Alkoxysilyl-containing adhesive sealants with intrinsically reduced viscosity

Abstract

The present invention provides specific alkoxylation products, a process for preparing them, compositions comprising these alkoxylation products, and their use.

Claims

1. A composition comprising alkoxylation product mixtures with intrinsically reduced viscosity, obtained by alkoxylation of epoxy-functional compounds in the presence of at least two different OH-functional starters, a starter (1) and a starter (2), wherein the starter (1) has a molar mass of greater than 400 g/mol and the starter (2) has a molar mass of less than or equal to 400 g/mol, wherein the epoxy functional compounds comprise an epoxide carrying an alkoxysilyl group, an alkoxysilylalkyl glycidyl ether group, or both.

2. The composition according to claim 1, wherein the molar mass of the starter (1) exceeds the molar mass of the starter (2) by at least 200 g/mol.

3. The composition according to claim 1, wherein the molar mass of the starter (1) exceeds the molar mass of the starter (2) by at least 600 g/mol.

4. The composition according to claim 1, wherein the starter (1) has t OH groups and the starter (2) has t1 OH groups, wherein t=2 to 8.

5. The composition according to claim 1, wherein the alkoxylation products (1) from the starter (1) are obtained from alkylene oxide, from at least one epoxide carrying alkoxysilyl groups, and optionally from further monomers, and the alkoxylation products (2) from the starter (2) are obtained from alkylene oxide and optionally from at least one epoxide carrying alkoxylsilyl groups, from further monomers, or both.

6. The composition according to claim 5, wherein the starter 1 is polypropylene glycol, the starter 2 is selected from the group consisting of 1-butanol, 2-propyl-1-heptanol, 2-ethyl-1-hexanol, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, the alkylene oxide is propylene oxide, and the epoxide carrying alkoxysilyl is (3-glycidyloxypropyl)triethoxysilane, and wherein the composition has an intrinsic viscosity of less than 10 Pa.Math.s at 25 C.

7. The composition according to claim 1, wherein the alkoxylation products (1) from the starter (1) are obtained from ethylene oxide, propylene oxide, or both, from at least one alkoxysilylalkyl glycidyl ether and optionally from further monomers, and the alkoxylation products (2) from the starter (2) are obtained from ethylene oxide, propylene oxide, or both, and from at least one alkoxysilylalkyl glycidyl ether, from further monomers or both.

8. The composition according to claim 1, wherein the alkoxylation products (1) are obtained from the following monomer fractions, comprising: 10 to 97 wt % of propylene oxide, 0 to 60 wt % of ethylene oxide, 0 to 25 wt % of alkoxysilylalkyl glycidyl ethers and 0 to 25 wt % of further monomers, based on the total weight of the alkoxylation products (1); and the alkoxylation products (2) are obtained from the following monomer fractions, comprising: 10 to 97 wt % of propylene oxide, 0 to 60 wt % of ethylene oxide, 0 to 25 wt % of alkoxysiylalkyl glycidyl ethers and 0 to 25 wt % of further monomers, based on the total weight of the alkoxylation products (2).

9. The composition according to claim 8, wherein the alkoxylation products (1), the alkoxylation products (2) or both are obtained from monomer fractions comprising 0.1 to 25 wt % of alkoxysilylalkyl glycidyl ethers based on the total weight of the alkoxylation products.

10. The composition according to claim 1, wherein the starter (1) is selected from the group consisting of polyetherols, polycarbonate polyols, polyethercarbonates, and mixtures thereof.

11. The composition according to claim 1, wherein the starter (2) is selected from the group consisting of butanol, ethanol, ethylhexanol, and mixtures thereof.

