HYDROGENATED POLYETHER-MODIFIED POLYBUTADIENES AND PROCESSES FOR PREPARATION THEREOF

Abstract

A process for preparing hydrogenated polyether-modified polybutadienes includes: reacting at least one polybutadiene with at least one epoxidizing reagent to give at least one epoxy-functional polybutadiene; reacting the at least one epoxy-functional polybutadiene with at least one hydroxy-functional compound to give at least one hydroxy-functional polybutadiene; reacting the at least one hydroxy-functional polybutadiene with at least one epoxy-functional compound to give at least one polyether-modified polybutadiene; and hydrogenating the at least one polyether-modified polybutadiene to give at least one hydrogenated polyether-modified polybutadiene.

Claims

1. A process for preparing one or more hydrogenated 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); 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); and d) hydrogenating the at least one polyether-modified polybutadiene (G) to give at least one hydrogenated polyether-modified polybutadiene (H).

2. The process according to claim 1, further comprising precisely one of the two steps: cc) reacting at least one polyether-modified polybutadiene (G) without end-capped polyether radicals with at least one end-capping reagent (I) to give at least one polyether-modified polybutadiene (G) comprising end-capped polyether radicals; and dd) reacting at least one hydrogenated polyether-modified poly butadiene (H) without end-capped polyether radicals with at least one end-capping reagent (I) to give at least one hydrogenated polyether-modified polybutadiene (H) comprising end-capped polyether radicals.

3. The process according to claim 1 wherein in a)>0% to <100% of the double bonds of the at least one polybutadiene (A) are epoxidized.

4. The process according to claim 1, wherein the at least one epoxidizing reagent (B) is or comprises performic acid.

5. The process according to claim 1, wherein the at least one hydroxy-functional compound (D) is at least one selected from the group consisting of the monofunctional alcohols having 1 to 6 carbon atoms.

6. The process according to claim 1, wherein the at least one epoxy-functional compound used in c) is at least one selected a. from the group consisting of alkylene oxides, and/or b. from the group consisting of glycidyl compounds.

7. The process according to claim 1, wherein in process step d), at least 30% of the double bonds of the at least one polyether-modified polybutadiene (G) are hydrogenated.

8. The process according to claim 1, wherein step d) is carried out with hydrogen in the presence of at least one hydrogenation catalyst.

9. A hydrogenated polyether-modified polybutadiene (H), obtainable by the process according to claim 1.

10. The hydrogenated polyether-modified polybutadiene (H) according to claim 9, which comprises units selected both from the group consisting of divalent radicals (S), (T) and (U): ##STR00020## and from the group consisting of divalent radicals (V) and (W): ##STR00021## and optionally from the group consisting of divalent radicals (X), (Y) and (Z): ##STR00022## where A is in each case independently a monovalent organic radical or a hydrogen radical; B is in each case independently selected from the group consisting of radicals of the formula (4a) ##STR00023## R.sup.1 is in each case independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 16 carbon atoms R.sup.2 is a radical of the formula CH.sub.2OR.sup.3; R.sup.3 is in each case independently selected from the group consisting of monovalent hydrocarbon radicals 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 hydrogen; 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; and each permutation of the units in the radical B, the number of which is specified by the indices m, n, o, p and q, is included.

11. The hydrogenated polyether-modified polybutadiene (H) according to claim 9, wherein a sum total of all units (S), (T) and (U) divided by a sum total of all units (S), (T), (U), (V), (W), (X), (Y) and (Z) is >0%.

12. The hydrogenated polyether-modified poly butadiene (H) according to claim 9, wherein a sum total of all units (V) and (W) divided by a sum total of all units (V), (W), (X), (Y) and (Z) of the at least one polyether-modified polybutadiene (H) is at least 30%.

13. The hydrogenated polyether-modified polybutadiene (H) according to claim 9, wherein a number-average molar mass M.sub.n of the original polybutadiene moiety is from 200 g/mol to 20 000 g/mol.

14. The hydrogenated polyether-modified polybutadiene (H) according to claim 9, wherein a average molar mass of the B radical is from 100 g/mol to 20 000 g/mol.

15. The hydrogenated polyether-modified poly butadiene (H) according to claim 9, wherein a number-average molar mass M.sub.n is from 300 g/mol to 60 000 g/mol.

