EP1778701A1 - Cyclische organosiliciumverbindungen und deren verwendung - Google Patents

Cyclische organosiliciumverbindungen und deren verwendung

Info

Publication number
EP1778701A1
EP1778701A1 EP05770276A EP05770276A EP1778701A1 EP 1778701 A1 EP1778701 A1 EP 1778701A1 EP 05770276 A EP05770276 A EP 05770276A EP 05770276 A EP05770276 A EP 05770276A EP 1778701 A1 EP1778701 A1 EP 1778701A1
Authority
EP
European Patent Office
Prior art keywords
radical
radicals
organosilicon compounds
formula
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Withdrawn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
EP05770276A
Other languages
German (de)
English (en)
French (fr)
Inventor
Wolfgang Ziche
Ernst Selbertinger
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
Publication of EP1778701A1 publication Critical patent/EP1778701A1/de
Withdrawn legal-status Critical Current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
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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

Definitions

  • the invention relates to cyclic organosilicon compounds and their use, in particular in processes for the preparation of copolymers.
  • siloxane-urea block copolymers For this purpose, for example, refer to EP-A 250 248.
  • aminoalkyl-functional siloxanes are prepared via equilibration reactions.
  • the processes described in EP-A 250 248 for the preparation of such siloxanes have disadvantages: the reaction is lengthy, special catalysts are required, these have to be deactivated in the product, resulting in yellowing when using the products, and the product contains silicone cycles.
  • DE-A1 101 37 855 describes a better synthesis using specific cyclic silazanes.
  • the invention relates to cyclic organosilicon compounds of the formula (I)
  • A denotes a divalent or polyvalent organic radical
  • a represents a value> _ 2 in accordance with the valence of radical A
  • R 1 may be identical or different and is a monovalent organic radical
  • R 2 may be identical or different and represents hydrogen atom or a monovalent, optionally substituted hydrocarbon radical
  • R 3 represents hydrogen or a monovalent, optionally substituted hydrocarbon radical.
  • Radical A is preferably a divalent or polyvalent hydrocarbon radical which is optionally substituted by fluorine or chlorine and in which methylene units which are not adjacent to one another are represented by groups -O-, -COO-, -OCO-, -CO-NH or -OCOO- er ⁇ can be, more preferably bivalent alkylene radicals having 1 to 60 carbon atoms, in particularteilwer ⁇ tige alkylene radicals 6-24 carbon atoms.
  • Examples of radicals A are alkylene radicals f such as the methylene, ethylene, n-propylene, iso-propylene ,.
  • n-butylene iso-butylene f- tert-butylene, n-pentylene, iso-pentylene, neo-pentylene, tert-pentylene, hexylene, such as the n-hexylene, heptylene, like the n-heptylene, octylene, such as the n-octylene and iso-Octylenres- te, such as the 2, 2, 4-Trimethylpentylenrest, nonylene, such as the n-narylene, decylene, such as the n-decylene, dodecylene, such as n-dodecylene radical; Alkenylene radicals, such as the vinylene and the allyl radicals; Cycloalkylene radicals such Isophoronylen-, 4, 4 f -Dicyclohexylme- thylen-, cycl
  • the preferred value for a is 2.
  • radical R 1 independently of one another, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms and / or attached via heteroatoms liciumatom to the Si.
  • radicals R 1 are SiC-bonded hydrocarbon radicals, such as, for example, alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso Butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • alkyl radicals such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso Butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • Hexyl radicals such as the n-hexyl radical
  • Heptyl radicals such as the n-heptyl radical
  • Octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2,2,4-trimethylpentyl radical
  • Nonyl radicals such as the n-nonyl radical
  • Decyl radicals such as the n-decyl radical
  • Dodecyl radicals such as the n-dodecyl radical
  • Octadecyl radicals such as the n-octadecyl radical
  • cycloalkyl such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals
  • Alkenyl radicals such as the vinyl, 1-propenyl and 2-propenyl radicals
  • Aryl radicals such as the phenyl, napheptyl radicals
  • the radical R 1 is particularly preferably SiC-bonded hydrocarbon radicals and SiOC-bonded alkoxy radicals, very particularly preferably the methyl, ethyl, phenyl, ethoxy and methoxy radicals, in particular the methyl and methoxy radicals - rest.
  • the radical R 2 is preferably hydrogen atom and
  • Methyl or ethyl radical more preferably hydrogen or methyl radical, in particular hydrogen atom.
  • radical R 2 are the examples of SiC-bonded, optionally substituted Kohlenwasserstoff ⁇ radicals given for R 1 .
  • Radical Z is preferably alkylene radicals, with methylene and propylene radical being particularly preferred.
  • radical Z are the divalent hydrocarbon radicals indicated for radical A.
  • Radicals R are preferably alkyl, aryl or alkoxy radicals, alkyl radicals being particularly preferred, in particular the methyl radical.
  • radical R examples are the examples given for radical R 1 .
  • Radical R 3 is preferably alkyl radicals and hydrogen, with hydrogen being particularly preferred.
