ACRYLATE-TERMINATED URETHANE POLYBUTADIENES FROM LOW-MONOMER 1:1 MONOADDUCTS FROM REACTIVE OLEFINIC COMPOUNDS AND DIISOCYANATES AND HYDROXY-TERMINATED POLYBUTADIENES FOR LIQUID OPTICALLY CLEAR ADHESIVES (LOCAs)

Abstract

The present invention relates to a process for producing hydrosilylatable, eugenol-based polyethers, to the conversion thereof into polyether siloxanes and also to the products that may be produced by this process and to the use of said products as surfactants.

Claims

1-24. (canceled)

25. A product of formula (I) ##STR00006## where a=1 to 1000, b=0 to 1000, c=0 to 1000, d=0 to 1000, e=1 to 10, f=0 to 500, with the proviso that the sum of a+b+c+d+f is not less than 3 and with the proviso that the groups with the indices a, b, c, d, and f are freely permutable over the molecule chain and neither of the groups with the indices c and d may follow itself or the respective other group and with the proviso that the different monomer units and the fragments with the indices a, b and f may be in a blockwise structure with one another, where individual blocks may also occur multiple times and may be randomly distributed among one another, or else are subject to a random distribution and further are freely permutable with one another, in the sense that they may be arranged in any desired sequence, subject to the restriction that neither of the groups with the indices c and d may follow itself or the respective other group, and where R.sup.1=independently at each occurrence a hydrogen radical or a C.sub.1-C.sub.8 alkyl group, R.sup.2=independently at each occurrence a hydrogen radical, a C.sub.1-C.sub.20 alkyl group, an aryl or alkaryl group, or R.sup.1 and one of the radicals R.sup.2 may together form a ring which includes the atoms to which R.sup.1 and R.sup.2 are bonded, R.sup.3=independently at each occurrence a saturated or unsaturated, aliphatic or aromatic, hydrocarbon radical comprising 2 to 30 carbon atoms, which is optionally further substituted, R.sup.4, R.sup.7=independently at each occurrence hydrogen and/or an organic radical, or else optionally R.sup.4 and/or R.sup.7 may be absent, where, when R.sup.4 and R.sup.7 are absent, there is a CC double bond in place of the radicals R.sup.4 and R.sup.7, the bridging fragment Z may be present or absent; when the bridging fragment Z is absent, then R.sup.5, R.sup.6=independently at each occurrence hydrogen and/or an organic radical, where, when one of the radicals R.sup.4 or R.sup.7 is absent, the respective geminal radical (i.e. R.sup.5 when R.sup.4 is absent and R.sup.6 when R.sup.7 is absent) is an alkylidene radical; when the bridging fragment Z is present, then R.sup.5, R.sup.6=hydrocarbon radicals which are bridged cycloaliphatically or aromatically via fragment Z, where Z represents a divalent alkylene or alkenylene radical which may be further substituted, R.sup.10=independently at each occurrence a hydrogen radical or a C.sub.1-C.sub.8 alkyl group or an ester group C(O)R.sup.11 or an acetoacetate group C(O)CH.sub.2C(O)R.sup.12 or a silyl ether group Si(R.sup.13).sub.3 or a urethane group C(O)N(R.sup.14).sub.2 where R.sup.11, R.sup.12, R.sup.13=independently at each occurrence a linear or branched, saturated or unsaturated, optionally further substituted C.sub.1-C.sub.30 alkyl group, an aryl or alkaryl group, and R.sup.14=independently at each occurrence hydrogen and/or a linear or branched, saturated or unsaturated, optionally further substituted C.sub.1-C.sub.30 alkyl group, an aryl or alkaryl group.

26. The product according to claim 25, wherein the product is obtained by reacting at least one epoxide with eugenol in the presence of a double metal cyanide catalyst.

