WO2015082264A1 - Alkoxysilylhaltige klebdichtstoffe mit intrinsisch reduzierter viskosität - Google Patents
Alkoxysilylhaltige klebdichtstoffe mit intrinsisch reduzierter viskosität Download PDFInfo
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- WO2015082264A1 WO2015082264A1 PCT/EP2014/075607 EP2014075607W WO2015082264A1 WO 2015082264 A1 WO2015082264 A1 WO 2015082264A1 EP 2014075607 W EP2014075607 W EP 2014075607W WO 2015082264 A1 WO2015082264 A1 WO 2015082264A1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- C08G2170/00—Compositions for adhesives
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
- C08G2650/24—Polymeric initiators
Definitions
- the present invention relates to specific alkoxylation products, a process for their preparation, compositions containing these alkoxylation and their use, in particular as alkoxysilyl-containing adhesives and sealants.
- bonding In comparison with the joining of different materials, bonding also has the advantage that it can compensate for the different deformation behavior and differences in the thermal expansion coefficients of the materials, in particular when using elastic adhesives, and thus makes it possible to join such material combinations.
- silylated polyurethanes include (SPUR products, such as Desmoseal ® S, Bayer Materials Science).
- SPUR products such as Desmoseal ® S, Bayer Materials Science.
- the use of polyether backbones in these products is particularly advantageous because of their low glass transition temperature and the elastic deformation characteristics thus ensured even at low temperatures.
- silylated polyethers do not have the optimum profile for use in adhesives or sealants because of their weak intermolecular interaction under conditions of use and the associated reduced intermolecular transmission of forces .
- Silylated polyurethanes as described in DE 69831518 (WO 98/47939 A1), are clearly advantageous in this case, since the urethane functions and the urea functions, which are also present depending on the product, enable strong intermolecular force transmission and thus high bond strengths.
- silylated polyurethanes are also associated with the polyurethane-associated problems, such as the lack of temperature and yellowing resistance, as well as insufficient UV stability for some applications.
- Alkoxylation products can according to the prior art by the reaction of an OH group (n) bearing initiator with propylene oxide and one or more epoxy-containing alkoxysilyl compound (s) and, depending on the embodiment, one or more comonomers by double metal cyanide (DMC) catalysts, according to EP 2093244 (US 2010/0041910) and the after-treatment process described in EP 2415796 (US 2012/028022) and EP 2415797 (US 2012/029090) as well as the as yet unpublished application DE 10 2012 203737.
- DMC double metal cyanide
- the object of the present invention was therefore to prepare compositions comprising alkoxysilyl-modified polymers which have lower viscosities even without the aid of further substances, such as, for example, plasticizers or reactive diluents, than comparable known compositions with alkoxysilyl-modified polymers.
- Another object of the present invention was to provide a simple process for preparing such compositions, and to provide curable compositions based on such base polymers.
- compositions with intrinsically reduced viscosity containing certain mixtures of alkoxysilyl-modified polymers.
- compositions with intrinsically reduced viscosity are understood as meaning compositions containing alkoxysilyl-modified polymers which have a reduced viscosity compared to comparable alkoxysilyl-modified polymers known in the art and whose reduced viscosity is not due to the addition of one or more auxiliary components but the reduced viscosity thereof is intrinsically caused "from the inside.”
- the expression reduced viscosity in the context of this patent application covers all viscosities which are reduced by at least 5%, preferably by at least 10%, based on the viscosity of a composition containing alkoxysilyl-modified polymer with intrinsic reduced viscosity compared to comparable, compositions containing alkoxysilyl-modified polymers, under the same measurement conditions.
- Intrinsically reduced viscosity compositions of the invention are preferably obtained by the method described in this invention.
- compositions containing alkoxysilyl-modified polymers with intrinsically reduced viscosity can be obtained if, during the production process of the alkoxysilyl-modified polymers from an OH-functional initiator (1) in the alkoxylation step with the alkylene oxide addition proportionately another OH-functional Starter (2) is added.
- the viscosity of the products according to the invention is markedly reduced in comparison to analogous polymers which have been prepared without the addition of OH-functional starters (2), while the performance properties surprisingly do not differ at all or do not differ significantly.
- the subject of the present invention is therefore a process for the preparation of alkoxylation products with intrinsically reduced viscosity as described below.
- Another object of the present invention are compositions with intrinsically reduced viscosity containing Alkyoxyl michs consist from at least two different starters.
- compositions with intrinsically reduced viscosity comprising alkoxylation products of at least two different starters and further components and their use, in particular the use of these alkoxylation products of at least two different starters in curable compositions.
- the compositions according to the invention, the process for their preparation and their use are described below by way of example, without the invention being restricted to these exemplary embodiments.
- ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be.
- the hydrophilic or hydrophobic character of the final alkoxysilyl-functional polymers of intrinsically reduced viscosity may be introduced by the nature and structure of the OH group (s) bearing initiators (1) and (2) and / or one or more comonomers introduced during the synthesis will be set.
- the viscosity of the final alkoxysilyl-functional polymer with intrinsically reduced viscosity can be adjusted in a targeted manner by the type and amount as well as the time of addition of the OH-functional starters (2).
- alkoxysilyl-bearing alkoxylation products were prepared for the first time, which, in contrast to the hitherto known prior art, blockwise or randomly generates alkoxysilyl groups along the polyether chain distributed and are not located only at the termini of the chain. Furthermore, these compounds are characterized by a reaction-related terminal OH group.
- Storage stability is understood in this context to mean the stability against crosslinking or gelling of the finished, catalyst-containing formulation when stored in a commercially available thick-walled cartridge.
- the compounds mentioned include, in particular, those of the formula (I).
- alkoxylation products or polyethers encompasses both polyethers, polyetherols, polyether alcohols, polyetheresterols and also polyethercarbonateols, which are optionally used synonymously with one another. It is not necessary for the term "poly” to be associated with a multitude of ether functionalities or alcohol functionalities in the molecule or polymer.
- the word fragment "poly” encompasses not only exclusively compounds having at least 3 repeat units of one or more monomers in the molecule, but in particular those compositions of compounds which have a molecular weight distribution and thereby have an average molecular weight of at least 200 g / mol.
- This definition takes into account the fact that it is common practice in the field of technology considered to refer to such compounds as polymers even if they do not seem to satisfy a polymer definition analogous to OECD or REACH directives.
- the various fragments in the following formulas (Ia), (II) and (IIa) may be randomly distributed.
- Statistical distributions can be constructed block by block with any number of blocks and any sequence or they can be subject to a randomized distribution, they can also be of alternating design or also form a gradient over the chain, in particular they can also form all mixed forms, where appropriate Groups of different distributions can follow one another.
- the formulas (I), (Ia), (II) and (IIa) describe polymers which have a molecular weight distribution. Therefore, the indices represent the numerical average over all monomer units.
- index numbers a, b, c, d, e, f, g, h, i, j, k, I, m, n, o, p, q, r, s, t, u, v used in the formulas w, x and y as well as the value ranges of the specified indices can be understood as average values of the possible statistical distribution of the actual existing structures and / or their mixtures. This also applies to structural formulas exactly reproduced as such per se, as for example for formula (Ia), (II) and (IIa)
- compositions comprising alkoxylation products of at least two different OH-functional starters have an intrinsically reduced viscosity. It is essential to the invention that the composition with intrinsically reduced viscosity contains at least one alkoxylation product of a starter (1) and at least one alkoxylation product of a starter (2), wherein starter (1) and starter (2) must be different from one another.
- starter (1) and starter (2) can both be different alcohols, preferably the alcohols mentioned below.
- In starter (2) are preferably alcohols or polyols such as methanol, 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol, available for example from Exxon), octanol, decanol, dodecanol, ethanol, propanol , iso-propanol, butanol, isobutanol, tert-butanol, all isomeric pentanols, fatty alcohols such as caproic alcohol, eananthalcohol, caprylic alcohol, pelargonic, capric alcohol, 1-undecanol, lauryl alcohol, 1-tridecanol, isotridecyl alcohol, myristyl alcohol, 1-pentadecanol, Cetyl alcohol, palmoleyl alcohol, 1-heptadecanol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl
- starter (1) and starter (2), in particular starter (1) are preferably relatively high molecular weight compounds, preferably having molecular weights greater than 200 g / mol, more preferably greater than 300 g / mol and particularly preferably greater than 400 g / mol, preferably selected from polyethylene oxides, polypropylene oxides, polyesters, polycarbonates,
- Starter (1) is particularly preferably selected from polyetherols, polycarbonate polyols and polyether carbonates.
- Polycarbonate polyols for the purposes of this invention are preferably ⁇ , ⁇ -dihydroxy-functional reaction products having at least 3 carbonate units, preferably 3 to
- Preferred polycarbonate polyols are reaction products of
- Preferred polycarbonate polyols are available under the brand names ETERNACOLL ® PH of the UBE Chemical Europe SA, polyol C series of Kuraray Europe GmbH, Durez ® th S Sumitomo Bakelite Europe, for example, on the market or
- Polyether carbonates in the context of this invention are preferably reaction products of the previously defined polycarbonate polyols with alkylene oxides.
- Polyetherols are preferably reaction products of alkylene oxides, preferably the polyetherols are polyethylene oxides, polypropylene oxides.
- initiators (1) selected from polyetherols, polycarbonate polyols and polyether carbonates, in particular in the previously described preferred embodiments, and starters (2), preferably selected from butanol, ethanol or ethylhexanol.
- alkoxylation products (1) are obtained by reacting starter (1), preferably with alkylene oxides and alkoxylation products (2), by reacting starter (2), preferably with alkylene oxides.
- the compositions having an intrinsically reduced viscosity comprising alkoxylation products are preferably those in which the alkoxylation products (1) of initiator (1) are composed of alkylene oxide, preferably at least ethylene oxide and / or propylene oxide, at least one epoxide carrying alkoxysilyl groups and optionally further monomers and the alkoxylation products (2) of initiator (2) are composed of alkylene oxide, preferably at least ethylene oxide and / or propylene oxide and optionally at least one alkoxysilyl-carrying epoxide and / or further monomers.
- the alkoxylation products (2) of starter (2) are preferably composed of alkylene oxide and at least one epoxide bearing alkoxysilyl groups.
