EP2563846A2 - Polyorganosiloxanes hydrophiles - Google Patents

Polyorganosiloxanes hydrophiles

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Publication number
EP2563846A2
EP2563846A2 EP11716239A EP11716239A EP2563846A2 EP 2563846 A2 EP2563846 A2 EP 2563846A2 EP 11716239 A EP11716239 A EP 11716239A EP 11716239 A EP11716239 A EP 11716239A EP 2563846 A2 EP2563846 A2 EP 2563846A2
Authority
EP
European Patent Office
Prior art keywords
formula
compounds
glycidol
polyorganosiloxane
polyorganosiloxane compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11716239A
Other languages
German (de)
English (en)
Inventor
Paul Boehm
Holger Frey
Tammo J. Menke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Momentive Performance Materials GmbH
Momentive Performance Materials Inc
Original Assignee
Momentive Performance Materials GmbH
Momentive Performance Materials Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Momentive Performance Materials GmbH, Momentive Performance Materials Inc filed Critical Momentive Performance Materials GmbH
Publication of EP2563846A2 publication Critical patent/EP2563846A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • 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
    • 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
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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

Definitions

  • the invention relates to hydrophilic polyorganosiloxane compounds which are prepared by reacting functionalized polyorganosiloxane compounds with glycidol.
  • the hydrophilic polyorganosiloxane compounds have special properties which make them suitable for particular as additives, the surface treatment, modi ficators and raw materials for elastomers or foams, emulsifiers, wetting agents, lubricants applications as well as foam stabilizers, defoamers or the like.
  • Hydrophilic polyorganosiloxane compounds are used, for example, for the hydrophilization of surfaces such as silicone elastomers, as a reactive component in foams, as defoamers in hydrocarbons or as foam stabilizers in the production of rigid or flexible polyurethane foams.
  • polar groups such as polyether groups or ionic groups have been introduced into polyorganosiloxane compounds (e.g., DE 19748606 A1, EP 881249 A1).
  • these known in the art hydrophilic polyorganosiloxane compounds have in some applications too low hydrophilicity, which is expressed by a too large contact angle at the interface to water or limited solubility in polar solvents such as alcohols.
  • EP 035080 biomedical moldings based on crosslinkable polyorganosiloxanes are known, for example, have silicon-bonded propoxypropane-l, 2-diol residues by hydrosilylation reaction with protected 3-AUyloxy-propane-1,2-diol and subsequent cleavage the protective group can be obtained. Similar compounds are described in EP-A-0266895 and US 6255429 Bl.
  • Glycidol functionalized polyorganosiloxanes having more than one glycidol unit per siloxane unit are not described.
  • a further object of the present invention is to provide novel hydrophilic polyorganosiloxane To provide compounds with increased durability on hydrophobic surfaces, especially on polyorganosiloxanes.
  • the inventors of the present patent application succeeded in providing new polyorganosiloxane compounds having increased hydrophilicity or increased solubility in polar media by grafting functionalized polyorganosiloxane starting compounds with glycidol.
  • the invention therefore provides polyorganosiloxane compounds obtainable by reacting polyorganosiloxane compounds of the formula (I):
  • R having Polyglycidolreste of the formula - (glycidol) x , wherein x> 1, wherein the Polyglycidolrest is formed by ring-opening polymerization of the epoxy groups of the glycidol of the formula (II).
  • R is methylene such that the preferred glycidol compound of formula (II) is glycidol of the following formula:
  • glycidol compounds include, for example.
  • the introduction of several glycidol groups into the side chains of the polyorganosiloxanes achieves a significant increase in the hydrophilicity by formation of hydroxyl groups and ether groups.
  • the polyglycidol side chains in particular have at least three hydroxyl groups and at least two ether groups (-O-), as can be seen, for example, in the following formula:
  • the starting compounds of formula (I) are generally prepared by hydrosilylation of SiH-functional polyorganosiloxane compounds with unsaturated functionalized compounds containing at least one group selected from -OH, -SH, -NH- and -NH 2 or protected derivatives from those in which hydrogen has been replaced in the groups mentioned by protective groups, which can be converted in an additional step again in -OH, -SH, -NH or -NH 2 groups.