16. The process according to claim 3, wherein 4% to 20% of the double bonds of the at least one polybutadiene (A) are epoxidized.

17. The process according to claim 4, wherein performic acid is formed in situ from formic acid and hydrogen peroxide.

18. The process according to claim 5, wherein the at least one hydroxy-functional compound (D) is at least one selected from the group consisting of ethanol, I-propanol, isopropanol, I-butanol, 2-butanol and isobutanol.

19. The process according to claim 6, wherein the at least one epoxy-functional compound used in c) is at least one selected a. from the group consisting of ethylene oxide, propylene oxide, 1-butylene oxide, cis-2-butylene oxide, trans-2-butylene oxide, isobutylene oxide and styrene oxide, and/or b. from the group consisting of phenyl glycidyl ether, o-cresyl glycidyl ether, tert-butylphenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C.sub.12/C.sub.14 fatty alcohol glycidyl ether and C.sub.13/C.sub.15 fatty alcohol glycidyl ether.

20. The process according to claim 7, wherein at least 95% of the double bonds of the at least one polyether-modified polybutadiene (G) are hydrogenated.

Description

EXAMPLES

General Methods:

Gel Permeation Chromatography (GPC):

[0195] 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 ? 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.

Determination of the Content of the 1,4-Cis, 1,4-Trans and 1,2 Units in the Polybutadiene:

[0196] 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.

Determination of the Content of Epoxy Groups in the Epoxy-Functional Polybutadiene (C) (Epoxy Content, Degree of Epoxidation):

[0197] The content of epoxy groups was determined with the aid of .sup.13C-NMR spectroscopy. A Bruker Avance 400 NMR spectrometer was used. The samples were for this purpose dissolved in deuterochloroform. The epoxy content is defined as the proportion of epoxidized butadiene units in mol % based on the entirety of all epoxidized and non-epoxidized butadiene units present in the sample. This corresponds to the number of epoxy groups in the epoxy-functional polybutadiene (C) divided by the number of double bonds in the polybutadiene (A) used.

Determination of the Degree of Hydrogenation:

[0198] The determination of the degree of hydrogenation was carried out with the aid of .sup.1H-NMR spectroscopy. A Bruker Avance 400 NMR spectrometer was used. The samples were for this purpose dissolved in deuterochloroform.

[0199] The double bond content of the polyether-modified polybutadiene (G) (i.e. prior to hydrogenation) was first determined, and also the double bond content of the hydrogenated polyether-modified polybutadiene (H) after hydrogenation. For this purpose, the integrals of the .sup.1H-NMR spectra between 4.8 and 6.3 ppm were determined before and after hydrogenation, which are proportional to the number of double bonds in the polybutadiene (PB) before (I.sub.PB,before) and after (I.sub.PB,after) hydrogenation. For the purpose of normalization, these integrals were based in this case in relation to the integrals of the .sup.1H-NMR spectra between 2.8 and 4.2, which are proportional to the (unchanged) number of hydrogen atoms in the polyether backbone (PE), here also in each case before (IPE before) and after (IPE, after) hydrogenation. The degree of hydrogenation is then determined according to the following equation:

[00001]$\mathrm{Degree}\mathrm{of}\mathrm{hydrogenation}=1-\left[\left(I_{\mathrm{PB},\mathrm{after}}/I_{\mathrm{PE},\mathrm{after}}\right)/\left(I_{\mathrm{PB},\mathrm{before}}/I_{\mathrm{PE},\mathrm{before}}\right)\right]$$I_{\mathrm{PB},\mathrm{after}}=\mathrm{Integral}\mathrm{of}{\mathrm{the}}^{1}H-\mathrm{NMR}\mathrm{spectrum}\mathrm{between}4.8\mathrm{and}6.3\mathrm{ppm}\mathrm{after}\mathrm{hydrogenation}$$I_{\mathrm{PE},\mathrm{after}}=\mathrm{Integral}\mathrm{of}{\mathrm{the}}^{1}H-\mathrm{NMR}\mathrm{spectrum}\mathrm{between}2.8\mathrm{and}4.2\mathrm{ppm}\mathrm{after}\mathrm{hydrogenation}$$I_{\mathrm{PB},\mathrm{before}}=\mathrm{Integral}\mathrm{of}{\mathrm{the}}^{1}H-\mathrm{NMR}\mathrm{spectrum}\mathrm{between}4.8\mathrm{and}6.3\mathrm{ppm}\mathrm{before}\mathrm{hydrogenation}$$I_{\mathrm{PE},\mathrm{before}}=\mathrm{Integral}\mathrm{of}{\mathrm{the}}^{1}H-\mathrm{NMR}\mathrm{spectrum}\mathrm{between}2.8\mathrm{and}4.2\mathrm{ppm}\mathrm{before}\mathrm{hydrogenation}$