12. The composition according to claim 1, wherein the composition comprises at least an alkoxylation product (1) and an alkoxylation product (2), wherein the alkoxylation product (1) obtained by the starter (1) conforms to formula (I) and the alkoxylation product (2) obtained by the starter (2) conforms to formula (IIa):
M.sub.iD.sub.jT.sub.kQ.sub.lUR.sub.uAP.sub.vformula (I) wherein fragments M, D, T, and Q are linked not to one another but instead with one another via the groups UR, AP, or both and the groups UR and AP are not linked to one another but are linked with one another via fragments M, D, T, or Q, wherein i=0 to 16, j=0 to 10, k=0 to 6, l=0 to 4, u=0 to 17, and v=0 to 6, with the proviso that i+j+k+1 is greater than or equal to 1, M independently at each occurrence is an oxygen-radical carrying hydrocarbon radical having a minimum numerical molar mass of 32 g/mol, which may optionally be interrupted by heteroatoms, Or is a radical of the formula (Ia) or of the formula (Ib) or of the formula (Ic) with ##STR00010## wherein a=0 to 100, b=1 to 1000, c=0 to 200, d=0 to 200, m is an integer from 0 to 200, n is an integer from 0 to 500, e=1 to 10, f=0 to 2 g=1 to 3 with the proviso that g+f=3 and g is at least 1, and h=0 to 10 with the proviso that the various monomer units of the fragments with the indices a, b, c, d, w, and y may be constructed blockwise among one another or else are subject to a statistical distribution and are freely permutable among one another, it being disallowed for each of the groups with the indices w and y to follow itself or the other respective group, and wherein R.sup.1=independently at each occurrence a saturated or unsaturated, linear or branched organic hydrocarbon radical which may contain at least one of O, S and N as heteroatoms, R.sup.2=independently at each occurrence an alkyl group having 1 to 8 carbon atoms, R.sup.3=independently at each occurrence an alkyl group having 1 to 8 carbon atoms, R.sup.4=independently at each occurrence a hydrogen radical, an alkyl group having 1 to 20 carbon atoms, or an aryl or alkaryl group, or R.sup.4 and one of the radicals R.sup.5 may together form a ring which includes the atoms to which R.sup.4 and R.sup.5 are bonded, R.sup.5=independently at each occurrence a hydrogen radical or an alkyl group having 1 to 8 carbon atoms, R.sup.6, R.sup.7=independently at each occurrence a hydrogen radical, an alkyl group having 1 to 20 carbon atoms, or at least one of an aryl or alkaryl group, and an alkoxy group, R.sup.11=independently at each occurrence a saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 2 to 30 C atoms, which is optionally substituted, R.sup.13, R.sup.14=independently at each occurrence hydrogen, an organic radical, or both, or else optionally R.sup.13, R.sup.14, or both may be absent, and, if R.sup.13 and R.sup.14 are absent, there is a CC double bond in place of the radicals R.sup.13 and R.sup.14, the bridging fragment Z may be present or absent; if the bridging fragment Z is absent, then R.sup.15, R.sup.16=independently at each occurrence hydrogen, and/or an organic radical, or both, and, if one of the radicals R.sup.13 or R.sup.14 is absent, the respective germinal radical, R.sup.15 if R.sup.13 is absent and R.sup.16 if R.sup.14 is absent, is an alkylidene radical, if the bridging fragment Z is present, then R.sup.15 and R.sup.16=hydrocarbon radicals which are bridged cycloaliphatically or aromatically via the fragment Z, Z representing a divalent alkylene or alkenylene radical which may be further substituted, ##STR00011## wherein R.sup.17=independently at each occurrence a linear or branched, saturated or unsaturated, optionally further-substituted alkyl group having 1 to 30 carbon atoms, or an aryl or alkaryl group, ##STR00012## wherein R.sup.18=independently at each occurrence a divalent linear or cyclic, saturated or unsaturated alkyl or aryl group, which may be substituted, and wherein, for the fragments D, T and Q: D is a polyether radical -(D.sup.A).sub.tD.sup.X where t is 2, T is a polyether radical -(D.sup.A).sub.tD.sup.X where t is 3, and Q is a polyether radical -(D.sup.A).sub.tD.sup.X where t is 4, wherein D.sup.X is a t-valent functional, saturated or unsaturated, linear or branched organic hydrocarbon radical, which may contain at least one of O, S, Si and N as heteroatoms, with each of the radicals D.sup.A being covalently bonded to the radical D.sup.X, and wherein D.sup.A is a fragment of formula (II) ##STR00013## wherein a to h, w, x and y and R.sup.2 to R.sup.16 independently at each occurrence are defined as in formula (Ia), with the proviso that the sum of all the indices a from formula (Ia) and formula (II) must be greater than or equal to 1, UR independently at each occurrence are identical or different divalent radicals of the formula U-D.sup.C-U, or a monovalent radical of the form D.sup.D-U, or a trivalent radical of the form D.sup.EU.sub.3, or a tetravalent radical of the form D.sup.FU.sub.4, wherein U is a C(O)NH group which is bonded via the nitrogen to D.sup.C, D.sup.E, D.sup.F, or D.sup.D, and D.sup.C independently at each occurrence is a divalent substituted or unsubstituted, linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, selected from alkyl, alkenyl, aryl or alkaryl radicals, which may optionally be interrupted by at least one of O, N, and S as heteroatoms, and D.sup.D independently at each occurrence is a monovalent linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, selected from alkyl, alkenyl, aryl or alkaryl radicals, which may be interrupted by at least one of O, N, and S as heteroatoms, may carry further functional groups, or both, and D.sup.E independently at each occurrence is a trivalent substituted or unsubstituted, linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, selected from alkyl, alkenyl, aryl or alkaryl radicals, which may be interrupted by at least one of O, N, and S as heteroatoms, may carry further functional groups, or both, and D.sup.F independently at each occurrence is a tetravalent substituted or unsubstituted, linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, selected from alkyl, alkenyl, aryl or alkaryl radicals, which may be interrupted by at least one of O, N, and S as heteroatoms, may carry further functional groups, or both, and AP independently at each occurrence are identical or different radicals of the general formula (IIIa), (IIIb) or (IIIc) ##STR00014## or if polyisocyanates with the structural units D.sup.E, D.sup.F, or both are used, additionally structural elements analogous to formula (IIIa), formula (IIIb), or both where the three urethane units bonded to D.sup.E, the four urethane units bonded to D.sup.F, or both independently at each occurrence, have all or in part been further reacted to give allophanate structural units in the formulae (IIIa) and (IIIb), and with the alkoxylation product (2) of the formula (IIa) ##STR00015## wherein a=1 to 100, b=1 to 200, c=0 to 100, d=0 to 100, w=0 to 100, y=0 to 50, e=1 to 10, f=0 to 2 g=1 to 3 with the proviso that the groups with the indices a, b, c, d and y are freely permutable over the molecule chain, it being disallowed for each of the groups having the index y to follow themselves, and with the proviso that the different monomer units and the fragments with the indices, a, b, c, d and y may be constructed blockwise among one another, in which case individual blocks may also occur multiply and may be distributed statistically among one another, or else are subject to a statistical distribution and are freely permutable among one another being for arrangement in any desired sequence, subject to the restriction that each of the groups with the indices w and y is not allowed to follow itself or the other respective group, and with the radicals R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.11, R.sup.13, R.sup.14, R.sup.15 and R.sup.16being as defined in formula (Ia), and wherein R.sup.27=independently at each occurrence a saturated or unsaturated, linear or branched organic hydrocarbon radical which may contain at least one of O, S and N as heteroatoms; R.sup.28=independently at each occurrence hydrogen or a fragment, bonded via UR or AP, of the formulae (II) or (IIa).