  • radical R 3 examples of radical R 3 are the examples given for radical R 2 .
  • organosilicon compounds of the formula (I) according to the invention are examples of the organosilicon compounds of the formula (I) according to the invention.
  • the organosilicon compounds according to the invention are moisture-sensitive compounds and can be liquid or solid at room temperature and the pressure of the surrounding atmosphere, ie between 900 and 1100 hPa, preferably liquid.
  • organosilicon compounds according to the invention are liquids, they have a viscosity of preferably 20 to 100,000 mm 2 / s at 25 ° C.
  • the organosilicon compounds of the formula (I) according to the invention can now be prepared by any processes known in silicon chemistry.
  • the organosilicon compounds according to the invention are preferably prepared by reacting azasilacyclopentane with polyisocyanate.
  • Another object of the invention is a method for
  • Poly both polymeric, oligomeric and dimeric compounds are included.
  • the azasilacyclopentane and polyisocyanate are preferably reacted with the exclusion of water and moisture.
  • the inventive process is at a temperature of preferably 0 to 100 ° C P particularly preferably from 20 to 5O 0 C and a pressure of the surrounding atmosphere, ie from 900 to 1100 hPa.
  • azasilacyclopentane is in the stoichiometric ratio to the isocyanate groups of the polyisocyanate used of preferably from 0.9: 1 to 1: 0.9, particularly preferably 1: 1, used.
  • the process according to the invention can be carried out in the presence of polar organic solvents, such as acetone, tetrahydrofuran or isopropanol. However, preferably no polar organic solvent is used. If polar solvents are used in the process according to the invention, they do not necessarily have to be removed before further processing of the compounds (I) according to the invention.
  • polar organic solvents such as acetone, tetrahydrofuran or isopropanol.
  • azasilacyclopentane used according to the invention are commercially available products or can be prepared by processes customary in silicon chemistry, such as, for example, in DE-A1 10137855 mentioned above.
  • the organosilicon compounds according to the invention can now be used for all purposes for which cyclic organosilicon compounds hitherto could also be used. In particular, they are suitable for the preparation of copolymers.
  • the invention further provides a process for preparing copolymers, which comprises reacting cyclic organosilicon compounds of the formula (I) with compounds (2) having hydroxyl groups in a first step and optionally in a second step the reaction product thus obtained Polyisocyanate (3) is brought to Re ⁇ action.
  • Hydroxyl-containing compound (2) can be used in the process according to the invention for the preparation of copolymers, any organic and organosilicon hydroxyl compounds.
  • the compounds (2) preferably contain two hydroxyl groups.
  • the hydroxyl-containing compounds (2) used according to the invention are preferably alcohols and organosilicon compounds, more preferably organosilicon compounds.
  • organosilicon compounds are used as the compound (2) used according to the invention, these are preferably those containing units of the formula
  • R 4 may be the same or different and has one of the meanings given for R 2 , b is 1, 2 or 3 and c is 0, 1 or 2, with the proviso that the sum b + c is less than or equal to 4 and at least one Si-bonded hydroxyl group is present per molecule.
  • the organosilicon compounds used according to the invention are preferably organopolysiloxanes, in particular essentially linear ones which consist of units of the formula (II).
  • radical R 4 are the examples of SiC-bonded, optionally substituted Kohlenwasserstoff ⁇ radicals given for R 1 .
  • Radical R 4 is preferably hydrocarbon radicals, particularly preferably hydrocarbon radicals having 1 to 4 carbon atoms, in particular the methyl radical.
  • b has a value of 2.
  • c has a value of 0 or 1.
  • Examples of compound (2) used according to the invention are monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, n-propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, 1-butanol, 2-butanol, tert-butanol, 1,4-butanediol, 1-pentanol, 2-pentanol, 3-pentanol, 1,5-pentanediol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 1-decanol, lauryl alcohol, myristyl alcohol - stearyl alcohol, benzyl alcohol, diethylene glycol, triethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, E ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
  • organopolysiloxanes such as ⁇ , ⁇ -silanol-terminated polydiorganosiloxanes, preferably ⁇ , ⁇ -silanol-terminated polydimethylsiloxanes, and silanols, such as diphenylsilanediol.
  • nosilicium interventions to organisms as used in the invention compound (2), these have a viscosity of preferably 5 to 500,000 MRA 2 / s, particularly preferably 50 to 5 000 mm 2 / s, both at 25 ° C.
  • the first step of the process according to the invention is the stoichiometric ratio of the hydroxyl groups in the compound
  • the compounds of the formula (I) and the compound (2) according to the invention are preferably reacted with the exclusion of water and moisture.
