Process for preparing a macromonomer

Abstract

The present invention relates to a process for preparing hydrophobically associating macromonomers M and to the novel macromonomers prepared by means of the process according to the invention. The macromonomers M comprise a copolymerizable, ethylenically unsaturated group and a polyether structure in block form, the latter consisting of a polyethyleneoxy block and a hydrophobic polyalkyleneoxy block consisting of alkyleneoxy units having at least 4 carbon atoms. Optionally, the macromonomers M may have a terminal polyethyleneoxy block. The macromonomers prepared by the process according to the invention are suitable for reaction with further monomers, especially with acrylamide, to give a water-soluble, hydrophobically associating copolymer.

Claims

1. A process for preparing a macromonomer M of the general formula (I)
H.sub.2CC(R.sup.1)R.sup.2O(CH.sub.2CH.sub.2O).sub.k(CH.sub.2CH(R.sup.3)O).sub.l(CH.sub.2CH.sub.2O).sub.mR.sup.4(I) where the (CH.sub.2CH.sub.2O).sub.k and (CH.sub.2CH(R.sup.3)O).sub.l and optionally (CH.sub.2CH.sub.2O).sub.m units are arranged in block structure in the sequence shown in formula (I); where the radicals and indices are each defined as follows: k: is a number from 10 to 150; l: is a number from 5 to 25; m: is a number from 0 to 15; R.sup.1: is H or methyl; R.sup.2: is independently a single bond or a divalent linking group selected from the group consisting of (C.sub.nH.sub.2n) and O(C.sub.nH.sub.2n), where n is a natural number from 1 to 6 and n is a natural number from 2 to 6; R.sup.3: is independently a hydrocarbyl radical having at least 2 carbon atoms or an ether group of the general formula CH.sub.2OR.sup.3 where R.sup.3 is a hydrocarbyl radical having at least 2 carbon atoms; with the proviso that the sum total of carbon atoms in all hydrocarbyl radicals R.sup.3 or R.sup.3 is in the range from 25.5 to 34.5; R.sup.4 is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms; comprising the steps of a) reacting a monoethylenically unsaturated alcohol A1 of the general formula (II)
H.sub.2CC(R.sup.1)R.sup.2OH(II) with ethylene oxide, where the R.sup.1 and R.sup.2 radicals are each as defined above; with addition of an alkaline catalyst C1 comprising KOMe and/or NaOMe to obtain an alkoxylated alcohol A2; b) reacting the alkoxylated alcohol A2 with at least one alkylene oxide Z of the formula (Z) ##STR00003## where R.sup.3 is as defined above; with addition of an alkaline catalyst C2; where the concentration of potassium ions in the reaction in step b) is in the range from 0.01 to 0.5 mol %, based on the alcohol A2 used; and where the reaction in step b) is performed at a temperature less than or equal to 135 C., to obtain an alkoxylated alcohol A3 of the formula (III)
H.sub.2CC(R.sup.1)R.sup.2O(CH.sub.2CH.sub.2O).sub.k(CH.sub.2CH(R.sup.3)O).sub.lR.sup.4(III) where R.sup.4H, where the R.sup.1, R.sup.2 and R.sup.3 radicals and the indices k and 1 are each as defined above; c) optionally reacting at least a portion of the alkoxylated alcohol A3 with ethylene oxide to obtain an alkoxylated alcohol A4 corresponding to the macromonomer M of the formula (I) where R.sup.4H and m is greater than 0; d) optionally etherifying the alkoxylated alcohol A3 and/or A4 with a compound
R.sup.4X where R.sup.4 is as defined above and X is a leaving group; to obtain a macromonomer M of the formula (I) and/or (III) where R.sup.4=hydrocarbyl radical having 1 to 4 carbon atoms.

2. The process for preparing a macromonomer M according to claim 1, wherein the alkaline catalyst C2 comprises at least one basic sodium compound.

3. The process for preparing a macromonomer M according to claim 1, wherein a catalyst C2 comprising at least one basic sodium compound is used in step b), the concentration of sodium ions in the reaction in step b) being in the range from 3.5 to 12 mol %, based on the alcohol A2 used.

4. The process for preparing a macromonomer M according to claim 1, wherein step b) is performed at temperatures of 120 to 135 C.

5. The process for preparing a macromonomer M according to claim 1, wherein step b) comprises the addition of the at least one alkylene oxide Z to a mixture of alcohol A2 and alkaline catalyst C2 at a pressure in the range from 1 to 3.1 bar.

6. The process for preparing a macromonomer M according to claim 1, wherein R.sup.3 is a hydrocarbyl radical having 2 carbon atoms and step b) comprises the addition of the at least one alkylene oxide Z to a mixture of alcohol A2 and alkaline catalyst C2 at a pressure in the range from 1 to 3.1 bar, or R.sup.3 is a hydrocarbyl radical having at least 3 carbon atoms and step b) comprises the addition of the at least one alkylene oxide Z to a mixture of alcohol A2 and alkaline catalyst C2 at a pressure in the range from 1 to 2.1 bar.

7. The process for preparing a macromonomer according to claim 1, wherein k is a number from 23 to 26.

8. The process for preparing a macromonomer according to claim 1, wherein the radicals and indices are each defined as follows: k: is a number from 20 to 28; l: is a number from 5 to 25; m: is a number from 0 to 15; R.sup.1: is H; R.sup.2: is independently a divalent linking group O(C.sub.nH.sub.2) where n is a natural number from 3 to 5, R.sup.3: is independently a hydrocarbyl radical having 2 to 4 carbon atoms, with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R.sup.3 or R.sup.3 is in the range from 25.5 to 34.5; R.sup.4: is H.

9. The process for preparing a macromonomer according to claim 1, wherein the radicals and indices are each defined as follows: k: is a number from 23 to 26; l: is a number from 5 to 25; m: is a number from 0 to 15; R.sup.1: is H; R.sup.2: is independently a divalent linking group O(C.sub.nH.sub.2n) where n is a natural number from 3 to 5, R.sup.3: is independently a hydrocarbyl radical having 2 to 4 carbon atoms, with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R.sup.3 or R.sup.3 is in the range from 25.5 to 34.5; R.sup.4: is H.

10. The process for preparing a macromonomer according to claim 1, wherein the radicals and indices are each defined as follows: k: is a number from 23 to 26; l: is a number from 7.5 to 25; m: is a number from 0 to 15; R.sup.1: is H; R.sup.2: is independently a divalent linking group O(C.sub.nH.sub.2n) where n is a natural number from 3 to 5, R.sup.3: is ethyl; R.sup.4: is H.