27. A product of formula (II)
M.sub.gM.sub.hD.sub.iD.sub.jD.sub.mT.sub.kQ.sub.lformula (II) where M=[R.sup.15.sub.3SiO.sub.1/2] M=[R.sup.16R.sup.15.sub.2SiO.sub.1/2] D=[R.sup.15.sub.2SiO.sub.2/2] D=[R.sup.16R.sup.15SiO.sub.2/2] D=[R.sup.17R.sup.15SiO.sub.2/2] T=[R.sup.15SiO.sub.3/2] Q=[SiO.sub.4/2] g=0-20, h=0-20, i=0-1000, j=0-20, k=0-20, l=0-20, m=0-20, with the proviso that the sum of g+h+i+j+k+l+m is not less than 3 and that the sum of h+j1 and R.sup.15=independently at each occurrence identical or different C.sub.1-C.sub.16 hydrocarbon radicals, or H, R.sup.16=independently at each occurrence identical or different polyether radicals, with the proviso that at least 10% of the radicals are eugenol-based polyether radicals; R.sup.17=independently at each occurrence identical or different C.sub.1-C.sub.16 hydrocarbon radicals which also comprise heteroatoms and may be further substituted,

28. The product according to claim 27, wherein the product is obtained by reacting at least one epoxide with eugenol in the presence of a double metal cyanide catalyst.

29. The product according to claim 25, wherein in the formulae (I), the fragment with the index b is at least one member selected from the group consisting of methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, 2-pentyl glycidyl ether, 3-pentyl glycidyl ether, 2-methylbutyl glycidyl ether, 3-methylbutyl glycidyl ether, 2-methyl-2-butyl glycidyl ether, 3-methyl-2-butyl glycidyl ether, 2,2-dimethylpropyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-propylheptyl glycidyl ether, 2-butyloctanyl glycidyl ether, 2-methylundecyl glycidyl ether, 2-propylnonyl glycidyl ether, 2-ethyldecyl glycidyl ether, 2-pentylheptyl glycidyl ether, 2-hexyldecyl glycidyl ether, 2-butyltetradecyl glycidyl ether, 2-dodecylhexadecyl glycidyl ether, 2-tetradecyloctadecyl glycidyl ether, 3,5,5-trimethylhexyl glycidylether, isononanyl glycidyl ether, isotridecyl glycidyl ether, isomyristyl glycidyl ether, isostearyl glycidyl ether, 2-octyldodecyl glycidyl ether, triphenylmethyl glycidylether, C(O)(CH.sub.2).sub.5C(CH.sub.3).sub.3 glycidyl ether, C.sub.12/C.sub.14-alkyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, tert-butylphenyl glycidyl ether, benzyl glycidyl ether, 3-glycidyloxypropyl-trimethoxysilan, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropyltriisopropoxysilane, bis(3-glycidyloxypropyl)dimethoxysilane, bis(3-glycidyloxypropyl)diethoxysilane, 3-glycidyloxyhexyltrimethoxysilane, 3-glycidyloxyhexyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropylethyldiethoxysilane.

30. The product according to claim 27, wherein the eugenol-based polyether radicals correspond to general formula (III) ##STR00007## and non-eugenol-based polyethers correspond to radicals of general formula (IV), ##STR00008## and wherein, in formulae (II), (III), and (IV), the fragment with the index b is at least one member selected from the group consisting of methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, 2-pentyl glycidyl ether, 3-pentyl glycidyl ether, 2-methylbutyl glycidyl ether, 3-methylbutyl glycidyl ether, 2-methyl-2-butyl glycidyl ether, 3-methyl-2-butyl glycidyl ether, 2,2-dimethylpropyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-propylheptyl glycidyl ether, 2-butyloctanyl glycidyl ether, 2-methylundecyl glycidyl ether, 2-propylnonyl glycidyl ether, 2-ethyldecyl glycidyl ether, 2-pentylheptyl glycidyl ether, 2-hexyldecyl glycidyl ether, 2-butyltetradecyl glycidyl ether, 2-dodecylhexadecyl glycidyl ether, 2-tetradecyloctadecyl glycidyl ether, 3,5,5-trimethylhexyl glycidylether, isononanyl glycidyl ether, isotridecyl glycidyl ether, isomyristyl glycidyl ether, isostearyl glycidyl ether, 2-octyldodecyl glycidyl ether, triphenylmethyl glycidylether, C(O)(CH.sub.2).sub.5C(CH.sub.3).sub.3 glycidyl ether, C.sub.12/C.sub.14-alkyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, tert-butylphenyl glycidyl ether, benzyl glycidyl ether, 3-glycidyloxypropyl-trimethoxysilan, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropyltriisopropoxysilane, bis(3-glycidyloxypropyl)dimethoxysilane, bis(3-glycidyloxypropyl)diethoxysilane, 3-glycidyloxyhexyltrimethoxysilane, 3-glycidyloxyhexyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropylethyldiethoxysilane.

