EP2099810A1 - Silanes contenant des groupes méthylol - Google Patents
Silanes contenant des groupes méthylolInfo
- Publication number
- EP2099810A1 EP2099810A1 EP07847457A EP07847457A EP2099810A1 EP 2099810 A1 EP2099810 A1 EP 2099810A1 EP 07847457 A EP07847457 A EP 07847457A EP 07847457 A EP07847457 A EP 07847457A EP 2099810 A1 EP2099810 A1 EP 2099810A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radical
- alkyl
- aryl
- cycloalkyl
- alkenyl
- 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- Withdrawn
Links
- -1 methylol groups Chemical group 0.000 title claims description 57
- 150000004756 silanes Chemical class 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 50
- 125000003342 alkenyl group Chemical group 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 125000003118 aryl group Chemical group 0.000 claims description 38
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 38
- 229910052736 halogen Inorganic materials 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 28
- 150000003254 radicals Chemical class 0.000 claims description 27
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000000758 substrate Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 229920005573 silicon-containing polymer Polymers 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical group NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ARZLUCYKIWYSHR-UHFFFAOYSA-N hydroxymethoxymethanol Chemical class OCOCO ARZLUCYKIWYSHR-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 229940024463 silicone emollient and protective product Drugs 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Definitions
- the present invention relates to methylolated organofunctional silanes, their preparation and use for condensation to polysiloxanes.
- Silicone or silicone-containing formulations and composites are known and are used in the form of films, coatings and coatings in large quantities for the modification and equipment of various materials and fibers.
- silicones or silicone-containing formulations are superior to purely organic films, coatings and coatings in many respects.
- the use of silicone products leads to a vast improvement in otherwise unavailable, but usually desirable properties, such as flow behavior, gas permeability, abrasion resistance, hydrophobicity, smoothness, feel or gloss of the treated substrate.
- the coating can either be easily removed mechanically, for example by rubbing or rubbing, or by chemical stress, such as contact with various solvents and / or exposure to certain pH environments (as used, for example, in washing processes occur), again from the substrate can solve.
- One approach to solving the problem of lack of permanence is to add the individual silicone polymer chains both to one another and to the substrate to be treated network and thus increase the mechanical and chemical resistance and thus the permanence of the entire system.
- Crosslinking and binding to the substrate can be effected both by non-covalent interactions and by covalent bonds.
- thermoplastic silicone elastomers with each other for an increased network density and by interaction with hydrogen bond forming groups of the substrate (eg., Hydroxyechen in cellulose surfaces) also for a certain fixation.
- the substrate eg., Hydroxyticianen in cellulose surfaces
- thermoplastic silicone elastomers are described in detail, inter alia, in the publications EP 0 606 532 A1 and EP 0 342 826 A2.
- Another noncovalent crosslinking mechanism is based on acid-base interactions between Lewis basic / Lewis acidic groups of the silicone polymer with Lewis acidic / Lewis basic groups of the substrate or polymer.
- these are amino-functional silicone oils which, as is known, in particular have a positive influence on the hydrophobicity and softness of textiles and, because of their Lewis-basic amino functionalities, have the property of being 'grown up' on the Lewis acidic fibers.
- Such silicone amine oils and their applications are described for example in EP 1555011 A.
- Polymer is done to each other by forming covalent bonds.
- a covalent crosslinking can for example take place in that the silicone polymers already in the preparation by using z.
- B. trifunctional building blocks are crosslinked.
- the resulting polymers are thereby adversely affected in their processing properties (eg, melt viscosities, deformability, solubility in an application aid).
- a fixation to the substrate is usually no longer possible. Subsequent fixation / cross-linking following a successful application is therefore always more useful.
- Such subsequent fixation / crosslinking may be effected, for example, by the presence of alkoxysilyl groups in the silicone polymer which provide better permanence by hydrolysis and condensation with hydroxy groups of the substrate or hydroxy groups of other silicone polymers.
- alkoxysilyl-containing silicone polymers are described for example in EP 1544223 Al.
- Forming comparatively stable siloxane bonds Si-O-Si is required however, usually again a previous treatment of the substrate with corresponding silanes.
- N-methylol crosslinking Another crosslinking mechanism which is already known in the field of purely organic polymers concerns the so-called N-methylol crosslinking.
- polymers which carry N-methylolamide groups are produced by copolymerization with suitable monomers. These are known to bind covalently to alcoholic groups even at lower temperatures in the absence of water at elevated temperature or in the presence of acidic catalysts. Likewise, they can react with each other and thus cause a crosslinking of the polymer.
- covalent ether bonds or methylene bridge bonds are formed, which are known to be very strong and are only broken again under extreme physical or chemical stresses.
- EP 0 143 175 A utilizes this effect, for example, which uses free-radical emulsion polymerization to produce polymer dispersions which can be post-crosslinked via the methylol mechanism just discussed.