Determination of the Acid Value:

[0200] The acid value was determined by a titration method in accordance with DIN EN ISO 2114.

Determination of the Colour Lightening:

[0201] The colour lightening was determined by the change in the Gardner colour number (determined in accordance with DIN EN ISO 4630).

Synthesis Examples

Step a), Preparation of Epoxidized Polybutadienes

Example A1

[0202] 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 2.5L four-necked flask was initially charged with 800 g of Polyvest? 110 and 43.2 g of conc. formic acid in 800 g of chloroform at room temperature under a nitrogen atmosphere. Subsequently, 160 g of 30% H.sub.2O.sub.2 solution (30% by weight 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 7.5 hours. After the reaction had ended, the mixture was cooled to room temperature, the organic phase was separated off and washed four times with dist. H2O. Excess chloroform and residual water were distilled off. 755 g of the product were obtained, which was admixed with 1000 ppm of Irganox? 1135 and stored under nitrogen.

[0203] Evaluation by means of .sup.13C NMR gave an epoxidation level of about 8.3% of the double bonds.

[00002]$M_w=4817g/\mathrm{mol};M_n=1997g/\mathrm{mol};M_w/M_n=2.4$

Example A2

[0204] In accordance with the process described in Example A1, a 2L four-necked flask was initially charged with 800 g of Polyvest? 110 and 43.2 g of conc. formic acid in 800 g of chloroform, and 24 g of 30% H.sub.2O.sub.2 solution (30% by weight H.sub.2O.sub.2, based on the total mass of the aqueous solution) were added. After 8 hours at 50? C., phase separation, washing with dist. H.sub.2O and subsequent distillation, 746 g of an epoxidized polybutadiene having an epoxidation level of ca. 8.6% of the double bonds by .sup.13C-NMR analysis were achieved.

[00003]$M_w=4444g/\mathrm{mol};M_n=1940g/\mathrm{mol};M_w/M_n=2.3$

Example A3

[0205] In accordance with the process described in Example A1, a 5L four-necked flask was initially charged with 1500 g of Polyvest? 110 and 81 g of conc. formic acid in 1500 g of chloroform, and 300 g of 30% H.sub.2O.sub.2 solution (30% by weight H.sub.2O.sub.2, based on the total mass of the aqueous solution) were added. After 6.5 hours at 50? C., phase separation, washing with dist. H.sub.2O and subsequent distillation, 1453 g of an epoxidized polybutadiene having an epoxidation level of ca. 7.6% of the double bonds by .sup.13C-NMR analysis were achieved.

[00004]$M_w=4698g/\mathrm{mol};M_n=1982g/\mathrm{mol};M_w/M_n=2.4$

Example A4

[0206] In accordance with the process described in Example A1, a 5L four-necked flask was initially charged with 1500 g of Polyvest? 110 and 81 g of conc. formic acid in 1500 g of chloroform, and 300 g of 30% H.sub.2O.sub.2 solution (30% by weight H.sub.2O.sub.2, based on the total mass of the aqueous solution) were added. After 6.5 hours at 50? C., phase separation, washing with dist. H.sub.2O and subsequent distillation, 1462 g of an epoxidized polybutadiene having an epoxidation level of ca. 8.3% of the double bonds by .sup.13C-NMR analysis were achieved.