31. A method of dispersing a compound in a condensed fluid medium, the method comprising: mixing the compound and a product according to claim 25 in a condensed fluid medium.

32. A method of dispersing a compound in a condensed fluid medium, the method comprising: mixing the compound and a product according to claim 27 in a condensed fluid medium.

33. The product according to claim 25, wherein a=4 to 50, b=0 to 50, c=0 to 50, d=0 to 50, f=0 to 100, R.sup.1=independently at each occurrence a hydrogen, R.sup.2=independently at each occurrence is hydrogen, methyl, or ethyl, or R.sup.1 and one of the radicals R.sup.2 may together form a ring comprising 5 to 8 carbon atoms, R.sup.3=independently at each occurrence a saturated or unsaturated, aliphatic or aromatic, hydrocarbon radical comprising 2 to 24 carbon atoms, which is optionally further substituted, R.sup.4, R.sup.7=independently at each occurrence is selected from the group consisting of alkyl, alkenyl, alkylidene, alkoxy, aryl and aralkyl, or else optionally R.sup.4 and/or R.sup.7 may be absent, where, when R.sup.4 and R.sup.7 are absent, there is a CC double bond in place of the radicals R.sup.4 and R.sup.7, the bridging fragment Z may be present or absent; when the bridging fragment Z is absent, then R.sup.5, R.sup.6=independently at each occurrence is selected from the group consisting of alkyl, alkenyl, alkylidene, alkoxy, aryl or aralkyl, where, when one of the radicals R.sup.4 or R.sup.7 is absent, the respective geminal radical (i.e. R.sup.5 when R.sup.4 is absent and R.sup.6 when R.sup.7 is absent) is methylidene (CH.sub.2).

34. The product according to claim 27, wherein g=0-10, h=0-10, i=0-500, j=1-15, k=0-10, l=0-10, m=1-15, and R.sup.15=independently at each occurrence identical or different is selected from the group consisting of methyl, ethyl, and phenyl.

35. The product according to claim 27, wherein g=2, h=0, i=0-200, j=1-10, k=0, l=0, m=1-10, and R.sup.15=independently at each occurrence is methyl.

Description

EXAMPLE 1: SYNTHESIS OF A EUGENOL-BASED POLYETHER (INVENTIVE)

[0163] A 5 liter autoclave was initially charged with 351 g of eugenol and said eugenol was admixed with 100 ppm (based on the total batch) of a zinc hexacyanocobaltate double metal cyanide catalyst. The reactor was inertized by charging with nitrogen to a pressure of 3 bar and subsequent decompression to atmospheric pressure. This operation was repeated twice more.

[0164] While stirring, the reactor contents were heated to 100 C. and evacuated to about 20 mbar to remove volatile components. After 30 minutes, the temperature was elevated to 130 C. and 100 g of propylene oxide were metered into the evacuated reactor to activate the catalyst. The internal pressure initially rose to about 0.8 bar. The pressure began to drop slowly and had dropped to 0.1 bar after about 7 minutes. A further 50 g of PO were then metered in which caused the pressure to rise to 0.8 bar once more. After 12 minutes, the pressure had dropped to 0.1 bar and a further 50 g of PO were metered in. Once the pressure had dropped to 0 bar, slow, continuous metered addition of PO was commenced. After a total of 210 g of PO had been added, the pressure dropped suddenly to 0.9 bar which was taken to indicate true onset of the reaction. 38 g of propylene oxide were then metered in continuously over about 10 minutes. This was followed by one hour of post-reaction. A mixture of 1110 g of EO and 1290 g of PO were then metered in continuously such that the temperature remained constant. After a further half hour of post-reaction the batch was deodorized by application of pressure (P<20 mbar) to remove residues of unconverted alkylene oxide. 500 ppm of ANOX 20 AM were subsequently stirred in over 15 minutes. This afforded a colorless to yellowish product having an OH number of 40.2 mg KOH/g and an AN of 0.1 mg KOH/g. The molecular weight according to OH number was 1395 g/mol. According to GPC, M.sub.w=1394 g/mol, M.sub.n=1316 g/mol and the PDI was 1.06.