- Preferred alkoxylation products (1) are composed of the following monomer proportions 10 to 97 wt .-%, preferably 20 to 95 wt .-%, particularly preferably 30 to 90 wt .-% propylene oxide, 0 to 60 wt .-%, preferably 3 to 40 Wt .-%, particularly preferably 5 to 30 wt .-% ethylene oxide, 0 to 25 wt .-%, preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-% alkoxysilyl-carrying epoxy and 0 to 25 wt .-%, preferably 0.1 to 20 wt .-%, particularly preferably 0 to 10 wt .-% further monomers, preferably selected from propylene oxide and ethylene oxide different alkylene oxides,
- Preferred alkoxylation products (2) are composed of the following 10 to 97 wt .-%, preferably 20 to 95 wt .-%, particularly preferably 30 to 90 wt .-% propylene oxide, 0 to 60 wt .-%, preferably 3 to 40 wt .-%, particularly preferably 5 to 30 wt .-% ethylene oxide, 0 to 25 wt .-%, preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-% alkoxysilyl groups bearing Epoxide and 0 to 25 wt .-%, preferably 0.1 to 20 wt .-%, particularly preferably
- wt .-% of other monomers preferably selected from propylene oxide and ethylene oxide different alkylene oxides such as butylene oxide, isobutylene oxide, styrene oxide and / or other comonomers such as ⁇ -caprolactone, phthalic anhydride, glycidyl ethers such as tert-butylphenylglycidylether, C12 / C14 fatty alcohol glycidyl ether and 2-Ethylhexylglycidylether all wt .-% based on the total weight of the alkoxylation (2).
- propylene oxide and ethylene oxide different alkylene oxides such as butylene oxide, isobutylene oxide, styrene oxide and / or other comonomers such as ⁇ -caprolactone, phthalic anhydride, glycidyl ethers such as tert-butylphenylglycidylether, C12
- the OH functionality of the initiators can also be used to control the intrinsically reduced viscosity of the compositions according to the invention.
- the starter (1) has a higher OH functionality, ie more OH groups, than the starter (2).
- the intrinsically reduced viscosity compositions of the invention preferably contain alkoxylation products (1) from starter (1) containing the structural elements of formula (I)
- Mi D j T k Qi UR u AP V formula (I) are characterized by the fact that the fragments M, D, T, Q are not linked to each other, but via the groups UR and / or AP, and the groups UR and AP are not linked to each other, but are linked together via the fragments M, D, T or Q accordingly.
- 1 0 to 16, preferably 1 to 12, particularly preferably 2 to 6
- j 0 to 10, preferably 1 to 8, particularly preferably 2 to 6, particularly preferably greater, equal to 1
- k 0 to 6, preferably greater than 0 to 4, in particular 0.5 to 2,
- I 0 to 4, preferably greater than 0 to 3, in particular 0.5 to 2,
- a 0 to 100, preferably 1 to 50, more preferably greater than 1 to 10, particularly preferably 1 to 5, preferably 1, 2 or 3
- b 0 to 1000, preferably 1 to 500, more preferably greater than 1 to 400, particularly preferably 10 to 300
- c 0 to 200, preferably 1 to 100, more preferably greater than 1 to 80, particularly preferably 0 to 50
- d 0 to 200, preferably 1 to 100, more preferably greater than 1 to 80, particularly preferably 0 to 50
- w 0 to 200, preferably 1 to 100, more preferably greater than 1 to 80, particularly preferably 0 to 50
- h 0 to 10, preferably 1 to 6, particularly preferably 1, 2 or 3
- the groups with the indices a, b, c, d, w and y are freely permutable over the molecular chain, wherein the groups with the indices w and y are not allowed to follow each other or to the other group and with the proviso that the various monomer units of both the fragments with the indices a, b, c, d, w and y and the optionally present polyoxyalkylene of the substituent R 1 can be constructed in blocks with each other, wherein individual blocks can also occur multiple times and may be distributed statistically among themselves, or subject to a statistical distribution and also freely permute each other, in order to be arranged in any order, with the restriction that the groups with the indices w and y each not on themselves or on the other Allowed to follow group,
- R 1 independently of one another is a saturated or unsaturated, linear or branched organic hydrocarbon radical which, as heteroatoms, may contain O, S and / or N,
- the hydrocarbon radical preferably contains 1 to 400 carbon atoms, preferably 2, 3 or 4 to 200 carbon atoms,
- R 2 independently of one another an alkyl group having 1 to 8 carbon atoms, in particular methyl or ethyl, propyl, isopropyl,
- R 3 independently of one another an alkyl group having 1 to 8 carbon atoms, in particular methyl, ethyl, propyl, isopropyl,
- R 4 independently of one another a hydrogen radical, an alkyl group having 1 to 20
- Benzyl particularly preferably hydrogen, methyl or ethyl
- R 5 independently of one another a hydrogen radical or an alkyl group with 1 to
- R 4 and one of R 5 may together form a ring which includes the atoms to which R 4 and R 5 are bonded, preferably this ring contains from 5 to 8 carbon atoms,
- R 6 and R 7 independently of one another a hydrogen radical, an alkyl group having 1 to 20 carbon atoms, an aryl or alkaryl group and / or a
- Alkoxy group preferably a methyl group
- R 11 independently of one another a saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 2 to 30 C atoms, in particular up to 24 C atoms, which is optionally substituted, it is preferably an alkyl group having 1 to 16 carbon atoms, more preferably With
- Neodecanoic acid C 2 / C 4 alkyl, phenyl, cresyl, tert-butylphenyl or benzyl, particularly preferably a 2-ethylhexyl, C (0) - (CH2) 5-C (CH 3) 3- (radical of neodecanoic acid), Ci 2 / Ci 4 alkyl, phenyl, cresyl, tert-butylphenyl group, very particularly preferably a tert-butylphenyl or 2-ethylhexyl group,
- the bridging fragment Z may be present or absent is the bridging fragment Z not available so are
- R 16 hydrocarbon radicals which are bridged cycloaliphatically or aromatically via the fragment Z, where Z is a divalent alkylene or alkenylene radical which may be further substituted,
- the fragment with the index y can be obtained, for example, by the incorporation of cyclic anhydrides
- preferred cyclic anhydrides are succinic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, phthalic anhydride,
- Hexahydrophthalic anhydride and trimellitic anhydride and polyfunctional acid anhydrides such as pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride or radically polymerized homo- or copolymers of maleic anhydride with ethylene, isobutylenes, Acrylonitrile, vinyl acetate or styrene, particularly preferred anhydrides are succinic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, where formula (Ib)
- R 17 independently of one another a linear or branched, saturated or unsaturated, optionally further substituted alkyl group having 1 to 30 carbon atoms, an aryl or alkaryl group, preferably methyl, ethyl, Octyl, decyl, dodecyl, phenyl, benzyl, more preferably methyl or ethyl, wherein formula (Ic):
- R 18 is independently a divalent linear or cyclic, saturated or unsaturated alkyl group which may be substituted, preferably a methyl, ethyl, propyl or isopropyl group, or
- an aryl group preferably a phenyl group or
- an aryl group which is at least doubly substituted and which may preferably carry at least one further carboxylic acid function, preferably acetate radical, propionate radical, phthalic acid radical, itaconic acid radical, hexahydrophthalic acid radical or maleic acid radical, and where the following applies to the fragments D, T and Q:
- D is a polyether radical - (D A ) t -D x with t equal to 2,
- T is a polyether radical - (D A ) t -D x with t equal to 3 and
- Q is a polyether radical - (D A ) t -D x with t equal to 4,
- D x is a t-valent functional, saturated or unsaturated, linear or branched organic hydrocarbon radical which, as heteroatoms O, S,
- Si and / or N may contain, wherein each of the radicals D A is covalently bound to the radical D x ,
- the hydrocarbon radical preferably contains 8 to 1500 carbon atoms, preferably the carbon chain of the hydrocarbon radical is interrupted by oxygen atoms,
- the hydrocarbon radical contains silicon atom-containing substituents
- the silicon atom-containing substituents are preferably alkoxysilyl groups
- the hydrocarbon radical interrupted by oxygen atoms is preferably a polyoxyalkylene radical, polyether radical and / or polyetheralkoxy radical, or may be a singly or multiply fused phenolic group, or particularly preferably D x is a t-valent radical of a t-hydroxylated alcohol, polyetherol, polyesterol , Siloxane, perfluorinated polyetherol, (poly) urethane or saccharide, preferably OH-functional polyethers, polyesters, polycarbonates, polyetheresters or perfluorinated polyethers and copolymers thereof, more preferably OH-functional polyethers or polyesters, and wherein D A is a fragment of Formula (II)
- Formula (II) is defined independently with a to h, w and y and R 2 to R 16 as in Formal (la),
- the sum of all indices b of the formulas (Ia) and (II) gives at least 1, preferably at least 2, in particular preferably at least 3, and the sum of all indices a of the formulas (Ia) and (II) is equal to or greater than 1 have to be.
- the polyether radicals D may be polyethers started with a dihydroxy-substituted compound
- Polyether radicals T can be a polyether started with a trihydroxy-substituted compound
- the polyether radicals Q can be polyethers started with a tetrahydroxy-substituted compound and / or the fragment M may be a polyether started with a monohydroxy substituted compound.
- UR are independently identical or different divalent radicals of the form -UD c -U-,
- U is a -C (O) -NH group, which is bonded via the nitrogen to D c , D E , D F or D D , and
- D c is independently a divalent substituted or unsubstituted, linear or branched, saturated or unsaturated hydrocarbon radical having from 1 to 30 carbon atoms selected from alkyl, alkenyl, aryl or alkaryl radicals optionally interrupted by heteroatoms such as O, N and / or S.
- D is an aryl or alkaryl group, preferably D c is a divalent hydrocarbon radical having 6 to 30 carbon atoms, particularly preferably D c is an isophorone radical,
- D E is independently a trivalent substituted or
- D F is independently a tetravalent substituted or
- D D independently of one another 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 are optionally substituted by heteroatoms such as O, N and / or S may be interrupted and further substituted, for example with alkyltrialkoxysilane or alkyl-alkyldialkoxysilane groups, wherein the hydrocarbon radical preferably has from 1 to 30, preferably from 2 to 18 and more preferably from 3 to 10 carbon atoms, and in particular a methyl, ethyl, propyl or butyl radical, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, D D is preferably a monovalent hydrocarbon radical having 4 to 20 carbon atoms, more preferably methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, octyl, decyl, dodecyl, phenyl, toluyl, benzyl, isopropylphenyl or stearyl group, more
- Isopropylphenyl or stearyl group, very particularly preferably D is a butyl radical are independently identical or different radicals of
- the fragment UR may be referred to as a urethane unit.