- methylolamide groups can be prepared by reacting amines with formaldehyde, but as a rule, the reaction leads to polymeric condensation products, with the result that polymeric networks ultimately result via imine intermediates.
- This reaction of amines with formaldehyde has already been described: US Pat. No. 3,461,100 describes condensation products of aldehydes and primary diamines and monoamines. The resulting high polymer condensation products are discussed as protective coatings.
- DE 10047643 A1 describes polymeric condensation products of aldehydes and silicon amines, which are, however, exclusively high polymer and highly crosslinked. In both documents the product is already highly polymer after conversion. It is thus no longer a reactive form, as it is the monoaddition product of a formaldehyde molecule to an amine, and is therefore no longer available for subsequent reactions on substrates or post-crosslinking reactions with each other.
- the invention relates to compounds (V) of the general formula (1)
- R 1 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, wherein the carbon chain interrupted by non-adjacent oxygen, sulfur or -NR 1 ⁇ - groups and optionally with -CN or - halogen may be substituted;
- R 2 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, wherein the carbon chain is replaced by non-adjacent oxygen, sulfur or -NR 1 ⁇ - Interrupted groups and may optionally be substituted by -CN or - halogen; a is 0, 1, or 2;
- R 1 is a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having in each case 1 to 20 C atoms, the carbon chain being denoted by non-adjacent - (CO) -, -O-,
- -S- or -NR ⁇ - groups may be interrupted and optionally substituted with -CN or -halogen;
- R 4 is a -CH 2 OR 6 radical or is a -CH (OH) group covalently linked to R ⁇ or an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical covalently linked to R c each with 1 to 20 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent - (CO) -, -0-, -S- or -NR ⁇ - groups and may optionally be substituted by -CN or -halogen;
- R5 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms or a radical - (CO) -OR 7 or
- R 6 is a hydrogen atom, an alkyl, cycloalkyl, alkenyl,
- -S- or -NR 10 - may be interrupted groups and optionally substituted with -CN or -halogen;
- R ' is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain by non-adjacent - (CO) -, -0-, -S- or -NR 10 - groups may be interrupted and optionally substituted with -CN or -halogen and may be terminated by a residue SiR ⁇ a (OR 1 ) 3_ a ;
- R8 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain is interrupted by non-adjacent - (CO) -, -O-, -S- or -NR 10 - groups and optionally substituted with -CN or -halogen and may optionally be covalently bonded to R ⁇
- R ⁇ is a radical -CH 2 OH or a group -CH (OH) - which is covalently linked to R 1;
- R 10 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR 11 - groups interrupted and optionally substituted with -CN or -halogen;
- R 11 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms;
- radicals R 1 and R 2 can be covalently bonded, with the proviso that
- the compounds (V) Preferably, in the compounds (V) at least one free radical -CH 2 OH or a group -CH (OH) - present.
- the compounds (V) are stable in storage in the suitable organic solvents and, using methods known to those skilled in the art, to the methylol groups -CH 2 OH and / or
- R! preferably denotes alkyl radicals having in each case 1 to 6 C atoms, preferably n-propyl, i-propyl, ethyl and methyl radical, in particular the methyl radical.
- R 1 is preferably an alkyl radical having 1 to 6 C atoms or an aryl radical having 5 to 10 C atoms, preferably n-propyl, i-propyl, ethyl and methyl, in particular the methyl radical; particularly preferably the methyl radical.
- R 1 is preferably a divalent hydrocarbon radical, such as --CH 2 - and - (- 2) 3 -; particularly preferably -CH2-.
- R ⁇ alkyl radicals each having 1 to 6 carbon atoms which may be terminated by a radical -SiR ⁇ a (OR ⁇ ) 3_ a or a radical - (CO) -OR 7 or - (CO ) -NR 8 R 9 .
- Particularly preferred are the methyl radical, the radical - (Cf ⁇ ) n "
- R 1 is preferably a hydrogen atom or an alkyl radical having 1 to 6 C atoms or an aryl radical having 5 to 10 C atoms, such as the phenyl radical. Particularly preferred is the hydrogen atom or the methyl radical.
- R 8, R 10 and R 11 are each preferably an alkyl radical having 1 to 6 C atoms or an aryl radical having 5 to 10 C atoms, such as the phenyl radical. Particularly preferred is the methyl radical.
- Halogen radicals are preferably fluorine, chlorine and bromine.