13. A process for preparing a composition according to claim 12, the process comprising: reacting at least one starter (1) with a glycidyl ether, at least one alkylene oxide or both; and reacting at least one starter (2) with the glycidyl ether, at least one alkylene oxide or both; wherein the glycidyl ether is a compound of the general formula (V) ##STR00016## wherein the starter (1), the starter (2), or both are reacted with the glycidyl ether; and wherein the starter (1) and the starter (2) are OH-functional compounds, and the starter (1) has a molar mass of greater than 400 g/mol and the starter (2) has a molar mass of less than or equal to 400 g/mol.

14. A curable composition comprising at least one composition according to claim 1 and at least one curing catalyst.

15. A process for preparing compositions comprising alkoxylation products (1) and alkoxylation products (2), comprising: a. reacting at least one starter (1) with at least one alkylene oxide; and b. reacting at least one starter (2) with at least one alkylene oxide; wherein the starter (1) and the starter (2) are OH-functional compounds, and the starter (1) has a molar mass of greater than 400 g/mol and the starter (2) has a molar mass of less than or equal to 400 g/mol, wherein the at least one starter (1), the at least one starter (2), or both, are reacted with greater than 0.1 to 25 wt % of alkoxysilylalkyl glycidyl ethers based on the total weight of monomers used.

16. The process according to claim 15, in wherein the reacting step b) takes places during the ongoing alkoxylation of the reacting step a).

17. The process according claim 15, wherein the molar mass of the starter (1) exceeds the molar mass of the starter (2) by at least 600 g/mol.

18. The process according to claim 15, wherein the starter (1) has t OH groups and the starter (2) has t1 OH groups, wherein t=2 to 8.

19. The process according to claim 15, further comprising: c. reacting at least one starter (1) with 10 to 97 wt % of propylene oxide, 0 to 60 wt % of ethylene oxide, greater than 0.1 to 25 wt % of alkoxysilyl glycidyl ethers and 0 to 25 wt % of further monomers, based on the total weight of the monomers used, d. reacting at least one starter (2) with 10 to 97 wt % of propylene oxide, 0 to 60 wt % of ethylene oxide, greater than 0.1 to 25 wt % of alkoxysilyl-glycidyl ethers and 0 to 25 wt % of further monomers, based on the total weight of the monomers used.