- the fragment AP may be referred to as allophanate moiety.
- the polymerization of the (meth) acrylic groups can take place after the preparation of the polyether. It can also be carried out with the alkoxylation products according to the invention, with the products of the process according to the invention, as well as after the use according to the invention.
- the intrinsically reduced viscosity compositions of the invention preferably contain alkoxylation products (2) containing the structural elements of formula (IIa) wherein R 27 results from the initiator (2)
- a 0 to 100, preferably 1 to 50, more preferably greater than 1 to 10, particularly preferably 1 to 5
- b 0 to 200, preferably 1 to 100, more preferably greater than 2 to 50, particularly preferably 3 to 30
- c 0 to 100, preferably 1 to 10, more preferably greater than 1 to 8, particularly preferably 0 to 5
- y 0 to 50, preferably 1 to 30, particularly preferably 2 to 20 and particularly preferably 0 to 10,
- h 0 to 10, preferably 1 to 6, particularly preferably 1, 2 or 3
- R 27 independently of one another is a saturated or unsaturated, linear or branched organic hydrocarbon radical which may contain, as heteroatoms, O, S and / or N, preferably the hydrocarbon radical contains 1 to 50 carbon atoms, preferably 2, 3 or 4 to 30 carbon atoms ,
- the radicals R 27 result from monovalent alcohols such as
- R independently of one another is hydrogen or a fragment of the formula (II) or (IIa) bound via UR or AP.
- R independently of one another is hydrogen or a fragment of the formula (II) or (IIa) bound via UR or AP.
- R independently of one another is hydrogen or a fragment of the formula (II) or (IIa) bound via UR or AP.
- the functionality is characterized in that it is capable of initiating a polymerization of alkylene oxides, cyclic acid anhydrides and / or acid lactones with ring opening.
- the polymerization can optionally be carried out catalytically.
- catalysts acids, bases and metal atom-containing complexes can serve.
- DMC catalysts are used.
- the usual addition rules known to the person skilled in the art apply, for example, that the starter reacts preferentially on the lower substituted side of the alkylene oxides or on the carbonyl carbon of the lactones. In the case of the formula (II), this corresponds to the left side of the respective fragment of the formula.
- the OH functions of the alkoxylation products (1) and (2) can, if desired, react with isocyanate functions to form urethanes.
- a series of side reactions eg addition of an isocyanate group to a urethane unit to the allophanate group usually occurs, the extent of which can be controlled by the choice of reaction conditions.
- alkoxylation products according to the invention with intrinsically reduced viscosity of the formula (I) in which t (starter (2)) ⁇ t (starter (1) since these alkoxylation products have a particularly excellent flowability and facilitate the preparation process to a particularly high degree
- the alkoxylation products (1) of the formula (I) according to the invention are characterized in that the viscosity of mixtures of the alkoxylation product (1) of the formula (I) with alkoxylation product (2 ) by at least 10%, preferably by at least 15%, more preferably by at least 20%, 30%, 40%, 50%, 60% or 70%, reduced compared to the otherwise identical alkoxylation product (1) without addition of starter (2) during the alkoxylation.
- alkoxylation products / polymers of the starter (1) H-D A
- mixtures of divalent polyethers HD A
- PO propylene oxide
- GLYEO 3-glycidyloxypropyltriethoxysilane
- EO ethylene oxide
- EO ethylene oxide
- methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol exxon), octanol, 2-ethylhexanol, 2-Propylheptanol, allyl alcohol, decanol, dodecanol, Ci 2 / Ci 4 fatty alcohol, phenol, all constitution isomers of cresol, benzyl alcohol, stearyl alcohol, in particular butanol, 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol of Exxon), allyl alcohol, 2-ethylhexanol or 2-propylheptanol.
- the OH-functional hydrocarbon radical contains 7 to 100 carbon atoms, wherein the carbon chain of the hydrocarbon radical is preferably interrupted by oxygen atoms, preferably the hydrocarbon radical interrupted by oxygen atoms is a polyoxyalkylene radical, polyether radical and / or polyetheralkoxy radical, or else a polyester , Polycarbonate, polyetherester radical or mixtures of the abovementioned radicals.
- the monohydroxy-functional compounds are preferably compounds having molecular weights of from 32 to 2,000 g / mol, particularly preferably from 50 to 1000 g / mol, in particular from 60 to 200 g / mol. These compounds can be used in any mixtures with each other or as a pure substance. It is also possible to use laterally substituents containing alkoxysilyl groups or hydroxy compounds substituted directly with alkoxysilyl groups, such as the silyl polyethers described in EP 2093244 as starters (2).
- the preferably monohydroxy-functional compounds of the initiator (2) are added to the ongoing alkoxylation process and can thus also be referred to as starter molecules, since they can function as new chain starters for the construction of a polymer / polyether due to the presence of the OH group in the molecule.
- the fragment D x of the starter (HD A ) t D x with t equal to 2 is preferably a compound selected from low molecular weight compounds such as ethylene glycol, propylene glycol, di- / triethylene glycol, 1,2-propylene glycol, di- / tripropylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 2-hexanediol and 1, 6-hexanediol, trimethylolpropane or glycerol monoether such.
- low molecular weight compounds such as ethylene glycol, propylene glycol, di- / triethylene glycol, 1,2-propylene glycol, di- / tripropylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 2-hexanediol and 1, 6-hexanediol, trimethylolpropane or glycerol monoether such.
- the fragment D x of the starter (HD A ) t D x with t greater than 2 is preferably a compound selected from commercially available sugar alcohols such as erythritol, xylitol and in particular the 6-valent reduction products of the monosaccharides such as mannitol and sorbitol.
- Preferred initiators D x are hydroxyl-terminated polyethers prepared by a reaction of ethylene oxide, optionally in combination with propylene oxide. All mentioned starters can also be used in any mixtures.
- Particularly preferred starters D x are hydroxyl-containing polyesters such.
- Particularly preferred initiators are polypropylene glycols and polytetrahydrofurans (available in various molecular weights as Terathane® (Invista) and PolyTHF® (BASF) eg PolyTHF 2000)).
- alkoxylation products according to the invention which, based on the individual molecule, have more than one alkoxysilyl group per group UR on a numerical average.
- i 2 to 10, preferably greater than 2 to 6, particularly preferably 2
- j 0 to 6, preferably 1, 2, 3 or 4
- k 0, 1 or 2, preferably 0
- I 0, 1 or 2, preferably 0
- a 0 to 50, preferably 2 to 20, more preferably 1 to 4,
- b 10 to 500, more preferably 12 to 400
- c 0 to 20, preferably 0 to 4
- d 0 to 20, preferably 0
- w 0 to 20, preferably 0
- y 0 to 20, preferably 0,
- R 1 independently of one another is a saturated or unsaturated, linear or branched organic hydrocarbon radical which may contain O, S and / or N as heteroatoms, preferably the hydrocarbon radical contains 1 to 400 carbon atoms, preferably 2, 3 or 4 to 200 carbon atoms , particularly preferably an alkyl radical having 2 to 12, preferably having 3 to 6 carbon atoms, more preferably a butyl radical,
- R 27 independently of one another is a saturated or unsaturated, linear or branched organic hydrocarbon radical which may contain, as heteroatoms, O, S and / or N, preferably the hydrocarbon radical contains 1 to 50 carbon atoms, preferably 2, 3 or 4 to 30 carbon atoms , preferably the radicals R 27 result from monovalent alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol,
- 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol exxon), octanol, 2-ethylhexanol, 2-propylheptanol, decanol, dodecanol, 2 Ci / Ci4-fatty alcohol, phenol, all constitutional isomers of cresol, benzyl alcohol, stearyl alcohol, more preferably butanol, 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate ( Texanol exxon), 2-ethylhexanol, allyl alcohol, 1-hexenol or 2-propylheptanol, especially butanol or allyl alcohol,
- R 28 independently of one another is hydrogen or a fragment of the formula (II) or (I Ia) bonded via UR or AP.
- a 1 to 50, preferably greater than 1 to 20, more preferably 2 to 10, in particular 0 to 6,
- c 0 to 20, preferably 0
- d 0 to 20, preferably 0
- w 0 to 20, preferably 0
- y 0 to 20, preferably 0,
- R 2 independently of one another a methyl or ethyl, propyl, or isopropyl group, preferably a methyl or ethyl group
- R 3 independently of one another a methyl or ethyl, propyl, or isopropyl group, preferably a methyl or ethyl group
- R 4 independently of one another hydrogen or a methyl, ethyl, octyl, decyl, dodecyl, phenyl or benzyl group, particularly preferably hydrogen or a methyl or ethyl group,
- R 5 independently of one another hydrogen, methyl or ethyl, in particular preferably hydrogen,
- R 11 independently of one another is an optionally substituted alkyl chain having 4 to 20 carbon atoms, preferably having 5 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, preferably selected from methyl, ethyl, propyl, butyl, isobutyl , tert-butyl, 2-pentyl, 3-pentyl, 2
- (CH 3 ) 3 - (radical of neodecanoic acid), Ci 2 / Ci 4 alkyl, phenyl, cresyl, tert-butylphenyl or benzyl group, particularly preferably a 2-ethylhexyl, C (OHCH 2 ) 5 -C - (CH 3) 3- (rest of neodecanoic acid), d 2 / C 4 alkyl, phenyl, cresyl, t-butylphenyl group, most preferably a tert-butylphenyl or 2-ethylhexyl group,
- UR are independently the same or different divalent radicals of the form
- D c independently of one another a divalent substituted or unsubstituted, linear or branched, saturated or unsaturated
- compositions containing these alkoxylation products (1) in combination with the alkoxylation products (2) have a particularly excellent flowability and also facilitate the production process to an extraordinarily high degree.
- EP 2 093 244 describes that alkoxysilanes bearing epoxide functions can be selectively alkoxylated in an advantageous manner in the presence of known double metal cyanide catalysts.
- the method disclosed there opens up the possibility of carrying out the mono- and / or multiple alkoxysilyl group modification of polyoxyalkylene compounds in a reproducible manner not only terminally but also within the sequence of oxyalkylene units.
- the disclosure of EP 2 093 244 is to be considered in its entirety as part and part of this description.
- compositions according to the invention can be prepared by one of the methods mentioned below.
- Another object of the present invention is a process for the preparation of compositions with intrinsically reduced viscosity containing alkoxylation products (1) and (2).
- step b) still takes place during the ongoing alkoxylation of step a).
- the addition of the initiator (2) preferably takes place after the addition of the initiator (1) has been completed.
