WO2013017365A1 - Procédé de production de polyéthersiloxanes contenant des squelettes polyéthercarbonate - Google Patents
Procédé de production de polyéthersiloxanes contenant des squelettes polyéthercarbonate Download PDFInfo
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- WO2013017365A1 WO2013017365A1 PCT/EP2012/062976 EP2012062976W WO2013017365A1 WO 2013017365 A1 WO2013017365 A1 WO 2013017365A1 EP 2012062976 W EP2012062976 W EP 2012062976W WO 2013017365 A1 WO2013017365 A1 WO 2013017365A1
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- C—CHEMISTRY; METALLURGY
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
Definitions
- the present invention relates to polyethersiloxanes containing carbonate groups, to a process for their preparation and to their use. More particularly, the present invention relates to a process for the preparation of polysiloxanes in which unsaturated polyether carbonates are added to SiH-bearing alkyl siloxanes.
- the unsaturated polyether carbonates are prepared by a technically easy to implement three-step one-pot process, wherein the incorporation of glycerol units, which cause the branching in the polyether carbonate backbone, preferably takes place between two alkoxylation steps.
- hydrosilylated polyglycerols in both cases are base-catalyzed reaction products of allyl alcohol and several moles of glycidol.
- a process for producing such polyglycerols is also described in DE 10 2007 043618 (US 2008085980).
- a base-catalyzed addition of glycidol to allyl alcohol or glycerol monoallyl ether is described.
- the start connection is through the Addition of NaOH or sodium methylate deprotonated as a catalyst and the resulting by-products water or methanol are removed in vacuo.
- the glycidol addition is carried out at temperatures below 100 ° C to avoid unwanted side reactions.
- the rearrangement of allyl groups into corresponding 2-propenyl groups should be mentioned.
- This grouping is less reactive in subsequent reactions such as hydrosilylations and thus reduces the content of reactive molecules in the polyglycerol composite.
- the reduced reaction temperature as well as the necessary distillation step prolongs the process time, moreover, provision must be made for a distillation step on an industrial scale, which comes with a significant financial investment.
- EP 0 116 978 (US 07 / 356,359) describes the Lewis acid and alkali metal hydroxide catalyzed polymerization of glycidol and ethylene oxide onto polyhydroxy-functional polyethers. However, the use of these compounds to modify polysiloxanes is not described.
- the branched polyethers described in WO 2007/075927 (US2010234518) are based on the reaction of allyl alcohol with alkylene oxides and glycidol or hydroxy-functional oxetanes as branching component. Also in the application DE 10 2006 031 152 (US 2010240842) describes a corresponding structural motif based on hydroxy-functional oxetanes as branching component.
- glycidol z. B obtained by dehydrochlorination of 3-chloropropane-1, 2-diol, based on epichlorohydrin as the starting component.
- toxic halogens such as chlorine
- unusable by-products large amounts of unusable by-products.
- only petrochemical raw materials are irrevocably consumed and large quantities of unusable by-products are produced, both of which contribute to an extraordinary burden on our ecosystem.
- glycidol also carries a high health-relevant hazard potential in itself, since it is carcinogenic and can also lead to serious eye damage in case of eye contact.
- Glycerine carbonate is the much more advantageous compound from an ecotoxicological point of view. It is obtained on an industrial scale from the renewable raw material glycerine. Glycerine is increasingly a by-product of the production of biodiesel from fatty acid esters. The glycerol carbonate can finally be obtained by transesterification with dimethyl carbonate or condensation with urea. The glycerine carbonate is a stable, colorless compound that is toxicologically harmless and not is subject to labeling. In addition, unlike glycidol, glycerol carbonate can be distilled without decomposition, which considerably facilitates any necessary purification.
- the object of the present invention was to provide a process for the preparation of polyethersiloxanes which have one or more branched polyether components, which are preferably highly hydrophilic, and do not have one or more of the disadvantages of the processes of the prior art.
