EP1723193A1 - Preparation en continu de siloxanes aminofonctionels - Google Patents

Preparation en continu de siloxanes aminofonctionels

Info

Publication number
EP1723193A1
EP1723193A1 EP05707621A EP05707621A EP1723193A1 EP 1723193 A1 EP1723193 A1 EP 1723193A1 EP 05707621 A EP05707621 A EP 05707621A EP 05707621 A EP05707621 A EP 05707621A EP 1723193 A1 EP1723193 A1 EP 1723193A1
Authority
EP
European Patent Office
Prior art keywords
general formula
organosiloxane
silazane
groups
halogen
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Withdrawn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
EP05707621A
Other languages
German (de)
English (en)
Inventor
Sabine Delica
Oliver SCHÄFER
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
Consortium fuer Elektrochemische Industrie GmbH
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 Consortium fuer Elektrochemische Industrie GmbH, Wacker Chemie AG filed Critical Consortium fuer Elektrochemische Industrie GmbH
Publication of EP1723193A1 publication Critical patent/EP1723193A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • 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
    • 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
    • C08G77/06—Preparatory processes
    • 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

Definitions

  • the invention relates to a continuous process for the preparation of amino-functional siloxanes using cyclic silazanes.
  • a inoalkyl polysiloxanes and a inoalkyl silicone resins are useful in many fields of application, including the manufacture of polyimides and polyetherimides. ' However, the commercial use of these compounds on a larger scale is prevented by a relatively expensive manufacturing process.
  • R ⁇ is a carbon chain with at least 3 and a maximum of 6 carbon atoms
  • the radical R is hydrogen, an unsubstituted cyclic silazane is obtained which can be used for the functionalization of hydroxy-terminated silanols.
  • the advantage of the reaction of these cyclic silazanes is that these very quickly with Si-OH groups due to their ring strain at elevated temperatures react quantitatively. The response times are sometimes in the single-digit minute range.
  • a disadvantage of the previously known batchwise production of, for example, linear alpha, omega-substituted silicone oils is, however, that they have to be heated to temperatures of about 60-140 ° C. in order to achieve short reaction times. This is especially in the case of silicone oils of which carry only a small proportion of amine groups, since the reaction extremely 'runs angsam 1 due to the low reaction of the reactants at room temperature door.
  • this has the technical disadvantage that the actual reaction times at elevated temperatures are very short, the time for heating up the reaction mixture or for cooling the product mixture is very long, especially on an industrial scale, and thus nullify the advantage of the reactivity of the cyclic silazanes can.
  • a process was therefore sought which allows cyclic silazanes with Si-OH functional groups to be converted very quickly to amino-functional siloxanes.
  • the invention relates to a continuous process for the preparation of amino-functional organosiloxane of the general formula III,
  • R 3 is hydrogen or a C] _- C] _o ⁇ hydrocarbon radical which is optionally substituted by -CN, -NR X or halogen, e values of greater than or equal to 0, s values of at least 1, r values of at least 1, s + t den Value of r and k + m + p + q mean values of at least 2, the silazane of the general formula V and the
  • Reactor are fed, mixed there, react with each other and then removed from the reactor area.
  • Another advantage is that, due to the high surface / volume ratio in the continuously operated reactor, the product can be rendered inert or saturated at the same time, for example with nitrogen, which displaces the oxygen contained in the starting materials. The resulting amine is therefore significantly less yellowing.
  • the cyclic silazanes of the general formula V used can be prepared simply and in high yields. Even without the formation of by-products, they react with hydroxy-functional siloxanes of the general formula IV without the use of special catalysts.
  • R can be aliphatic saturated or unsaturated, aromatic, straight-chain or branched.
  • R is preferably an unbranched C3-C5 alkylene radical which can be substituted by halogen atoms, in particular fluorine and chlorine. 3 atoms are preferably arranged between the silicon atom and the nitrogen atom of the ring.
  • the C3_-C20 _ ⁇ ° hydrogen fluoride and C_-C20 _ ⁇ ° hydrogen oxy radicals R ⁇ can be aliphatically saturated or unsaturated, aromatic, straight-chain or branched.
  • R- 1 - preferably has 1 to 12 atoms, in particular 1 to 6 atoms, preferably only carbon atoms, or
  • R 1 is preferably a straight-chain or branched C 1 -C 6 -alkyl radical.
  • the methyl, ethyl, phenyl, 'vinyl, and trifluoropropyl are particularly preferred.
  • the radical R 2 is preferably hydrogen or a C1-C3
  • Hydrocarbon radical or a radical of the general formula VIII is preferred as the radical R 3 .
  • All R 2 is particularly preferably hydrogen, methyl or a radical of the general formula VIII.
  • E is preferably 0 or 1, very particularly preferably 0.
  • R is a propylene radical and is methyl, ethyl, phenyl, vinyl or trifluoropropyl.
  • the amino-functional organosiloxane of the general formula III can be linear, cyclic or branched.
  • the sum of k, m, p, q, s and t is preferably a number from 2 to 20,000, in particular 8 to 1,000.
  • r must be> 0, ie the organosiloxane of the general formula IV must contain hydroxyl groups.
  • organosilicone resin A preferred variant for a branched organosiloxane of the general formula III is organosilicone resin. This can consist of several units, as indicated in the general formula III, the mole percent of the units contained being denoted by the indices k,, p, q, r, s and t. A value of 0.1 to 20% of units r is preferred, based on the sum of k, m, p, q and r. At the same time, however, k + m must also be> 0. In the case of the organosiloxane resin of the general formula III, s> 0 and s + t must be r.