11. The process for preparing a macromonomer according to claim 1, wherein the radicals and indices are each defined as follows: k: is a number from 23 to 26; l: is a number from 8.5 to 11.5; m: is a number from 0 to 15; R.sup.1: is H; R.sup.2: is independently a divalent linking group O(C.sub.nH.sub.2n) where n is a natural number from 3 to 5, R.sup.3: is n-propyl; R.sup.4: is H.

12. The process for preparing a macromonomer according to claim 1, wherein the macromonomer M is a mixture of a macromonomer M of the formula (I) where m=0 and a macromonomer M of the formula (I) where m=1 to 15.

13. The process for preparing a macromonomer according to claim 12, wherein the weight ratio of the macromonomer of the formula (I) where m=0 and the macromonomer of the formula (I) where m=1 to 15 is in the range from 19:1 to 1:19.

14. A macromonomer M of the general formula (I)
H.sub.2CC(R.sup.1)R.sup.2O(CH.sub.2CH.sub.2O).sub.k(CH.sub.2CH(R.sup.3)O).sub.l(CH.sub.2CH.sub.2O).sub.mR.sup.4(I) where the (CH.sub.2CH.sub.2O).sub.k and (CH.sub.2CH(R.sup.3)O).sub.l and optionally (CH.sub.2CH.sub.2O).sub.m units are arranged in block structure in the sequence shown in formula (I); where the radicals and indices are each defined as follows: k: is a number from 20 to 28; l: is a number from 5 to 25; m: is a number from 0 to 15; R.sup.1: is H or methyl; R.sup.2: is independently a single bond or a divalent linking group selected from the group consisting of (C.sub.nH.sub.2n) and O(C.sub.nH.sub.2n), where n is a natural number from 1 to 6 and n is a natural number from 2 to 6; R.sup.3: is independently a hydrocarbyl radical having at least 2 carbon atoms, with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R.sup.3 is in the range from 25.5 to 34.5; R.sup.4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms; obtained by the process according to claim 1.

15. A macromonomer M according to claim 14, wherein the radicals and indices of the formula (I) are each defined as follows: k: is a number from 23 to 26; l: is a number from 5 to 25; m: is a number from 0 to 15; R.sup.1: is H or methyl; R.sup.2: is independently a single bond or a divalent linking group selected from the group consisting of (C.sub.nH.sub.2n) and O(C.sub.nH.sub.2n), where n is a natural number from 1 to 6 and n is a natural number from 2 to 6; R.sup.3: is independently a hydrocarbyl radical having at least 2 carbon atoms, with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R.sup.3 is in the range from 25.5 to 34.5; R.sup.4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms.

16. A macromonomer M according to claim 14, wherein the radicals and indices of the formula (I) are each defined as follows: k: is a number from 23 to 26; l: is a number from 5 to 25; m: is a number from 0 to 15; R.sup.1: is H; R.sup.2: is independently a divalent linking group O(C.sub.nH.sub.2n) where n is a natural number from 3 to 5, R.sup.3: is independently a hydrocarbyl radical having 2 to 4 carbon atoms, with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R.sup.3 is in the range from 25.5 to 34.5; R.sup.4: is H.

17. A macromonomer M of the general formula (I)
H.sub.2CC(R.sup.1)R.sup.2O(CH.sub.2CH.sub.2O).sub.k(CH.sub.2CH(R.sup.3)O).sub.l(CH.sub.2CH.sub.2O).sub.mR.sup.4(I) where the (CH.sub.2CH.sub.2O).sub.k and (CH.sub.2CH(R.sup.3)O).sub.l and optionally (CH.sub.2CH.sub.2O).sub.m units are arranged in block structure in the sequence shown in formula (I); where the radicals and indices are each defined as follows: k: is a number from 20 to 28; l: is a number from 5 to 25; m: is a number from 0.1 to 15; R.sup.1: is H or methyl; R.sup.2: is independently a single bond or a divalent linking group selected from the group consisting of (C.sub.nH.sub.2n) and O(C.sub.nH.sub.2n), where n is a natural number from 1 to 6 and n is a natural number from 2 to 6; R.sup.3; is independently a hydrocarbyl radical having at least 2 carbon atoms, with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R.sup.3 is in the range from 15 to 50; R.sup.4; is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms.

18. A macromonomer M of the general formula (I)
H.sub.2CC(R.sup.1)R.sup.2O(CH.sub.2CH.sub.2O).sub.k(CH.sub.2CH(R.sup.3)O).sub.l(CH.sub.2CH.sub.2O).sub.mR.sup.4(I) where the (CH.sub.2CH.sub.2O).sub.k and (CH.sub.2CH(R.sup.3)O).sub.l and optionally (CH.sub.2CH.sub.2O).sub.m units are arranged in block structure in the sequence shown in formula (I); where the radicals and indices are each defined as follows: k: is a number from 10 to 150; l: is a number from 5 to 25; m: is a number from 0.1 to 15; R.sup.1: is H or methyl; R.sup.2: is independently a single bond or a divalent linking group selected from the group consisting of (C.sub.nH.sub.2n) and O(C.sub.nH.sub.2n), where n is a natural number from 1 to 6 and n is a natural number from 2 to 6; R.sup.3: is independently a hydrocarbyl radical having 2 to 4 carbon atoms or an ether group of the general formula CH.sub.2OR.sup.3 where R.sup.3 is a hydrocarbyl radical having at least 2 carbon atoms, with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R.sup.3 is in the range from 15 to 50; R.sup.4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms.

Description

PART I: SYNTHESES

I-a Preparation of the Macromonomers

(1) Unless mentioned explicitly, the reactions were conducted in such a way that the target fill level at the end of the alkoxylation was approx. 65% of the reactor volume.

Example M1

HBVE-22 EO (0.4 mol % of Potassium Ions)

(2) A 2 l pressure autoclave with anchor stirrer was initially charged with 135.3 g (1.16 mol) of hydroxybutyl vinyl ether (HBVE) (stabilized with 100 ppm of potassium hydroxide (KOH)) and the stirrer was switched on. 1.06 g of potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH), corresponding to 0.0048 mol of potassium) were fed in and the stirred vessel was evacuated to a pressure less than 10 mbar, heated to 80 C. and operated at 80 C. and a pressure of less than 10 mbar for 70 min. MeOH was distilled off.