- High reductions in viscosity are achieved in particular if starter (1) has a molecular weight of greater than 400 g / mol and starter (2) has a molar mass of less than or equal to 400 g / mol.
- starter (1) has a molecular weight of greater than 400 g / mol
- starter (2) has a molar mass of less than or equal to 400 g / mol.
- a particularly good reduction of the viscosity can be achieved if the molecular weight of initiator (1) the molecular weight of initiator (2) by at least 200 g / mol, preferably by at least 600 g / mol, more preferably by at least 1000th g / mol, exceeds.
- the molecular weight of starter (1) is at least twice as large as the molecular weight of starter (2). Methods in which such initiators are used are therefore particularly preferred.
- the alkylene oxides of process step (a) are preferably ethylene oxide and / or propylene oxide and at least one epoxide bearing alkoxysilyl groups and the alkylene oxides of process (b) are ethylene oxide and / or propylene oxide and optionally at least one epoxide bearing alkoxysilyl groups and / or other monomers. Preference is given to using monomers in the following proportions: 10 to 97% by weight, preferably 20 to 95% by weight, particularly preferably 30 to 90% by weight of propylene oxide, 0 to 60% by weight, preferably 3 to 40% by weight.
- % more preferably 5 to 30 wt .-% of ethylene oxide, 0 to 25 wt .-%, preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-% alkoxysilyl-carrying epoxide and 0 to 25 wt.
- % preferably 0.1 to 20 wt .-%, particularly preferably 0 to 10 wt .-% further monomers, preferably selected from propylene oxide and ethylene oxide different alkylene oxides, such as butylene oxide, isobutylene oxide, styrene oxide and / or other comonomers such as ⁇ - caprolactone, phthalic anhydride, glycidyl ethers such as tert-butylphenyl glycidyl ether, Ci2 / Ci4-Fettalkoholglycidylether and 2- Ethylhexylglycidylether based on the total weight of the monomers used.
- propylene oxide and ethylene oxide different alkylene oxides such as butylene oxide, isobutylene oxide, styrene oxide and / or other comonomers such as ⁇ - caprolactone, phthalic anhydride, glycidyl ethers such as
- a particularly preferred process which is particularly advantageous for the reduction of the viscosity of the process products is a process for the preparation of alkoxylation products comprising the steps
- starter (1) and (2) are OH-functional compounds, preferably as defined above, in that the starter (1) has a higher OH functionality, ie more OH groups, than the starter (2)
- DMC catalysts double metal cyanide catalysts
- alkoxylation products according to the invention are preferably obtainable by adding to such initiators at least one glycidyl ether of the general formula (V) Formula (V) with
- R 2 independently of one another an alkyl group having 1 to 8 carbon atoms
- R 3 independently of one another an alkyl group having 1 to 8 carbon atoms
- At least one further polymerizable monomer preferably selected from alkylene oxides, glycidyl ethers, lactones, cyclic dicarboxylic acid anhydrides and mixtures thereof, in particular alkylene oxides, more preferably monomers which in the finished product to fragments with the index b, c, d, w and / or y, particular preference is given to fragments having the index b, the formulas (Ia), (II) and (IIa) which are reacted with one another such that the starter (2) is not present together with starter (1) at the beginning of the reaction, but instead be added together with one or more of the aforementioned monomers during the ongoing alkoxylation.
- alkylene oxides preferably selected from alkylene oxides, glycidyl ethers, lactones, cyclic dicarboxylic acid anhydrides and mixtures thereof, in particular alkylene oxides, more preferably monomers which in the finished product to fragments with the index b, c, d
- alkylene oxide compounds which lead to the fragments with the index b indicated in the formulas (Ia), (II) and (IIa) are known e.g. Ethylene oxide, 1,2-epoxypropane (propylene oxide), 1,2-epoxy-2-methylpropane (isobutylene oxide), epichlorohydrin, 2,3-epoxy-1-propanol, 1,2-epoxybutane (butylene oxide), 2,3-epoxybutane , 2,3-dimethyl-2,3-epoxybutane, 1,2-epoxy pentane, 1,2-epoxy-3-methylpentane, 1,2-epoxyhexane, 1,2-epoxycyclohexane, 1,2-epoxyheptane, 1,2 Epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, styrene
- lactones which by ring opening lead to the fragments with the subscript d given in formulas (la), (II) and (IIa) are valerolactones or caprolactones, both unsubstituted or with alkyl groups, preferably methyl groups , may be substituted. Preference is given to using ⁇ -caprolactone or ⁇ -valerolactone, in particular ⁇ -caprolactone.
- Succinic anhydride, oct (en) yl, dec (en) yl and dodec (en) yl-succinic anhydride, maleic anhydride, itaconic anhydride are preferably used as saturated, unsaturated or aromatic cyclic dicarboxylic acid anhydrides which lead by reaction to the fragments with the index y .
- Phthalic anhydride, hexahydro, tetrahydro, dihydro, methylhexahydro and Methyltetrahydrophthal Acidanhydrid used.
- the respective Anhydridmonomere be copolymerized in any order and variable amount sequentially or temporally parallel to Epoxidfeed under ring opening to polyether esters. It is also possible to use mixtures of the stated anhydrides. Furthermore, it is possible to add the anhydrides to the starter D x before the start of the reaction and to dispense with a zudosage as described above. However, it is also possible to add both the starter D x anhydrides and to add further anhydride during the course of the alkoxylation in the further course of the reaction.
- Succinic anhydride, maleic anhydride, phthalic anhydride, and hexahydrophthalic anhydride are particularly preferably used, in particular maleic anhydride and hexahydrophthalic anhydride.
- glycidyl ethers which lead to the in the formulas (la), (II) and (IIa) indicated fragments with the index c correspond to the general formula (IV).
- R is formula (IV) with R 11 as defined above.
- R 11 corresponds to a methyl, ethyl, iso-butyl, tert-butyl, hexyl, octyl, 2-ethylhexyl, -C (OHCH 2 ) 5 -C- (CH 3 ) 3 ( remainder of the neodecanoic acid, obtainable, for example, as Cardura E 10 P in Momentive), C 12/14, phenyl, cresyl or tert-butylphenyl group or / and an allyl group, more preferably an allyl, cresyl, 2- Ethylhexyl, -C (OHCH 2 ) 5 -C- (CH 3 ) 3 or Ci 2 / Ci 4 group.
- Particularly preferred are 2-ethylhexyl (available, for example, as Grilonit RV 1807, Grilonit RV 1807 4.1 or IPOX RD 17)
- glycidyl ethers are also suitable as glycidyl ethers, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
- Cyclohexandimethanoldiglycidylether Neopentylglykoldiglycidylether, Polyethylenglykoldiglycidylether, polypropylene glycol diglycidyl ether, polyglycerol-3-glycidyl ether, Glycerintriglycidether, trimethylolpropane triglycidylether or Pentraerythrittetraglycidylether be used, whereby branched structural elements in the final alkoxylation of the formulas (I) according to the formulas (la), (II) and (IIa) can be introduced.
- modified alkoxylation products according to formula (I) can be prepared, as well as any desired mixtures.
- Useful alkylene oxide compounds which lead to the fragments having the subscript a given in the formulas (Ia), (II) and (IIa) can be represented by the general formula (V) Formula (V) with f, g, h, R 2 and R 3 as defined above, correspond.
- a non-exhaustive collection of epoxy group-substituted alkoxysilanes according to formula (V) includes, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3
- Glycidyloxypropyltripropoxysilane 3-glycidyloxypropyltriisopropoxysilane, bis (3-glycidyloxypropyl) dimethoxysilane, bis (3-glycidyloxypropyl) diethoxysilane, 3-glycidyloxyhexyltrimethoxysilane, 3-glycidyloxyhexyltriethoxysilane, 3
- Glycidyloxypropyl-methyl-dimethoxysilane 3-glycidyloxypropyl-ethyl-diethoxysilane.
- DYNASYLAN ® GLYMO and GLYEO DYNASYLAN ® are obtainable in the inventive process as compounds of formula (V) 3-glycidyloxy-propyltrimethoxy- or triethoxysilane are preferably used.
- Particularly preferred is the use of glycidyloxy-propyltriethoxysilane, since methanol emissions can be avoided in this way when used as moisture-crosslinking components.
- the radical R 1 is preferably derived from a hydroxyl-containing compound of the formula (VI)
- alkoxysilyl groups or hydroxy compounds substituted directly with alkoxysilyl groups such as the silyl polyethers described in EP 2093244, as starting compounds.
- the compounds of the type R 1 -H as starters (2) during the alkoxylation, so that alkoxylation products, in particular of the formula (Ia), form, which are formed by the addition of epoxide-functional Monomers and possibly further comonomers is obtained.
- the compound of the formula R 1 -H used in the process according to the invention is preferably selected from the group of alcohols, polyetherols or phenols.
- the starting compound used is preferably a monovalent or polyvalent one Polyether alcohol or alcohol used. Preference is given to using monohydric to tetravalent polyether alcohols or alcohols. Particular preference is given to using monohydric polyether alcohols or alcohols.
- low molecular weight polyetherols having molecular weights of 50 to 2000 g / mol, which in turn were previously prepared by DMC-catalyzed alkoxylation used.
- any compounds having OH functions are suitable. These include, for example, phenol, alkyl and arylphenols.
- OH-functional starters (1) and (2) are preferably compounds having molecular weights of 62 to 10,000 g / mol, preferably 92 to 7000 g / mol, more preferably 122 to 5000 g / mol, and for starter (1), particularly preferably 2000 to 4000 g / mol.
- the starting compounds can be used in any mixtures with each other or as a pure substance. It is also possible to use substituents containing alkoxysilyl groups on the side or hydroxyl compounds substituted directly by alkoxysilyl groups, such as the silyl polyethers described in EP 2093244, as starting compounds.
- low molecular weight polyetherols having molecular weights of 62 to 4000 g / mol, which in turn were previously prepared by DMC-catalyzed alkoxylation, used as starter compounds.
- any compounds having OH functions are suitable. These include, for example, phenol, alkyl and aryl phenols or carbohydrates such as. Saccharides, in particular bisphenol A and novolaks are suitable as starting compounds.
- the average molar masses M w of the alkoxylation products of the unit (s) D according to formula (I) are preferably between 4000 and 50,000 g / mol, preferably between 8000 and 20,000 g / mol and more preferably from 10,000 to 16,000 g / mol.
- the alkoxylation products of formula (I) are liquid at room temperature.