  • Resins are preferred in which 5% ⁇ k + m ⁇ 90%, based on the sum of k, m, p, q, r, s and t, and preferably t is 0.
  • the radical R is a propyl radical and R 1 is a methyl radical.
  • Another preferred variant for an amino-functional organosiloxane of the general formula III is linear organosiloxane of the general formula VI,
  • cyclic silazane of the general formula V above, where u is 0 or 1, v is 1 - u and n is a number from 1 to 20,000.
  • n preferably has values from 1 to 20,000, in particular 8 to
  • linear organosiloxanes of the general formula VI represented in this way can essentially be characterized by 3 different sizes: viscosity (or molecular weight) amine content Degree of amino functionality of the end groups
  • a suitable organosiloxane of the general formula VII below is selected as the silicone component, which gives the end product the desired viscosity, and a cyclic silazane of the general formula V is used for the functionalization, namely in the amount which should correspond to the amine content of the final product.
  • the compounds of the general formula VI furthermore have the advantage that, if u> 0, they can be condensed either with themselves or with compounds of the general formula VII, optionally with the aid of a catalyst, in order also to compounds of the general formula VI to produce, which however have a higher molecular weight, ie the numerical value of the number n increases.
  • n stands for a number from 15 to 50 before the condensation and 50 to 2000 after the condensation.
  • the amount of the silazanes of the general formula V used depends on the amount of the silane groups to be functionalized.
  • the silazane must be added in at least equimolar amounts. If the cyclic silazane is used in excess, the unreacted silazane can then either be distilled off or hydrolyzed and then, if appropriate, removed.
  • the process is preferably carried out at 0 ° C. to 100 ° C., particularly preferably at least 10 ° C. to at least 40 ° C. If necessary, the process is carried out under vacuum or under superatmospheric pressure or at normal pressure (0.1 MPa).
  • a protective gas such as e.g. Nitrogen or argon worked.
  • Preferred reactors are continuous kneaders, extruders, single, twin or multi-screw extruders, either in the same or opposite directions, and glass reactors or static or dynamic mixers. Two-screw kneaders (or twin-screw extruders) and static mixers are very particularly preferred.
  • the process can be carried out using solvents or without the use of solvents.
  • solvents inert, in particular aprotic, solvents such as aliphatic hydrocarbons, for example heptane or decane, and aromatic hydrocarbons, for example toluene or xylene, are preferred.
  • Ethers such as THF, diethyl ether or MTBE can also be used.
  • the amount of solvent should be sufficient to ensure adequate homogenization of the reaction mixture. Solvents or solvent mixtures with a boiling point or boiling range of up to 120 ° C. at 0.1 MPa are preferred.
  • silazane of the general formula VI is added to the organosiloxane of the general formula IV in deficit, unreacted Si-OH groups can remain in the amino-functional organosiloxane of the general formula III or be reacted with other silazanes of the following general formula VIII:
  • Silazanes of the general formula VIII can be used simultaneously with cyclic silazane of the general formula V or according to the Implementation of the silazane of the general formula V can be used.
  • Amino-functional organosiloxanes of the general formula IX which have been prepared by using silazanes of the general formula VIII and with cyclic silazane of the general formula V can be used, for example, to increase the amine number in highly viscous aminosilicones. It is achieved / by using these mixtures of aminosilicones and aminosilicone resins that mixtures are obtained which combine a high amine number with a high viscosity. This is a combination that can be so not achieved with pure bifunctional aminosilicones'.
  • This second termination may also be omitted, however, but it offers significant advantages with regard to the stability of the materials at elevated temperatures, since Si-OH groups tend to condense at higher temperatures and thus increase the viscosity of the solutions obtained.
  • a silazane of the general formula V can be prepared by a process in which haloalkyl dialkylchlorosilane of the general formula XI
  • R 2 has the meanings of R ⁇ and
  • R- 3 - and R have the meanings given above, is reacted with ammonia, preferably under pressure.
  • the speed was 50 rpm, and colorless bisaminopropyl-polydimethylsiloxane was continuously removed from the extruder die, which was cooled and showed an Si-OH content of ⁇ 30 ppm according to Si-NMR.
  • Example 2 In a twin-shaft kneader from Collin,
  • N- ((3-aminopropyl) -dimethylsilyl) -2, 2 ; -dimethyl-l-aza-2-silacyclopentane (M 230 g / mol, 97%) at 2.45 g / min
  • the temperature profile of the heating zones was programmed as follows: Zone 1 50 ° C, Zone 2 100 ° C, Zone 3 120 ° C, Zone 4 120 ° C , Zone 5 120 ° C., Zone 6 120 ° C. The speed was 50 rpm. Colorless bisaminopropyl-polydimethylsiloxane could be taken off continuously at the extruder nozzle, which was cooled and according to Si-NMR had a Si-OH content of
  • Example 3 In a twin-shaft kneader from Collin,
  • Heating zone N- ((3-aminopropyl) dimethylsilyl) -2 ⁇ -dimethyl-l-aza-2-silacyclopentane (M-230 g / mol, 97%) was metered in at 0.238 g / min.
  • the temperature profile of the heating zones was programmed as follows: Zone 1 50 ° C, Zone 2 100 ° C, Zone 3 120 ° C, Zone 4 120 ° C, Zone 5 120 ° C, Zone 6 120 ° C. The speed was 50 rpm. Colorless bisaminopropyl-polydimethylsiloxane was continuously removed from the extruder nozzle, which was cooled and, according to Si-NMR, had a Si-OH content of