  • SiH-functional polyorganosiloxane compounds include, for example:
  • T RSi0 3/2
  • T H HSi0 3/2
  • Q Si0 4/2 , in which these units are preferably selected from MeHSiO- or Me 2 HSiOo, 5 units in addition to optionally other organosiloxy units, preferably dimethylsiloxy units
  • the polyorganohydrogen siloxanes can be described, for example, by the general formula (III) in which the symbols M * for M and M, D * for D and D and T * for T and T are shown for the sake of brevity: wherein the indices ae are as defined above.
  • the siloxy units can be present in blocks or randomly linked to one another in the polymer chain. Each siloxane unit of the polyorganosiloxane chain may carry identical or different radicals.
  • the indices of the formula (IH) describe the average degree of polymerization P n, measured as number average M n per GPC, which relate to polyhydrogenmethylsiloxanes. Within the given viscosity limits, other siloxy groups thus give different molecular weights.
  • the preferred polyorganohydrogensiloxanes are structures selected from the group which can be described by the formulas (I-Ha-I-Hf)
  • R 5 0i / 2 is a C 1 to C 6 alkoxy radical on the silicon
  • R e hydrogen (H) or R, where at least one R 6 must be hydrogen.
  • HMe 2 SiO (Me 2 SiO) z (MeHSiO) p SiMe 2 H (I-Hb) where p 0, ie, ⁇ , ⁇ -dimethylhydrogen-terminated polydimethylsiloxanes.
  • the unsaturated compounds which are reacted by means of hydrosilylation reaction with the polyorganohydrogensiloxanes and which serve to introduce the functional groups selected from -OH, -SH, -NH- and -NH 2 are, for example, selected from:
  • Carbon atoms which may contain one or more groups selected from -O- and, and having at least one group selected from -OH, -SH, -NH- and - H 2 or correspondingly protected radicals of these groups.
  • Preferred such compounds are, for example:
  • R 7 is a hydroxy-protecting group, such as trimethylsilyl, or two R 7 groups represent an alkanediyl radical to form a cyclic dioxolane compound, such as 4-allyloxymethyl-2,2-dimethyl- [1,3-dioxolane: , the deprotected derivative (without protecting group) thereof:
  • Typical hydrosilylation catalysts include, for example:
  • Transition metals selected from the group of platinum, rhodium, ruthenium, palladium, nickel, iridium and their compounds. Preference is given to using platinum or compounds of platinum as hydrosilylation catalyst. Preference is given to vinylpolysiloxane-Pt (0) complex compounds, alkenylpolysiloxane-Pt (0) complex compounds, cyclohexene-Pt (0) complex compounds or the like described, for example, in B. Marciniec: Comprehensive Handbook on Hydrosilylation Pergamon Press Ltd. ,
  • the amount of hydrosilylation catalyst, in particular of the platinum catalyst is 0.1-1000 ppm, calculated as metal, based on the weight of the hydrogen siloxane compound and the unsaturated, functionalized compound. More preferred are 1-50 ppm of metal or metal compounds, especially platinum or platinum compounds, the amount referring to the metal (especially platinum), more preferably 2-24 ppm, even more preferably 3 to 15, most preferably 4 to 9, 5 ppm.
  • the hydrosilylation catalyst is selected, for example from the Pt catalysts, in particular Pt ° complex compounds Olefms, particularly preferably with vinylsiloxanes, such as, for example, 1: 1 complexes with 1,3-divinyltetra methyldisiloxane and / or tetravinyltetramethyltetracyclosiloxane, amine, azo or phosphite complex compounds.
  • Pt catalysts are exemplified in US 3,715,334 or US 3,419,593.
  • the preferred Pt 0 -Olefmkomplexe one prepares in the presence of 1,3-di-vinyl-tetramethyldisiloxane (M Vl 2 ) by reduction of hexachloroplatinic acid or other platinum chlorides.