- the hydrophilicity / hydrophobicity of the molecular moieties M, D, T, Q of the alkoxylation products according to the invention can be adjusted by the choice of suitable starter molecules and / or suitable comonomers for the alkoxylation.
- the alkoxylation products according to the invention can be obtained in various ways.
- the preparation of the alkoxylation products according to the invention is preferably carried out by the process according to the invention described below.
- the alkoxylation products of the formula (I) are distinguished by the fact that they can be prepared in a targeted and reproducible manner with regard to structure structure and molecular weight.
- the sequence of the monomer units can be made variable within wide limits.
- Epoxy monomers can be strung together as desired in blocks or randomly incorporated into the polymer chain.
- the inserted by the reaction under ring opening of the reaction components in the resulting polymer chain fragments are freely permutatable in their sequence with each other, to arrange in any order, with the proviso that cyclic anhydrides and carbon dioxide randomly inserted, so not in homologous blocks, in the Polyether structure are present, as well as not in direct neighborhood to each other.
- index numbers reproduced in the formulas given here and the value ranges of the specified indices are therefore to be understood as the average values of the possible statistical distribution of the actual structures present and / or their mixtures. This also applies to such exactly reproduced structural formulas, such as for formula (Ia) and / or (II) and / or (IIa).
- alkoxysilyl unit in the compound of the formulas (Ia), (II) and (IIa) is preferably a trialkoxysilyl unit, in particular triethoxysilyl unit.
- the alkyl radical R 3 bonded to the silicon via an oxygen atom is exchanged formally for a long-chain modified alkoxysilyl polymer radical.
- Bimodal as well as multimodal GPC curves show that the alkoxylation products in addition to the non-transesterified species, as shown in formula (I) are those containing twice, in some cases three times or even many molar mass. Formula (I) thus only reproduces the complex chemical reality in a simplified way.
- the alkoxylation products are mixtures which may also contain compounds in which the sum of the indices f + g in the formulas (Ia), (II) and (IIa) is less than 3 on average since a part of the OR Groups can be replaced by Silylpolyether phenomenon.
- the compositions thus contain species which are formed on the silicon atom with elimination of R 3 -OH and condensation reaction with the reactive OH group of another molecule of the formulas (Ia) and / or (II) and / or (IIa). This reaction can take place several times until, for example, all R 3 0 groups on the silicon have been replaced by further molecules of the formulas (Ia) and / or (II) and / or (IIa).
- the presence of more than one signal in typical 29 Si NMR spectra of these compounds underpins the appearance of silyl groups with different substitution patterns.
- the products according to the invention can be prepared in many different ways, in particular by processes which are based on the process described in EP 2 093 244, EP 2415796 (US 2012/028022) or EP 2415797 (US 2012/029090).
- the alkoxylation products according to the invention are preferably prepared by the process according to the invention described below.
- a preferred process according to the invention for the preparation of an alkoxylation product according to the invention with intrinsically reduced viscosity according to formula (I) is characterized in that at least one starting molecule (H-D A ) t D x with t greater than or equal to 2 with at least one glycidyl ether of the general formula (V ) and optionally at least one alkylene oxide are reacted in such a way that in the course of the alkoxylation temporarily at least one starter (2) with t greater than or equal to 1 is added.
- the preferred monohydroxy-functional starter compounds (2) are added to the ongoing alkoxylation process, comprising starter (1), preferably in the presence of a double metal cyanide catalyst, and can thus also be referred to as starter molecules since they are characterized by the presence of the OH group in the molecule as a new chain starter for the construction of a polymer / polyethers can act.
- starter molecules preferably in the presence of a double metal cyanide catalyst
- alkoxylation products are obtained with significantly reduced viscosity. This is all the more astonishing as the skilled person could not expect any change in the product due to the so-called "catch-up" behavior of DMC catalysts.
- the process according to the invention for the preparation of an alkoxylation product according to the invention with intrinsically reduced viscosity may preferably consist of up to two process steps.
- process step A an alkoxylation reaction which can be carried out in several stages is preferably carried out, followed, if appropriate, by a process step B, a so-called end-capping reaction.
- step A is a DMC-catalyzed alkoxylation of a starter (1) with epoxide-containing compounds (alkylene oxides and Glycidyl ethers) carried out in the course of the reaction, starter (2) are added.
- epoxide-containing compounds alkylene oxides and Glycidyl ethers
- the starting mixture consisting of one or more OH-functional initiator (1) D x and the double metal cyanide catalyst, which was optionally previously slurried in a suspending agent, placed in the reactor.
- a polyether or inert solvent can be used or advantageously also one or more starting compounds, or alternatively a mixture of both components.
- the initial mixture is added propylene oxide or at least one other epoxy compounds added.
- the molar ratio of epoxide to the reactive groups of the initiator, in particular the OH groups in the starting mixture, in the starting phase is preferably between 0.1: 1 and 10: 1, preferably between 0.2: 1 and 5: 1, in particular between 0.4 to 1 to 3 to 1. It may be advantageous if, if appropriate, before the addition of the epoxide existing, the reaction inhibiting substances from the reaction mixture optionally removed in vacuo by distillation.
- Starting the exothermic reaction may e.g. be detected by a pressure and / or temperature monitoring.
- a sudden drop in pressure in the reactor indicates, in the case of gaseous alkylene oxides, that the alkylene oxide is incorporated, thus initiating the reaction and reaching the end of the start-up phase.
- the onset of the reaction is indicated by the incipient heat of reaction.
- any mixture of different alkylene oxide compounds and compounds of the formulas (IV) and (V) can also be added, and these can also be added separately in any order one after the other.
- the reaction can be carried out, for example, for the purpose of reducing the viscosity of the reaction mixture in an inert solvent.
- Suitable inert solvents are hydrocarbons, in particular toluene, xylene or cyclohexane. However, this is less preferred.
- the addition of the alkylene oxide compounds is preferably carried out at a temperature of 60 to 250 ° C, more preferably at a temperature of 90 to 160 ° C.
- the pressure at which the alkoxylation takes place is preferably 0.02 bar to 100 bar, particularly preferably 0.05 to 20 bar and in particular from 0.2 to 2 bar absolute.
- the alkoxylation may be carried out in the presence of an inert gas (e.g., nitrogen) or, in the presence of carbon dioxide, to produce polyethercarbonates, even at an overpressure of preferably 1 to 20 bars absolute.
- lactones or cyclic anhydrides which can be used for the preparation of ester-modified polyethers can be added to the mixture of initiator (1) and catalyst both in the starting phase and at a later time in parallel to the alkylene oxide feed.
- the comonomers mentioned can also be metered into the reactor in succession alternately with alkylene oxides.
- the molar ratio of the alkylene oxide monomers to cyclic anhydrides is variable. Usually, at least equimolar amounts of alkylene oxide monomers based on anhydrides are used. It is preferred to use the alkylene oxides in a molar excess to ensure complete anhydride conversion.
- Lactones may be added during the alkoxylation optionally in stoichiometric excess or excess based on the alkylene oxide monomers.
- starters (2) can be done within wide limits in terms of concentration, type and number of compounds, as well as the nature of the reaction, which allows the user a high flexibility.
- starters (2) can be done once at a specific time or even several times in portions at several times.
- the total amount of starter (2) can be equal to the desired number divided into portions, but it is also possible to divide the total amount of different sized portions.
- the addition can also be carried out continuously.
- the continuous addition may be carried out once during the alkoxylation reaction or several times.
- the addition of starters (2) preferably takes place continuously.
- the addition of starters (2) takes place once and then in a continuous manner.
- the dosage rate of the starter (2) can also be varied widely, depending on the respective requirements, without negatively influencing the properties of the product mixtures according to formula (I).
- starters (2) are added to the reaction mixture, it is possible to mix the compounds before the dosage and then add them as a mixture continuously or discontinuously, but it is also possible to supply all the starter (2) separately continuously or discontinuously to the reaction mixture , In this case, it is also possible first to add the first starter (2) and then in a second portion another starter (2). If further addition steps are desired then it is possible in the following to add the first starter (2) again and thus - if the second connection follows again - to realize an alternating addition protocol, but it is also possible to implement any other starter (II) in one or more starters several portions are added.
- II any other starter
- the concentration of the metered starters (2) in relation to the molar amount of the initiator used (1) can be varied within wide limits.
- the molar ratio of all starter molecules (1) used to all starters (2) added is preferably between 1: 0.001 and 0.001: 1, more preferably between 1: 0.01 and 0.01: 1 and particularly preferably between 1: 0.1 and 0.1: 1.
- the functionality of the starters used (1) and (2), ie the value of t of the starter (HD A ) t -D x is freely selectable within wide limits.
- t (starter (1))> t (starter (2)).
- any residues of unreacted monomer and possibly other volatile constituents are removed, usually by vacuum distillation, gas stripping or other methods of deodorization.
- the removal of volatile secondary components can be carried out either batchwise or continuously. In the case of the method based on DMC catalysis according to the invention, it is normally possible to dispense with filtration.
- the process steps can be carried out at identical or different temperatures.
- the mixture of starter substance, DMC catalyst and, if appropriate, suspending agent initially introduced in the reactor in accordance with the teaching of WO 98/52689 can be pretreated by stripping before starting the monomer metering.
- an inert gas is added to the reaction mixture via the reactor feed and by means of a vacuum system connected to the reactor system, more volatile components are removed by applying a reduced pressure from the reaction mixture.
- more volatile components are removed by applying a reduced pressure from the reaction mixture.
- the addition of inert gas and the simultaneous removal of the more volatile components may be particularly advantageous when starting / starting the reaction, since by the addition of the reactants or by side reactions also inhibiting compounds can get into the reaction mixture.
- double metal cyanide catalysts DMC catalysts
- the DMC catalysts described in EP 2 093 244 in particular the DMC catalysts described there as being preferred or particularly preferred, are preferably used in the process according to the invention.
- the catalyst concentration is preferably> 0 to 1 000 ppm by weight (ppm by mass), preferably from> 0 to 500 ppm by weight, more preferably from 0.1 to 300 ppm by weight and very particularly preferably from 1 to 200 ppm by weight. This concentration is based on the total mass of the resulting alkoxylation.
- the catalyst is dosed only once in the reactor.
- the amount of catalyst should be adjusted to provide sufficient catalytic activity for the process.
