Polyether-modified polybutadienes and processes for preparation thereof

Abstract

A process can be used for preparing polyether-modified polybutadienes. The process involves reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to give at least one epoxy-functional polybutadiene (C). The at least one epoxy-functional polybutadiene (C) is then reacted with at least one hydroxy-functional compound (D) to give at least one hydroxy-functional polybutadiene (E). The at least one hydroxy-functional polybutadiene (E) is finally reacted with at least one epoxy-functional compound (F) to give at least one polyether-modified polybutadiene (G).

Claims

1: A process for preparing one or more polyether-modified polybutadienes, comprising: a) reacting at least one polybutadiene (A) with at least one epoxidizing reagent (B) to give at least one epoxy-functional polybutadiene (C); b) reacting the at least one epoxy-functional polybutadiene (C) with at least one hydroxy-functional compound (D) to give at least one hydroxy-functional polybutadiene (E); and c) reacting the at least one hydroxy-functional polybutadiene (E) with at least one epoxy-functional compound (F) to give at least one polyether-modified polybutadiene (G).

2: The process according to claim 1, further comprising: d) reacting the at least one polyether-modified polybutadiene (G) with at least one end-capping reagent (H) to give at least one polyether-modified polybutadiene (K) containing end-capped polyether radicals.

3: The process according to claim 2, further comprising: e) lightening a colour of the at least one polyether-modified polybutadiene (G) or the at least one polyether-modified polybutadiene (K).

4: The process according to claim 1, wherein the at least one polybutadiene (A) has double bonds which are 0% to 80% 1,2-vinyl double bonds and 20% to 100% 1,4 double bonds.

5: The process according to claim 1, wherein a number-average molar mass M.sub.n of the at least one polybutadiene (A) is from 200 g/mol to 20,000 g/mol.

6: The process according to claim 1, wherein >0% to 70% of double bonds of the at least one polybutadiene (A) are epoxidized.

7: The process according to claim 1, wherein the at least one epoxidizing reagent (B) contains performic acid.

8: The process according to claim 1, wherein the at least one hydroxy-functional compound (D) is at least one monofunctional alcohol having 1 to 6 carbon atoms.

9: The process according to claim 1, wherein in b), a total number of hydroxyl groups in the at least one hydroxy-functional compound (D) to a total number of epoxy groups in the at least one epoxy-functional polybutadiene (C) is from >1:1 to 50:1.

10: The process according to claim 1, wherein in b), an acid is used as a catalyst.

11: The process according to claim 1, wherein the at least one epoxy-functional compound (F) used in c) is selected from the group consisting of an alkylene oxide having 2 to 18 carbon atoms, a glycidyl compound, and a mixture thereof.

12: The process according to claim 1, wherein an alkoxylation catalyst is used in c).

13: The at least one polyether-modified polybutadiene (G), obtainable by the process according to claim 1.

14: A polyether-modified polybutadiene, comprising repeat units selected from the group consisting of divalent radicals ##STR00018## wherein A is in each case independently a monovalent organic radical or a hydrogen radical, B is in each case independently a radical of the formula (4a) ##STR00019## R.sup.1 is in each case independently a monovalent hydrocarbon radical having 1 to 16 carbon atoms, R.sup.2 is a radical of the formula —CH.sub.2—O—R.sup.3; R.sup.3 is in each case independently a monovalent hydrocarbon radical having 3 to 18 carbon atoms, R.sup.4 is in each case independently a monovalent organic radical having 1 to 18 carbon atoms or hydrogel; and m, n, o, p and q are each independently 0 to 300, with the proviso that the sum total of m, n, o, p and q is greater than 1; for every permutation of the repeat units (U), (V), (W), (X), (Y) and (Z) and of repeat units in B.

15: The polyether-modified polybutadiene according to claim 14, wherein a sum total of all repeat units (U), (V) and (W) divided by a sum total of all repeat units (U), (V), (W), (X), (Y) and (Z) is from >0% to 70%.

16: The polyether-modified polybutadiene according to claim 14, wherein the polyether-modified polybutadiene is of the formula (5) ##STR00020## wherein a proportion of polyether-modified repeat units shown in formula (5), based on a sum total of all repeat units shown in formula (5), is >0% to 70%, where the proportion is calculated as [(d+e+f)/(a+b+c+d+e+f)]*100%.

17: The polyether-modified polybutadiene according to claim 14, wherein a number-average molar mass M.sub.n of a polybutadiene moiety is from 200 g/mol to 20,000 g/mol.