  • M Vl 2 1,3-di-vinyl-tetramethyldisiloxane
  • other platinum compounds as far as they allow rapid crosslinking can be used, such as the photoactivatable Pt catalysts of EP 122008, EP 146307 or US 2003-0199603.
  • amounts between 10 and 300 ppm of metal are preferred, amounts below 10 ppm ensure only a low conversion rate or can be inhibited by impurities.
  • carriers for the catalysts all solids can be selected as long as they do not undesirably inhibit hydrosilylation.
  • the carriers can be selected from the group of powdered silicas or gels or organic resins or polymers. They are suitably selected so that a good separation of the solid can be carried out
  • the polyorganosiloxane compounds of the formula (I) derived from the reaction of the polyorganohydrogensiloxane compounds with unsaturated functionalized compounds preferably comprise siloxy units selected from the following formulas:
  • R when more of said siloxy units are present, may be the same or different and is selected from C 1 to C 22 alkyl, which may be optionally substituted by one or more fluorine atoms, C 2 to C 22 alkenyl, and C 6 to Cio aryl,
  • R 1 is as defined above, and
  • f is from 0-600.
  • the D units further comprise siloxygrapps of the following formula wherein R in a single siloxy unit may be the same or different, or, when plural siloxy units are present, may be the same or different in different ones of the siloxy units and is selected from C) to C 22 alkyl which may optionally be substituted by one or more fluorine atoms, C 2 to C 22 alkenyl and C 10 -C 10 aryl, and
  • g is from 0-700
  • R when more of said siloxy units are present, may be the same or different and is selected from C 1 to C 22 alkyl, which may optionally be substituted by one or more fluorine atoms, C 2 to C 22 alkenyl and C 6 to C 10 -Aryl, and h is 0-10,
  • R 1 is as defined above, and
  • R when more of said siloxy units are present, may be the same or different and is selected from C 1 to C 22 alkyl, which may optionally be substituted by one or more fluorine atoms, C 2 to C 22 alkenyl and C 6 to C 10 -Aryl, R 1 is as defined above, and
  • R when more of said siloxy units are present, may be the same or different and is selected from C 1 to C 22 alkyl, which may be optionally substituted by one or more fluorine atoms, C 2 to C 22 alkenyl and C 6, to Cio-aryl , and k is from 0-30,
  • the C 2 to C 22 alkenyl groups are useful after hydro silylation but before the reaction with glycidol by a Aquilibr michs- or condensation reaction inserted because they should not participate in this hydrosilylation reaction.
  • the polyorganosiloxane compounds have two or more, preferably from 2 to 1000, radicals R 1 .
  • the starting compounds of the formula (I) fulfill one or more of the following merlanals:
  • R is selected from: C 1 to C 10 -alkyl which may optionally be substituted by 1 to 13 fluorine atoms, preferably methyl , C2 to Cs alkenyl, and phenyl,
  • R 1 is selected from: monovalent, straight-chain, cyclic or branched, saturated or unsaturated C] to Cio hydrocarbon radicals having one or more groups
  • the compounds of the formula (I) fulfill one or more of the following features:
  • R is selected from: C 1 - to C 6 -alkyl which may optionally be substituted by 1 to 13 fluorine atoms, preference is given to methyl, C 2 to C 5 -alkenyl, preferably vinyl, and phenyl,
  • R 1 is selected from: monovalent, straight-chain, cyclic or branched, saturated or unsaturated C 2 to C 10 hydrocarbon radicals which have one or more
  • Groups selected from -O- and may contain, and the at least one
  • the polyorganosiloxane compounds according to the invention have radicals R 2 which have arisen from the reaction of radicals R 1 with several glycidol molecules in each case by ring-opening of the epoxide, as shown below, for example:
  • reaction scheme is to be understood schematically.