- the catalyst can be metered in as a solid or in the form of a catalyst suspension. If a suspension is used, in particular the starter D x is suitable as suspending agent. Preferably, however, waives a suspension. It may be advantageous if process step A of the process according to the invention is carried out in such a way that the alkoxylation is carried out in at least three stages. In step 1, the initiator (1) is reacted with a small amount of propylene oxide in the presence of the DMC catalyst as previously described.
- propylene oxide is further added, whereby in this way preferably a maximum molecular weight of 500 to 10,000 g / mol, more preferably at most 1000 to 3,000 g / mol is built up in addition to the starter used.
- stage 2 the addition of further propylene oxide and / or ethylene oxide with the addition of at least one initiator (2) and optionally one or more of the abovementioned glycidyl ethers of the formula (IV); in step 3, the addition of one or more of the compounds of formula (V) is optionally carried out with further addition of propylene oxide and / or ethylene oxide; wherein the stages 2 and 3 can also be combined into one stage.
- stage 2b before stage 3, in which only alkylene oxides, preferably propylene oxide and / or ethylene oxide, optionally together with glycidyl ethers of the formula (IV) are added.
- alkylene oxides preferably propylene oxide and / or ethylene oxide
- glycidyl ethers of the formula (IV) are added.
- the alkoxysilane functionality is randomly introduced through the polymer chains / blocks.
- the order of execution of stages 2 and 3 is arbitrary. Preferably, after stage 1, stage 2 is first performed before stage 3 is performed. Steps 2 and 3 can be performed several times in succession.
- the alkylene oxides used and the components of the formulas (IV), (V) and the initiator (2) may be the same or different.
- the detailed description of the method described above is merely for better illustration and represents a preferred dosage sequence of the reactants. From this no strict blockwise structure of the alkoxylation products according to the invention with reduced viscosity may be derived.
- Step 1 is preferably carried out at a temperature of 70-160 ° C, preferably at 80-150 ° C, more preferably at a temperature of 100-145 ° C, most preferably at 110-105 ° C.
- Step 2 is preferably carried out at a temperature of 70-160 ° C, preferably at 80-150 ° C, more preferably at a temperature of 100-145 ° C, most preferably at 110-103 ° C.
- Step 3 is preferably carried out at a temperature of 70-140 ° C, preferably at 75-120 ° C, more preferably at a temperature of 80-1 ° C. If steps 2 and 3 are summarized, then the reaction temperature is to be adjusted to the preferred temperature under step 3.
- a process step B is carried out in which the terminal (s) OH group (s) of the alkoxylation product is / are reacted such that no free OH group is no longer present.
- reaction can be carried out with silanol-formers or monoisocyanates, preferably with a monoisocyanate, as described in application EP 2415797 (US 2012/029090).
- Suitable monoisocyanates can be used in the simplest case alkyl, aryl, arylalkyl isocyanates. Preference is given to using methyl, ethyl, butyl, hexyl, octyl, dodecyl and stearyl isocyanate, particular preference being given to butyl isocyanate.
- Particularly suitable monofunctional isocyanates are also those which in turn carry crosslinkable alkoxysilyl groups in the molecule. These preferably include isocyanatoalkyl-trialkoxysilanes and isocyanatoalkyl-alkyldialkoxysilanes.
- Suitable alkoxysilane-functional monoisocyanates may be isocyanatotrimethoxysilane, isocyanatomethyltriethoxysilane, (isocyanatomethyl) methyldimethoxysilane, (isocyanatomethyl) methyldiethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3 Isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyl-diethoxysilane be used.
- Preferred here is the use of 3-isocyanatopropyltrimethoxysilane and triethoxysilane.
- process step B for the preparation of the alkoxylation products according to the invention with intrinsically reduced viscosity of the formula (I) it is characterized in that in a first reaction step (a) polyethers of the formula PE are reacted with diisocyanates and in a second reaction step ( b) the product / product mixture of the first reaction step (a) are reacted with a molecule of the formula HM.
- the polyethers of the formula PE are described above.
- the molecules of the formula HM are compounds containing hydrogen bound to the fragment M, which is described above.
- the diisocyanates are preferably used in a molar excess over the OH groups of the polyethers resulting from t starter (1) plus t (starter 2), ie t starter (1) + t (starter 2) ⁇ c (diisocyanate).
- di-, tri- or tetramers of the alkoxysilylpolyether fragments M can thus be synthesized via a corresponding polyisocyanate, depending on the number of isocyanate groups in the polyisocyanate.
- the alkoxylation products (1) and (2) are selected such that more alkoxysilyl groups than groups UR are present in the product.
- the two reactions (a) and (b) are preferably carried out with a time separation from one another.
- the stoichiometric ratios determine the number of UR fragments in the product.
- the unreacted isocyanate groups are preferably reacted with the molecule HM.
- starter (2) is a starter with only one OH group
- HM may preferably be alkoxylation product (2).
- the reaction with the molecule H-M corresponds to an endcapping method. It is sought with this reaction step, preferably to bring all isocyanate groups to the Abreaction.
- Process step B of the process according to the invention for preparing alkoxysilyl compounds of formula (I) is preferably carried out with isophorone diisocyanate in the presence of a transition metal catalyst and described in detail in unpublished patent application DE 10 2012 203737.
- isocyanates are suitable as compounds containing isocyanate groups.
- Aromatic, aliphatic and cycloaliphatic polyisocyanates having a number-average molecular weight of less than 800 g / mol are preferred for the purposes of the teaching according to the invention.
- TDDI 2,2,4-trimethylhe
- Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and / or 4,4'-diisocyanatodicyclohexylmethane can be used as preferred diisocyanates for the preparation of the alkoxylation products of the formula (I), in particular isophorone diisocyanate (IPDI) can preferably be used.
- isocyanate-containing starting components are reaction products of the aforementioned isocyanates with themselves or with one another to uretdiones or isocyanurates. Examples include Desmodur® N3300, Desmodur® N3400 or Desmodur® N3600 (all Bayer MaterialScience, Leverkusen, DE).
- isocyanates such as allophanates or biurets.
- examples include Desmodur® N100, Desmodur® N75MPA BA or Desmodur® VPLS2102 (all Bayer MaterialScience, Leverkusen, DE).
- the documents EP 2415797 (US 2012/029090), the disclosure of which with respect to the methods disclosed therein are hereby incorporated in their entirety as part of this application.
- process step B is carried out such that> 20% by weight, preferably> 50% by weight and particularly preferably> 75% by weight of the alkoxylation products obtained no longer has a free OH group.
- the alkoxylation products of the invention may, for. B. be used for the preparation of curable compositions.
- Curable compositions according to the invention are distinguished by having one or more of the above-described alkoxylation products according to the invention of the formula (I) and at least one curing catalyst.
- the proportion of alkoxylation products according to the invention in the composition according to the invention is preferably from 10 to less than 90 wt .-%, preferably from 15 to 70 wt .-%, and particularly preferably from 20 wt .-% to 65 wt .-%.
- curing catalysts for the crosslinking or polymerization of the composition of the invention or their chemical fixation on particle or macroscopic surfaces
- the catalysts commonly used for the hydrolysis and condensation of alkoxysilanes can be used.
- organic tin compounds e.g. Dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin diacetate, dibutyltin dioctoate, or dioctyltin dilaurate,
- zinc salts such as zinc octoate, zinc acetylacetonate and zinc 2-ethylcaproate, or
- Tetraalkylammonium compounds such as N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide, N, N, N-trimethyl-N-2-hydroxypropylammonium-2 ethylhexanoate or choline-2-ethylhexanoate.
- bismuth catalysts for example Borchi ® catalysts, titanates such as titanium (IV) isopropoxide, iron (III) compounds such as iron (III) - acetylacetonate, aluminum compounds such as aluminum triisopropoxide, aluminum trihydroxide sec-butylate and other alcoholates, and Aluminum acetylacetonate, calcium compounds, such as calcium disodium ethylenediaminetetraacetate or calcium diacetylacetonate, or also amines, for example triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1, 5
- Diazabicyclo [4.3.0] non-5-ene N, N-bis (N, N-dimethyl-2-aminoethyl) methylamine, N, N-dimethylcyclohexylamine, ⁇ , ⁇ -dimethylphenylamine, N-ethylmorpholine, etc., be used.
- organic or inorganic Bronsted acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid or benzoyl chloride, hydrochloric acid, phosphoric acid their mono- and / or diesters such.
- Butyl phosphate, (iso) propyl phosphate, dibutyl phosphate, etc. are suitable as catalysts. Of course, combinations of several catalysts can be used.
- the proportion of the curing catalysts in the composition of the invention is preferably from 0.1 wt .-% to 5 wt .-%, preferably from 0.15 to 2 wt .-% and particularly preferably from 0.2 to 0.75 wt .-%, based on the total composition.
- the composition according to the invention may contain further additives selected from the group of plasticizers, fillers, solvents, adhesion promoters, flowability adjusting additives, so-called rheology additives and drying agents, in particular chemical moisture-drying agents.
- composition according to the invention preferably comprises one or more adhesion promoters and / or one or more drying agents, in particular chemical moisture drying agents.
- Adhesion promoters which may be present are the adhesion promoters known from the prior art, in particular aminosilanes, in the composition according to the invention.
- adhesion promoters it is possible to use compounds bearing alkoxysilyl groups which additionally have primary or secondary amine groups, Vinyl groups, thiol groups, aryl groups, or alternatively have oxirane groups such as 3-aminopropyltrimethoxysilane (Dynasylan AMMO ® (Evonik), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Dynasylan DAMO ® (Evonik)), N- (n-butyl) aminopropyltrimethoxysilane (Dynasylan 1189 (Evonik)), 3-mercaptopropyl trimethoxysilane (Dynasylan MTMO ®, Evonik), 3-glycidyloxy propyl triethoxysilane (Dynasylan ® GLYEO, Evonik) 3-
- Phenyltrimethoxysilane (Dynasylan ® 9165 or Dynasylan ® 9265, Evonik) or oligomeric amino / alkyl-alkoxysilanes such as Dynasylan ® 1 146 (Evonik) are respectively used alone or in mixture.
- Preferred existing adhesion promoters are z. B.