18: The polyether-modified polybutadiene according to claim 14, wherein 0% to 80% of double bonds present are 1,2 vinyl double bonds, and 20% to 100% of the double bonds present are 1,4 double bonds.

19: The polyether-modified polybutadiene according to claim 14, wherein an average molar mass of B is from 100 g/mol to 20,000 g/mol.

20: The at least one polyether-modified polybutadiene (K), obtainable by the process according to claim 2.

Description

EXAMPLES

[0178] General Methods:

[0179] Gel Permeation Chromatogaphy (GPC):

[0180] GPC measurements for determination of polydispersity (M.sub.w/M.sub.n), weight-average molar mass (M.sub.w) and number-average molar mass (M.sub.n) were conducted under the following measurement conditions: SDV 1000/10 000 Å column combination (length 65 cm), temperature 30° C. THF as mobile phase, flow rate 1 ml/min, sample concentration 10 g/l, RI detector, evaluation against polypropylene glycol standard.

[0181] Determination of the Content of the 1,4-Cis, 1,4-Trans and 1,2 Units in the Polybutadlene:

[0182] The content of 1,4-cis, 1,4-trans and 1,2 units can be determined with the aid of .sup.1H NMR spectroscopy. This method is familiar to the person skilled in the art.

[0183] Determination of the Content of Epoxy Groups in the Polybutadiene (Epoxy Content, Epoxidation Level):

[0184] The content of epoxy groups was determined with the aid of .sup.13C NMR spectroscopy. A Bruker Avance 400 NMR spectrometer was used. For this purpose, the samples were dissolved in deuterochloroform. The epoxy content is defined as the proportion of epoxidized butadiene units in mol % based on the entirety of all repeat units present in the sample. This corresponds to the number of epoxy groups in the epoxidized polybutadiene divided by the number of double bonds in the polybutadiene used.

[0185] Determination of Acid Number:

[0186] Acid number determination was performed by a titration method in accordance with DIN EN ISO 2114.

[0187] Determination of Colour Lightening:

[0188] Colour lightening was ascertained by the change in Gardner colour number (determined to DIN ISO 4630).

SYNTHESIS EXAMPLES

[0189] Step a), Preparation of Epoxidized Polybutadienes

Example A1

[0190] An epoxidized polybutadiene was prepared using a polybutadiene of the formula (1) having the structure x=1%, y=24% and z=75% (Polyvest® 110). According to the prior art, a 20 L reactor under a nitrogen atmosphere was initially charged with 1600 g of Polyvest® 110 and 86.4 g of conc. formic acid in 4000 g of chloroform at room temperature. Subsequently, 320 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2 based on the total mass of the aqueous solution) was slowly added dropwise and then the solution was heated to 50° C. for 7 h. After the reaction had ended, the mixture was cooled down to room temperature, and the organic phase was removed and washed four times with dist. H.sub.2O. Excess chloroform and residual water were distilled off. 1556 g of the product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0191] Evaluation by means of .sup.13C NMR gave an epoxidation level of about 8.9% of the double bonds.

[0192] M.sub.w=4669 g/mol; M.sub.n=1931 g/mol; M.sub.w/M.sub.n=2.4

Example A2

[0193] By the process described in Example A1, a 2 L four-neck flask was initially charged with 200 g of Polyvest® 110 and 6.5 g of conc. formic acid in 200 g of chloroform, and 24 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2, based on the total mass of the aqueous solution) was added. After 7 hours at 50° C., phase separation, washing with dist. H.sub.2O and subsequent distillation. 191 g of an epoxidized polybutadiene with an epoxidation level or about 6.7% of the double bonds by .sup.13C NMR analysis was achieved.

[0194] M.sub.w=4624 g/mol; M.sub.n=2022 g/mol; M.sub.w/M.sub.n=2.3

Example A3

[0195] By the process described in Example A1, a 2 L four-neck flask was initially charged with 200 g of Polyvest® 110 and 19.5 g of conc. formic acid in 200 g of chloroform, and 72 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2, based on the total mass of the aqueous solution) was added. After 7 hours at 50° C., phase separation, washing with dist. H.sub.2O and subsequent distillation, 196 g of an epoxidized polybutadiene with an epoxidation level of about 16.2% of the double bonds by .sup.3C NMR analysis was achieved.

