was 35 mol %. A total of 30 ppm of platinum in the form of a platinum(0) catalyst modified according to EP 1520870 were metered in portions with a syringe within 8.5 h. During the reaction, the temperature was increased first to 70° C., then to 100° C. The conversion determined by gas volumetric means was quantitative after 20 hours. The polyether siloxane obtained was cloudy.

Example C2

(22) A linear polydimethylsiloxane having an average of 35 Si units and a mean number of 5—O—Si(CH.sub.3)H— units in the chain and the precursor from Example B8 were heated to 50° C. while stirring in a four-neck flask equipped with a precision glass stirrer, an internal thermometer and a reflux condenser. The excess of allyl groups in the polyether over SiH groups in the siloxane here was 35 mol %. A total of 40 ppm of platinum in the form of a platinum(0) catalyst modified according to EP 1520870 were metered in portions with a syringe within 8.5 h. During the reaction, the temperature was increased to 70° C. The conversion determined by gas volumetric means was quantitative after 14 hours. The polyether siloxane obtained was cloudy.