(3) According to an alternative procedure the potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH)) were fed in and the stirred vessel was evacuated to a pressure of 10-20 mbar, heated to 65 C. and operated at 65 C. and a pressure of 10-20 mbar for 70 min. MeOH was distilled off.

(4) The mixture was purged three times with N.sub.2 (nitrogen). Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set and the mixture was heated to 120 C. The mixture was decompressed to 1 bar absolute and 1126 g (25.6 mol) of ethylene oxide (EO) were metered in until p.sub.max was 3.9 bar absolute and T.sub.max was 150 C. After 300 g of EO had been metered in, the metered addition was stopped (about 3 h after commencement) for a wait period of 30 min and the mixture was decompressed to 1.3 bar absolute. Thereafter, the rest of the EO was metered in. The metered addition of EO including the decompression took a total of 10 h.

(5) Stirring was continued to constant pressure at approx. 145-150 C. (1 h), and the mixture was cooled to 100 C. and freed of low boilers at a pressure of less than 10 mbar for 1 h. The material was transferred at 80 C. under N.sub.2.

(6) The analysis (OH number, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M2

HBVE-22 EO-10.6 PeO (0.4 mol % of Potassium Ions, 4.6 mol % of Sodium Ions), Addition of the PeO at 140 C. to 3.2 bar

(7) A 2 l pressure autoclave with anchor stirrer was initially charged with 135.3 g (1.16 mol) of hydroxybutyl vinyl ether (stabilized with 100 ppm of KOH) and the stirrer was switched on. 1.06 g of KOMe solution (32% KOMe in MeOH, corresponding to 0.0048 mol of K) were fed in and the stirred vessel was evacuated to <10 mbar, heated to 80 C. and operated at 80 C. and <10 mbar for 70 min. MeOH was distilled off.

(8) According to an alternative procedure the potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH)) were fed in and the stirred vessel was evacuated to a pressure of 10-20 mbar, heated to 65 C. and operated at 65 C. and a pressure of 10-20 mbar for 70 min. MeOH was distilled off.

(9) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set and the mixture was heated to 120 C. The mixture was decompressed to 1 bar absolute and 255 g (5.8 mol) of EO were metered in until p.sub.max was 3.9 bar absolute and T.sub.max was 150 C. Stirring was continued up to constant pressure at approx. 145-150 C. (1 h), and the mixture was cooled to 100 C. and freed of low boilers at a pressure of less than 10 mbar for 1 h. The material (HBVE-5 EO) was transferred at 80 C. under N.sub.2.

(10) A 2 l pressure autoclave with anchor stirrer was initially charged with 180 g (0.54 mol) of the above HBVE-5 EO and the stirrer was switched on. Thereafter, 4.32 g of 30% NaOMe (sodium methoxide) in MeOH solution (0.024 mol of NaOMe, 1.30 g of NaOMe) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the MeOH. The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set and the mixture was heated to 150 C. The mixture was decompressed to 1.0 bar absolute. 398 g (9.04 mol) of EO were metered in up to a pressure of 2 bar absolute and the mixture was allowed to react further for 1 h. The mixture was cooled to 140 C. and 502 g (5.83 mol) of PeO (pentene oxide) were metered in at 1.2 bar absolute and 140 C. until the pressure rose to 3.2 bar absolute. The PeO was metered in within two hours. The mixture was cooled to 80 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT (butylhydroxytoluene) were added. The transfer was effected at 80 C. under N.sub.2.

(11) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M3

HBVE-22 EO-10.5 PeO (0.4 mol % of Potassium Ions, 3.3 mol % of Sodium Ions), Addition of the PeO at 140 C. to 2.1 bar

(12) A 2 l pressure autoclave with anchor stirrer was initially charged with 135.3 g (1.16 mol) of hydroxybutyl vinyl ether (stabilized with 100 ppm of KOH) and the stirrer was switched on. 1.06 g of KOMe solution (32% KOMe in MeOH, corresponding to 0.0048 mol of K) were fed in and the stirred vessel was evacuated to <10 mbar, heated to 80 C. and operated at 80 C. and <10 mbar for 70 min. MeOH was distilled off.

(13) According to an alternative procedure the potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH)) were fed in and the stirred vessel was evacuated to a pressure of 10-20 mbar, heated to 65 C. and operated at 65 C. and a pressure of 10-20 mbar for 70 min. MeOH was distilled off.

(14) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set and the mixture was heated to 120 C. The mixture was decompressed to 1 bar absolute and 255 g (5.8 mol) of EO were metered in until p.sub.max was 3.9 bar absolute and T.sub.max was 150 C. Stirring was continued up to constant pressure at approx. 145-150 C. (1 h), and the mixture was cooled to 100 C. and freed of low boilers at a pressure of less than 10 mbar for 1 h. The material (HBVE-5 EO) was transferred at 80 C. under N.sub.2.

(15) A 2 l pressure autoclave with anchor stirrer was initially charged with 180 g (0.54 mol) of HBVE-5 EO and the stirrer was switched on. Thereafter, 3.18 g of 30% NaOMe in MeOH solution (0.018 mol of NaOMe, 0.95 g of NaOMe) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the MeOH. The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set and the mixture was heated to 150 C. The mixture was decompressed to 1.0 bar absolute. 398 g (9.04 mol) of EO were metered in up to a pressure of 2 bar absolute, reaction was allowed to continue for 1 h, then the mixture was cooled to 100 C. and freed of low boilers at a pressure of less than 10 mbar for 1 h. The material (HBVE-22 EO) was transferred at 80 C. under N.sub.2.

(16) A 1 l autoclave with anchor stirrer was initially charged with 450 g (0.425 mol) of the above HBVE-22 EO and the stirrer was switched on. The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set and the mixture was heated to 140 C. The mixture was decompressed to 1.0 bar absolute.

(17) Then, at 1.4 bar absolute and 140 C., 384 g (5.83 mol) of PeO were metered in at 48 g/h until the pressure rose to 2.1 bar absolute. Two interruptions were necessary. The mixture was left to react at 140 C. until the pressure fell again. The PeO was metered in within two days. The mixture was cooled to 80 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(18) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M4

HBVE-22 EO-10 PeO (0.4 mol % of Potassium Ions, 4.6 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(19) The starting material used was macromonomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 745 g (0.69 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 5.36 g of 32% NaOMe in MeOH solution (0.0317 mol of NaOMe, 1.71 g of NaOMe) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 80 C. and kept there for 80 min, in order to distill off the MeOH.