[0196] M.sub.w=4943 g/mol; M.sub.n=2083 g/mol: M.sub.w/M.sub.n=2.4

Example A4

[0197] By the process described in Example A1, a 2 L four-neck flask was initially charged with 200 g or Polyvest® 110 and 24.2 g of conc. formic acid in 200 g of chloroform, and 89.3 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2, based on the total mass of the aqueous solution) was added. After 7 hours at 50° C., phase separation, washing with dist. H.sub.2O and subsequent distillation. 204 g of an epoxidized polybutadiene with an epoxidation level or about 21.0% of the double bonds by .sup.13C NMR analysis was achieved.

[0198] M.sub.w=4843 g/mol; M.sub.n=2025 g/mol; M.sub.w/M.sub.n=2.4

Example A5

[0199] By the process described in Example A1, a 2 L four-neck flask was initially charged with 200 g of Polyvest® 110 and 10.8 g of conc. formic acid in 200 g of toluene, and 40 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2, based on the total mass or the aqueous solution) was added. After 10 hours at 50° C., phase separation, washing with sat. NaHCO.sub.3 solution and subsequent distillation, 172 g of an epoxidized polybutadiene with an epoxidation level of about 7.6% of the double bonds by .sup.13C NMR analysis was achieved.

[0200] M.sub.w=4634 g/mol; M.sub.n=2020 g/mol; M.sub.w/M.sub.n=2.3

Example A6

[0201] By the process described in Example A1, a 20 L reactor was initially charged with 2000 g of a polybutadiene of the formula (1) with the structure of x=1%, y=22% and z=77% (Polyvest® 130) and 191 g of conc. formic acid in 5000 g of chloroform, and 710 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2, based on the total mass of the aqueous solution) was added. After 7 hours at 50° C., phase separation, washing with dist. H.sub.2O and subsequent distillation, 1980 g of an epoxidized polybutadiene with an epoxidation level of about 14.6% of the double bonds by .sup.13C NMR analysis was achieved.

[0202] M.sub.w=15 333 g/mol; M.sub.n=3455 g/mol; M.sub.w/M.sub.n=4.4

Example A7

[0203] By the process described in Example A1, a 21 four-neck flask was initially charged with 800 g of Polyvest® 110 and 432 g of conc. formic acid in 800 g of chloroform, and 160 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2 based on the total mass of the aqueous solution) was added. After 5 hours at 50° C., phase separation, washing with dist. H.sub.2O and subsequent distillation, 755 g of an epoxidized polybutadiene having an epoxidation level of about 8.7% of the double bonds by .sup.13C NMR analysis was achieved.

[0204] M.sub.w=4593 g/mol: M.sub.n=1975 g/mol: M.sub.w/M.sub.n=2.3

Example A8

[0205] By the process described in Example A1, a 2 l four-neck flask was initially charged with 200 g of a polybutadiene of the formula (1) having the structure x=40%, y+z=60% (Lithene ultra AL) and 122 g of conc. formic acid in 200 g of chloroform, and 299 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2 based on the total mass of the aqueous solution) was added. After 7 hours at 50° C., phase separation, washing with dist. H.sub.2O and subsequent distillation, 218 g of an epoxidized polybutadiene having an epoxidation level of about 60% of the double bonds by .sup.13C NMR analysis was achieved.

[0206] M.sub.w=1670 g/mol; M.sub.n=832 g/mol; M.sub.w/M.sub.n=2.0

Example A9

[0207] By the process described in Example A1, a 2 l four-neck flask was initially charged with 200 g of a polybutadiene of the formula (1) having the structure x=70%, y+z=30% (Lithene ActiV 50) and 61 g of conc. formic acid in 200 g chloroform and 151 g of 30% H.sub.2O.sub.2 solution (30% by weight of H.sub.2O.sub.2 based on the total mass of the aqueous solution) was added. After 6 hours at 50° C., phase separation, washing with dist. H.sub.2O and subsequent distillation, 205 g of an epoxidized polybutadiene having an epoxidation level of about 30% of the double bonds by .sup.13C NMR analysis was achieved.

[0208] M.sub.w=1821 g/mol; M.sub.n=1045 g/mol; M.sub.w/M.sub.n=1.7

[0209] Step b), Preparation of OH-Functional Polybutadienes

Example B1

[0210] A hydroxylated polybutadiene having a hydroxylation level of about 21% was prepared using the epoxidized polybutadiene prepared in Example A4. The hydroxylation level here Is the number of OH groups of the OH-functional polybutadiene divided by the number of double bonds in the polybutadiene used in step a). For the preparation, a 100 ml four-neck flask under a nitrogen atmosphere was Initially charged with 18 g of the epoxidized polybutadlene in 45 g of n-propanol, and 80 ppmw of trlfluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in n-propanol (1% solution) was added while stirring. This was followed by heating to 70° C. and stirring of the mixture at that temperature for 8 hours. The reaction mixture became clear during the reaction. After the reaction had ended, the mixture was cooled down to room temperature and the solution was neutralized by adding 0.8 mg of solid NaHCO.sub.3 and then filtered. The excess alcohol was distilled off under reduced pressure. The alcohol recovered by distillation can be reused in subsequent syntheses. 16.9 g of a brownish product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0211] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which gives a hydroxylation level of about 21%.