- polyethersiloxanes having branched polyether components can be prepared in a simple manner by a process comprising the steps of (a) providing branched polyethercarbonates having at least one olefinically unsaturated group, (b) providing SiH-functional siloxanes, and (c) reacting the SiH-functional siloxanes from (b) with the branched polyethercarbonates having at least one olefinically unsaturated group from step (a) to form SiC linkages. It was also completely surprising that the carbonate-containing polyether carbonates are stable. In the IR spectra before and after three weeks storage at 60 ° C, no differences were seen.
- the present invention therefore provides a process for the preparation of polyether carbonate-containing polysiloxanes containing branched structures, which is characterized in that it comprises the steps of (a) providing branched polyether carbonates having at least one olefinically unsaturated group and at least one structural unit -O-C (0) -0-, (b) providing SiH-functional siloxanes, and (c) reacting the SiH-functional siloxanes of (b) with the branched polyethercarbonates having at least one olefinically unsaturated group from step (a) to form SiC linkages.
- polysiloxane compounds according to the invention of the formulas (IV) and (V) described below and the compositions according to the invention can be used for a wide variety of applications.
- the use is to be mentioned as surface-active substances, such as.
- nonionic surfactants such as.
- emulsifiers or wetting agents such as.
- An example is the possible H-bonding of the terminal OH groups (if present) of the branched structures.
- the compounds of the invention or the compositions of the invention may, for.
- Example 2 as an additive for ceramic formulations, as an additive in coating compositions, polymeric molding materials or thermoplastics, as crosslinking agents and as an additive for polyurethane compounds, in the manufacture of paints, varnishes, adhesives, as a support of catalysts or in biomedical technology are commonly used.
- a Use as an additive for cosmetic formulations and detergents is also possible.
- the process according to the invention also has the advantage that the hydrosilylation process step can also be carried out in the absence of solvents and / or acid-buffering agents without any loss of product quality having to be accepted. Also, the undesirable side reactions reported in EP 1 489 128 A1 could not be observed with the method according to the invention.
- a further advantage of the present invention is that it is possible to dispense with the removal of the alcohols produced in the preparation of the polyether carbonates without having to accept any loss of quality of the end product.
- branched polyether carbonate here stands for a polyether carbonate in which both the main chain and at least one side chain contain polyether and / or polyether carbonate structures.
- Branched polyether carbonates which have at least one olefinically unsaturated group and at least one structural unit -O-C (O) -O- are preferably of the formula (I)
- i 1 to 10, preferably 1 to 5, preferably 2 to 3,
- Z any organic, terminally unsaturated, radical, preferably terminally unsaturated, linear, cyclic or branched, aliphatic or aromatic hydrocarbon radical which may also contain heteroatoms, as well as further substituted, functional, organic, saturated or unsaturated radicals,
- X is O, NH, N-alkyl, N-aryl or S, preferably O or NH, particularly preferably O
- J independently of one another hydrogen, a linear, cydic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 30 C atoms, a carboxylic acid radical having 1 to 30 carbon atoms or a heteroatom-substituted, functional, organic, saturated or unsaturated Radical, preferably hydrogen, a linear or branched, saturated hydrocarbon radical having 1 to 18 carbon atoms or a carboxylic acid radical having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl or acetyl radical,
- Y independently of one another is a linear, cydic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 2 to 30 C atoms, which may also contain heteroatoms,
- the monomers M1 to M9 may be arranged in any ratios, both blockwise, alternately or randomly, and may have a distribution gradient, and in particular the monomers M1 to M4 are freely permutable, with the provisos that i9> 0, preferably from 0 , 1 and 100, preferably 0.5 to 50 and particularly preferably 1 to 10, that preferably at least one unit M5 or M6 is contained, in which no radical J joins directly at any end, and that two monomer units of the type M9 not follow one another.
- the radical J in formula (I) is a hydrogen atom, a methyl or acetyl radical.
- the sum ⁇ i5 to i9 is preferably> i + 1, preferably> i + 2.
- i1 is greater than 0 and i2, i3 and i4 are equal to zero.