(20) The mixture was purged three times with N.sub.2. Thereafter, the vessel was tested for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 127 C. and then the pressure was set to 1 bar absolute.

(21) 591 g (6.9 mol) of PeO were metered in at 127 C.; p.sub.max was 2.1 bar absolute. Two intermediate decompressions were necessary owing to increasing fill level. The PeO metering was stopped, and the mixture was left to react for 2 h until the pressure was constant and decompressed to 1.0 bar absolute. Thereafter, the metered addition of PeO was continued. P.sub.max was still 2.1 bar. After metered addition of PeO had ended, reaction was allowed to continue to constant pressure or for 4 h. The mixture was cooled to 110 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 110 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(22) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M5

HBVE-22 EO-11 PeO (0.4 mol % of Potassium Ions, 4.6 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(23) The preparation was analogous to example M4, except that 11 rather than 10 eq (molar equivalents) of PeO were added.

Example M6

HBVE-24.5 EO-11 PeO (0.4 mol % of Potassium Ions, 4.6 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(24) The starting material used was macromonomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 650 g (0.60 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 5.96 g of 25% NaOMe in MeOH solution (0.0276 mol of NaOMe, 1.49 g of NaOMe) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the MeOH.

(25) The mixture was purged three times with N.sub.2. Thereafter, the vessel was tested for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 120 C. and then the pressure was set to 1 bar absolute. 66 g (1.577 mol) of EO were metered in up to a temperature of 127 C.; p.sub.max was 2.1 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(26) 567 g (6.6 mol) of PeO were metered in at 127 C.; p.sub.max was 2.1 bar absolute. Two intermediate decompressions were necessary owing to increasing fill level. The PeO metering was stopped, and the mixture was left to react for 2 h until the pressure was constant and decompressed to 1.0 bar absolute. Thereafter, the metered addition of PeO was continued. P.sub.max was still 2.1 bar. After metered addition of PeO had ended, reaction was allowed to continue to constant pressure or for 4 h. The mixture was cooled to 110 C. and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 110 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(27) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M7

HBVE-24.5 EO-10 PeO (0.4 mol % of Potassium Ions, 4.6 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(28) Preparation was analogous to example M6, except that 10 rather than 11 eq of pentene oxide were added.

Example M8

HBVE-24.5 EO-10 PeO (0.9 mol % of Potassium Ions, 4.1 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(29) The preparation was analogous to example M6, except that the catalyst concentration was 0.9 mol % of potassium ions and 4.1 mol % of sodium ions and 10 rather than 11 eq of PeO were added.

Example M9

HBVE-24.5 EO-10 PeO (1.5 mol % of Potassium Ions, 4.6 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(30) The preparation was analogous to example M6, except that the catalyst concentration was 1.5 mol % of potassium ions and 4.1 mol % of sodium ions and 10 rather than 11 eq of PeO were added.

Example M10

HBVE-24.5 EO-10 PeO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(31) The starting material used was macromonomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 684.0 g (0.631 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 2.78 g of 50% NaOH (sodium hydroxide) solution (0.0348 mol of NaOH, 1.39 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(32) The mixture was purged three times with N.sub.2. Thereafter, the vessel was tested for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 120 C. and then the pressure was set to 1.6 bar absolute. 69.4 g (1.577 mol) of EO were metered in at 127 C.; p.sub.max was 2.1 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(33) 542.5 g (6.03 mol) of PeO were metered in at 127 C.; p.sub.max was 2.1 bar absolute. One intermediate decompression was necessary owing to increasing fill level. The PeO metering was stopped, and the mixture was left to react for 1 h until the pressure was constant and decompressed to 1.0 bar absolute. Thereafter, the metered addition of PeO was continued. P.sub.max was still 2.1 bar (first decompression after 399 g of PeO, total PeO metering time 7 h incl. decompression break). After metered addition of PeO had ended, reaction was allowed to continue to constant pressure or for 3 h. The mixture was cooled to 110 C., and residual oxide was removed under reduced pressure until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 110 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(34) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M11

HBVE-24.5 EO-9 PeO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(35) The preparation was analogous to example M10, except that 9 rather than 10 eq of PeO were added.

Example M12

HBVE-24.5 EO-9 PeO (5.8 mol % of Potassium Ions), Addition of the PeO at 127 C. to 2.1 bar

(36) The starting material used was macromonomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 889.2 g (0.820 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 9.69 g of 32% KOMe in MeOH solution (0.0443 mol of

(37) KOMe, 3.11 g KOMe) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 80 C. and kept there for 80 min, in order to distill off MeOH.

(38) The mixture was purged three times with N.sub.2. Thereafter, the vessel was tested for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 120 C. and then the pressure was set to 1 bar absolute. 90.2 g (2.050 mol) of EO were metered in up to 140 C. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute at 120 C.

(39) A relatively large sample was taken, such that 789 g (0.66 mol) of HBVE-24.5 EO remained in the reactor. For safety, the mixture was inertized again with N.sub.2, set to 1.0 bar absolute and heated to 127 C. 511 g (5.95 mol) of PeO were metered in at 127 C.; p.sub.max, was 2.1 bar absolute. One intermediate decompression was necessary owing to increasing fill level. The PeO metering was stopped, and the mixture was left to react for 2 h until pressure was constant and decompressed to 1.0 bar absolute. Thereafter, the metered addition of PeO was continued. P.sub.max was still 2.1 bar. After metered addition of PeO had ended, reaction was allowed to continue to constant pressure or for 3 h. The mixture was cooled to 110 C., and residual oxide was removed under reduced pressure until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 110 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(40) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M13

HBVE-24.5 EO-8 PeO (0.4 mol % of Potassium Ions, 4.6 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(41) The preparation was analogous to example M6, except that 8 rather than 11 eq of PeO were added.

Example M14

HBVE-26.5 EO-10 PeO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the PeO at 127 C. to 2.1 bar

(42) The preparation was analogous to example M10, except that, proceeding from HBVE-22 EO, 4.5 eq of EO rather than 2.5 eq of EO were added.

Example M15

HBVE-24.5 EO-10 PeO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the PeO at 122 C. to 2.1 bar

(43) The preparation was analogous to example M10, except that PeO was added at 122 C. rather than 127 C.

Example M16

HBVE-24.5 EO-10 PeO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the PeO at 132 C. to 2.1 bar

(44) The preparation was analogous to example M10, except that PeO was added at 132 C. rather than 127 C.