[0212] M.sub.w=14 463 g/mol; M.sub.n=2789 g/mol; M.sub.w/M.sub.n=5.2

Example B2

[0213] For preparation of a hydroxylated polybutadiene having a hydroxylation level of about 8.9%, by the process described in Example B1, 20 g of the epoxidized polybutadiene prepared in Example A1 was initially charged in 45 g of n-propanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in n-propanol (1% solution) was added while stirring. After stirring at 70° C. for 7 hours, the reaction mixture was neutralized at room temperature (RT) with 0.9 mg of solid NaHCO.sub.3 and filtered, and the excess alcohol was distilled off under reduced pressure. 18 g of a brownish product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0214] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which gives a hydroxylation level of about 8.9%.

[0215] M.sub.w=28 138 g/mol; M.sub.n=2534 g/mol; M.sub.w/M.sub.n=11.1

Example B3

[0216] For preparation of a hydroxylated polybutadlene having a hydroxylation level of about 21%, by the process described in Example B1, 18 g of the epoxidized polybutadiene prepared in Example A4 was initially charged in 45 g of isopropanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isopropanol (1% solution) was added while stirring. After stirring at 70° C. for 7 hours, the reaction mixture was neutralized at RT with 0.8 mg of solid NaHCO.sub.3 and filtered, and the excess alcohol was distilled off under reduced pressure. 16.4 g of a brownish product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0217] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which gives a hydroxylation level of about 21%.

[0218] M.sub.w=14 012 g/mol: M.sub.n=2534 g/mol; M.sub.w/M.sub.n=5.5

Example B4

[0219] For preparation of a hydroxylated polybutadiene having a hydroxylation level of about 21%, by the process described in Example B1, 54 g of the epoxidized polybutadlene prepared in Example A4 was Initially charged in 135 g of isobutanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) was added while stirring. After stirring at 70° C. for 5 hours, the reaction mixture was neutralized at RT with 2.4 mg of solid NaHCO.sub.3 and filtered, and the excess alcohol was distilled off under reduced pressure. 50 g of a brownish product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0220] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which gives a hydroxylation level of about 21%.

[0221] M.sub.w=11 357 g/mol: M.sub.n=2890 g/mol; M.sub.w/M.sub.n=4.2

Example B5

[0222] For preparation of a hydroxylated polybutadlene having a hydroxylation level of about 8.9%, by the process described in Example B1, a 20 L reactor was Initially charged with 1500 g of the epoxidized polybutadiene prepared in Example A1 in 3150 g of isobutanol, which was recovered by distillation in Example B8, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) was added while stirring. After stirring at 70° C. for 5 hours, the reaction mixture was neutralized at RT with 67.5 mg of solid NaHCO.sub.3 and filtered, and the excess alcohol was distilled off under reduced pressure. 1380 g of a brownish product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0223] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which gives a hydroxylation level of about 8.9%.

[0224] M.sub.w=8597 g/mol; M.sub.n=2306 g/mol; M.sub.w/M.sub.n=3.7

Example B8

[0225] For preparation of a hydroxylated polybutadlene having a hydroxylation level of about 14.6%, by the process described in Example B1, a 20 L reactor was initially charged with 1600 g of the epoxidized polybutadiene prepared in Example A8 in 4500 g of isobutanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) was added while stirring. After stirring at 70° C. for 10 hours, the reaction mixture was neutralized at RT with 72 mg of solid NaHCO.sub.3 and filtered, and the excess alcohol was distilled off under reduced pressure. 1470 g of a brownish product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0226] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which gives a hydroxylation level of about 14.6%.

[0227] M.sub.w=51 674 g/mol; M.sub.n=4081 g/mol; M.sub.w/M.sub.n=12.7

Example B7

[0228] For preparation of a hydroxylated polybutadiene having a hydroxylation level of about 8,7%, a 2 l reactor, by the method described in Example B1, was initially charged with 720 g of the epoxidized polybutadiene prepared in Example A7 in 720 g of Isobutanol, and 80 ppmw of trfluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) was added while stirring. After stirring at 70° C. for 7 hours, the reaction mixture was admixed at room temperature with 10 ml of saturated aqueous NaHCO.sub.3 solution, and chloroform to clarify the mixture. After stirring for 1.5 hours, the mixture was filtered, and the excess water, alcohol and chloroform were distilled off under reduced pressure. 742 g of a pale yellow product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0229] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which results in a hydroxylation level of about 8.7%.