  • the addition of the glycidol molecules can also be carried out to other hydroxy groups, for example to form branched, dendrimeric hydrophilic side chains, such as, for example: polysiloxane
  • the reaction of the starting compounds of the formula (I) with glycidol is preferably carried out in polar organic solvents, such as tetrahydrofuran, dioxane, DMF etc., at temperatures of 20 to 100 ° C and subsequent removal of excess glycidol and solvents.
  • Glycidol is naturally used in a molar excess based on the molar amount of the radicals R, so that on average at least about two, preferably at least three, more preferably at least four glycidol molecules have added to a NHR, NH 2 , SH or OH-modified siloxy unit (- (Gly)> 2).
  • the reaction is preferably carried out in the presence of basic catalysts which do not react with glycidol, and which do not depolymerize the polysiloxane chain, such as, for example, alkali metal alkoxides, such as tert-butylpotassium.
  • basic catalysts which do not react with glycidol, and which do not depolymerize the polysiloxane chain
  • alkali metal alkoxides such as tert-butylpotassium.
  • polysiloxane compounds according to the invention thus expediently have polyglycidol radicals of the formula
  • (Glycidol) x wherein x is from 2 to 20, preferably 4 to 18, and the polyglydol residue is formed by ring-opening polymerization of the epoxy groups of the glycidol, as explained above.
  • radicals R 1 in the compounds of the formula (I) are suitably selected from radicals of the formula:
  • R is selected from monovalent, linear, branched or cyclic alkyl radicals having up to 20 carbon atoms which may have one or more ether groups -O-, where appropriate, and which may be substituted with one or more hydroxyl groups, optionally, and wherein Y is at least one group selected from -OH, -SH, -NH 2 or -NHR 4 , wherein R is selected from straight, branched or cyclic alkyl radicals having up to 10 carbon atoms.
  • the glycidol compounds of the formula (II) add to these compounds:
  • R is as defined above, in particular glycidol: to the radicals Y with ring opening of the epoxide ring and continuation of the oligomerization or polymerization of further Glycidolmoleküle to the continuously formed free hydroxy groups.
  • the polyorganosiloxane compounds are prepared from compounds of formula (I) wherein R 1 is selected from radicals of the formula:
  • z and Y are as defined above, preferably hydroxy or amino, (CH 2 ) -Y wherein n is 1 to 8 and Y is as defined above, preferably hydroxy or amino, and P- ⁇ 3
  • R is an alkyl group having 8 to 20 carbon atoms which contains a cycloalkyl group and Y is as defined above, preferably hydroxy or amino.
  • the starting compounds of the formula (I) have, based on the total amount of the siloxy units, at least 25 mol% siloxy units which have radicals R 1 which have functional groups which are reacted with the glycidol compounds of the formula (II ) are capable of reaction.
  • the molar ratio of the radicals R 1 to the glycidol compound units relative to the glycidol compounds of the formula (II) in the polyorganosiloxane compounds obtained is at least 1: 4, preferably at least 1 : 5.
  • these have at least 8 mmol hydroxyl groups per gram of the polysiloxane compound according to the invention.
  • the polyglycidol side chains have, in particular, at least three (3), preferably at least 4, more preferably at least 5 hydroxyl groups per side chain R, as can be seen, for example, in the following formula:
  • f 1 to 200, preferably 1 to 100, preferably 1 to 50, preferably 1 to 30, preferably 3 to 30, preferably 5 to 30,
  • g 10 to 700, preferably 10 to 200, preferably 10 to 150, preferably 20 to
  • n 0 to 20
  • Glycidol means a glycidol moiety resulting from the epoxide ring opening reaction of glydol compounds of formula (II).
  • the present invention furthermore relates to a process for the preparation of the polyorganosiloxane compounds according to the invention, which comprises reacting compounds of the formula (I) with glycidol compounds of the formula (II), preferably with glycidol itself.
  • reaction conditions reference may be made to the above descriptions as well as to the examples.
  • the higher the excess of the glycidol compounds used the higher the number of glycidol units in the radicals R and the higher the hydrophilicity of the resulting polysiloxane compounds.