Example M17

HBVE-24.5 EO-10 BuO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 2.1 bar

(45) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 730.8 g (0.674 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 2.97 g of 50% NaOH solution (0.0371 mol of NaOH, 0.85 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(46) The mixture was purged three times with N.sub.2. Thereafter, the vessel was tested for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 120 C. and then the pressure was set to 1.6 bar absolute. 74.1 g (1.685 mol) of EO were metered in up to 127 C.; p.sub.max was 3.9 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(47) 485.3 g (6.74 mol) of BuO (butylene oxide) were metered in at 127 C.; p.sub.max was 2.1 bar absolute. One intermediate decompression was necessary owing to increasing fill level. The BuO metering was stopped, and the mixture was left to react for 1 h until pressure was constant and decompressed to 1.0 bar absolute. Thereafter, the metered addition of BuO was continued. P.sub.max was still 2.1 bar (first decompression after 246 g of BuO, total BuO metering time 10 h incl. decompression break). After metered addition of BuO had ended, reaction was allowed to continue to constant pressure or for 3 h. The mixture was cooled to 110 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 110 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(48) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M18

HBVE-24.5 EO-12 BuO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 2.1 bar

(49) The preparation was analogous to example M17, except that 12 rather than 10 eq of BuO were added.

Example M19

HBVE-24.5 EO-14 BuO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 2.1 bar

(50) The preparation was analogous to example M17, except that 14 rather than 10 eq of BuO were added.

Example M20

HBVE-24.5 EO-16 BuO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 2.1 bar

(51) The preparation was analogous to example M17, except that 16 rather than 10 eq of BuO were added.

Example M21

HBVE-24.5 EO-18 BuO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 2.1 bar

(52) The preparation was analogous to example M17, except that 18 rather than 10 eq of BuO were added.

Example M22

HBVE-24.5 EO-16 BuO (5.8 mol % of Potassium Ions), Addition of the BuO at 127 C. to 3.1 bar

(53) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 622.8 g (0.575 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 6.92 g of 32% KOMe in MeOH solution (0.0316 mol of KOMe, 2.21 g of KOMe) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 80 C. and kept there for 80 min, in order to distill off the methanol.

(54) The mixture was purged three times with N.sub.2. Thereafter, the vessel was tested for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 120 C. and then the pressure was set to 1.6 bar absolute. 50.3 g (1.144 mol) of EO were metered in up to 127 C.; p.sub.max was 3.9 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(55) 662 g (9.19 mol) of BuO were metered in at 127 C.; p.sub.max was 3.1 bar absolute. After metered addition of BuO had ended, reaction was allowed to continue to constant pressure or for 5 h. The mixture was cooled to 110 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 110 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(56) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M23

HBVE-24.5 EO-16 BuO (0.4 mol % of Potassium Ions, 11 mol % of Sodium Ions), Addition of the BuO at 127 C. to 3.1 bar

(57) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 595.1 g (0.549 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 4.83 g of 50% NaOH solution (0.060 mol of NaOH, 2.41 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(58) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 120 C. and then the pressure was set to 1.6 bar absolute. 60.4 g (1.373 mol) of EO were metered in up to 127 C.; p.sub.max was 3.9 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(59) 632.2 g (8.748 mol) of BuO were metered in at 127 C.; p.sub.max was 3.1 bar absolute. One intermediate decompression was necessary owing to increasing fill level. The BuO metering was stopped, and the mixture was left to react for 1 h until pressure was constant and decompressed to 1.0 bar absolute. Thereafter, the metered addition of BuO was continued. P.sub.max was still 3.1 bar (first decompression after 334 g of BuO, total BuO metering time 5 h incl. decompression break). After metered addition of BuO had ended, the mixture was heated to 135 C. and reaction was allowed to continue for 3.5 h. The mixture was cooled to 100 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 120 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(60) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M24

HBVE-23 EO-17 BuO-2.5 EO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 3.1 bar

(61) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 576.7 g (0.532 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 2.33 g of 50% NaOH solution (0.029 mol of NaOH, 1.17 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(62) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 127 C. and then the pressure was set to 1.6 bar absolute. 23.4 g (0.532 mol) of EO were metered in at 127 C.; p.sub.max was 3.9 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(63) 651.2 g (9.044 mol) of BuO were metered in at 127 C.; p.sub.max was 3.1 bar absolute. After metered addition of BuO had ended, the mixture was heated to 135 C. and reaction was allowed to continue for 2 h. Thereafter 58.5 g (1.331 mol) of EO were metered at 135 C.; p.sub.max was 3.2 bar absolute. After metered addition of EO had ended, the reaction was allowed to continue for 2 h.

(64) The mixture was cooled to 100 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 120 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(65) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M25

HBVE-24.5 EO-16 BuO-3.5 EO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 3.1 bar

(66) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 588.6 g (0.543 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 2.39 g of 50% NaOH solution (0.030 mol of NaOH, 1.19 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(67) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 127 C. and then the pressure was set to 1.6 bar absolute. 59.7 g (1.358 mol) of EO were metered in at 127 C.; p.sub.max was 3.9 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(68) 625.5 g (8.688 mol) of BuO were metered in at 127 C.; p.sub.max was 3.1 bar absolute. One intermediate decompression was necessary owing to increasing fill level. The BuO metering was stopped, and the mixture was left to react for 1 h until pressure was constant and decompressed to 1.0 bar absolute. Thereafter, the metered addition of BuO was continued. P.sub.max was still 3.1 bar (first decompression after 610 g of BuO, total BuO metering time 8 h incl. decompression break). After metered addition of BuO had ended, the reaction was allowed to continue for 8 h and thereafter the mixture was heated to 135 C. Thereafter 83.6 g (1.901 mol) of EO were metered at 135 C.; p.sub.max was 3.1 bar absolute. After metered addition of EO had ended, the reaction was allowed to continue for 4 h. The mixture was cooled to 100 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 120 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(69) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M26

HBVE-24.5 EO-16 BuO-5 EO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 3.1 bar

(70) The starting material used was monomer M1 from example M1. The preparation was analogous to example M25, except that 5 rather than 3.5 eq of EO were added after addition of BuO and polymerisation, i.e. 119.5 g (2.715 mol) of EO were metered at 135 C.