[0230] M.sub.w=8674 g/mol; M.sub.n=2459 g/mol; M.sub.w/M.sub.n=3.5

Example B8

[0231] For preparation of a hydroxylated polybutadiene having a hydroxylation level of about 60%, by the method described in Example B1, 200 g of the epoxidized polybutadiene prepared in Example A8 was initially charged in 500 g of isobutanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) was added while stirring. After stirring at 70° C. for 6 hours, the reaction mixture was neutralized at RT with 9.0 mg of solid NaHCO.sub.3 and filtered, and the excess alcohol was distilled off under reduced pressure. 318 g of a brownish product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0232] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which results in a hydroxylation level of about 60%.

[0233] M.sub.w=3140 g/mol; M.sub.n=1264 g/mol; M.sub.w/M.sub.n=2.5

Example B9

[0234] For preparation of a hydroxylated polybutadiene having a hydroxylation level or about 30%, by the method described in Example B1, 150 g of the epoxidized polybutadiene prepared in Example A9 was initially charged in 375 g of isobutanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) was added while stirring. After stirring at 70° C. for 7 hours, the reaction mixture was neutralized at RT with 6.8 mg of solid NaHCO.sub.3 and filtered, and the excess alcohol was distilled off under reduced pressure. 192 g of a brownish product was obtained, which was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0235] Evaluation by means of .sup.13C NMR showed complete conversion of all epoxy groups, which results in a hydroxylation level or about 30%.

[0236] M.sub.w=2972 g/mol; M.sub.n=1100 g/mol; M.sub.w/M.sub.n=2.7

[0237] Step c), Alkoxylation of OH-Functional Polybutadienes

[0238] Alkoxylations by Means of DMC Catalyst:

Example C1

[0239] A 3 litre autoclave was Initially charged with 335 g of the hydroxylated polybutadiene prepared in Example B5 and 0.45 g of zinc hexacyanocobaltate DMC catalyst under nitrogen, and heated up 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. The DMC catalyst was activated by feeding a portion of 41.0 g of propylene oxide. After 15 min and startup of the reaction (drop in internal reactor pressure), a further 144.3 g of propylene oxide was metered in continuously and while cooling within 1 h at 130° C. and max, internal reactor pressure 0.6 bar (absolute). Continued reaction at 130° C. for 30 minutes was followed by degassing. Volatile components such as residual propylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C., and a portion of 165.5 g was discharged. The moderately viscous and orange-coloured, cloudy alkoxylated polybutadiene was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0240] M.sub.w=14 310 g/mol; M.sub.n=2698 g/mol; M.sub.w/M.sub.n=5.3

[0241] The amount remaining in the reactor was heated again to 130° C., and then 126.4 g of propylene oxide was added continuously. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again and a further sample of 171.3 g of product was taken. The moderately viscous and orange-coloured, cloudy alkoxylated polybutadiene was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0242] M.sub.w=13 450 g/mol; M.sub.n=3139 g/mol; M.sub.w/M.sub.n=4.3

[0243] The amount remaining in the reactor was heated again to 130° C., and then 81.0 g of propylene oxide was added continuously. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again and the entire reactor contents of 391.3 g were discharged. The moderately viscous and orange-coloured, cloudy alkoxylated polybutadiene was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0244] M.sub.w=15 430 g/mol; M.sub.n=3723 g/mol; M.sub.w/M.sub.n=4.1

Example C2

[0245] A 3 litre autoclave was initially charged with 211 g of the hydroxylated polybutadiene prepared in Example B5 and 0.26 g of zinc hexacyanocobaltate DMC catalyst under nitrogen, and heated up 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. The DMC catalyst was activated by feeding a portion of 28.0 g of an equimolar mixture of propylene oxide and ethylene oxide. After 20 min and startup of the reaction (drop in internal reactor pressure), a further 74.3 g of the EO/PO mixture was metered in continuously and while cooling within 40 minutes at 130° C. and max, internal reactor pressure 0.6 bar (absolute). Continued reaction at 130° C. for 30 minutes was followed by degassing. Volatile components such as residual propylene oxide and ethylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C., and a portion of 54 g was discharged. The moderately viscous and orange-coloured, cloudy alkoxylated polybutadiene was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0246] M.sub.w=13 690 g/mol; M.sub.n=2547 g/mol; M.sub.w/M.sub.n=5.4