  • the present invention further relates to the use of the polyorganosiloxane compounds according to the invention as
  • Foam stabilizer in particular for polyurethane hard and soft foams, crosslinking component in the production of elastomers or elastomeric foams.
  • the present invention furthermore relates to the use of the polyorganosiloxane compounds according to the invention for the preparation of cosmetic formulations.
  • the polyorganosiloxane compounds according to the invention are preferred as emulsifiers, in dishwasher, in detergent compositions, hydrophilizing additive, wetting agent or adjuvant for the efficient application of pesticides, as additives for oil-water phase separation in crude oil production, as plasticizers for natural and artificial Fibers and pulps including paper, as a defoamer for diesel fuel, as an antistatic agent, as a hydrogen generating additive in Si-H group-containing compositions and / or foam stabilizer, in particular used in the production of polyurethane foams.
  • W / O or O / W emulsifiers based on polyethylene oxide by emulsifiers, which have the lowest possible effect for triggering allergies.
  • the assignment to the group of W / O or O / W emulsifiers can be made on the basis of the so-called HLB values (hydrophilic-lipohilic balance).
  • W / O emulsifiers preferably have a value of ⁇ 8.
  • the hydrophilicity of the polyorganosiloxane compounds according to the invention can be controlled in particular by two parameters:
  • the molar ratio of the hydrophilic siloxy radicals with the indices f, i and / or j to the lipophilic, ie "unmodified", only R-containing siloxy units having the indices g, h and / or k is preferably in the polysiloxane compounds according to the invention from 5: 1 to 1:10, more preferably from 2: 1 to 1: 7, even more preferably from 1: 1 to 1: 5.
  • the polysiloxane compounds in which the ratio of the hydrophilic groups with the indices (f + i + j) to the hydrophobic groups (g + h + k) is ⁇ 1 are preferably used for their use as W / O emulsifiers, as a foam stabilizer for polyurethane hard and soft foams, especially rigid foams, or as defoamers as in defoamer formulations in hydrocarbons such as for diesel fuels or as a defoamer.
  • this group of compounds has an HLB value of ⁇ 8.
  • Another preferred embodiment of the invention is the use of the less highly hydrophilically modified polyorganosiloxanes as emulsifier or adjuvant in compositions for forestry and agriculture and horticulture.
  • the preferred polysiloxane compounds herein in which the ratio (f + i + j) to (g + h + k) ⁇ 1 are preferably linear polyorganosiloxanes having an average chain length of 1 for this use. 100 D units according to the indices g + f. These compounds improve the dispersibility of the active materials and stabilize the emulsions as they are diluted with additional water.
  • the adjuvant is a wetting agent that performs many other functions. It can, inter alia also help to transport the bioactive agents through the cell wall.
  • the adjuvants can be admixed both directly to the crop protection compositions and as an additional component from a separate auxiliary tank. Typical compositions are mentioned, for example, in WO 2008/116863 pages 16-18, which are to be included here for a detailed explanation of the description by citing:
  • the polysiloxanes of the present invention are present in an amount of from 0.005% to 2% by weight. This concerns the undiluted as well as the diluted crop protection composition.
  • the crop protection compositions may contain adjuvants, cosurfactants, solvents, antifoaming agents, addition aids, drift retardants, fertilizers and the like.
  • Solvents include; Solvents which are liquid at 25 ° C, for example water, alcohols, aromatic solvents, oils (ie mineral oils, vegetable oils, silicone oils, etc.), Q-Cs-alkyl esters of vegetable oils, fatty acids, glycols, as well as 2,4-trimethyl, 1, 3-pentanediol, N-methylpyrrolidone and other solvents mentioned in US 5674832 for reference.
  • compositions may contain the compounds of the present invention as a wetting agent or as a surfactant compound for emulsification, compatibilizing the coating components, leveling agents, flow improvers, deaerators for reducing surface disruption.
  • the compounds of the invention can improve the properties of the dried, cured paint film, such as improved scratch resistance, anti-blocking properties, hydrophilic or hydrophobic properties.