(71) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M27

HBVE-24.5 EO-10 BuO-3.5 EO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 3.1 bar

(72) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 685.2 g (0.632 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 2.78 g of 50% NaOH solution (0.035 mol of NaOH, 1.39 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(73) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 127 C. and then the pressure was set to 1.6 bar absolute. 69.8 g (1.587 mol) of EO were metered in at 127 C.; p.sub.max was 3.9 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(74) 455.2 g (6.322 mol) of BuO were metered in at 127 C.; p.sub.max was 3.1 bar absolute. After metered addition of BuO had ended, the reaction was allowed to continue for 7 h. Thereafter 97.4 g (2.213 mol) of EO were metered at 127 C.; p.sub.max was 3.1 bar absolute. After metered addition of EO had ended, the reaction was allowed to continue for 2 h. The mixture was cooled to 100 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 120 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(75) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M28

HBVE-24.5 EO-5 BuO-3.5 EO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 3.1 bar

(76) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 822.0 g (0.758 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 3.34 g of 50% NaOH solution (0.042 mol of NaOH, 1.67 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(77) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 127 C. and then the pressure was set to 1.6 bar absolute. 83.4 g (1.895 mol) of EO were metered in at 127 C.; p.sub.max was 3.9 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(78) 273.0 g (3.792 mol) of BuO were metered in at 127 C.; p.sub.max was 3.1 bar absolute. After metered addition of BuO had ended, the reaction was allowed to continue for 15 h. Thereafter 116.8 g (2.654 mol) of EO were metered at 127 C.; p.sub.max was 3.1 bar absolute. After metered addition of EO had ended, the reaction was allowed to continue for 4 h. The mixture was cooled to 100 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 120 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(79) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M29

HBVE-24.5 EO-22 BuO-3.5 EO (0.4 mol % of Potassium Ions, 5.5 mol % of Sodium Ions), Addition of the BuO at 127 C. to 3.1 bar

(80) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 493.3 g (0.455 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 2.00 g of 50% NaOH solution (0.025 mol of NaOH, 1.00 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(81) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 127 C. and then the pressure was set to 1.6 bar absolute. 50.0 g (1.138 mol) of EO were metered in at 127 C.; p.sub.max was 3.9 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 1.0 bar absolute.

(82) 720.9 g (10.012 mol) of BuO were metered in at 127 C.; p.sub.max was 3.1 bar absolute. After metered addition of BuO had ended, the reaction was allowed to continue for 9 h. The mixture was heated to 135 C. Thereafter 70.1 g (1.593 mol) of EO were metered at 135 C.; p.sub.max was 3.1 bar absolute. After metered addition of EO had ended, the reaction was allowed to continue for 2 h. The mixture was cooled to 100 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. Then 0.5% water was added at 120 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(83) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

Example M30

HBVE-24.5 EO-16 BuO-3.5 EO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the BuO at 127 C. at from 4 to 6 bar

(84) The starting material used was monomer M1 from example M1. A 2 l pressure autoclave with anchor stirrer was initially charged with 568.6 g (0.525 mol) of HBVE-22 EO and the stirrer was switched on. Thereafter, 2.31 g of 50% NaOH solution (0.029 mol of NaOH, 1.16 g of NaOH) were added, a reduced pressure of <10 mbar was applied, and the mixture was heated to 100 C. and kept there for 80 min, in order to distill off the water.

(85) The mixture was purged three times with N.sub.2. Thereafter, the vessel was checked for pressure retention, 0.5 bar gauge (1.5 bar absolute) was set, the mixture was heated to 127 C. and then the pressure was set to 3 bar absolute. 57.7 g (1.311 mol) of EO were metered in at 127 C.; p.sub.max was 6 bar absolute. After waiting for 30 min for establishment of constant pressure, the mixture was decompressed to 4.0 bar absolute.

(86) 604.2 g (8.392 mol) of BuO were metered in at 127 C.; p.sub.max was 6 bar absolute. One intermediate decompression was necessary owing to increasing fill level. The BuO metering was stopped, and the mixture was left to react for 1 h until pressure was constant and decompressed to 4.0 bar absolute. Thereafter, the metered addition of BuO was continued. P.sub.max was still 6 bar (first decompression after 505 g of BuO, total BuO metering time 11 h incl. decompression break). After metered addition of BuO had ended, the reaction was allowed to continue for 6 h at 127 C. It was decompressed to 4 bar absolute.

(87) Thereafter 80.8 g (1.836 mol) of EO were metered at 127 C.; p.sub.max was 6 bar absolute. After metered addition of EO had ended, the reaction was allowed to continue for 4 h. The mixture was cooled to 100 C., and residual oxide was drawn off until the pressure was below 10 mbar for at least 10 min. About 1400 ppm of volatile components were removed. Then 0.5% water was added at 120 C. and volatiles were subsequently drawn off until the pressure was below 10 mbar for at least 10 min. The vacuum was broken with N.sub.2 and 100 ppm of BHT were added. The transfer was effected at 80 C. under N.sub.2.

(88) The analysis (mass spectrum, GPC, 1H NMR in CDCl.sub.3, 1H NMR in MeOD) confirmed the structure.

I-b Preparation of the Copolymers Based on Macromonomers (M2-M30)

Example C1

General Preparation of a Copolymer from 2% by Weight of Macromonomer M, 50% by Weight of Acrylamide and 48% by Weight of 2-acrylamido-2-methylpropanesulfonic acid

(89) A plastic bucket with a magnetic stirrer, pH meter and thermometer was initially charged with 121.2 g of a 50% aqueous solution of NaATBS (2-acrylamido-2-methylpropanesulfonic acid, Na salt), followed by successive addition of 155 g of distilled water, 0.6 g of a defoamer (Surfynol DF-58), 0.2 g of a silicone defoamer (Baysilon EN), 2.3 g of monomer M, 114.4 g of a 50% aqueous solution of acrylamide, 1.2 g of pentasodium diethylenetriaminepentaacetate (complexing agent, as a 5% aqueous solution) and 2.4 g of a nonionic surfactant (isotridecanol, alkoxylated with 15 units of ethylene oxide).

(90) After adjusting the pH with a 20% or 2% sulfuric acid solution to a value of 6 and adding the rest of the water, the monomer solution was adjusted to the start temperature of 5 C. The total amount of the water was such thatafter the polymerizationa solids concentration of approx. 30 to 36% by weight was attained. The solution was transferred into a thermos flask, a temperature sensor was provided for temperature recording and the solution was purged with N.sub.2 for 30 minutes. The polymerization was subsequently initiated by addition of 1.6 ml of a 10% aqueous solution of a water-soluble cationic azo initiator 2,2-azobis(2-amidinopropane)dihydrochloride (Wako V-50), 0.12 ml of a 1% aqueous solution of tert-butyl hydroperoxide and 0.24 ml of a 1% sodium sulfite solution. After the initiators had been added, the temperature rose to approx. 80 C. within 15 to 30 min. After 30 min, the reaction vessel was placed in a drying cabinet at approx. 80 C. for approx. 2 h to complete the polymerization. The total polymerization time was approx. 2 h to 2.5 h.