- 3-aminopropyltriethoxysilane (Geniosil ® GF 93 (Wacker), Dynasylan AMEO ® (Evonik ®)) and / or (3-Aminopropy) methyldiethoxysilane (Dynasylan ® 1505 (Evonik ®)), 3-aminopropyltrimethoxysilane (Dynasylan AMMO ® (Evonik ), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Dynasylan DAMO ® (Evonik)), Dynasylan ® 1 146 (Evonik), more preferably 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3- aminopropyltrimethoxysilane, Dynasylan ® 1 146, and particularly preferred are
- the proportion of the adhesion promoters in the composition according to the invention is preferably from greater than 0 to 5 wt .-%, preferably from 0.5 to 4 wt .-% and particularly preferably from 1 to 2.5 wt .-% based on the total composition. It may be advantageous if the composition of the invention comprises a drying agent, for. B. for binding introduced by formulation components, or subsequently introduced by the filling process or storage of water or moisture. In principle, all drying agents known from the prior art can be used as drying agents in the compositions according to the invention.
- vinyltriethoxysilane (DYNASYLAN ® VTEO, Evonik or Geniosil ® GF 56, Wacker), vinyltriacetoxysilane (Geniosil ® GF 62, Wacker), N- can, for example vinyltrimethoxysilane (Dynasylan ® VTMO, Evonik or Geniosil ® XL 10, Wacker AG), trimethoxysilylmethyl-O-methylcarbamate (Geniosil ® XL 63, Wacker), N-dimethoxy (methyl) silylmethyl-0-methyl-carbamate, N-methyl [3- (trimethoxysilyl) - propyl] carbamate (Geniosil ® GF 60, Wacker ), vinyldimethoxymethylsilane (Geniosil ® XL 12, Wacker), vinyltris (2-methoxyethoxy) silane (Geniosil ® GF GF
- vinyltrimethoxysilane (Dynasylan ® VTMO, Evonik or Geniosil ® XL 10, Wacker AG), vinyltriethoxysilane (DYNASYLAN ® VTEO, Evonik or Geniosil ® GF 56, Wacker) was used as drying agent.
- the inventive composition preferably contains vinyl trimethoxysilane (Dynasylan ® VTMO, Evonik or Geniosil ® XL 10, Wacker AG).
- a physical desiccant such as zeolites, molecular sieves, anhydrous sodium sulfate or anhydrous magnesium sulfate may be used.
- the proportion of drying agent in the composition of the invention is preferably from greater than 0 to 5 wt .-%, preferably from 0.2 to 3 wt .-% based on the total composition.
- composition according to the invention may comprise one or more additives selected from the group of plasticizers, fillers, solvents and rheological additives (rheology additives).
- the plasticizers may, for. B. be selected from the group of phthalates, the polyester, alkyl sulfonic acid esters of phenol, cyclohexanedicarboxylic or polyether.
- the plasticizers used are only those compounds which are different from the alkoxylation products of the formula (I) according to the invention.
- the proportion of plasticizer in the composition according to the invention is preferably from greater than 0% by weight to 90% by weight, preferably from 2% by weight to 70% by weight, particularly preferably 5% by weight % to 50% by weight based on the total composition.
- fillers z Example, precipitated or ground chalk, inorganic carbonates in general, precipitated or ground silicates, precipitated or pyrogenic silicic acids, glass powders, glass bubbles (so-called Bubbles), metal oxides, such as Ti0 2 , Al 2 0 3 , natural or precipitated barium sulfate reinforcing fibers, such as glass fibers or carbon fibers, long or short fibrous wollastonites, cork, soot or Graphite can be used.
- hydrophobic fillers can be used, since these products have a lower water input and improve the storage stability of the formulations.
- the proportion of fillers in the composition according to the invention preferably from 1 to 70 wt .-% based on the total composition, wherein for the fillers mentioned here, except for the fumed silicic acid concentrations of 30 to 65 wt. -% are particularly preferred. If fumed silicas are used, a proportion of the fumed silicas of 2 to 20 wt .-% is particularly preferred.
- rheological additives preferably contain, in addition to the filler may be selected from the group of amide waxes, available for example from Cray Valley under the trade name Crayvallac ®, hydrogenated vegetable oils and fats, fumed silicas, such as Aerosil ® R202, or R805 (both available from Evonik) or Cab-O- Sil® TS 720 or TS 620 or TS 630 (sold by Cabot). If pyrogenic silicas are already used as fillers, the addition of a rheological additive can be omitted.
- the proportion of rheology additives in the composition according to the invention is preferably greater than 0% by weight to 10% by weight, preferably from 2% by weight to 6% by weight. based on the total composition.
- compositions of the invention may contain solvents.
- the solvents may serve, for example, to lower the viscosity of the uncrosslinked mixtures or may favor the application to the surface.
- Suitable solvents are in principle all solvents and solvent mixtures into consideration.
- Preferred examples of such solvents are ethers such as t-butyl methyl ether, esters such as ethyl acetate or butyl acetate or diethyl carbonate and alcohols such as methanol, ethanol and the various regioisomers of propanol and butanol or application-specific selected glycol types.
- aromatic and / or aliphatic solvents as well as halogenated solvents, such as dichloromethane, chloroform, carbon tetrachloride, hydrofluorocarbons (FREON), etc. can be used, but also inorganic solvents such as Water, CS 2 , supercritical C0 2 and so on.
- halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, hydrofluorocarbons (FREON), etc.
- inorganic solvents such as Water, CS 2 , supercritical C0 2 and so on.
- compositions according to the invention may also contain one or more substances selected from the group consisting of co-crosslinkers, flame retardants, deaerators, antimicrobial and preservatives, dyes, colorants and pigments, antifreeze agents, fungicides and / or reactive diluents and complexing agents, spray aids, wetting agents, Fragrances, light stabilizers, radical scavengers, UV absorbers and stabilizers, especially stabilizers against thermal and / or chemical stress and / or exposure to ultraviolet and visible light.
- substances selected from the group consisting of co-crosslinkers, flame retardants, deaerators, antimicrobial and preservatives, dyes, colorants and pigments, antifreeze agents, fungicides and / or reactive diluents and complexing agents, spray aids, wetting agents, Fragrances, light stabilizers, radical scavengers, UV absorbers and stabilizers, especially stabilizers against thermal and / or chemical stress and / or exposure to ultraviolet
- UV stabilizers z. B known products based on hindered phenolic systems are used. As light stabilizers z. B. so-called HALS amines can be used. As stabilizers z. B. the known to the expert products or product combinations of eg Tinuvin ® - stabilizers (Ciba), such as. B. Tinuvin ® stabilizers (Ciba), for example, Tinuvin ® 1130, Tinuvin ® 292 or Tinuvin ® 400 also preferably, Tinuvin ® be used in combination with 1130 Tinuvin ® 292nd Their quantity depends on the degree of stabilization required.
- co-crosslinkers for increasing mechanical hardness and reducing flow tendency can be added to the curable compositions.
- Such co-crosslinkers are typically substances which are capable of providing 3, 4 or more crosslinkable groups. Examples in the context of this invention are 3-aminopropyltriethoxysilane, tetramethoxysilane or tetraethoxysilane.
- compositions according to the invention comprise at least one alkoxylation product of the formula (I) and a plasticizer, a filler, an adhesion promoter, a drying agent or a (curing) catalyst.
- compositions according to the invention have from 10 to 90% by weight or less than 80% by weight, based on the total composition of the alkoxylation product of the formula (I), preferably on average between 2.0 and 8.0, of ethoxysilyl functions per alkoxylation product of the formula (I), from 0.3 wt .-% to 5.0 wt .-%, preferably from 0.5 wt .-% to 4.0 wt .-%, and particularly preferably from 1, 0 wt .-% to 2.5 wt .-% based on the total composition of adhesion promoters, less than 30 wt .-% based on the total composition of plasticizer, more preferably the mass ratio of the alkoxylation product of formula (I) and plasticizer is less than 1, 1 times the alkoxylation of formula (I), from 1 to 70 wt .-% based on the total composition of fillers , from 0.2 to 3.0% by weight, based on the total composition, of chemical moisture-
- the stated proportions of the formulation constituents are selected so that the total sum of the proportions totals 100% by weight.
- compositions of the invention may, for. As sealant or adhesive or be used to produce a sealant or adhesive.
- the composition according to the invention in particular the composition according to the invention thus obtained, cures in, compared to previously commercially available and technically used products comparable periods, and cross-linked, if it was applied in thicker layers, also very well in depth.
- the flank adhesion and connection to various substrates, such as steel, aluminum, various plastics and mineral substrates such as stone, concrete and mortar, is particularly good.
- compositions according to the invention can be used in particular for the reinforcement, leveling, modification, bonding, sealing and / or coating of substrates.
- Suitable substrates are for.
- MDF medium density fiberboard
- WPC Wood Plastic Composites
- compositions according to the invention are particularly preferred for sealing and / or coating particulate or flat substrates, in the construction industry or in vehicle construction, for sealing and Bonding of construction elements and components, as well as for the coating of porous or non-porous, particulate or flat substrates, for coating and modification of surfaces and for applications on metals, in particular on construction materials such as iron, steel, stainless steel and cast iron, for use on ceramic materials , in particular based on solid metal or non-metal oxides or carbides, aluminum oxide, magnesium oxide or calcium oxide, mineral substrates or organic substrates, in particular cork and / or wood, for binding, reinforcement and leveling of uneven, porous or brittle substrates, such as mineral Substrates, chipboards and fibreboards made of wood or cork, composite materials such as wood composites such as MDF (medium density fiberboard), WPC (Wood Plastic Composites), chipboard, cork, laminated articles, ceramics, but also natural fibers and synthetic fibers, or Mi mixtures of different substrates.
- compositions of the invention are preferably applied in a temperature range of 10 ° C-40 ° C and cure well under these conditions. Due to the moisture-dependent hardening mechanism, a relative humidity of min. 35% to max. 75% is particularly preferred for good curing.
- the cured bond (composition) can be used in a temperature range from -10 ° C to 80 ° C.
- the bonds produced with the compositions according to the invention are resistant to water at T ⁇ 60 ° C. and to non-swelling solvents. Not resistant is the bonding against the formulation of swelling solvent, such as methanol, ethanol, toluene, tetrahydrofuran, acetone, isopropanol.
- Example 2 The syntheses were carried out analogously to Example 1, wherein the target product was built up by addition of three blocks to the respective starting molecule. After attachment of the first block, which was built up from PO as alkylene oxide, followed by a 30-minute post-reaction, a second block in which a mixture of PO and the respective starter (2) was added. After the dosage, followed by a one-hour reaction.
- Molar ratio 2 1 produced.
- 2524 g of polyether from Example 16 are mixed with 438 g of polyether from Example 17 in a 4 L glass flask and homogenized by stirring for 30 minutes at room temperature and then determines the viscosity. This was 4.6 Pa ⁇ s at 25 ° C.