EXAMPLE 2: SYNTHESIS OF A EUGENOL-BASED POLYETHER (INVENTIVE)

[0165] A 5 liter autoclave was initially charged with 164.2 g of eugenol and said eugenol was admixed with 100 ppm (based on the total batch) of a zinc hexacyanocobaltate double metal cyanide catalyst. The reactor was inertized by charging with nitrogen to a pressure of 3 bar and subsequent decompression to atmospheric pressure. This operation was repeated twice more. While stirring, the reactor contents were heated to 100 C. and evacuated to about 20 mbar to remove volatile components. After 30 minutes, the temperature was elevated to 130 C. and 70 g of propylene oxide were metered into the evacuated reactor to activate the catalyst. The internal pressure initially rose to about 0.8 bar. The pressure began to drop slowly and had dropped to 0.4 bar after about 30 minutes. Slow, continuous addition of propylene oxide was then commenced. After addition of a further 56 g of PO the pressure rose to 0.7 bar and then dropped suddenly to 0.8 bar after addition of a total of 200 g of PO and this sudden drop was taken to indicate true onset of the reaction. 1673 g of propylene oxide were then metered in continuously such that the temperature remained constant. After a further half hour of post-reaction the batch was deodorized by application of pressure (P<20 mbar) to remove residues of unconverted alkylene oxide. 500 ppm of ANOX 20 AM were subsequently stirred in over 15 minutes. This afforded a colorless to yellowish product having an OH number of 26.8 mg KOH/g and an AN of 0.1 mg KOH/g. The molecular weight according to OH number was 2093 g/mol. According to GPC, M.sub.w=1957 g/mol, M.sub.n=1830 g/mol and the PDI was 1.07.

EXAMPLE 3: SYNTHESIS OF A EUGENOL-BASED POLYETHER (INVENTIVE)

[0166] A 5 liter autoclave was initially charged with 544 g of eugenol and said eugenol was admixed with 200 ppm (based on the total batch) of a zinc hexacyanocobaltate double metal cyanide catalyst. The reactor was inertized by charging with nitrogen to a pressure of 3 bar and subsequent decompression to atmospheric pressure. This operation was repeated twice more. While stirring, the contents of the reactor were heated to 80 C. and evacuated to about 20 mbar to remove volatile components. After 30 minutes, the temperature was elevated to 140 C. and 80 g of propylene oxide were metered into the evacuated reactor to activate the catalyst. The internal pressure initially rose to about 0.6 bar. The pressure began to drop slowly and had dropped to 0.2 bar after about 10 minutes. A further 74 g of PO were then metered in which caused the pressure to drop slowly to 0.8 bar over 60 minutes. Metered addition of a mixture of 612 g of ethylene oxide and 691 g of propylene oxide was then commenced. 110 g of the EO/PO mixture were metered in over 30 minutes causing the pressure in the reactor to rise to 0.5 bar. A further 54 g of the mixture were then added over 15 minutes. The pressure rose to 1.5 bar before dropping suddenly to 0.5 bar which was taken to indicate true onset of the reaction. The remaining alkylene oxide mixture (1139 g) was then continuously metered in over 40 minutes. After a further half hour of post-reaction the batch was deodorized by application of pressure (P<20 mbar) to remove residues of unconverted alkylene oxide. 500 ppm of ANOX 20 AM were subsequently stirred in over 15 minutes. This afforded a colorless to yellowish product having an OH number of 81.8 mg KOH/g and an AN of 0.1 mg KOH/g. The molecular weight according to OH number was 685 g/mol. According to GPC, M.sub.w=640 g/mol, M.sub.n=583 g/mol and the PDI was 1.10.