Description

EXAMPLES

General Details

(1) The viscosity was determined shear rate-dependently at 25 C. with the MCR301 rheometer from Anton Paar in a plate/plate arrangement with a gap width of 1 mm. The diameter of the upper plate was 40 mm. The viscosity at a shear rate of 10 s.sup.1 was read off and is set out in tables 2 and 3.

Example 1

Synthesis of a PPG-Based, Alkoxysilyl-Functional PolyetherUsed for Non-Inventive Formulations (Comparative Example)

(2) A 5 liter autoclave was charged with 353 g of PPG 2000, and 150 ppm (based on the total batch) of a zinc hexacyanocobaltate double metal cyanide catalyst were added. For inertization, the reactor was charged with nitrogen up to 3 bar and let down to atmospheric pressure. The operation was repeated twice more. With stirring, the contents of the reactor were heated to 130 C. and evacuated to approximately 20 mbar in order to remove volatile components. After 30 minutes, the catalyst was activated by the metered introduction into the evacuated reactor of 80 g of propylene oxide. The internal pressure rose initially to about 0.8 bar. After about 6 minutes, the reaction set in, this being noticeable through a drop in the reactor pressure. Then 1218 g of propylene oxide were metered in continuously over the course of about 50 minutes. A one-hour afterreaction ensued, during which the temperature was lowered to 95 C. At this temperature, a mixture of 196 g of Dynasylan GLYEO (from Evonik) and 1233 g of propylene oxide was metered in continuously at a rate such that the temperature remained constant. After a further one-hour afterreaction, the batch was deodorized by application of a pressure (P<100 mbar), in order to remove residues of unreacted alkylene oxide. Then 500 ppm of Irganox 1135 (from BASF) were stirred in for 15 minutes. A colourless, highly viscous product was obtained. The respective molar ratios of the reactants employed, relative to 1 mol of starter, can be seen in table 2.

Examples 2-15, 18 and 19

Synthesis of Alkoxysilyl-Functional Polyethers with Intrinsically Reduced Viscosity (Examples 2-7, 11 and 13-15 Inventive, Examples 8-10, 12, 18 and 19 Comparative Examples)

(3) The syntheses were carried out as for Example 1, with the target product being synthesized by addition of three blocks onto the respective starting molecule. After the addition of the first block, which was synthesized from PO as an alkylene oxide, and after a 30-minute afterreaction, a second block followed, in which a mixture of PO and the respective starter (2) was metered in. Completed metering was followed by a one-hour afterreaction.

(4) In the final third block, the addition took place of a mixture of Dynasylan GLYEO and PO, followed by a one-hour afterreaction time. The two first blocks were added at 130 C., the third block at 95 C. Finally, the reaction mixture was degassed at 95 C. for 15 minutes, and 500 ppm of antioxidant (Irganox 1135) were stirred in. The molar ratios of the reactants employed, relative to 1 mol of starter, can be seen in table 2.

Examples 16 and 17

Synthesis of Alkoxysilyl-Functional Polyethers (not Inventive)

(5) The syntheses were carried out as for Example 1, with the starter and the amounts used being adapted correspondingly, in order to ensure the construction documented in table 1.

(6) TABLE-US-00001 TABLE 1 Construction of the silyl polyethers of Examples 16 and 17 1. 2. 3. n.sub.PO n.sub.PO n.sub.GLYEO n.sub.PO Ex. Starter (1) [mol] [mol] [mol] [mol] 16 PPG 2000* 18 46 2.67 68.67 17 BPG 400** 0 17.5 1.33 34.33 *Polypropylene glycol polyether with an average molecular weight of 2000 g/mol **Butanol-started polypropylene glycol with an average molar mass of 400 g/mol

Example 20

Preparation of a Polymer Mixture of Silyl Polyethers of Examples 16+17, in Order to Prepare a Silyl Polyether Analogously to Example 2 (Comparative Example)

(7) A mixture of the silyl polyethers of Examples 16 and 17 in a molar ratio of 2:1 is prepared. This is done by adding 438 g of polyether from Example 17 to 2524 g of polyether from Example 16 in a 4 L glass flask, homogenizing the mixture at room temperature by stirring for 30 minutes, and then determining the viscosity. The viscosity at 25 C. was 4.6 Pas.