(91) A gel block was obtained, which, after the polymerization had ended, was comminuted with a meat grinder. The gel granules thus obtained were dried in a fluidized bed drier at 55 C. for two hours. Hard white granules were obtained, which were converted to a pulverulent state by means of a centrifugal mill. A copolymer was obtained with a weight-average molecular weight of about 1 000 000 g/mol to 30 000 000 g/mol.

Example C2

Copolymer Based on Macromonomer

(92) The copolymer was obtained according to the above general preparation method by using macromonomer from comparative example M2.

Examples C3 to C30

(93) Copolymers C3 to C30 were prepared by the above general method by using the respective monomers M3 to M30.

PART II: PERFORMANCE TESTS

(94) The resulting copolymers based on the above macromonomers were used to conduct the tests which follow, in order to assess the suitability thereof for tertiary mineral oil production.

(95) Description of the Test Methods

(96) a) Determination of Solubility

(97) The copolymers were dissolved in synthetic seawater to DIN 50900 (salt content 35 g/l) so as to give a polymer concentration of 2000 ppm: 0.5 g of the respective copolymer was stirred in 249 g of synthetic seawater (DIN 50900) for 24 h until complete dissolution (the precision glass stirrer used should preferably be a paddle stirrer; the polymer was scattered gradually into the vortex which forms).

(98) b) Determination of Viscosity

(99) The viscosities of the abovementioned copolymer solutions were determined using a Haake rheometer with double gap geometry at 7 Hz and 60 C. After approx. 5 min, a plateau value was established for the viscosity, which was read off. Very good values were considered to be viscosities greater than or equal 150 mPas (2000 ppm of copolymer in synthetic seawater at 60 C. and 7 Hz). Good values were considered to be viscosities greater of 120 mPas to 149 mPas. Moderate viscosity values were considered to be from 80 to 119 mPas. Viscosities of less than 80 mPas were considered to be poor.

(100) c) Determination of Filterability

(101) Prior to the actual filtration test, the polymer solution was filtered through a 200 m Retsch sieve to determine the gel content thereof.

(102) The filtration test to determine the MPFR valuethe ratio of the flow rate of the first quarter to that of the fourth quarter is called the Millipore filter ratio (MPFR)was conducted by means of a Sartorius 16249 pressure filtration cell (filter diameter 47 mm) and an Isopore polycarbonate membrane filter (diameter 47 mm, pore size 3 m) at room temperature and 1 bar gauge. 210-220 g of polymer solution were used. In the test, at least 180 g of filtrate were to pass through within 30 minutes. Good values were considered to be MPFR of less than or equal to 1.3. If they are between 1.3 and 1.6, filterability was considered to be moderate. If less than 30 g of filtrate passed through, the sample was considered to be unfilterable.

(103) d) Determination of the Gel Content

(104) 1 g of the respective copolymer from preparation examples 2-30 was stirred in 249 g of synthetic seawater to DIN 50900 (salt content 35 g/l) until complete dissolution for 24 h. Subsequently, the solution was filtered through a sieve of mesh size 200 m and the volume of the residue remaining on the sieve was measured. The value obtained corresponds to the gel content.

(105) Test Results:

(106) The test results are compiled in the table which follows.

(107) TABLE-US-00001 Example Copolymer soluble Viscosity Filterability Gel content 2 C2 based on M2 yes good good 0 ml HBVE - 22 EO - 10.6 PeO (0.4 mol % of potassium ions, 4.6 mol % of sodium ions), addition of the PeO at 140 C. to 3.2 bar 3 C3 based on M3 yes good unfilterable 2 ml HBVE - 22 EO - 10.5 PeO (0.4 mol % of potassium ions, 3.3 mol % of sodium ions), addition of the PeO at 140 C. to 2.1 bar 4 C4 based on M4 yes good good 0 ml HBVE - 22 EO - 10 PeO (0.4 mol % of potassium ions, 4.6 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 5 C5 based on M5 yes good unfilterable 12 ml HBVE - 22 EO - 11 PeO (0.4 mol % of potassium ions, 4.6 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 6 C6 based on M6 yes good good 0 ml HBVE - 24.5 EO - 11 PeO (0.4 mol % of potassium ions, 4.6 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 7 C7 based on M7 yes good good 0 ml HBVE - 24.5 EO - 10 PeO (0.4 mol % of potassium ions, 4.6 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 8 C8 based on M8 yes good moderate 0-1 ml HBVE - 24.5 EO - 10 PeO (0.9 mol % of potassium ions, 4.1 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 9 C9 based on M9 yes good unfilterable 3 ml HBVE - 24.5 EO - 10 PeO (1.5 mol % of potassium ions, 4.6 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 10 C10 based on M10 yes good good 0 ml HBVE - 24.5 EO - 10 PeO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 11 C11 based on M11 yes good good 0 ml HBVE - 24.5 EO - 9 PeO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 12 C12 based on M12 yes good unfilterable 48 ml HBVE - 24.5 EO - 9 PeO (5.8 mol % of potassium ions), addition of the PeO at 127 C. to 2.1 bar 13 C13 based on M13 yes good moderate 0-1 ml HBVE - 24.5 EO - 8 PeO (0.4 mol % of potassium ions, 4.6 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 14 C14 based on M14 yes good moderate 0-1 ml HBVE - 26.5 EO - 10 PeO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the PeO at 127 C. to 2.1 bar 15 C15 based on M15 yes good good 0 ml HBVE - 24.5 EO - 10 PeO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the PeO at 122 C. to 2.1 bar 16 C16 based on M16 yes good good 0 ml HBVE - 24.5 EO - 10 PeO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the PeO at 132 C. to 2.1 bar 17 C17 based on M17 yes poor good 0 ml HBVE - 24.5 EO - 10 BuO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the BuO at 127 C. to 2.1 bar 18 C18 based on M18 yes poor good 0 ml HBVE - 24.5 EO - 12 BuO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the BuO at 127 C. to 2.1 bar 19 C19 based on M19 yes good good 0 ml HBVE - 24.5 EO - 14 BuO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the BuO at 127 C. to 2.1 bar 20 C20 based on M20 yes good good 0 ml HBVE - 24.5 EO - 16 BuO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the BuO at 127 C. to 2.1 bar 21 C21 based on M21 yes good unfilterable 2 ml HBVE - 24.5 EO - 18 BuO (0.4 mol % of potassium ions, 5.5 mol % of sodium ions), addition of the BuO at 127 C. to 2.1 bar 22 C22 based on M22 yes good unfilterable 5-10 ml HBVE - 24.5 EO - 16 BuO (5.8 mol % of potassium ions), addition of the BuO at 127 C. to 3.1 bar 23 C23 based on M23 yes good good 0 ml HBVE - 24.5 EO - 16 BuO (0.4 mol % potassium ions, 11 mol % sodium ions), addition of the BuO at 127 C. to 3.1 bar 24 C24 based on M24 yes very good good 0 ml HBVE - 23 EO - 17 BuO - 2.5 EO (0.4 mol % potassium ions, 5.5 mol % sodium ions), addition of the BuO at 127 C. to 3.1 bar 25 C25 based on M25 yes very good good 0 ml HBVE - 24.5 EO - 16 BuO - 3.5 EO (0.4 mol % potassium ions, 5.5 mol % sodium ions), addition of the BuO at 127 C. to 3.1 bar 26 C26 based on M26 yes very good good 0 ml HBVE - 24.5 EO - 16 BuO - 5 EO (0.4 mol % potassium ions, 5.5 mol % sodium ions), addition of the BuO at 127 C. to 3.1 bar 27 C27 based on M27 yes moderate good 0 ml HBVE - 24.5 EO - 10 BuO - 3.5 EO (0.4 mol % potassium ions, 5.5 mol % sodium ions), addition of the BuO at 127 C. to 3.1 bar 28 C28 based on M28 yes moderate good 0 ml HBVE - 24.5 EO - 5 BuO - 3.5 EO (0.4 mol % potassium ions, 5.5 mol % sodium ions), addition of the BuO at 127 C. to 3.1 bar 29 C29 based on M29 yes very good very good 0 ml HBVE - 24.5 EO - 22 BuO - 3.5 EO (0.4 mol % potassium ions, 5.5 mol % sodium ions), addition of the BuO at 127 C. to 3.1 bar 30 C30 based on M30 yes very good good 0 ml HBVE - 24.5 EO - 16 BuO - 3.5 EO (0.4 mol % potassium ions, 5.5 mol % sodium ions), addition of the BuO at 127 C. at 4 to 6 bar