  • the coating compositions may be present as both solvent and water based coating or powder compositions.
  • the coating compositions cover architectural coatings, original part coatings such as automotive coatings and coil coatings, special applications such as coatings for industrial maintenance and shipbuilding and other marine applications, ie in particular seawater contact.
  • Typical binders include polyester, alkyd, acrylic, epoxy and polyurethane resins or polymers.
  • the less hydrophilically modified polysiloxanes in which the indices of the siloxy units have a ratio of (f + i + j) to (g + h + k) ⁇ 1 are used for defoaming diesel oils or diesel fuels, wherein the concentration of silicon in the diesel oil is below 5 ppm, more preferably below 2 ppm.
  • Another preferred use is the use of less hydrophilic modified polysiloxanes with (f + i + j) to (g + h + k) ⁇ 1 as a foam stabilizer in cold or thermosetting polyurethane hard or soft foams, preferably in amounts of 0 , 5 to 5 wt.%, More preferably 1 to 3 wt.% Per used polyol component with additional blowing agents whose boiling points is between -60 to 50 ° C, in particular cyclopentane, iso-pentane and / or iso-butane.
  • the ratio of (f + i + j) to (g + h + k) is preferably 1: 1 to 15, more preferably 1: 2 to 9.
  • the sum of the siloxy units (f + i + j + g + h + k) is 15 to 200, more preferably 30 to 150, measured as the average degree of polymerization Pn based on the average number average Mn from a gel chromatographic molecular weight determination (GPC).
  • Preference is given to using linear polyorganosiloxanes with the siloxy units having the indices f and g.
  • the ratio of hydrophilic indices to the lipophilic indices is equal to or greater than 1, in particular effects such as reduced sliding friction and antistatic properties on hydrophobized surfaces can be achieved. If the ratio (f + i + j) to (g + h + k) is 1 or greater than 1 (more hydrophilic compounds) is a use as a wetting agent, compatibilizer against lipophilic phases, eg emulsifier in O / W emulsions.
  • the HLB values for these more hydrophilic polysiloxanes are preferably> 8.
  • heat-sensitisable coagulants heat-sensitisable phase release agents, coagulants
  • rubber latex compositions for the production of rubber articles from latexes of various emulsion polymers, such as SBR or NBR and natural rubber latex.
  • the latices serve to produce gums gloves, condoms or other balloons.
  • the use of the hydrophilic polysiloxanes according to the invention prevents premature heat-activated coagulation of the latices at room temperature. The coagulation point is shifted to> 35 ° C.
  • the polyorganosiloxanes of this group can also be used as phase breakers for breaking emulsions in the oil and gas industry for more efficient separation of crude oil and water.
  • thermoplastic or elastomer additive for hydrophilization and improved wettability of thermoplastic or elastomeric surfaces, as explained below, possible and as a wetting agent for foam stabilization in liquid all-purpose cleaners, hydrous soaps or liquid dishwashing detergents, if the HLB value is greater than 8 is.
  • hydrophilically modified polysiloxanes can be used as anti-blocking additives, as lubricants or lubricant additives, as softeners for cotton or paper towels, as plasticizers or in softening compositions for self-emulsifying alkylene oxide-free or shear-stable emulsifiers in textile treatment compositions become.
  • hydrophilic compounds have improved solubility in polar solvents such as alcohols, other oxygen, sulfur and nitrogen containing hydrocarbons compared to pure polydimethylsiloxanes.
  • this relates to the use of the hydrophilic lipophilic modified polysiloxane compounds according to the invention for the preparation of viscosity regulators, antistatic agents, mixture components for silicone rubbers which can be crosslinked peroxide or by hydrosilylation (platinum catalysis) to form elastomers, and there for the modification of surface properties, to modify the diffusion of gases, liquids, etc., or modify the swelling behavior of the silicone elastomers, for example, to water.
  • the use as an additive for hydrophilizing surfaces of polydimethylsiloxane elastomers in general or as a viscosity modifier (eg, thickener) in non-crosslinked siliceous silicone rubbers is preferred.