EXAMPLE 4: SYNTHESIS OF A EUGENOL-BASED POLYETHER (INVENTIVE)

[0167] A 5 liter autoclave was initially charged with 503 g of eugenol and said eugenol was admixed with 100 ppm (based on the total batch) of a zinc hexacyanocobaltate double metal cyanide catalyst. The reactor was inertized by charging with nitrogen to a pressure of 3 bar and subsequent decompression to atmospheric pressure. This operation was repeated twice more. While stirring, the contents of the reactor ware heated to 120 C. and evacuated to about 20 mbar to remove volatile components. After 30 minutes, the temperature was elevated to 130 C. and 70 g of propylene oxide were metered into the evacuated reactor to activate the catalyst. The internal pressure initially rose to about 0.5 bar. The pressure began to drop slowly and had dropped to 0.9 bar after about 20 minutes. 196 g of PO were then slowly metered in over a period of 40 minutes which caused the pressure to rise to 0.5 bar After thirty minutes of postreaction the pressure dropped to 0.4 bar and metered addition of a mixture of 1078 g of EO and 1154 g of PO was commenced. 60 g of the EO/PO mixture were metered in over 30 minutes which caused the pressure in the reactor to initially rise to a slight positive pressure and then drop suddenly to 0.9 bar which was taken to indicate true onset of the reaction. The remaining alkylene oxide mixture (2172 g) was then continuously metered in over 75 minutes. After a further half hour of post-reaction the batch was deodorized by application of pressure (P<20 mbar) to remove residues of unconverted alkylene oxide. 500 ppm of ANOX 20 AM were subsequently stirred in over 15 minutes. This afforded a colorless to yellowish product having an OH number of 51.6 mg KOH/g and an AN of 0.1 mg KOH/g. The molecular weight according to OH number was 1087 g/mol. According to GPC, M.sub.w=1012 g/mol, M.sub.n=945 g/mol and the PDI was 1.07.

EXAMPLE 5: ACETYLATION OF A EUGENOL-BASED POLYETHER FROM EXAMPLE 1 (INVENTIVE)

[0168] Under protective gas, a 2 liter three-necked flask fitted with a dropping funnel and a reflux cooler was initially charged with the eugenol-based polyether from Example 1 and a catalytic amount of concentrated hydrochloric acid and the resulting mixture was heated. Acetic anhydride was then added slowly. Once addition was complete the mixture was stirred for a further 4 h. Any residual acid was then distilled off to afford a colorless to yellowish product having an OH number of 0.1 mg KOH/g and an AN of 0.1 mg KOH/g. Within the bounds of analytical measurement inaccuracies of two independent measurements the OH number suggests that quantitative acetylation of the terminal OH groups of the poly ether has been achieved. Within the bounds of measurement inaccuracies the GPC remained unchanged compared to the polyether from Example 1. According to GPC, M.sub.w=1424 g/mol, M.sub.n=1316 g/mol and the PDI was 1.08.

EXAMPLE 6: SYNTHESIS OF A 2-NAPHTHOL-BASED POLYETHER (COMPARATIVE EXAMPLE)

[0169] The reaction was performed analogously to Example 2. 144.1 g of 2-naphthol and 200 ppm (based on the total batch) of a zinc hexacyanocobaltate double metal cyanide catalyst were initially charged and 1856 g of PO were added on. Portion-wise addition of 215 g of PO was necessary prior to onset of the reaction. This caused the pressure to rise to a maximum of 2 bar before it dropped to 0.9 bar over 12 minutes after addition of the final portion of PO. The remaining propylene oxide was metered in over 75 minutes. This afforded a colorless to yellowish product having an OH number of 31.8 mg KOH/g and an AN of 0.2 mg KOH/g. The molecular weight according to OH number was 1764 g/mol. According to GPC, M.sub.w=1945 g/mol, M.sub.n=1730 g/mol and the PDI was 1.12.

EXAMPLE 7: SYNTHESIS OF A GUALACOL-BASED POLYETHER (COMPARATIVE EXAMPLE)

[0170] The reaction was performed analogously to Example 2. 125 g of guaiacol and 100 ppm (based on the total batch) of a zinc hexacyanocobaltate double metal cyanide catalyst were initially charged and 1894 g of PO were added on. This afforded a colorless to yellowish product having an OH number of 31.7 mg KOH/g and an AN of 0.1 mg KOH/g. The molecular weight according to OH number was 1769 g/mol. According to GPC, Mw=1936 g/mol, Mn=1667 g/mol and the PDI was 1.16.