(8) TABLE-US-00002 TABLE 2 Construction and viscosity of the alkoxysilyl polyethers of Examples 1-15 and 18-20 1. 2. 3. Viscosity n.sub.PO n.sub.PO n.sub.Starter (2) n.sub.GLYEO n.sub.PO [Pas] Ex. Starter (1) Starter (2) [mol] [mol] [mol] [mol] [mol] (at 25 C.) 1 PPG 2000* 87 0 0 4 103 12.1 2 PPG 2000* 1-Butanol 18 69 0.5 4 103 4.2 3 PPG 2000* Texanol 18 69 0.5 4 103 4.3 4 PPG 2000* 2-Propyl-1-heptanol 18 69 0.5 4 103 4.2 5 PPG 2000* 2-Propyl-1-heptanol 37 50 0.5 4 103 3.9 6 PPG 2000* 2-Ethyl-1-hexanol 18 69 0.25 4 103 5.1 7 PPG 2000* 2-Ethyl-1-hexanol 18 69 0.8 4 103 3.0 8 PPG 2000* Dipropylene glycol 18 69 0.25 4 103 8.6 9 PPG 2000* Dipropylene glycol 18 69 0.5 4 103 7.3 10 PPG 2000* Glycerol 18 69 0.5 4 103 7.0 11 PPG 2000* BPG 400** 18 69 0.5 4 103 4.1 12 PPG 2000* PPG 2000* 18 69 0.25 4 103 8.4 18 Desmophen 106 0 0 4 84 79.1 C 2200.sup.+ 13.sup.# Desmophen 1-Butanol 18 0 0.5 4 120 46.7 C 2200.sup.+ 14 Desmophen 1-Butanol 18 69 0.5 4 103 37.5 C 2200.sup.+ 19 Baycoll AD 121 0 0 4 84 29.8 2055.sup.++ 15 Baycoll AD 1-Butanol 18 69 0.5 4 119 11.9 2055.sup.++ 20 2:1 mixture of Examples 16 + 17 4.6 *Polypropylene glycol polyether with an average molecular weight of 2000 g/mol **Butanol-started polypropylene glycol with an average molar mass of 400 g/mol .sup.+terminally dihydroxy-functional polycarbonate with an average molecular weight of 2000 g/mol (available from Bayer Material Science) .sup.++terminally dihydroxy-functional polyester with an average molecular weight of 2000 g/mol (available from Bayer Material Science) .sup.#In Example 13, after the 1st block, initially in block 2a, 0.5 mol of 1-butanol alone was metered in, and in a subsequent block 2b a mixture of 30.6 mol of EO and 27.7 mol of PO was metered in. Lastly, the block 3 documented in table 2 was added on accordingly.

(9) Endcapping (Method According to DE 102012203737):

(10) The alkoxylation products prepared in Examples 1-12 and 20 were subsequently reacted using IPDI according to process A.

(11) The alkoxylation products prepared in Examples 1, 13-15, 18 and 19 were subsequently reacted using IPDI in accordance with process B.

(12) Examples according to process A:

Example 21

(13) 706.8 g of silyl polyether from Example 1 were introduced and heated to 60 C. Then 26.68 g of IPDI were added, the mixture was stirred for five minutes, and 0.8 g of TIB Kat 722 was added. The mixture was stirred for 45 minutes and heated to 80 C. and 53.5 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 22

(14) 2541 g of silyl polyether from Example 2 were introduced and heated to 60 C. Then 96 g of IPDI were added, the mixture was stirred for five minutes, and 2.83 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 30 minutes and heated to 80 C. and 192 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 5 hours.

Example 23

(15) 2544 g of silyl polyether from Example 3 were introduced and heated to 60 C. Then 95 g of IPDI were added, the mixture was stirred for five minutes, and 2.83 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 191 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 24

(16) 2556 g of silyl polyether from Example 4 were introduced and heated to 60 C. Then 96 g of IPDI were added, the mixture was stirred for five minutes, and 2.84 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 192 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 25

(17) 2550 g of silyl polyether from Example 5 were introduced and heated to 60 C. Then 96 g of IPDI were added, the mixture was stirred for five minutes, and 2.83 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 191 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 26

(18) 2497 g of silyl polyether from Example 6 were introduced and heated to 60 C. Then 94 g of IPDI were added, the mixture was stirred for five minutes, and 2.78 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 189 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 27

(19) 2538 g of silyl polyether from Example 7 were introduced and heated to 60 C. Then 95 g of IPDI were added, the mixture was stirred for five minutes, and 2.82 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 190 g of polyether of the general formula

(20) C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 28

(21) 890 g of silyl polyether from Example 9 were introduced and heated to 60 C. Then 50 g of IPDI were added, the mixture was stirred for five minutes, and 1.04 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 101 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 29

(22) 1349 g of silyl polyether from Example 11 were introduced and heated to 60 C. Then 50 g of IPDI were added, the mixture was stirred for five minutes, and 1.5 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 101 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 30