  • Silicone rubbers here are in particular low-viscosity casting or sealing compounds known as room-temperature-crosslinking (RTV) -l or 2-component rubbers.
  • RTV room-temperature-crosslinking
  • 2-K rubbers the setting of high or low flow limits is desired depending on the application.
  • the polysiloxanes according to the invention are used in amounts of from 0.5 to 55% by weight, based on the silicone rubbers, in the preparation of the rubber mixture or on the surface of the respective elastomers.
  • Hydrophilic surfaces here means that according to the invention hydrophilic organo-modified polydimethylsiloxanes in pure form has a contact angle to water of clearly showing at 90 ° preferably less than 75 0, measured as indicated below, after the dynamic determination method.
  • the statically determined contact angle is less than 50 °.
  • a dynamic contact angle of more than 120 ° is measured on non-hydrophilically modified polydimethylsiloxanes.
  • They can also be applied as a lubricant by dipping, pouring or brushing on the surface and be removed after proper use or assembly in part again by rubbing or rinsing.
  • hydroxyl group-containing siloxanes are used in hydrogen-foamed siloxane foams, especially when the compounds according to the invention additionally contain alkenyl groups, such as vinyl groups.
  • the compounds according to the invention in these mixtures with the SiH crosslinkers in the presence of hydrosilylation catalysts during the crosslinking reaction on the one hand generate hydrogen for the cell structure and, on the other hand, participate in the network structure of the elastomer matrix.
  • crosslinked hydrophilic polyorganosiloxane foams are obtained. These are preferably used, for example, where Siloxane foams are intended for skin contact, such as decubitus pads, wound dressings or wound plasters, if necessary, with antimicrobial agents etc.
  • this relates to the use of the hydrophilic / lipophilic functionalized polysiloxane compounds according to the invention for the preparation of modifiers for thermoplastic materials, such as polyolefins, polyamides, polyurethanes, poly (meth) acrylates, polycarbonates.
  • modifiers for thermoplastic materials such as polyolefins, polyamides, polyurethanes, poly (meth) acrylates, polycarbonates.
  • the polyorganosiloxane compounds according to the invention can themselves be used directly as modifiers or else be provided in advance in a suitable form by coating, mixing, compounding or masterbatching.
  • copolymers of the invention are coatings such as anti-fouling, non-stick coatings, body-tissue compatible coatings, and materials.
  • a mold release agent as a biocompatible material in medical applications such as contact lenses, as a coating material for as a coating material for wood, paper, cardboard, natural and synthetic fibers and pulps, textile fibers or textile fabrics, as a coating material for natural products such as Leather and furs.
  • the hydroxyl-modified polyorganosiloxanes according to the invention can thereby replace conventional hydroxyl-containing siloxanes or other siloxanes with organofunctional groups in compositions in processes for leather production or preparation, fat-liquoring, retanning.
  • These uses include the preparation of fabric softeners for treating textile fibers before, during and after washing, agents for modifying natural and synthetic fibers such as hair, cotton fibers and synthetic fibers such as polyester fibers and polyamide fibers, and the like Blended fabrics, textile finishing agents, and detergent-containing formulations, such as detergents or cleaners.
  • the preferred amounts here are 0.1 to 5 wt.% 0.3 to 3 wt.% Based on the pulp.
  • hydrophilically modified polyorganosiloxanes having predominantly hydrophilic properties as an additive for hydrophilization, improved wettability and antistatic finish of thermoplastic and elastomeric surfaces.
  • the preferred amounts are from 0.2 to 15 wt.% 0.5 to 10 wt.% Based on the thermoplastic or elastomer composition.
  • hydrophilic modified polyorganosiloxanes Since an identifiable tendency for micelle formation is observed in the hydrophilic modified polyorganosiloxanes according to the invention, they provide a suitable basis for the coating of active ingredients, in particular in aggregated form, and allow the rheological properties of cosmetic creams in particular to be influenced.