(108) Examples 2 and 3 show that the pressure window for the PeO metering at 140 C. has a great influence on the product quality. A larger pressure window enables rapid metering and a short cycle time (2 h for PeO). If, however, the pressure window required by the safety specifications is observed, as in example 3, the reaction is prolonged (2 days for PeO). As a result of the high temperature, there are side reactions and formation of crosslinkers, the effect of which is that the later copolymerization forms a thickening copolymer which is no longer filterable, and this is no longer employable for uses in a porous matrix (for example mineral oil-bearing rock strata, thickeners in mineral oil production).

(109) Example 4 shows that lowering the reaction temperature while maintaining the small pressure window can produce copolymers free of crosslinkers. As can be seen in the examples, the concentration of potassium ions is of central significance. As examples 9 and 12 show, above 0.9 mol % of potassium ions, the polymer is no longer filterable in spite of temperatures of 127 C. in the PeO metering. A potassium ion concentration greater than 0.9 mol % apparently leads to the formation of crosslinking compounds which lead to a copolymer which is no longer filterable. In addition, the exact content of sodium ion catalyst appears also to play an important role.

(110) It is additionally considered to be surprising that the hydrophilic/hydrophobic ratio of the macromonomer is also of great significance. In spite of crosslinker-free operation, the copolymer according to example 5 has somewhat poorer filterability than copolymers based on macromonomers with only 1 eq of PeO less (example 4). If monomers with 24.5 units of EO are used, the variation in the PeO units has no influence on the filterability of the copolymers (comparison of examples 6 and 7 and comparison of examples 10 and 11). The specific selection of a hydrophilic/hydrophobic ratio, i.e. ratio of EO and PeO units, led to surprising robustness of the process. In examples 10 and 11 (24.5 EO units), no variation in the PeO content was perceptible. This gives good stability for industrial scale production, where variations of less than 1 eq of alkylene oxide are not easy to guarantee. Deviations in process and structure are thus much better tolerated in the later copolymer synthesis or application.

(111) A similar picture is found in the case of copolymers based on macromonomers M with terminal BuO groups. A comparison of examples 20 and 22 shows that, in the case of preparation of copolymers based on macromonomers with terminal BuO groups too, a concentration of potassium ions of less than 0.9 mol % surprisingly leads to improved copolymers. Excessively high values for potassium ions in the copolymer lead to unfilterable structures.

(112) Examples 19 and 20 show that optimal product properties (good viscosities and good filterability) can be achieved especially at a butoxylation level above 12 and below 18. A comparison of the results relating to macromonomers with terminal PeO groups and relating to macromonomers with terminal BuO groups has additionally shown that the total number of carbon atoms in the side chains of the macromonomers, especially in the terminal alkylene oxide blocks, is of crucial significance for the properties of the resulting copolymers. For example, the total number of carbon atoms in the side chains of the terminal alkylene oxide block from examples 19 and 20 (total of 28 to 32 carbon atoms in side chains) coincides with the total number range in examples 6, 10 and 11 (total of 27 to 33 carbon atoms in side chains) relating to macromonomers with terminal PeO groups. Other butoxylation levels as in examples 17, 18 and 21 lead to properties of the macromonomer which are no longer optimal in all areas.

(113) Further, it has been shown that macromonomers with BuO blocks, in particular with blocks having 16 to 22 BuO units, can advantageously be modified with an terminal EO block. Thus, copolymers with very good viscosity properties and good filterability can be obtained (examples 24 to 26 and 29). Contrary, it seems that the introduction of an terminal EO block in macromonomers having an BuO block with less than 12 BuO units do not result in an advantageous effect (examples 27 and 28).

(114) Example 23 shows that the concentration of sodium ions can be up to at least 11 mol % during the addition of butylene oxide.

(115) Example 30 shows that the addition of butylene oxide can also advantageously be carried out at a pressure in the range of 4 to 6 bar.