  • the first step of the method for Herstel ⁇ lung from the copolymer is at temperatures of preferably 0 to 200 0 C, particularly preferably at 20 to 150 0 C, and the pressure of the surrounding atmosphere, ie from about 900 to 1100 hPa, Vietnamesege leads.
  • the first step of the process of the present invention may be to produce copolymers in the presence of polar organic solvent such as acetone, tetrahydrofuran or isopropanol.
  • polar organic solvent such as acetone, tetrahydrofuran or isopropanol.
  • the reaction mass is preferably maintained at a temperature at which the lower viscosity is not greater than 10,000 Pas. If polar solvents are used, they do not necessarily have to be removed before the optionally performed second step of the process according to the invention.
  • Examples of the polyisocyanate (3) used in the optionally performed second step of the process according to the invention are hexylene diisocyanate, 4,4'-methylenedicyclohexylene diisocyanate, 4,4'-methylenediphenylene diisocyanate, 1,3-diazetidine-2,4-dione bis (4,4'-methylenedicyclohexyl) diisocyanate, 1, 3-diazetidine-2,4-dione-bis (4,4'-methylene diphenyl) diisocyanate, iso-socyanatohexyltriisocyanurate, tetramethylxylylene diisocyanate and isophorone diisocyanate.
  • the polyisocyanates (3) used according to the invention are preferably diisocyanates such as hexylene diisocyanate, 4,4'-methylenedicyclohexylene diisocyanate, 4,4'-methylenediphenylene diisocyanate, 1,3-diazetidine-2,4-dione bis (4, 4) '-methylenedi ⁇ cyclohexyl) diisocyanate, 1, 3-diazetidine-2, 4-dione-bis (4,4' -Methylendiphenyl) diisocyanate, tetramethylxylylene diisocyanate and isophorone diisocyanate, particularly preferably Hexylendiisocya- nat, 4, 4 '-Methylendicyclohexylendiisocyanat , 4, 4 '-Methylendi ⁇ phenylene diisocyanate, tetramethylxylylene diisocyanate and
  • reaction product of preferably 0.9: 1 to 1: 0.9, particularly preferably 1: 1, used.
  • chain extenders known to the person skilled in the art may be used in the optional second step of the process according to the invention for the preparation of copolymers in polyurethane chemistry, which is not preferred.
  • chain extenders which can be used in the second stage of the process according to the invention are di-functional organic compounds, such as e.g. Diols and diamines.
  • the reaction product obtained in the first stage is reacted with the polyisocyanate (3), preferably with the exclusion of water and moisture.
  • the second step of the method for Her ⁇ position of copolymers is at temperatures of preferably 0 to 200 0 C, particularly preferably at 20 to 150 0 C, and the pressure of the surrounding atmosphere, ie from about 900 to 1100 hPa, carried leads.
  • the second step of the process of the present invention may be carried out to produce copolymers in the presence of polar organic solvent such as acetone, tetrahydrofuran or isopropanol.
  • polar organic solvent such as acetone, tetrahydrofuran or isopropanol.
  • no polar organic solvent is used, in which case the reaction mass is preferably maintained at a temperature at which the lower viscosity is not greater than 10,000 Pas.
  • the process according to the invention for the preparation of copolymers can be carried out either batchwise or continuously. If desired, the preparation according to the invention of the cyclic organosilicon compound of the formula (I) can be used directly as a precursor in the one-pot process, e.g. in an extrusion process.
  • copolymers prepared according to the invention can now be isolated by methods known per se, e.g. Removal of any solvent used by Kurzweg ⁇ distillation.
  • the copolymers prepared according to the invention are preferably thermoplastic elastomers and have a numerical weight average M n of> 100,000, preferably> 500,000.
  • copolymers prepared according to the invention can be used for all purposes for which urea copolymers have hitherto also been used. In particular, they are suitable as
  • cyclic organosilicon compounds of the formula (I) according to the invention have the advantage that they react by-product-free in a rapid reaction with hydroxyl groups. Moreover, they are easy to manufacture.
  • the process according to the invention for the preparation of the organosilicon compounds of the formula (I) has the advantage that it is simple, as a rule solvent-free, catalyst-free and, above all, fast, which permits a continuous procedure.
  • the inventive method for the preparation of copolymers has the advantage that no procedurally and time consuming derivatization of base polymers is necessary.
  • the Shore A hardness is determined according to DIN (German Industrial Standard) 53505 (March 2000 edition).
  • one mole equivalent of an ⁇ , ⁇ -hydroxy-terminated polydimethylsiloxane having a molecular weight Mw of 3000 is added. It will hold a moisture-crosslinkable, transparent, thermoplastic siloxane-urea copolymer, which was pressed into 2 mm thick films.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Silicon Polymers (AREA)
EP05770276A 2004-08-19 2005-08-04 Cyclische organosiliciumverbindungen und deren verwendung Withdrawn EP1778701A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004040314A DE102004040314A1 (de) 2004-08-19 2004-08-19 Cyclische Organosiliciumverbindungen und deren Verwendung
PCT/EP2005/008460 WO2006018143A1 (de) 2004-08-19 2005-08-04 Cyclische organosiliciumverbindungen und deren verwendung