  • the polyorganosiloxanes modified according to the invention are adjusted to be less hydrophilic, they can replace conventional W / O emulsifiers in known standard formulations for cosmetic preparations.
  • hydrophilic / lipophilic modified polyorganosiloxanes can thus serve as cosmetics, personal care products, paint additives, additives in detergents, defoamer formulations and textile processing.
  • a typical exemplary composition of a W / O cream according to the invention which is not intended to limit the scope of the invention, contains the following components.
  • Viscosity and consistency regulator 0 - 10 wt.% Viscosity and consistency regulator
  • the GPC measurements in chloroform were performed in an apparatus consisting of a Waters 717 Plus Autosampler, a TSP P 100 pump, and a set of three PSS SDV columns (104/500/50 ⁇ ).
  • the signal was determined by means of a Wyatt Optilab DSP RI detector.
  • the measurements of contact angles with water were made on a Dataphysics Contact Angle System OCA 20 and were evaluated using the SCA 20 software.
  • the contact angles given are in each case average values from 5 measurements of a dynamic determination according to Halliwell, C.M .; Cass, A.E.G .; Analytical Chemistry 2001, 73, 2476-83.
  • compounds of the formula IV according to the invention can also be prepared by reacting hydrogenpolysiloxanes with allyl alcohol or protected allyl alcohol and subsequent reaction of the resulting hydroxypropyl polysiloxane compounds with glycidol, in accordance with the reaction route described in claim 1.
  • reaction product was stirred for 12 h at 70 ° C at 1 mbar. This gave 9.32 g (92% of theory) of a product having structural units of the general empirical formula (III).
  • the 'H-NMR confirmed an OH content of about 2 mmol / g. and 10 mol% modified siloxy units.
  • Example 1 was repeated in which, instead of the polydimethylmethylhydrogensiloxane mentioned there, 6.00 g of a polydimethylmethylhydrogensiloxane having the empirical formula MDiD.sub.M together with 16.40 g, 2-0-isopropylidene-3-allyloxy-1,2-propanediol in 30 ml of dioxane dissolved used.
  • Example 5a A 100 ml round bottom flask was charged with 1.00 g of the amino-functionalized polydimethylsiloxane and placed under argon atmosphere.
  • the polymer of Example 5a was dissolved by the addition of 30 ml of dry THF and the resulting solution was added with vigorous stirring with 3.62 g of glycidol.
  • the resulting mixture was stirred for 12 h at 25 ° C room temperature.
  • the solvent was evaporated in a rotary evaporator and then the unreacted glycidol by stirring at 80 ° C and 1 mbar.
  • the increase in the molecular weight corresponds to about 1 1 oligomerized glycidol units on average at each nitrogen.
  • the increase in the molecular weight corresponds to about 1 1 oligomerized glycidol units on average at each nitrogen.
  • a product of the general formula (VII) is obtained.
  • a polyorganosiloxane of the invention is prepared from MH n D 2 voM H n with allylamine and subsequent reaction with glycidol.
  • the increase in the molecular weight corresponds to about 11 oligomerized glycidol units on average at each nitrogen.
  • the 'H-NMR confirmed an OH content of about 1.3 mmol / g and 0.7 mol.% Modified siloxy units.
  • a product of the general formula (VII) with g 270 is obtained.
  • Table 1 summarizes the preparation examples. Table 1 - Examples 1 to 8:

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Abstract

L'invention concerne des composés polyorganosiloxanes modifiés à l'aide de glycérol, présentant une hydrophilie élevée, ainsi que leur utilisation.
EP11716239A 2010-04-26 2011-04-20 Polyorganosiloxanes hydrophiles Withdrawn EP2563846A2 (fr)

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DE102010028182A DE102010028182A1 (de) 2010-04-26 2010-04-26 Hydrophile Polyorganosiloxane
PCT/EP2011/056345 WO2011134869A2 (fr) 2010-04-26 2011-04-20 Polyorganosiloxanes hydrophiles

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