[0247] The amount remaining in the reactor was heated again to 130° C., and then 84.7 g of an equimolar mixture of propylene oxide and ethylene oxide was added continuously. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again and a further sample of 73.1 g of product was taken. The moderately viscous and orange-coloured, cloudy alkoxylated polybutadlene was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0248] M.sub.w=13 110 g/mol; M.sub.n=2868 g/mol; M.sub.w/M.sub.n=4.6

[0249] The amount remaining in the reactor was heated again to 130° C., and then 68.7 g of an equimolar mixture of propylene oxide and ethylene oxide was added continuously. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again and the entire reactor contents of 337.6 g were discharged. The moderately viscous and orange-coloured, cloudy alkoxylated polybutadiene was admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0250] M.sub.w=15 190 g/mol; M.sub.n=3845 g/mol; M.sub.w/M.sub.n=4.0

[0251] Alkoxylations by Means of Alkaline Catalysts:

Example C3

[0252] A 3 litre autoclave was initially charged with 196.1 g of the hydroxylated polybutadiene prepared in Example B5 and 11.1 g of 30% sodium methoxide solution (30% by weight of sodium methoxide in methanol based on total mass of the solution) under nitrogen, and the mixture was stirred at 50° C. for 1 h. Subsequently, the mixture was heated up to 115° C. while stirring and the reactor was evacuated down to an internal pressure of 30 mbar in order to distillatively remove excess methanol and other volatile ingredients present. 324 g of propylene oxide was metered in continuously and while cooling within 6 h at 115° C. and max, internal reactor pressure 3.5 bar (absolute). Continued reaction at 115° C. for 30 minutes was followed by degassing. Volatile components such as residual propylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C. A portion of 51 g was discharged, and this moderately viscous and orange-coloured, clear alkoxylated polybutadiene was neutralized with lactic acid to an acid number of 0.1 mg KOH/g, admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0253] M.sub.w=18 890 g/mol; M.sub.n=2888 g/mol; M.sub.w/M.sub.n=8.5

[0254] The amount remaining in the reactor was heated again to 115° C. and then 216 g of propylene oxide was added continuously. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again, cooled down to 95° C., neutralized with 30% H.sub.3PO.sub.4 (30% by weight of H.sub.3PO.sub.4 in water based on total mass of the solution), and admixed with 1000 ppm of Irganox® 1135. Water was removed in a vacuum distillation, and precipitated salts were filtered off. 675 g of the clear product having an acid number of 0.1 mg KOH/g was isolated, and was stored under nitrogen.

[0255] M.sub.w=22 850 g/mol; M.sub.n=3160 g/mol; M.sub.w/M.sub.n=7.2

Example C4

[0256] A 3 litre autoclave was Initially charged with 197.3 g of the hydroxylated polybutadiene prepared in Example B5 and 11.2 g of 30% sodium methoxide solution (30% by weight of sodium methoxide in methanol based on total mass of the solution) under nitrogen, and the mixture was stirred at 50° C. for 1 h. Subsequently, the mixture was heated up to 115° C. while stirring and the reactor was evacuated down to an internal pressure of 30 mbar in order to distillatively remove excess methanol and other volatile ingredients present. 82.5 g of ethylene oxide was metered in continuously and while cooling within 45 minutes at 115° C. and max. Internal reactor pressure 3.5 bar (absolute). Continued reaction at 115° C. for 30 minutes was followed by degassing. Volatile components such as residual ethylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C., and a portion of 49.7 g was discharged. The orange-coloured, clear alkoxylated polybutadiene that was solid at room temperature was neutralized with lactic acid to an acid number of 0.1 mg KOH/g, admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0257] M.sub.w=16100 g/mol; M.sub.n=2945 g/mol; M.sub.w/M.sub.n=5.5

[0258] The amount remaining in the reactor was heated again to 115° C. and then 68 g of ethylene oxide was added continuously. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again and cooled down to 95° C. A portion of 59 g was discharged, and this orange-coloured, clear alkoxylated polybutadiene that was solid at room temperature was neutralized with lactic acid to an acid number of 0.1 mg KOH/g, admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0259] M.sub.w=17 410 g/mol; M.sub.n=3413 g/mol; M.sub.w/M.sub.n=5.1