(23) 1414 g of silyl polyether from Example 11 were introduced and heated to 60 C. Then 66 g of IPDI were added, the mixture was stirred for five minutes, and 1.6 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 132 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 31

(24) 1499 g of silyl polyether from Example 12 were introduced and heated to 60 C. Then 55 g of IPDI were added, the mixture was stirred for five minutes, and 1.7 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 110 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 32

(25) 1302 g of silyl polyether from Example 12 were introduced and heated to 60 C. Then 59 g of IPDI were added, the mixture was stirred for five minutes, and 1.5 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 119 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Example 33

(26) 2863 g of silyl polyether from Example 20 were introduced and heated to 60 C. Then 108 g of IPDI were added, the mixture was stirred for five minutes, and 0.32 g of TIB Kat 722 (bismuth carboxylate) were added. The mixture was stirred for 45 minutes and heated to 80 C. and 216 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. This was followed by stirring for a further 3 hours.

Examples According to Process B

Example 34

(27) 2969 g of silyl polyether from Example 2 were introduced and heated to 70 C. Then 101 g of IPDI were added, the mixture was stirred for five minutes, and 0.2 g of TIB Kat 216 (dioctyltin dilaurate) were added. The mixture was stirred for 45 minutes and 202 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. The mixture was subsequently stirred at 70 C. for a further 5 hours.

Example 35

(28) 2925 g of silyl polyether from Example 13 were introduced and heated to 70 C. Then 100 g of IPDI were added, the mixture was stirred for five minutes, and 0.2 g of TIB Kat 216 (dioctyltin dilaurate) were added. The mixture was stirred for 45 minutes and 201 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. The mixture was subsequently stirred at 70 C. for a further 5 hours.

Example 36

(29) 2617 g of silyl polyether from Example 14 were introduced and heated to 70 C. Then 100 g of IPDI were added, the mixture was stirred for five minutes, and 0.2 g of TIB Kat 216 (dioctyltin dilaurate) were added. The mixture was stirred for 45 minutes and 200 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. The mixture was subsequently stirred at 70 C. for a further 5 hours.

Example 37

(30) 2684 g of silyl polyether from Example 15 were introduced and heated to 70 C. Then 95 g of IPDI were added, the mixture was stirred for five minutes, and 0.2 g of TIB Kat 216 (dioctyltin dilaurate) were added. The mixture was stirred for 45 minutes and 191 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H was added. The mixture was subsequently stirred at 70 C. for a further 5 hours.

Example 38

(31) 2679 g of silyl polyether from Example 18 were introduced and heated to 70 C. Then 95 g of IPDI were added, the mixture was stirred for five minutes, and 0.2 g of TIB Kat 216 (dioctyltin dilaurate) were added. The mixture was stirred for 45 minutes and 191 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H was added. The mixture was subsequently stirred at 70 C. for a further 5 hours.

Example 39

(32) 2690 g of silyl polyether from Example 19 were introduced and heated to 70 C. Then 96 g of IPDI were added, the mixture was stirred for five minutes, and 0.2 g of TIB Kat 216 (dioctyltin dilaurate) were added. The mixture was stirred for 45 minutes and 192 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H were added. The mixture was subsequently stirred at 70 C. for a further 5 hours.

Example 40

(33) 703.1 g of silyl polyether from Example 1 were introduced and heated to 70 C. Then 26.5 g of IPDI were added, the mixture was stirred for five minutes, and 0.05 g of TIB Kat 216 (dioctyltin dilaurate) were added. The mixture was stirred for 30 minutes and 53.2 g of polyether of the general formula C.sub.4H.sub.9O[CH.sub.2CH(CH.sub.3)O].sub.5.6H was added. The mixture was subsequently stirred for a further 5 hours.

(34) The endcapped examples from Table 3 are comparative examples in the case of Examples 21, 28, 31 to 33, 38, 39 and 40; the remaining examples are inventive.