- the branched polyethercarbonate to be hydrosilylated is preferably made up of a suitable initiator and various monomer units M.
- branched polyether carbonates in particular the branched polyether carbonates of the formula (I), are preferably prepared by reacting starters of the general formula (II)
- the starter Z (XH) j is preferably a polyether alcohol.
- Such initiators are preferably (meth) allylic compounds.
- (meth) allylic When the term "(meth) allylic” is used, it includes “allylic” and “methallylic” respectively.
- allylic starters are used in the context of this invention, this term always also encompasses the methallylic analogs, with the allylic compounds being preferred as starters in each case.
- Examples of mono-hydroxy-functional starters of the formula (II) which have an aromatic radical Z are, for example, B. allyl or methallyl-substituted phenol derivatives.
- Examples of preferably used ⁇ -hydroxy-co-alkenyl-substituted starters are in particular 5-hexen-1-ol and 10-undecene-1-ol, with 5-hexen-1-ol being particularly preferred.
- Suitable cyclic unsaturated, hydroxy-functional compounds are e.g. 2-cyclohexen-1-ol, 1-methyl-4-isopropenyl-6-cyclohexene-2-ol and 5-norbornene-2-methanol.
- Such polyhydroxy-functional starters are preferably monoallylically etherified di-, tri- or polyols, such as, for example, monoallyl ethers of glycerol, trimethylolethane and trimethylolpropane, monoallyl or mono (methallyl) ethers of di (trimethylol) ethane, di (trimethylol) propane and pentaerythritol.
- the starter according to formula (II) with j> 1 is particularly preferably derived from a compound from the group comprising 5,5-dihydroxymethyl-1,3-dioxane, 2-methyl-1,3-propanediol, 2-methyl-2- ethyl-1, 3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, dimethylpropane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di (trimethylolethane), di (trimethylolpropane), pentaerythritol, Di (pentaerythritol), anhydroenneaheptitol, sorbitol and mannitol.
- an allyl polyether is used as initiator, it may be possible to dispense with the first alkoxylation step. To ensure the preservation of well-defined structures, the reaction is carried out as an anionic ring-opening polymerization under controlled monomer addition.
- Particular preference is given to using ethylene oxide, propylene oxide, dodecene-1-oxide and styrene oxide.
- alkyl as used herein preferably linear or branched C1-C30, such as C1-C12 or C r C 8 -, - alkyls or alkenyls.
- alkyl particularly preferably represents methyl, ethyl, propyl, butyl, tert-butyl, 2-ethylhexyl, allyl and C12-C14.
- aryl is preferably phenylglycidyl ether and the term “alkaryl” is preferably o-cresylglycidyl ether, p-tert-butylphenylglycidyl ether or benzylglycidyl ether.
- alkoxy preferably represents methoxy, ethoxy, propoxy, butoxy, phenylethoxy and comprises between 1 and up to 30 alkoxy units or a combination of two or more alkoxy units.
- glycene carbonate is used in the process according to the invention.
- a branching agent is understood as meaning a molecule which, after reaction into the polyether skeleton, provides two reactive groups on which a further chain structure can take place.
- the glycene carbonate introduces into the polyether carbonate R v the monomer units M5 to M8 and M9 defined in the formula (I).
- the ideal parameter here is the percentage molar content of branching agent, based on the molar content of the sum of all monomers from which the polyethercarbonate skeleton is made, ignoring the mole of starting alcohol. This molar content should preferably be at most 80 mol%, more preferably at most 50 mol%, and most preferably at most 35 mol%.
- the XH groups are preferably at least partially deprotonated by alkali metal hydroxide or alkoxide, preferably sodium methoxide, potassium methoxide or potassium hydroxide, more preferably sodium methoxide.
- alkali metal hydroxide or alkoxide preferably sodium methoxide, potassium methoxide or potassium hydroxide, more preferably sodium methoxide.
- the amount of alkali metal hydroxide or alkoxide used is preferably from 5 to 25 mol%, preferably from 10 to 20 mol%, based on the number of XH groups, preferably OH groups of the initiators used.