[00005]$M_w=4464g/\mathrm{mol};M_n=1898g/\mathrm{mol};M_w/M_n=2.4$

Step b), Preparation of OH-Functional Polybutadienes

Example B1

[0207] A hydroxylated polybutadiene having a degree of hydroxylation of ca. 8.3% was prepared using the epoxidized polybutadiene prepared in Example A1. The degree of hydroxylation 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 four-necked flask was initially charged with 750 g of the epoxidized polybutadiene in 750 g of isobutanol under a nitrogen atmosphere, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution, i.e. 1% by weight trifluoromethanesulfonic acid based on the total mass of the solution) were added while stirring. This was followed by heating to 70? C. and stirring of the mixture at this temperature for 5 hours. The reaction mixture became clear during the reaction. After the reaction had ended, the mixture was cooled to room temperature and the solution was neutralized by adding 33.5 mg of solid NaHCO.sub.3 and then filtered. The excess alcohol was distilled off under reduced pressure. The alcohol recovered by distillation and optionally dried may be reused in subsequent syntheses, 785 g of a brownish product were obtained, which was admixed with 1000 ppm of Irganox? 1135 and stored under nitrogen.

[0208] Evaluation by means of .sup.13C-NMR showed complete conversion of all epoxy groups, which gives a degree of hydroxylation of ca. 8.3%.

[00006]$M_w=9201g/\mathrm{mol};M_n=2426g/\mathrm{mol};M_w/M_n=3.8$

Example B2

[0209] For preparation of a hydroxylated polybutadiene having a degree of hydroxylation of ca. 8.6%, by the process described in Example B1, 725 g of the epoxidized polybutadiene prepared in example A2 were initially charged in 725 g of isobutanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) were added while stirring. After stirring at 70? C. for 4.5 hours, the reaction mixture was neutralized at room temperature (RT) with 33.5 mg of solid NaHCO.sub.3, filtered, and the excess alcohol was distilled off under reduced pressure, 749 g of a brownish product were obtained, which was admixed with 1000 ppm of Irganox? 1135 and stored under nitrogen.

[0210] Evaluation by means of .sup.13C-NMR showed complete conversion of all epoxy groups, which gives a degree of hydroxylation of ca. 8.6%.

[00007]$M_w=10305g/\mathrm{mol};M_n=2483g/\mathrm{mol};M_w/M_n=4.2$

Example B3

[0211] For preparation of a hydroxylated polybutadiene having a degree of hydroxylation of ca. 7.6%, by the process described in Example B1, 1400 g of the epoxidized polybutadiene prepared in example A3 were initially charged in 1400 g of isobutanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) were added while stirring. After stirring at 70? C. for 7 hours, the reaction mixture was neutralized at RT with 62.7 mg of solid NaHCO.sub.3, filtered, and the excess alcohol was distilled off under reduced pressure, 1455.6 g of a brownish product were obtained, which was admixed with 1000 ppm of Irganox? 1135 and stored under nitrogen.

[0212] Evaluation by means of .sup.13C-NMR showed complete conversion of all epoxy groups, which gives a degree of hydroxylation of ca. 7.6%.

[00008]$M_w=7441g/\mathrm{mol};M_n=2231g/\mathrm{mol};M_w/M_n=3.3$

Example B4

[0213] For preparation of a hydroxylated polybutadiene having a degree of hydroxylation of ca. 8.3%, by the process described in Example B1, 1350 g of the epoxidized polybutadiene prepared in example A4 were initially charged in 1350 g of isobutanol, and 80 ppmw of trifluoromethanesulfonic acid (based on mass of epoxidized polybutadiene) dissolved in isobutanol (1% solution) were added while stirring. After stirring at 70? C. for 7 hours, the reaction mixture was neutralized at RT with 60.5 mg of solid NaHCO.sub.3, filtered, and the excess alcohol was distilled off under reduced pressure, 1342.1 g of a brownish product were 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 degree of hydroxylation of ca. 8.3%.

[00009]$M_w=8277g/\mathrm{mol};M_n=2340g/\mathrm{mol};M_w/M_n=3.5$

Step c), Alkoxylation of OH-Functional Polybutadienes

Example C1

[0215] A 3 litre autoclave was initially charged with 253 g of the hydroxylated polybutadiene prepared in Example B1 and 7.2 g of 30% sodium methoxide solution (30% by weight 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. A mixture of 106 g of ethylene oxide and 696 g of propylene oxide were metered in and with cooling over 17 hours at 115? C. and max, internal reactor pressure 3.5 bar (absolute). The mixture was allowed to react at 115? C. for a further 2 hours and was then degassed. Volatiles such as residual ethylene oxide and propylene oxide were distilled off under reduced pressure. The product was cooled to 95? C., neutralized with 30% H.sub.3PO.sub.4 to an acid number of 0.1 mg KOH/g, and admixed with 1000 ppm of Irganox? 1135. Water was removed by distillation under reduced pressure and precipitated salts were filtered off. 980 g of the medium-viscous and orange coloured, clear alkoxylated polybutadiene were isolated and stored under nitrogen.