TABLE-US-00001 TABLE 1 Summary of the analytical data from Examples 2, 6 and 7 GPC M Mw Mn I* (theory)** M*** Product [g/mol] [g/mol] PDI [%] [g/mol] [g/mol] Example 2 1957 1830 1.08 8 2038 2093 (inventive) Example 6 1945 1730 1.12 30 2000 1764 (comparative) Example 7 1936 1667 1.16 18 2000 1769 (comparative) *Proportion of high molecular weight compound determined by integration of the GPC signal; **Theoretical molecular weight according to starting weights; ***Molecular weight resulting from determined OH number.

EXAMPLE 8: PRODUCTION OF A POLYETHER SILOXANE WITH EUGENOL-BASED POLYETHER (INVENTIVE)

[0171] In a 500 mL three-necked flask with a thermometer, reflux cooler and KPG stirrer, 79.0 g of a SiH-functional siloxane of general formula [Me.sub.2SiHO.sub.1/2].sub.2[Me.sub.2SiO.sub.2/2].sub.37[MeSiHO.sub.2/2].sub.3 were admixed with 171 g of the eugenol-based polyether from Example 4. The mixture was stirred and heated to 90 C. The reaction mixture was subsequently admixed with 0.17 g of a solution of Karstedrs catalyst (CAS number 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. This afforded a yellowish, clear, monophasic liquid.

EXAMPLE 9: PRODUCTION OF A POLYETHER SILOXANE WITH EUGENOL-BASED POLYETHER (INVENTIVE)

[0172] In a 500 mL three-necked flask with a thermometer, reflux cooler and KPG stirrer, 44.3 g of a SiH-functional siloxane of general formula [Me.sub.3SiO.sub.1/2].sub.2[Me.sub.2SiO.sub.2/2].sub.13[MeSiHO.sub.2/2].sub.5 were admixed with 205.7 g of the eugenol-based polyether from Example 4. The mixture was stirred and heated to 90 C. The reaction mixture was subsequently admixed with 0.17 g of a solution of Karstedrs catalyst (CAS number 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. This afforded a yellowish, clear, monophasic liquid.

EXAMPLE 10: PRODUCTION OF A POLYETHER SILOXANE WITH EUGENOL-BASED POLYETHER AND NON-EUGENOL-BASED POLYETHER (INVENTIVE)

[0173] In a 500 mL three-necked flask with a thermometer, reflux cooler and KPG stirrer, 40.0 g of a SiH-functional siloxane of general formula [Me.sub.3SiO.sub.1/2].sub.2[Me.sub.2SiO.sub.2/2].sub.13[MeSiHO.sub.2/2].sub.5 were admixed with 94.8 g of the eugenol-based poly ether from Example 4 and 132.7 g of a polyether of general formula CH2CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.13(CH.sub.2CH(CH.sub.3)O).sub.13Me. The mixture was stirred and heated to 90 C. The reaction mixture was subsequently admixed with 0.18 g of a solution of Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. This afforded a yellowish, clear, monophasic liquid.

EXAMPLE 11: PRODUCTION OF A POLYETHER SILOXANE WITH EUGENOL-BASED POLYETHER (INVENTIVE)

[0174] In a 500 mL three-necked flask with a thermometer, reflux cooler and KPG stirrer, 112.0 g of a SiH-functional siloxane of general formula [Me.sub.2SiHO.sub.1/2].sub.2[Me2SiO.sub.2/2].sub.26 were admixed with 138.0 g of the eugenol-based polyether from Example 4. The mixture was stirred and heated to 90 C. The reaction mixture was subsequently admixed with 0.17 g of a solution of Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. This afforded a yellowish, clear, monophasic liquid.