- the mixture of alcohols and alcoholates thus obtained is in the first process step with alkylene oxides preferably at a temperature between 80 ° C and 200 ° C, preferably from 90 ° C to 170 ° C and more preferably reacted from 100 to 125 ° C.
- the reaction preferably takes place at pressures in the range from 0.001 to 100 bar, preferably in the range between 0.005 and 10 bar and very particularly preferably between 0.01 and 5 bar (in each case absolute pressures).
- a deodorization step may optionally follow to remove traces of unreacted alkylene oxides.
- the reactor is preferably at the temperature resulting from the alkoxylation, preferably up to a vacuum of less than or equal to 100 mbar, more preferably up to a vacuum of less than or equal to 60 mbar and more preferably to a vacuum of less than or equal to 30 mbar evacuated.
- the glycerol carbonate preferably at a temperature between 120 ° C and 220 ° C, more preferably between 140 ° C and 200 ° C and most preferably at a temperature between 160 ° C and 180 ° C. supplied to the reaction mixture.
- the ratio of glycerol carbonate-based branching units M5-M8 to carbonate ester segments M9 can be controlled.
- the addition of the branching agent takes place at a rate of 0.1 to 10, preferably 0.5 to 5 and particularly preferably 1 to 2.5 mol / h based on the number of (XH) groups of the starter used.
- the reaction of the glycerol carbonate can be partly due to the release of C0 2 and consequently by a pressure build-up in the reactor noticeable. This pressure build-up can be counteracted by continuous or periodic release.
- the rate of addition of the glycerol carbonate is preferably chosen so that the pressure in the reactor at no time exceeds a value of 2 bar (bar overpressure). Higher pressures in the reactor should be avoided, since at high temperatures and pressures, the rearrangement of allyl groups in no longer hydrosilylatable propenyl groups takes place increasingly and this would constitute an intolerable quality defect.
- the (living) anionic ring-opening polymerization is controlled in all three process steps by the rapid exchange of protons between the alcohol and alcoholate groups of the growing chains. Since an additional hydroxyl group is generated with each mole of branching agent reacted, the effective concentration of alkoxide ions decreases as a result of the process. As a result, the reaction speed of the third process step may be slower than that of the first process step. To take this effect into account, it may be advantageous to carry out a renewed catalyst dosing after the second reaction step. Of course, in order to achieve a faster conversion of the glycerol carbonate, renewed catalyst dosing may also take place after the first reaction step, but this is less preferred.
- the low molecular weight alcohol formed from the reaction of the catalyst with the molecule to be deprotonated can be distilled off both during the first process step and during the third process step in vacuo.
- this process step is preferably dispensed with.
- a neutralization step may follow, in which the alkali z. B. is neutralized by the addition of appropriate amounts of inorganic acids such as phosphoric acid or organic acids such as lactic acid. Treatment with an acidic ion exchanger is also possible, but less preferred.
- the branched polyethercarbonates have at least one branching generation, preferably at least two branching generations.
- the term "generation” is, as in WO 2002/40572 (US2004059086), in the present case also used to designate pseudo-generations.
- the C NMR shifts of the branched polyether carbonates were evaluated analogously to H. Frey et al., Macromolecules 1999, 32, 4240-1260.
- the polydispersity (MJM n ) of the branched polyethercarbonates of the formula (I), determined by means of GPC, is preferably ⁇ 3.5, preferably ⁇ 2.5 and particularly preferably from> 1.05 to ⁇ 1.8.
- hydroxy groups can also be used.
- the mentioned chemical reactions do not have to be quantitative.
- the free hydroxy groups may only partially, i. in particular at least one hydroxyl group to be chemically modified.
- the chemical modifications of the free hydroxy groups of the branched polyethercarbonates can be chemically modified both before and after the hydrosilylation reaction with the Si-H-functional polysiloxane
- the SiH-functional siloxanes are preferably prepared in process step (b) by carrying out the equilibration process known from the prior art.