- the invention likewise provides a process for preparing compounds (V) by reacting compounds (VI) of general formula (2),
- R 1 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, wherein the carbon chain is interrupted by non-adjacent oxygen, sulfur or -NR 1 ⁇ - groups and optionally with -CN or - Halogen may be substituted;
- R 1 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 100 carbon atoms, the carbon chain being interrupted by nonadjacent oxygen, sulfur or -NR 10 groups and optionally substituted by -CN or Halogen may be substituted;
- a is 0, 1, or 2;
- R 1 is a divalent alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having in each case 1 to 20 C atoms, the carbon chain being denoted by non-adjacent - (CO) -, -O-, -S- or -NH- Interrupted groups and optionally with - CN or -halogen may be substituted;
- R5 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms or a radical - (CO) -OR 7 or
- R ° is a hydrogen atom, an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being replaced by non-adjacent - (CO) -, -O-,
- -S- or -NR 10 - may be interrupted groups and optionally substituted with -CN or -halogen;
- R ' is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, said carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR 10 - groups may be interrupted and optionally substituted with -CN or -halogen and may be terminated by a radical SiR ⁇ a (OR 1 ) 3- a ;
- R8 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, wherein the carbon chain is interrupted by non-adjacent - (CO) -, -O-, -S- or -NR 10 - groups and optionally substituted with -CN or -halogen,
- R 10 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 carbon atoms, the carbon chain being defined by non-adjacent - (CO), -O-, -S- or -NR 11 - groups interrupted and optionally substituted with -CN or -halogen;
- R 11 is an alkyl, cycloalkyl, alkenyl, aryl or arylalkyl radical having 1 to 20 C atoms; with the proviso
- the formaldehyde used can be present for example in monomeric form of formaldehyde, such as, for example
- Formaldehyde gas but also in condensed form, such as paraformaldehyde, trioxane or others
- Formaldehyde condensates also, a formaldehyde derivative such as glyoxal can be used.
- the compounds (V) can be prepared in the form of organic solutions as well as in pure form.
- Solid substance carried out continuously or discontinuously.
- An optimal and homogeneous mixing of the constituents under the reaction conditions is preferably carried out, wherein a phase incompatibility between the reaction components is optionally prevented by solubilizers.
- the precursor compounds (VI) of the general formula (2) leading to the compounds (V) of the general formula (1) are preferably dissolved or suspended in a suitable solvent which is inert with respect to formaldehyde, and the formaldehyde is subsequently metered in.
- Preferred solubilizers are ethers, such as tetrahydrofuran and dioxane, hydrocarbons, such as toluene, xylene, chlorinated hydrocarbons, ketones, such as acetone and methyl ethyl ketone and esters, and mixtures thereof.
- Solubilizers having a boiling point or boiling range of up to 120 ° C. at 0.1 MPa are preferred.
- the compounds (V) present as methylol ethers, in which R 1 has a meaning other than hydrogen, are easily accessible from the resulting primary ethylols in which R ° is a hydrogen atom by consecutive etherification according to methods familiar to the person skilled in the art.
- the compounds (V) can be condensed to polysiloxanes.
- These polysiloxanes are storage-stable and are suitable in pure form or as a constituent of formulations as coating agents, binders and coating agents for a variety of substrates, especially fibers of any kind, such as textile fibers, cellulose fibers, cotton and paper fibers, as well as plastic fibers, including but not limited are on polyester, polyamide or polyurethane fibers. Also they are suitable for coating moldings and surfaces capable of chemically reacting with methylol functions, for example wood or wood composites, as well as paper-coated substrates and moldings.
- the treatment of the above substrates with the polysiloxanes obtainable by condensation of the compounds (V) gives the treated substrate typical silicone properties on its surface, such as, for example, hydrophobicity, anti-blocking effects or softening.