EXAMPLE 12: PRODUCTION OF A POLYETHER SILOXANE WITH EUGENOL-BASED POLYETHER (INVENTIVE)

[0175] In a 500 mL three-necked flask with a thermometer, reflux cooler and KPG stirrer, 32.0 g of a SiH-functional siloxane of general formula [Me.sub.3SiO.sub.1/2].sub.2[MeSiHO.sub.2/2].sub.1 were admixed with 218.0 g of the eugenol-based polyether from Example 4. The mixture was stirred and heated to 90 C. The reaction mixture was subsequently admixed with 0.2 g of a solution of Karstedt's catalyst (CAS number 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for five hours. This afforded a yellowish, clear, monophasic liquid.

EXAMPLE 13: PRODUCTION OF A POLYETHER SILOXANE WITH EUGENOL-BASED POLYETHER AND NON-EUGENOL-BASED POLYETHER (INVENTIVE)

[0176] In a 500 mL three-necked flask with a thermometer, reflux cooler and KPG stirrer, 150 g of a SiH-functional siloxane of general formula [Me.sub.3SiO.sub.1/2].sub.2[Me.sub.2SiO.sub.2/2].sub.113[MeSiHO.sub.2/2].sub.5 were admixed with 45.9 g of the eugenol=based polyether from Example 4 and 55.1 g of a polyether of general formula CH2CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.13(CH.sub.2CH(CH.sub.3)O).sub.2H. The mixture was stirred and heated to 90 C. The reaction mixture was subsequently admixed with 0.15 g of a solution of Karstedt's catalyst (CAS number: 68478-92-2) in xylene (1.5% Pt). An exothermic reaction was observed. The mixture was stirred for two hours. This afforded a yellowish, slightly cloudy liquid.

EXAMPLE 14: PRODUCTION OF A POLYETHER SILOXANE WITH EUGENOL-BASED POLYETHER AND DODECENE (INVENTIVE)

[0177] 164 g of a SiR-functional siloxane of general formula Me.sub.3SiO[SiMe.sub.2O].sub.70[SiHMeO].sub.20SiMe.sub.3 were initially charged into a 1 L three-necked flask. Said siloxane was heated to 80 C. and admixed with 6 mg of Pt in the form of Karstedt's catalyst. Subsequently, 44 g of 1-dodecene were slowly added dropwise. 424 g of the polyether from Example 4 were then metered in slowly. The reaction mixture was stirred at 80 C. for a further 2 h. This afforded a clear, homogeneous alkyl- and polyether-modified siloxane.

EXAMPLE 15A: PRODUCTION OF A POLYETHER SILOXANE WITH EUGENOL-BASED POLYETHER (INVENTIVE)

[0178] A 250 mL three-necked flask with a KPG stirrer and reflux cooler was initially charged with 80 g of a siloxane of general formula Me.sub.3SiO[SiMe.sub.2O].sub.61.5[SiMeH].sub.6.5SiMe.sub.3 and 112 g of a poly ether having the general formula shown below

##STR00004##

[0179] The excess of double bonds over SiH functions was 12%. The mixture was vigorously stirred and heated to 80 C. 8 ppm of Pt were added in the form of Karstedt's catalyst. The reaction mixture was stirred for 4 hours at 80 C. This afforded a clear product. The SiH conversion was 97%.

EXAMPLE 15B: PRODUCTION OF A POLYETHER SILOXANE WITH ALLYL-BASED POLYETHER (NON-INVENTIVE)

[0180] A 250 mL three-necked flask with a KPG stirrer and reflux cooler was initially charged with 80 g of a siloxane of general formula Me.sub.3SiO[SiMe.sub.2O].sub.61.5[SiMeH].sub.6.5SiMe.sub.3 and 100 g of a poly ether having the general formula shown below

##STR00005##

[0181] The excess of double bonds over SiH functions was 12%. The mixture was vigorously stirred and heated to 80 C. 8 ppm of Pt were added in the form of Karstedt's catalyst. The reaction mixture was stirred for 4 hours at 80 C. This afforded a clear product. The SiH conversion was only 89%. The SiH conversion did not improve even after a further 2 hours of reaction time.

[0182] Comparison of Examples 15a and 15b shows that the poly ether according to the invention makes it possible to use a smaller excess of polyether to achieve high SiH conversions. This means that a smaller amount of free polyether remains in the product. A further important advantage over commonly used poly ether siloxanes is that higher conversions are achieved.