Publications (1)

Publication Number Publication Date
EP1778701A1 true EP1778701A1 (de) 2007-05-02

Family

ID=35094082

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05770276A Withdrawn EP1778701A1 (de) 2004-08-19 2005-08-04 Cyclische organosiliciumverbindungen und deren verwendung

Country Status (7)

Country Link
US (1) US20070270563A1 (ko)
EP (1) EP1778701A1 (ko)
JP (1) JP2008509946A (ko)
KR (1) KR100838611B1 (ko)
CN (1) CN101006093A (ko)
DE (1) DE102004040314A1 (ko)
WO (1) WO2006018143A1 (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007016291A1 (de) * 2007-04-04 2008-10-09 Wacker Chemie Ag Organopolysiloxanhaltige Faser
EP3230293B1 (en) 2014-12-10 2019-10-16 Gelest Technologies Inc. High speed moisture-cure hybrid siloxane/silsesquioxane-urethane and siloxane/silsesquioxane-epoxy systems with adhesive properties
CN106832184B (zh) 2017-02-10 2020-09-01 美瑞新材料股份有限公司 一种热塑性有机硅聚氨酯弹性体及其制备方法
US12071562B2 (en) * 2021-09-29 2024-08-27 Shin-Etsu Chemical Co., Ltd. Cyclic silazane compound having alkoxysilyl group, method for producing same, and composition, cured product and covered substrate containing same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5110967A (en) * 1991-02-15 1992-05-05 Dow Corning Corporation Crosslinkers and chain extenders for room temperature vulcanization or crosslinking of polymers
US5354880A (en) * 1992-12-18 1994-10-11 Osi Specialties, Inc. Cyclic silylureas and process of preparation
US5777144A (en) * 1997-09-30 1998-07-07 General Electric Company Bi-functional siloxane compounds
DE10137855A1 (de) * 2001-08-02 2003-02-27 Consortium Elektrochem Ind Organopolysiloxan/Polyharnstoff/ Polyurethan-Blockcopolymere
US6815373B2 (en) * 2002-04-16 2004-11-09 Applied Materials Inc. Use of cyclic siloxanes for hardness improvement of low k dielectric films

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006018143A1 *

Also Published As

Publication number Publication date
DE102004040314A1 (de) 2006-02-23
US20070270563A1 (en) 2007-11-22
JP2008509946A (ja) 2008-04-03
CN101006093A (zh) 2007-07-25
KR100838611B1 (ko) 2008-06-16
WO2006018143A1 (de) 2006-02-23
KR20070033000A (ko) 2007-03-23

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