- silyl polyether from Example 6 2497 g were initially charged and heated to 60.degree. Subsequently, 94 g of IPDI was added, stirred for five minutes and 2.78 g of TIB Kat 722 (bismuth carboxylate) was added. The mixture was stirred for 45 minutes, heated to 80 ° C and 189 g of a polyether of the general formula C 4 H 9 0 [CH 2 CH (CH 3 ) 0] 5 , 6H added. The mixture was then stirred for a further 3 h.
- silyl polyether from Example 7 2538 g were initially charged and heated to 60.degree. Then, 95 g of IPDI was added, stirred for five minutes and 2.82 g of TIB Kat 722 (bismuth carboxylate) added. The mixture was stirred for 45 minutes, heated to 80 ° C and 190 g of a polyether of the general formula C 4 H 9 0 [CH 2 CH (CH 3 ) 0] 5 , 6H added. The mixture was then stirred for a further 3 h.
- silyl polyether from Example 12 were initially charged and heated to 60.degree. Subsequently, 59 g of IPDI were added, stirred for five minutes and 1.5 g of TIB Kat 722 (bismuth carboxylate) was added. The mixture was stirred for 45 minutes, heated to 80 ° C and 1 19 g of a polyether of the general formula C 4 H 9 0 [CH 2 CH (CH 3 ) 0] 5 , 6H added. The mixture was then stirred for a further 3 h.
- silyl polyether from Example 13 2925 g were initially charged and heated to 70.degree. Then, 100 g of IPDI was added, stirred for five minutes and 0.2 g of TIB Kat 216 (dioctyltin dilaurate) was added. The mixture was stirred for 45 minutes and 201 g of a polyether of the general formula C 4 H 9 0 [CH 2 CH (CH 3 ) 0] 5.6H added. The mixture was then stirred at 70 ° C. for a further 5 hours.
- silyl polyether from Example 14 2617 g were initially charged and heated to 70.degree. Then, 100 g of IPDI was added, stirred for five minutes and 0.2 g of TIB Kat 216 (dioctyltin dilaurate) was added. The mixture was stirred for 45 minutes and 200 g of a polyether of the general formula C 4 H 9 O [CH 2 CH (CH 3 ) 0] 5.6H added. The mixture was then stirred at 70 ° C. for a further 5 hours.
- the final formulation was transferred to PE cartridges and stored at room temperature prior to application of at least 24. Since the formulations of the alkoxylation products were identical in the above examples, in all cases, was the Result discussion based on the name of the used as the basis of the formulation alkoxylation carried out.
- the formulation was knife-coated with a layer thickness of 2 mm on a PE surface.
- the films were stored for 7 days at 23 ° C and 50% relative humidity. Subsequently, S2 shoulder bars were punched out of the films using a cutting die and a toggle press.
- Overlapping bonds were created with the prepared formulation. Two stainless steel substrates (V2A, 1 .4301) were used. The area of overlap bonding was 500 mm 2 . The curing of the bonds was carried out at 23 ° C and 50% relative humidity. After 21 days, the bonds were clamped in a universal testing machine (Shimadzu) and a force was applied to the bond at a constant speed (10 mm / min) until the bond broke. The breaking stress was determined.
- compositions which are not according to the invention have a viscosity which is at least 10% higher than the viscosity of the compositions according to the invention.
- Table 2 is in the alkoxylation products according to the invention having terminal OH groups from Examples 2-7 and 1 1, in which a polyether (PPG 2000) has been used as a starter to record a reduction in viscosity by at least 50%, compared to Comparative Example 1, where no starter (2) is used. If the functionality of starter (2) is identical to starter (1) or higher, then a noticeable reduction in viscosity compared to Example 1 is still observed, by about 30% (Examples 8, 9, 12). This lower viscosity reduction effect is clear evidence that it is particularly advantageous to use starters (2) with a functionality reduced by 1 compared with starter (1).
- PPG 2000 polyether
- Example 14 As Example 14 (with starter (2)) compared to Example 18 (without starter (2)) and Example 15 (with starter (2)) compared to Example 19 (without starter (2)), the effect can be the viscosity reduction also transferred to chemically different, (not polyether) starter.
- a polycarbonate (Desmophen C 2200 in Example 14 or 18) and a polyester (Baycoll AD 2055 in Example 15 and 19, respectively) were used in the process according to the invention and in both cases it was possible by adding 1-butanol as starter (2). a viscosity reduction of at least 40% to the comparative examples can be observed.
- Example 17 it was not started directly from butanol but from an adduct of butanol + 5.5 PO. These were taken into account in the recipe accordingly. Subsequently, these polymers were mixed in Example 20 and reacted in Example 33 with IPDI. From the viscosity of Example 20 it is clear that this mixing of differently functional silyl polyether leads to a comparable viscosity reduction, which is in the range of Examples 2-7 and 1 1 according to the invention, but this effect is not sustainable in the desired follow-up. Although the end-capped secondary product according to Example 33 still has a viscosity reduced by almost 60% compared to Comparative Example 21, the viscosity reduction effect in Reference Example 2 is still much greater, that is, almost twice as large. On the basis of the application properties of Comparative Example 33 shown in Table 4, no noticeable effect can be determined. Both breaking stress and elongation are comparable to Reference Example 21.
Abstract
Description
Claims
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JP2016526117A JP2017503869A (ja) | 2013-12-03 | 2014-11-26 | 本質的に低下した粘度を有するアルコキシシリル含有接着剤/シーラント |
KR1020167014489A KR20160094951A (ko) | 2013-12-03 | 2014-11-26 | 고유하게 감소된 점도를 갖는 알콕시실릴-함유 접착 실란트 |
PL14812149T PL3077440T3 (pl) | 2013-12-03 | 2014-11-26 | Substancje klejąco-uszczelniające zawierające alkilosilil o naturalnie niższej lepkości |
US15/101,819 US9896534B2 (en) | 2013-12-03 | 2014-11-26 | Alkoxysilyl-containing adhesive sealants with intrinsically reduced viscosity |
MX2016006863A MX2016006863A (es) | 2013-12-03 | 2014-11-26 | Selladores adhesivos que contienen alcoxisililo con viscosidad intrinsecamente reducida. |
AU2014359576A AU2014359576B2 (en) | 2013-12-03 | 2014-11-26 | Alkoxysilyl-containing adhesive sealants with intrinsically reduced viscosity |
EP14812149.4A EP3077440B1 (de) | 2013-12-03 | 2014-11-26 | Alkoxysilylhaltige klebdichtstoffe mit intrinsisch reduzierter viskosität |
ES14812149T ES2764094T3 (es) | 2013-12-03 | 2014-11-26 | Sellantes adhesivos que contienen alcoxisililo con viscosidad reducida intrínsecamente |
ZA2016/04326A ZA201604326B (en) | 2013-12-03 | 2016-06-27 | Alkoxysilyl-containing adhesive sealants with intrinsically reduced viscosity |
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DE102013224708.7A DE102013224708A1 (de) | 2013-12-03 | 2013-12-03 | Alkoxysilylhaltige Klebdichtstoffe mit intrinsisch reduzierter Viskosität |
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EP (1) | EP3077440B1 (de) |
JP (1) | JP2017503869A (de) |
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AU (1) | AU2014359576B2 (de) |
DE (1) | DE102013224708A1 (de) |
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EP3202816A1 (de) | 2016-02-04 | 2017-08-09 | Evonik Degussa GmbH | Alkoxysilylhaltige klebdichtstoffe mit verbessertem weiterreisswiderstand |
US10287448B2 (en) | 2016-07-08 | 2019-05-14 | Evonik Degussa Gmbh | Universal pigment preparation |
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KR101863817B1 (ko) * | 2017-01-17 | 2018-06-01 | 울산과학기술원 | 건식접착 구조물의 제조방법 |
PL3360912T3 (pl) | 2017-02-10 | 2020-01-31 | Evonik Degussa Gmbh | Sposób wytwarzania hydrosililowanych eterów polioksyalkilenowych |
KR101922549B1 (ko) | 2017-06-15 | 2018-11-28 | 순천대학교 산학협력단 | 폴리에테르 폴리올의 제조방법 |
EP3461864A1 (de) | 2017-09-28 | 2019-04-03 | Evonik Degussa GmbH | Härtbare zusammensetzung auf basis von polysiloxanen |
US10787464B2 (en) | 2017-10-17 | 2020-09-29 | Evonik Operations Gmbh | Zinc ketoiminate complexes as catalysts for the production of polyurethanes |
ES2834450T3 (es) | 2018-03-05 | 2021-06-17 | Evonik Operations Gmbh | Copolímeros en bloques de poliéter-siloxano reticulados, así como su empleo para la producción de espumas de poliuretano |
CA3116911A1 (en) | 2018-11-02 | 2020-05-07 | H.B. Fuller Company | Moisture curable hot melt sealant composition including silane functional polyurethane |
WO2020092938A1 (en) | 2018-11-02 | 2020-05-07 | H.B. Fuller Company | Moisture curable hot melt sealant composition |
EP3744745A1 (de) | 2019-05-28 | 2020-12-02 | Evonik Operations GmbH | Herstellung von pu-schaumstoffen |
CN116814211B (zh) * | 2023-06-06 | 2024-04-16 | 杭州之江有机硅化工有限公司 | 一种反应型密封胶树脂及其制备方法和应用 |
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- 2014-11-26 MX MX2016006863A patent/MX2016006863A/es unknown
- 2014-11-26 PL PL14812149T patent/PL3077440T3/pl unknown
- 2014-11-26 JP JP2016526117A patent/JP2017503869A/ja not_active Ceased
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---|---|---|---|---|
EP3202816A1 (de) | 2016-02-04 | 2017-08-09 | Evonik Degussa GmbH | Alkoxysilylhaltige klebdichtstoffe mit verbessertem weiterreisswiderstand |
US10287448B2 (en) | 2016-07-08 | 2019-05-14 | Evonik Degussa Gmbh | Universal pigment preparation |
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DE102013224708A1 (de) | 2015-06-03 |
ZA201604326B (en) | 2017-09-27 |
AU2014359576A1 (en) | 2016-05-12 |
JP2017503869A (ja) | 2017-02-02 |
EP3077440A1 (de) | 2016-10-12 |
PL3077440T3 (pl) | 2020-04-30 |
US20160311963A1 (en) | 2016-10-27 |
KR20160094951A (ko) | 2016-08-10 |
US9896534B2 (en) | 2018-02-20 |
EP3077440B1 (de) | 2019-10-30 |
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MX2016006863A (es) | 2016-08-17 |
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