[00010]$M_w=13388g/\mathrm{mol};M_n=3321g/\mathrm{mol};M_w/M_n=5.1$

Example C2

[0216] A 3 litre autoclave was initially charged with 455 g of the hydroxylated polybutadiene prepared in Example B2 and 25.9 g of 30% sodium methoxide solution (30% by weight 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, 752 g of propylene oxide were then metered in continuously and with cooling over 12 h at 115? C. and max, internal reactor pressure 3.5 bar (absolute). The mixture was allowed to react at 115? C. for a further 3.5 hours and was then degassed. Volatiles such as residual propylene oxide were distilled off under reduced pressure. The product was cooled to 95? C., neutralized with 30% H.sub.3PO.sub.4 to an acid number of 0.1 mg KOH/g, and admixed with 1000 ppm of Irganox? 1135. Water was removed by distillation under reduced pressure and precipitated salts were filtered off. 1134 g of the medium-viscous and orange coloured, clear alkoxylated polybutadiene were isolated and stored under nitrogen.

[00011]$M_w=15903g/\mathrm{mol};M_n=2672g/\mathrm{mol};M_w/M_n=6.$

Example C3

[0217] A 3 litre autoclave was initially charged with 710 g of the hydroxylated polybutadiene prepared in Example B3 and 32.3 g of 30% sodium methoxide solution (30% by weight 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, 1559 g of propylene oxide were then metered in continuously and with cooling over 10.5 h at 115? C. and max, internal reactor pressure 3.5 bar (absolute). The mixture was allowed to react at 115? C. for a further 5 hours and was then degassed. Volatiles such as residual propylene oxide were distilled off under reduced pressure. The product was cooled to 95? C., and a portion of 1397 g was discharged. This was neutralized with 30% H.sub.3PO.sub.4 to an acid number of 0.1 mg KOH/g and admixed with 1000 ppm of Irganox? 1135. Water was removed by distillation under reduced pressure and precipitated salts were filtered off. 1175 g of the medium-viscous and orange coloured, clear alkoxylated polybutadiene were isolated and stored under nitrogen.

[00012]$M_w=18236g/\mathrm{mol};M_n=3037g/\mathrm{mol};M_w/M_n=6.$

Example C4

[0218] The amount of 882 g of the still alkaline, alkoxylated polybutadiene remaining in the reactor in Example C3 were again heated to 115? C. and a further 606 g of propylene oxide were added continuously over 7 hours. The mixture was allowed to react at 115? C. for a further 2 hours and was then degassed. Volatiles such as residual propylene oxide were distilled off under reduced pressure. The product was cooled to 95? C., neutralized with 30% H.sub.3PO.sub.4 to an acid number of 0.1 mg KOH/g, and admixed with 1000 ppm of Irganox? 1135. Water was removed by distillation under reduced pressure and precipitated salts were filtered off, 1407 g of the medium-viscous and orange coloured, clear alkoxylated polybutadiene were isolated and stored under nitrogen.

[00013]$M_w=19573g/\mathrm{mol};M_n=2968g/\mathrm{mol};M_w/M_n=6.6$

Example C5

[0219] A 3 litre autoclave was initially charged with 415 g of the hydroxylated polybutadiene prepared in Example B4 and 20.2 g of 30% sodium methoxide solution (30% by weight 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, 974 g of propylene oxide were then metered in continuously and with cooling over 11 h at 115? C. and max, internal reactor pressure 3.5 bar (absolute). The mixture was allowed to react at 115? C. for a further hour and was then degassed. Volatiles such as residual propylene oxide were distilled off under reduced pressure. The product was cooled to 95? C., neutralized with 30% H.sub.3PO.sub.4 to an acid number of 0.1 mg KOH/g, and admixed with 1000 ppm of Irganox? 1135. Water was removed by distillation under reduced pressure and precipitated salts were filtered off. 1472 g of the medium-viscous and orange coloured, clear alkoxylated polybutadiene were isolated and stored under nitrogen.