- the equilibration of the branched or linear, optionally hydrosilylated, poly (organo) siloxanes having terminal and / or pendant SiH functions is in the prior art, for.
- EP 1 439 200 A1 US 2004147703
- DE 10 2007 055 485 A1 US 2010249339
- DE 10 2008 041 601 US2010056649
- the step (c) is preferably carried out as hydrosilylation.
- the olefinically unsaturated polyether carbonates from step (a) are SiC-linked with the SiH-functional siloxanes from step (b) by means of noble metal catalysis.
- the reactions may be carried out in accordance with procedure (c) in the presence or absence of saturated polyethers.
- process step (c) is carried out in the presence of saturated polyethers. It is possible to carry out process step c) in the presence of other solvents other than saturated polyethers. Preferably, no solvents other than saturated polyethers are used.
- Process step c) can also be carried out in the presence of acid-buffering agents. Preferably, however, it is carried out in the absence of acid-buffering agents.
- the process step is carried out in the absence of acid-buffering agents and solvents other than saturated polyethers.
- step (c) in addition to the branched polyether carbonates of (a), it is possible to use further linear and / or branched, unsaturated polyether compounds which are different from these. This is particularly advantageous if it is to be possible to adapt it to the compatibility with the application matrix of the polyether carbonate-containing polysiloxanes.
- polyethers can be prepared by any of the methods known in the art.
- the alkoxylation of unsaturated starting compounds can be both under base, acid or double metal cyanide (DMC) catalysis.
- DMC double metal cyanide
- the preparation and use of DMC alkoxylation catalysts has been known since the 1960's and is illustrated, for example, in US 3,427,256, US 3,427,334, US 3,427,335, US 3,278,457, US 3,278,458 or US 3,278,459.
- Even more effective DMC catalysts, in particular zinc-cobalt hexacyanocomplexes have been developed in the subsequent period, for example in US Pat. Nos. 5,470,813 and 5,482,908.
- the molar proportion of the unsaturated polyether carbonates used to the carbonate-free polyethers is preferably from 0.001 to 100 mol%, preferably from 0.5 to 70 mol% and particularly preferably 1 to 50 mol% based on the Sum of unsaturated polyether carbonates and carbonate-free unsaturated polyethers.
- the polysiloxane compounds described below can be prepared.
- a is independently 0 to 2000, preferably 0 to 1000, in particular 1 to 500,
- R 1 is independently R or -OR 4 ,
- R is independently R, R v, R P or-OR 4 1b
- R 4 independently of one another are alkyl radicals having 1 to 10 carbon atoms, preferably methyl, ethyl or isopropyl radical,
- k 0 to 9, preferably 0 to 5, preferably 1 to 3
- i + k 1 to 10, preferably 1 to 5, particularly preferably 1 to 3
- R 1b are of the type -OR 4 .
- d 0 to 10, preferably 0 to 5, preferably 0 or 1 to 3,
- k 0 to 9, preferably 0 to 5, preferably 1 to 3
- i + k 1 to 10, preferably 1 to 5, particularly preferably 1 to 3
- i1 to i10 each independently 0 to 500, preferably 0 to 100 and particularly preferably 0.1 to 30
- X 1 to X 4 independently of one another are hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 50 C atoms, preferably 2 to 50 C atoms, which may optionally contain halogen atoms, with the proviso that X 1 to X 4 are not chosen such that M3 is equal to M1 or M2,
- Y independently of one another is a linear, cydic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 2 to 30 C atoms, which may also contain heteroatoms,
- the number of residues J in R v depends on the number of branches, ie the number of units M5 and M6 and the indices i and k.
- the properties of the polysiloxane according to the invention can be influenced.
- M1 and M2 in the radical R v By varying proportions of M1 and M2 in the radical R v , the properties of the polysiloxane according to the invention can be influenced.
- M1: M2 ratios the hydrophobicity or respectively the hydrophilicity of the polysiloxane according to the invention are controlled.
- the hydrocarbon radicals Z may preferably have halogens.