- Example 4 In a procedure analogous to Example 1, 11.37 g (55.4 mmol) of the methylcarbamatosilane 4 and 1.67 g (55.5 mmol) of paraformaldehyde are suspended in 120 ml of dry xylene at room temperature. The reaction mixture is stirred at 90 ° C. for 6 hours. Product 4 'is obtained as a xylene solution containing 11.34 g (48.2 mmol, 87%) which is stable on storage for several days.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
L'invention concerne des composés (V) de formule générale (1) (R<SUP>1</SUP>O)<SUB>3</SUB>-<SUB>a</SUB>R<SUP>2</SUP>
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006056892A DE102006056892A1 (de) | 2006-12-01 | 2006-12-01 | Methylolgruppen enthaltende Silane |
PCT/EP2007/062934 WO2008065134A1 (fr) | 2006-12-01 | 2007-11-28 | Silanes contenant des groupes méthylol |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2099810A1 true EP2099810A1 (fr) | 2009-09-16 |
Family
ID=38982445
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07847457A Withdrawn EP2099810A1 (fr) | 2006-12-01 | 2007-11-28 | Silanes contenant des groupes méthylol |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2099810A1 (fr) |
DE (1) | DE102006056892A1 (fr) |
WO (1) | WO2008065134A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009047514A1 (de) * | 2009-12-04 | 2011-07-07 | Sgl Carbon Se, 65203 | Fasern zur Herstellung von Verbundwerkstoffen |
CN107916061A (zh) * | 2017-11-23 | 2018-04-17 | 河南省科学院化学研究所有限公司 | 条码碳带背涂层用树脂及其制备方法和条码碳带背涂液及其应用 |
JP6930484B2 (ja) * | 2018-04-17 | 2021-09-01 | 信越化学工業株式会社 | 有機ケイ素化合物およびその製造方法 |
WO2021113043A1 (fr) * | 2019-12-05 | 2021-06-10 | Dow Global Technologies Llc | Compositions de revêtement résistant aux intempéries et durables |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6262216B1 (en) * | 1998-10-13 | 2001-07-17 | Affymetrix, Inc. | Functionalized silicon compounds and methods for their synthesis and use |
-
2006
- 2006-12-01 DE DE102006056892A patent/DE102006056892A1/de not_active Withdrawn
-
2007
- 2007-11-28 EP EP07847457A patent/EP2099810A1/fr not_active Withdrawn
- 2007-11-28 WO PCT/EP2007/062934 patent/WO2008065134A1/fr active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2008065134A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2008065134A1 (fr) | 2008-06-05 |
DE102006056892A1 (de) | 2008-06-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE4009889C1 (fr) | ||
EP0963414B1 (fr) | Materiaux hybrides organiques-inorganiques | |
DE4344082C1 (de) | Verfahren zur Herstellung von Organopolysiloxanen mit über Kohlenstoff an Silicium gebundenen sekundären Aminoalkylgruppen | |
DE60215081T2 (de) | Silikonzusammensetzung und antiadhäsive Beschichtung | |
DE2223702A1 (de) | Selbstbindender,hitzehaertbarer Silikongummi | |
DE19932629A1 (de) | Organisch modifizierte, lagerstabile, UV-härtbare, NIR-durchlässige und in Schichtdicken von 1 bis 150 mum fotostrukturierbare Kieselsäurepolykondensate, deren Herstellung und deren Verwendung | |
EP3356444B1 (fr) | Additifs d'isocyanatoalkylalkosilane modifies par des intermediaires de silicium et leur utilisation | |
EP1745107A2 (fr) | Composition contenant des particules a fonction alcoxysilyle, reticulable sous l'effet de l'humidite | |
EP2099810A1 (fr) | Silanes contenant des groupes méthylol | |
WO2018011360A1 (fr) | Composition pour pâtes de caoutchouc silicone | |
WO2003008485A1 (fr) | Melanges de caoutchouc de silicone rtv-1 a reticulation par groupes alkoxy | |
EP2024408B1 (fr) | Polymère de silicone réticulable au niveau de groupements methylol | |
EP2134727B1 (fr) | Siloxanes contenant des groupes méthylol | |
DE102005001040B4 (de) | Mehrfachfunktionelle Polysiloxane mit über SiOC-Gruppen gebundenen (Meth)acrylsäureestergruppen und einem unmodifizierten Polysiloxan-Block, Verfahren zu deren Herstellung sowie deren Verwendung als strahlenhärtbare abhäsive Beschichtung | |
DE10331787A1 (de) | NCO-haltige Verbindungen mit kovalent gebundenen polyedrischen oligomeren Silizium-Sauerstoffclustereinheiten | |
EP3484897A1 (fr) | Durcisseur pour pâtes de caoutchouc silicone | |
WO2010072541A1 (fr) | Réticulation d'un composé organopolysiloxane présent sur un substrat au moyen d'un réactif aldéhyde gazeux | |
WO2010072531A1 (fr) | Réticulation thermique d'un composé organopolysiloxane présent sur un substrat au moyen d'un réactif aldéhyde | |
EP0617094B1 (fr) | Composition de revêtement antiadhésive avec additif influant sur le degré d'antiadhésion | |
WO2013007600A1 (fr) | Résine résol modifiée par du polysiloxane, corps moulés et composites pouvant être obtenus à partir de cette résine, et procédés de fabrication de cette résine, de ces corps moulés et de ces composites | |
EP0001775B1 (fr) | Procédé de préparation d'enduits contre l'adhérence de matières collantes à base de polysiloxanes et leur application au revêtement du papier | |
DE2216689A1 (de) | Selbstbindende, hitzehärtbare Silikongummi-Zusammensetzungen | |
EP4363484A1 (fr) | Polymères à terminaison organyloxysilyle à base de synthons copolymères de 1,3-dioxolane | |
DE2059110B2 (de) | Bei Raumtemperatur vutkanisierbare Klebstoffe, Überzugsfilme und elektrische Isoliermittel | |
DE1495919A1 (de) | Thermisch stabiles,festes,optisch klares und Loesungsmittel resistentes Organopolysiloxanharz sowie Verfahren zu dessen Herstellung |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20090515 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20100629 |