[00014]$M_w=20130g/\mathrm{mol};M_n=2928g/\mathrm{mol};M_w/M_n=6.9$

Step d), Hydrogenation of the Polyether-Modified Polybutadienes

Example D1

[0220] A 250 ml four-necked flask was initially charged with 120 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C1 and 0.006 g of citric acid and 1.2 g of water under argon. Then, 6.0 g of Raney nickel (aluminium/nickel 50/50) and 1.2 g of palladium catalyst Pd-cat/C (5% Pd on activated carbon, 50% water content) were added. After heating to 120? C., 0.15 lpm (lpm=litres per minute) of hydrogen is introduced under a strong stream of argon and with stirring for 12 hours. The solid product when cooled is diluted with 100 g each of ethanol/xylene and hot-filtered after addition of 2.4 g of Harbolite 800 filter aid (from Alfa Aeser GmbH & Co KG). Gel remains on the filter disc. The filtered liquid phase is filtered again through a finer filter and distilled under reduced pressure. This gives 98 g of a brown-black cloudy product which is solid when cooled. The degree of hydrogenation is 99.7%.

[00015]$M_w=20250g/\mathrm{mol};M_n=3156g/\mathrm{mol};M_w/M_n=6.42$

Example D2

[0221] A 500 ml four-necked flask was initially charged with 143 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C2 with 143 g of butyl acetate and 0.0071 g of citric acid and 1.43 g of water under argon. Then, 1.43 g palladium catalyst Pd-cat/C (5% Pd on activated carbon, 50% water content) were added. After heating to 120? C., 0.15 lpm of hydrogen is introduced under a strong stream of argon and with stirring for 14 hours. The solid product when cooled is diluted with 100 g of butyl acetate and hot-filtered after addition of 1.5 g of Harbolite 800 filter aid. After distillation under reduced pressure, a brown-black cloudy product is obtained which is solid when cooled. The degree of hydrogenation is 93.6%.

[00016]$M_w=16327g/\mathrm{mol};M_n=2394g/\mathrm{mol};M_w/M_n=6.82$

Example D3

[0222] A 500 ml four-necked flask was initially charged with 250 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C3 and 250 g of butyl acetate under argon. Then, 12.5 g of Raney nickel (aluminium/nickel 50/50) and 2.5 g of palladium catalyst Pd-cat/C (5% Pd on activated carbon, 50% water content) were added. After heating to 120? C., 0.10 lpm of hydrogen is introduced under a strong stream of argon and with stirring for 20 hours. The product is diluted again with 50 g of butyl acetate and hot-filtered after addition of 7.5 g of Harbolite 800 filter aid. After distillation under reduced pressure, a brown-black product is obtained which is solid when cooled. The degree of hydrogenation is 98.6%.

[00017]$M_w=17567g/\mathrm{mol};M_n=2690g/\mathrm{mol};M_w/M_n=6.53$

Example D4

[0223] A 500 ml four-necked flask was initially charged with 125 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C3 and 125 g of butyl acetate under argon. Then, 1.25 g palladium catalyst Pd-cat/C (5% Pd on activated carbon, 50% water content) were added. After heating to 120? C., 0.05-0.10 lpm of hydrogen is introduced under a strong stream of argon and with stirring for 19 hours. The product is diluted again with 50 g of xylene and hot-filtered after addition of 3.75 g of Harbolite 800 filter aid. After distillation under reduced pressure, 111 g of a brown-black cloudy product is obtained which is solid when cooled. The degree of hydrogenation is 97.5%.

[00018]$M_w=17504g/\mathrm{mol};M_n=2720g/\mathrm{mol};M_w/M_n=6.44$

Example D5

[0224] A 500 ml four-necked flask was initially charged with 125 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C3 with 125 g of xylene under argon. Then, 1.25 g palladium catalyst Pd-cat/C (5% Pd on activated carbon, 50% water content) were added. After heating to 120? C., 0.05-0.10 lpm of hydrogen is introduced under a strong stream of argon and with stirring for 28 hours. The product is diluted again with 50 g of xylene and hot-filtered after addition of 3.75 g of Harbolite 800 filter aid. After distillation under reduced pressure, 112 g of a brown-black product is obtained which is solid when cooled. The degree of hydrogenation is 91.2%.