(35) TABLE-US-00003 TABLE 3 Viscosities of the endcapped silyl polyethers from Examples 21-40 Reaction of alkoxylation Viscosity (25 C.) Example products from example Process [Pas] 21 1 A 72.0 22 2 A 23.6 23 3 A 22.8 24 4 A 22.4 25 5 A 24.0 26 6 A 26.3 27 7 A 20.6 28 9 A 35.3 29 11 A 25.9 30 11 A 16.9 31 12 A 55.2 32 12 A 41.2 33 20 A 41.0 40 1 B 34.5 34 2 B 20.5 38 18 B 186 35 13 B 152 36 14 B 125 39 19 B 85.6 37 15 B 34.5
Preparation of the Room-Temperature-Applicable Adhesive/Sealant Formulations:

(36) 25.9 wt % of the alkoxylation product from the respective examples was intensively mixed with 18.1 wt % of diisoundecyl phthalate, 51.1 wt % of precipitated chalk (Socal U1S2, Solvay), 0.5 wt % of titanium dioxide (Kronos 2360, Kronos), 1.4 wt % of adhesion promoter (Dynasylan AMMO, Evonik), 1.1 wt % of drying agent (Dynasylan VTMO, Evonik), 1.5 wt % of an antioxidant/stabilizer mixture (ratio of Irganox 1135 to Tinuvin 1130 to Tinuvin 292=1:2:2 ratio) and 0.4 wt % of the curing catalyst (TIB KAT 223, TIB) in a mixer (Speedmixer FVS 600, Hausschild). The completed formulation was transferred to PE cartridges, and was stored for at least 24 hours at room temperature prior to application. Given that the formulations of the alkoxylation products in the examples stated above were identical in all cases, the discussion of the results has been carried out with identification of the alkoxylation product utilized as the basis of the formulation.

(37) Determination of Tensile Stress at Break and Elongation at Break in Accordance with DIN 53504:

(38) The formulation was knifecoated in a film thickness of 2 mm on a PE surface. The films were stored for 7 days at 23 C. and 50% relative humidity. S2 dumbbell specimens were then punched from the films with the aid of a cutter and a toggle press.

(39) The dumbbell specimens thus produced were clamped for testing into a universal testing machine (from Shimadzu), and determinations were made of the tensile stress at break and elongation at break when the specimens were stretched at a constant velocity (200 mm/min).

(40) Determination of the Tensile Shear Strength of Overlap Bonds in Accordance with DIN EN 1465

(41) Overlap bonds were produced with the prepared formulation. For these bonds, two stainless steel substrates (V2A, 1.4301) were used. The region of the overlap bond amounted to 500 mm.sup.2. The bonds were cured at 23 C. and 50% relative humidity. After 21 days, the bonds were clamped into a universal testing machine (from Shimadzu), and a force was exerted on the adhesive bond at a constant rate (10 mm/min) until the bond fractured. The tensile shear strength was ascertained.

(42) TABLE-US-00004 TABLE 4 Mechanical characteristic values of the cured formulation on an S2 dumbbell specimen and on an overlap bond of two V2A steel plates: S2 dumbbell specimen Adhesive bond Elongation at tensile stress at tensile shear Polymer of break break strength example [%] [N/mm.sup.2] [N/mm.sup.2] 21 212 1.73 1.34 22 203 1.54 1.44 23 216 1.61 1.49 24 194 1.60 1.47 25 168 1.51 1.57 26 121 1.52 1.47 27 185 1.45 1.54 28 182 1.23 1.07 29 204 1.41 1.49 30 221 1.35 1.33 31 154 1.48 1.69 32 151 1.25 1.32 33 188 1.52 1.71 40 189 1.60 1.34 34 152 1.52 1.63 38 165 1.31 1.16 35 126 1.49 1.49 36 112 1.70 1.74 39 206 1.38 1.09 37 163 1.44 1.27

(43) It is clearly apparent from the viscosities shown in Tables 2 and 3 that the viscosity of the inventive alkoxylation products, prepared by the inventive process through the use of starters (2) during the alkoxylation, leads to a significant reduction in the viscosity. Non-inventive compositions have a viscosity which is higher by at least 10% than the viscosity of the inventive compositions.

(44) According to Table 2, in the case of the inventive alkoxylation products with terminal OH groups from Examples 2-7 and 11, for which a polyether (PPG 2000) was employed as starter, a reduction in the viscosity by at least 50% is recorded, relative to comparative Example 1, where no starter (2) is used. Where the functionality of starter (2) is identical to starter (1) or higher, there is always still a marked reduction observed in the viscosity by comparison with Example 1, of around 30% (Examples 8, 9, 12). This relatively small viscosity reduction effect is clear proof that it is particularly advantageous to use starter (2), with a functionality reduced by 1 relative to starter (1).

(45) As shown by Example 14 (with starter (2)) in comparison to starter 18 (without starter (2)) and by Example 15 (with starter (2)) in comparison to Example 19 (without starter (2)), the effect of the lowering of the viscosity can also be transposed to chemically different (non-polyether) starters. A polycarbonate (Desmophen C 2200 in Example 14 or 18) and a polyester (Baycoll AD 2055 in Example 15 or 19) were used in the inventive process, and in both cases a viscosity reduction of at least 40% was observed, relative to the comparative examples, through the addition of 1-butanol as starter (2).