- the hydrocarbons Z may in particular have nitrogen and / or oxygen, preferably oxygen.
- Particularly preferred hydrocarbon radicals Z have no substituents and no heteroatoms and very particularly preferably have from 2 to 20 carbon atoms.
- Compounds of the general formulas (IV) and (V) in which b1 is at least 1 are advantageously used in those systems which require compatibility adaptation; however, if b1 is zero then a necessary adaptation of the compatibility can also be achieved by the intrinsic structure of the branched polyether carbonate be achieved.
- the polysiloxane compounds according to the invention are preferably obtainable by the process according to the invention described above.
- compositions according to the invention in particular coating compositions, polymeric molding compounds or thermoplastics, are those which contain from 0.1 to 10% by weight of polysiloxane compounds according to the invention.
- Preferred novel coating compositions or polymeric molding compositions preferably comprise from 0.5 to 7.5% by weight, particularly preferably from 1 to 5% by weight, of at least one polysiloxane compound of the formulas (IV) and (V) according to the invention.
- Preferred thermoplastics according to the invention preferably contain from 0.1 to 5% by weight, preferably from 0.2 to 2% by weight, particularly preferably from 0.5 to 1% by weight, of at least one polysiloxane compound of the formulas (IV) and (V).
- the polysiloxane compounds of the formulas (IV) and (V) according to the invention and the compositions according to the invention can be used for a wide variety of applications. In particular, the use is to be mentioned as surface-active substances, such as.
- the methods described below are preferably used. In particular, these methods were used in the examples of the present patent.
- the levels of branching can be detected for example by NMR analysis or MALDI Tof analyzes.
- the NMR spectra were measured with a Bruker 400 MHz spectrometer using a 5 mm QMP head. Quantitative NMR spectra were measured in the presence of a suitable accelerating agent.
- the sample to be examined was dissolved in a suitable deuterated solvent (methanol, chloroform) and transferred into 5 mm or optionally 10 mm NMR tubes.
- MALDI-Tof analyzes were performed on a Shimadzu Biotech Axima (CFR 2.8.420081127) Reflectron device, with pulse extraction optimized to a molecular weight of 1000 g / mol.
- the sample was dissolved in chloroform (4-5 g / L) and 2 ⁇ of this solution was applied to graphite as a matrix.
- the carbonate segments (M9) can be detected by C-NMR analyzes or preferably by IR spectroscopy. In I R spectroscopy, the M9 units can be detected by bands at wavenumbers of about 1745 and possibly about 1805.
- weight-average and number-average molecular weights are calibrated for the prepared polyether carbonates against a polypropylene glycol standard (76-6000 g / mol) and the end products calibrated against a polystyrene standard are determined by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the GPC was run on an Agilent 1 1 00 equipped with a RI detector and an SDV 1000/10000 A column combination consisting of a 0.8 cm x 5 cm guard column and two 0.8 cm x 30 cm main columns at a temperature of 30 ° C and a flow rate of 1 mL / min (mobile phase: THF).
- the sample concentration was 10 g / L and the injection volume 20 ⁇ .
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Abstract
La présente invention concerne des polyéthersiloxanes contenant des groupes carbonate, un procédé pour les produire ainsi que leur utilisation.
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2011
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US12054635B2 (en) | 2017-10-13 | 2024-08-06 | Evonik Operations Gmbh | Curable composition for coatings having an anti-adhesive property |
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US11286351B2 (en) | 2019-05-28 | 2022-03-29 | Evonik Operations Gmbh | Process for producing acetoxy-bearing siloxanes |
US11286366B2 (en) | 2019-05-28 | 2022-03-29 | Evonik Operations Gmbh | Process for recycling silicones |
US11420985B2 (en) | 2019-05-28 | 2022-08-23 | Evonik Operations Gmbh | Acetoxy systems |
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US12053721B2 (en) | 2020-08-14 | 2024-08-06 | Evonik Operations Gmbh | Defoamer composition based on organofunctionally modified polysiloxanes |
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