[00019]$M_w=19011g/\mathrm{mol};M_n=2921g/\mathrm{mol};M_w/M_n=6.51$

Example D6

[0225] A 500 ml four-necked flask was initially charged with 92.2 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C3 and 276.6 g of butyl acetate under argon. Then, 0.92 g palladium catalyst Pd-cat/C (5% Pd on activated carbon, 50% water content) were added. After heating to 120? C., 0.05-0.10 lpm of hydrogen is introduced under a strong stream of argon and with stirring for 22 hours. The mixture was hot-filtered after addition of 2.8 g of Harbolite 800 filter aid. After distillation under reduced pressure, 82 g of a brown-black product is obtained which is solid when cooled. The degree of hydrogenation is 98.5%.

[00020]$M_w=16574g/\mathrm{mol};M_n=2637g/\mathrm{mol};M_w/M_n=6.29$

Example D7

[0226] A 350 ml pressure reactor was initially charged with 125 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C4 and 125 g of butyl acetate under argon. Then, 6.25 g of Raney nickel (aluminium/nickel 50/50) and 1.25 g of palladium catalyst Pd-cat/C (5% Pd on activated carbon, 50% water content) were added. After inertized heating to 140? C. and, while stirring, 5-8 bar hydrogen pressure is applied discontinuously for 40 hours. When hydrogen uptake is complete, a sample is filtered and distilled. This gives a brown-black product which is solid when cooled. The degree of hydrogenation is 47.4%.

[00021]$M_w=20107g/\mathrm{mol};M_n=3197g/\mathrm{mol};M_w/M_n=6.29$

Example D8

[0227] A 2000 ml four-necked flask was initially charged with 493 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C4 and 493 g of butyl acetate under argon. Then, 24.66 g of Raney nickel (aluminium/nickel 50/50) and 4.93 g of palladium catalyst Pd-cat/C (5% Pd on activated carbon, 50% water content) were added. After heating to 120? C., 0.10-0.15 lpm of hydrogen is introduced under a strong stream of argon and with stirring for 30 hours. The product is diluted again with 197 g of xylene and hot-filtered after addition of 14.8 g of Harbolite 800 filter aid. After distillation under reduced pressure, 458 g of a brown-black product is obtained which is solid when cooled. The degree of hydrogenation is 92.3%.

[00022]$M_w=17933g/\mathrm{mol};M_n=2687g/\mathrm{mol};M_w/M_n=6.67$

Example D9

[0228] A 500 ml four-necked flask was initially charged with 50 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C5 together with 150 g of xylene and 1.5 g of rhodium-100 (Wilkinson's catalyst) were added with stirring. After heating to 120? C., 0.025-0.05 lpm (lpm=litres per minute) of hydrogen is introduced under a strong stream of argon and with stirring for 10 hours. The mixture is hot-filtered after addition of 1.5 g of Harbolite 800 filter aid. The filtered liquid phase is distilled under reduced pressure. This gives 46 g of a brown-black cloudy product which is solid when cooled. The degree of hydrogenation is 97.8%.

[00023]$M_w=17225g/\mathrm{mol};M_n=2754g/\mathrm{mol};M_w/M_n=6.25$

Example D10

[0229] A 500 ml four-necked flask was initially charged with 50 g of the alkoxylated, hydroxylated polybutadiene prepared in Example C5 together with 150 g of xylene and 2.5 g of ruthenium on activated carbon (H105 XBA type) was added with stirring. After heating to 120? C., 0.025-0.05 lpm (lpm=litres per minute) of hydrogen is introduced under a strong stream of argon and with stirring for 27 hours. The mixture is hot-filtered after addition of 1.5 g of Harbolite 800 filter aid. The filtered liquid phase is distilled under reduced pressure. This gives 41 g of a brown-black cloudy product which is viscous when cooled. The degree of hydrogenation is 42.0%.

[00024]$M_w=16630g/\mathrm{mol};M_n=2988g/\mathrm{mol};M_w/M_n=5.55$