[0260] The amount remaining in the reactor was heated again to 115° C., and then 54.4 g of ethylene oxide was added continuously. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again and cooled down to 95° C. The remaining product of 280 g was discharged, and the orange-coloured, clear alkoxylated polybutadiene that was solid at room temperature was neutralized with lactic acid to an acid number of 0.1 mg KOH/g, admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0261] M.sub.w=19 000 g/mol; M.sub.n=3874 g/mol; M.sub.w/M.sub.n=4.9

Example C5

[0262] A 3 litre autoclave was initially charged with 194 g of the hydroxylated polybutadiene prepared in Example B5 and 11.0 g of 30% sodium methoxide solution (30% by weight of sodium methoxide in methanol based on total mass of the solution) under nitrogen, and the mixture was stirred at 50° C. for 1 h. Subsequently, the mixture was heated up to 115° C. while stirring and the reactor was evacuated down to an internal pressure of 30 mbar in order to distillatively remove excess methanol and other volatile ingredients present. 94.5 g or ethylene oxide and 53.4 g of propylene oxide were metered in at the same time continuously as a mixture and while cooling within 5.5 hours at 115° C. and max. Internal reactor pressure 3.5 bar (absolute). Continued reaction at 115° C. for 30 minutes was followed by degassing. Volatile components such as residual alkylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C., and a portion of 31.3 g was discharged. The orange-coloured, clear alkoxylated polybutadiene that was liquid at room temperature was neutralized with lactic acid to an acid number of 0.1 mg KOH/g, admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0263] M.sub.w=16 230 g/mol; M.sub.n=2810 g/mol; M.sub.w/M.sub.n=5.8

[0264] The amount remaining in the reactor was heated again to 115° C., and then 85.9 g of ethylene oxide and 48.5 g of propylene oxide were added continuously and simultaneously as a mixture. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again and cooled down to 95° C. A portion of 34.3 g was discharged, and this orange-coloured, clear alkoxylated polybutadiene that was liquid at room temperature was neutralized with lactic acid to an acid number of 0.1 mg KOH/g, admixed with 1000 ppm of Irganox® 1135 and stored under nitrogen.

[0265] M.sub.w=19 160 g/mol; M.sub.n=3014 g/mol; M.sub.w/M.sub.n=6.4

[0266] The amount remaining in the reactor was heated again to 115° C., and then 79.3 g of ethylene oxide and 44.9 g of propylene oxide were added continuously and simultaneously as a mixture. After completion of addition and continued reaction for 30 minutes, the mixture was degassed again, cooled down to 95° C., neutralized with 30% H.sub.3PO.sub.4, and admixed with 1000 ppm of Irganox® 1135. Water was removed in a vacuum distillation, and precipitated salts were filtered off. 522 g of the clear product having an acid number of 0.1 mg KOH/g was isolated, and was stored under nitrogen.

[0267] M.sub.w=24 030 g/mol; M.sub.n=3251 g/mol; M.sub.w/M.sub.n=7.4

Example C6

[0268] A 3 litre autoclave was initially charged with 208 g of the hydroxylated polybutadiene prepared in Example B5 and 4.6 g of solid potassium methoxide under nitrogen, and stirred at 50° C. for 1 h. Subsequently, the mixture was heated up to 115° C. while stirring and the reactor was evacuated down to an internal pressure of 30 mbar in order to distillatively remove volatile ingredients present. 115 g of propylene oxide was metered in continuously and while cooling within 2 hours at 115° C. and max. Internal reactor pressure 3.0 bar (absolute). Continued reaction at 115° C. for 30 minutes was followed by degassing. Volatile components such as residual propylene oxide were distilled off under reduced pressure. The product was cooled to below 80° C., neutralized with lactic acid to an acid number of 0.1 mg KOH/g, and admixed with 1000 ppm of Irganox® 1135. 315 g of the brown, clear alkoxylated polybutadiene that was liquid at room temperature was obtained and stored under nitrogen.

[0269] M.sub.w=14 350 g/mol; M.sub.n=2657 g/mol; M.sub.w/M.sub.n=5.4

Example C7

[0270] A 3 l autoclave was initially charged with 400 g of the hydroxylated polybutadiene prepared in Example B7 and 20.3 g of 30% sodium methoxide solution (30% by weight of sodium methoxide in methanol based on total mass of the solution) under nitrogen, and the mixture was stirred at 50° C. for 1 h. This was followed by heating to 115° C. while stirring and evacuation of the reactor down to an Internal pressure of 30 mbar, in order to remove excess methanol and other volatile Ingredients present by distillation. Subsequently, 488 g of propylene oxide was metered in continuously and while cooling within 6 hours at 115° C. and max, internal reactor pressure 3.5 bar (absolute). On completion of addition and after further reaction for 30 minutes, the mixture was degassed again and cooled to 95° C., neutralized with 30% H.sub.3PO.sub.4 (30% by weight of H.sub.3PO.sub.4 in water based on the total mass of the solution) and admixed with 1000 ppm of Irganox® 1135. Water was removed in a vacuum distillation, and precipitated salts were filtered off. 826 g of the reddish-brown, clear product having an acid number of 0.1 mg KOH/g was isolated, and was stored under nitrogen.

