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WO2008065134A1 - Silanes contenant des groupes méthylol - Google Patents

Silanes contenant des groupes méthylol Download PDF

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Publication number
WO2008065134A1
WO2008065134A1 PCT/EP2007/062934 EP2007062934W WO2008065134A1 WO 2008065134 A1 WO2008065134 A1 WO 2008065134A1 EP 2007062934 W EP2007062934 W EP 2007062934W WO 2008065134 A1 WO2008065134 A1 WO 2008065134A1
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WO
WIPO (PCT)
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.)
Ceased
Application number
PCT/EP2007/062934
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German (de)
English (en)
Inventor
Timo Hagemeister
Jürgen STOHRER
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.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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 Wacker Chemie AG filed Critical Wacker Chemie AG
Priority to EP07847457A priority Critical patent/EP2099810A1/fr
Publication of WO2008065134A1 publication Critical patent/WO2008065134A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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.

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  • 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>
PCT/EP2007/062934 2006-12-01 2007-11-28 Silanes contenant des groupes méthylol Ceased WO2008065134A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07847457A EP2099810A1 (fr) 2006-12-01 2007-11-28 Silanes contenant des groupes méthylol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006056892A DE102006056892A1 (de) 2006-12-01 2006-12-01 Methylolgruppen enthaltende Silane
DE102006056892.3 2006-12-01

Publications (1)

Publication Number Publication Date
WO2008065134A1 true WO2008065134A1 (fr) 2008-06-05

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Application Number Title Priority Date Filing Date
PCT/EP2007/062934 Ceased WO2008065134A1 (fr) 2006-12-01 2007-11-28 Silanes contenant des groupes méthylol

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EP (1) EP2099810A1 (fr)
DE (1) DE102006056892A1 (fr)
WO (1) WO2008065134A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019182815A (ja) * 2018-04-17 2019-10-24 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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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
JP7621355B2 (ja) 2019-12-05 2025-01-24 ダウ グローバル テクノロジーズ エルエルシー 耐候性および耐久性のあるコーティング組成物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000021967A1 (fr) * 1998-10-13 2000-04-20 Affymetrix, Inc. Composes a base de silicium fonctionnalise, synthese et utilisation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000021967A1 (fr) * 1998-10-13 2000-04-20 Affymetrix, Inc. Composes a base de silicium fonctionnalise, synthese et utilisation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019182815A (ja) * 2018-04-17 2019-10-24 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
WO2019202795A1 (fr) * 2018-04-17 2019-10-24 信越化学工業株式会社 Composé de silicium organique et procédé de production associé
US12240868B2 (en) 2018-04-17 2025-03-04 Shin-Etsu Chemical Co., Ltd. Organic silicon compound and production method therefor

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Publication number Publication date
EP2099810A1 (fr) 2009-09-16
DE102006056892A1 (de) 2008-06-05

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