(46) This trend can also be read off in Table 3, in the case of the alkoxylation products reacted with isocyanates. In the case of the alkoxylation products endcapped by process A, a reduction in viscosity of at least 60% is recorded when the alkoxylation products were prepared beforehand with starters (2) having a lower OH functionality than the starter (1). Where the OH functionality of the two starters is identical, a smaller viscosity is found in comparison to Example 21, where exclusively one starter (1) was used. The reduction is of the order of 20-50%. This trend is also continued for the alkoxylation products endcapped by process B. Here, however, a smaller absolute reduction in the viscosity is recorded. In Example 34, in comparison to Example 40, the viscosity is reduced by 40%, whereas for the analogous products endcapped by process A, a reduction of around 65% is recorded on comparison of Example 21 with Example 22.

(47) Where the alkoxylation products were prepared beforehand with starters (2) having a lower OH functionality than the starter (1), a particularly good reduction in viscosity is recorded. Also situated within a similar range are the viscosity reductions for the inventive products based on polycarbonates (reduction in viscosity by about 30%; see Example 38 relative to 36) or polyesters (reduction in viscosity by about 60%; see Example 39 relative to 37) as starters.

(48) Furthermore, from the results in Tables 2 and 3, it can be worked out that for a significant reduction of viscosity it is immaterial which kind of starter (2) is used, this being especially apparent for the inventive examples where starter (1) has a higher OH functionality than starter (2).

(49) From the results from Table 2, moreover, it can be discerned that the reduction in viscosity can be influenced by the amount of starter (2) added. The greater the amount of starter (2) employed, the greater the effect of the reduction in viscosity. For the endcapped compounds from Table 3, this effect is somewhat diminished, but still clearly apparent.

(50) From Examples 24, 25 and 35, moreover, it can be seen that the extent of the reduction in viscosity as well can be controlled through the timing of the addition of the starter (2).

(51) The mechanical characteristic values of the inventive alkoxylation products with intrinsically reduced viscosity are summarized in Table 4, and, surprisingly, for alkoxylation products endcapped by process A, they show no significant deviations from the mechanical characteristic values of comparative Example 21 with heightened viscosity. In contrast, in the case of the mechanical characteristic values of the alkoxylation products endcapped by process A, there is in fact overall a positive influence. While the elongations at break of the inventive Examples 34 to 37 are slightly reduced by comparison with comparative Examples 38 to 40, this effect is nevertheless more than compensated by a significant improvement in the breaking stress in the adhesive bond.

(52) Comparative Examples 20 and 33, hitherto disregarded, will be looked at separately and in somewhat more detail. These polyethers are silyl polyethers which in structural terms correspond to inventive Examples 2 and 22, respectively, but in contrast to them were not prepared by the inventive process. In order to copy the structure of Example 2, the starters (1) and (2) were reacted in two separate batches, and the moles of the monomers of blocks 2+3 as per Table 2 were added onto these starters (1) and (2), the molar amounts being in proportion with regard to the OH groups of the starter. In Example 16, therefore, of the monomers of blocks 2 and 3, in analogy to Example 2, were added onto PPG 2000. Analogously, in Example 17 of the respective monomers was added on. For the sake of simplicity, starting took place in Example 17 not directly from butanol, but instead from an adduct of butanol+5.5 PO. This was taken into account accordingly in the formulation.

(53) Subsequently, these polymers were mixed in Example 20 and reacted with IPDI in Example 33. From the viscosity of Example 20 it is clear that this mixing of silyl polyethers with different functionalities also results in a comparable reduction of viscosity, which is within the range of inventive Examples 2-7 and 11, but this effect is not sustained in the target subsequent reaction. The endcapped subsequent product as per Example 33 does still have a viscosity reduced by almost 60% in comparison to comparative Example 21; however, the viscosity reduction effect is still much greater in reference Example 2, being almost twice as large. On the basis of the applications properties of comparative Example 33, set out in Table 4, it is also impossible to discern any noticeable effect. Both breaking stress and elongation at break are comparable to reference Example 21.

(54) It is therefore found, surprisingly, that the change in the compositions of the inventive alkoxylation products through the use of starters (2) has no noticeable influence on the important application properties of the formulations, which derive from the inventive alkoxylation products prepared by the inventive process, and it is possible nevertheless to obtain products which are comparable in performance terms and have a noticeably reduced viscosity. All the more surprising is the fact that in the case of the adhesive application, it was in fact possible to improve the tensile shear strength.