EXAMPLE 16: PERFORMANCE EVALUATION

[0183] a.) Recipe for Producing a Pigment Preparation (Pigment Paste) with a Polyether According to the Invention:

TABLE-US-00002 Feedstocks 1 2 DI water 49 49 Tego Foamex 830.sup.a) 1 1 Polyether from Example 1 (inventive) 10 Polyether used in Example 15b 10 (comparative) Heliogen blue L7101f 40 40 Total 100 100 .sup.a)Defoamer, Evonik Industries AG

[0184] b.) Production and Test Method:

[0185] The feedstocks were successively weighed into a 250 mL wide-necked flask and homogenized. 200 g of glass beads of diameter 2.5-2.8 mm were then weighed into the mixture. The mixture was dispersed for 2 hours in a DAS H[/A] 200K disperser (vent stage 1). The still-warm samples were filtered through a 400 m rapid sieve and subsequently left to stand for 24 h.

[0186] A stock lacquer based on Neocryl XK 90 was produced for determination of color properties.

TABLE-US-00003 TABLE 2 Acrylate-based wood lacquer: Millbase 1 Tego Dispers 755 w.sup.a) 7.8 2 Demin. H.sub.2O 17.9 3 Tego Foamex 830.sup.b) 0.9 4 Parmetol K 40.sup.c) 0.1 5 Aerosil 200.sup.d) 0.3 6 Kronos 2310.sup.e) 63.0 Let Down 7 Neocryl XK 90.sup.f) 103.8 8 Texanol 3.2 9 Tego Wet KL 245.sup.g) 1.0 10 Visko Plus 3000.sup.h) 2.0 10 min dispersal Total 200.0 .sup.a)Dispersant, Evonik Industries AG .sup.b)Defoamer, Evonik Industries AG .sup.c)Preservative, Schulke & Mayr .sup.d)Thixotropic agent, Evonik Industries AG .sup.e)White pigment (titanium dioxide), Kronos .sup.f)Polyacrylate dispersion, DSM .sup.g)Substrate-wetting agent, Evonik Industries AG .sup.h)Rheology additive, Evonik Industries AG

[0187] Entries 1-6 in Table 2 were weighed into a 250 mL glass bottle. 100 g of glass pearls of diameter 2.5-2.8 mm were weighed into the mixture and the mixture was dispersed in a DAS H[/A] 200K disperser at vent stage 1 for 1 hour. Entries 7-10 were then added and the mixture was dispersed for a further 10 minutes. The lacquer was filtered through a 400 m rapid sieve and left to stand for 24 h at room temperature before use.

[0188] Tinting of the White Lacquer:

[0189] 10 g of lacquer and in each case 0.2 g of paste were weighed into small Dirrmann cosmetic beakers of 60 ml in volume. The mixture was homogenized at 3000 rpm for 1 minute in a DAC 150 FVZ Speedmixer. The colored lacquer was then applied to a Leneta 2DX contrast card using a 100 m wire-wound doctor blade. After three minutes of initial drying time, a rub-out test was carried out. After 24 hours of through-drying time, L*a*b* values were measured using an X-Rite SP 62 sphere spectrophotometer using the specular gloss included setting. The delta E value of non-rubbed surface vs rubbed surface and color strength were calculated. The colorimetric values are reproduced as constituents of the CIE L*a*b* color model (DIN 6174: Farbmetrische Bestimmung von Farbmapzahlen und Farbabstanden im angeniihert gleichfiirmigen CIELAB-Farbenraum [colorimetric evaluation of color coordinates and color differences according to the approximately uniform CIELAB color space]).

[0190] What are sought are mobile white-based pigment preparations showing high color strength and a low delta E value as is obtained by the inventive polyether from Example 1.

[0191] c.) Results

TABLE-US-00004 Paste Color Properties Sample Viscosity Appearance L* a* b* E F Polyether from mobile homoegenous, 68.06 21.99 32.60 0.68 50.42 Example 1 (inventive) foam-free Polyether used in highly viscous, inhomogeneous, 86.86 10.82 11.20 27.37 6.57 Example 15b (comparative) paste-like pigment flocs