[0271] M.sub.w=14 672 g/mol; M.sub.n=2740 g/mol; M.sub.w/M.sub.n=5.4

Example C8

[0272] A 3 l autoclave was initially charged with 250 g of the hydroxylated polybutadiene prepared in Example B8 and 49.7 g of 30% sodium methoxide solution (30% by weight of sodium methoxide in methanol based on total mass of the solution) under nitrogen, and the mixture was stirred at 50° C. for 1 h. This was followed by heating to 115° C. while stirring and evacuation of the reactor down to an Internal pressure of 30 mbar, in order to remove excess methanol and other volatile ingredients present by distillation. Subsequently, 1202 g of propylene oxide was metered in continuously and while cooling within 10 hours at 115° C. and max. Internal reactor pressure 3.5 bar (absolute). On completion of addition and after further reaction for 30 minutes, the mixture was degassed again and cooled to 95° C., neutralized with 30% H.sub.3PO.sub.4 (30% by weight of H.sub.3PO.sub.4 in water based on the total mass of the solution) and admixed with 1000 ppm of Irganox® 1135. Water was removed in a vacuum distillation, and precipitated salts were filtered off. 1365 g of the clear product having an acid number of 0.1 mg KOH/g was isolated, and was stored under nitrogen.

[0273] M.sub.w=11 072 g/mol; M.sub.n=2480 g/mol; M.sub.w/M.sub.n=4.5

Example C9

[0274] A 3 l autoclave was initially charged with 150 g of the hydroxylated polybutadiene prepared in Example B9 and 20.0 g of 30% sodium methoxide solution (30% by weight of sodium methoxide in methanol based on total mass of the solution) under nitrogen, and the mixture was stirred at 50° C. for 1 h. This was followed by heating to 115° C. while stirring and evacuation of the reactor down to an Internal pressure of 30 mbar, in order to remove excess methanol and other volatile Ingredients present by distillation. Subsequently, 484 g of propylene oxide was metered in continuously and while cooling within 6 hours at 115° C. and max. Internal reactor pressure 3.5 bar (absolute). On completion of addition and after further reaction for 30 minutes, the mixture was degassed again and cooled to 95° C., neutralized with 30% H.sub.3PO.sub.4 (30% by weight of H.sub.3PO.sub.4 in water based on the total mass of the solution) and admixed with 1000 ppm of Irganox® 1135. Water was removed in a vacuum distillation, and precipitated salts were filtered off. 599 g of the clear product having an acid number of 0.1 mg KOH/g was isolated, and was stored under nitrogen.

[0275] M.sub.w=8914 g/mol; M.sub.n=2073 g/mol; M.sub.w/M.sub.n=4.3

[0276] Step e), Aftertreatment for Colour Lightening

[0277] Colour Lightening by Addition of Activated Carbon:

Example E1

[0278] In a 100 ml one-neck flask. 20 g of the alkoxylated polybutadiene prepared in Example C7 (Gardner colour number: 4.3) was admixed with 10 ml of chloroform and 1 g of activated carbon (Norit SX 1). After stirring at room temperature for 2 hours, the activated carbon was filtered off and the excess solvent was removed under reduced pressure. 19 g of the lighter-coloured alkoxylated polybutadiene was Isolated.

[0279] Gardner colour number: 2.1

[0280] Colour Lightening by Addition of Hydrogen Peroxide:

Example E2

[0281] In a 100 ml one-neck flask with reflux condenser, 20 g of the alkoxylated polybutadiene prepared in Example C7 (Gardner colour number: 4.3) was equilibrated to 80° C. and admixed with 5% by weight of 30% hydrogen peroxide solution (30% by weight of H.sub.2O.sub.2 based on the total mass of the aqueous solution). The mixture was stirred at 80° C. for 2 hours, and water and excess hydrogen peroxide were then distilled off under full vacuum. 20 g of the lighter-coloured product was isolated (Gardner colour number 1.8).