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)

Abstract

Procédé continu de préparation d'organosiloxane aminofonctionel de formule générale (SiO4/2)k(R1SiO3/2)m(R12SiO2/2)p(R13SiO1/2)q[O1/2SiR12-R-NH2]s[O1/2H]t, selon lequel de l'organosiloxane de formule générale (SiO4/2)k(R1SiO3/2)m(R12SiO2/2)p(R13SiO1/2)q[O1/2H]r (IV) est mis en réaction avec un silazane cyclique de formule générale (V). Le silazane de formule générale (V) et l'organosiloxane de formule générale (IV) sont introduits en continu dans un réacteur, sont mélangés dans ledit réacteur, réagissent ensemble et sont ensuite évacués de la zone du réacteur. R, Rx, R1, R2, e, s, t, r, k, m, p et q possèdent la signification figurant dans la revendication 1.
EP05707621A 2004-03-11 2005-02-24 Preparation en continu de siloxanes aminofonctionels Withdrawn EP1723193A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004011992A DE102004011992A1 (de) 2004-03-11 2004-03-11 Kontinuierliche Herstellung von aminofunktionellen Siloxanen
PCT/EP2005/001968 WO2005087842A1 (fr) 2004-03-11 2005-02-24 Preparation en continu de siloxanes aminofonctionels

Publications (1)

Publication Number Publication Date
EP1723193A1 true EP1723193A1 (fr) 2006-11-22

Family

ID=34877588

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05707621A Withdrawn EP1723193A1 (fr) 2004-03-11 2005-02-24 Preparation en continu de siloxanes aminofonctionels

Country Status (7)

Country Link
US (1) US20070197757A1 (fr)
EP (1) EP1723193A1 (fr)
JP (1) JP2007527940A (fr)
KR (1) KR100894089B1 (fr)
CN (1) CN1930214A (fr)
DE (1) DE102004011992A1 (fr)
WO (1) WO2005087842A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007020568A1 (de) 2007-05-02 2008-11-06 Wacker Chemie Ag Verfahren zur kontinuierlichen Herstellung von Aminoalkylgruppen aufweisenden Organopolysiloxanen

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004014217A1 (de) * 2004-03-23 2005-10-13 Wacker-Chemie Gmbh Vernetzbare Massen auf der Basis von Organosiliciumverbindungen
DE102004059942B4 (de) * 2004-12-13 2006-10-26 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Kontinuierliches Verfahren für Silazanspaltungen, insbesondere für die Herstellung von molekularen Einkomponentenvorläufern für nichtoxidische Keramiken
DE102006031104A1 (de) * 2006-07-05 2008-01-10 Wacker Chemie Ag Verfahren zur Herstellung aminofunktioneller Siloxane
DE102008055039A1 (de) * 2008-12-19 2010-07-01 Wacker Chemie Ag Verfahren zur Herstellung von Aminogruppen aufweisenden Organosiliciumverbindungen
DE102016201633A1 (de) 2016-02-03 2017-08-03 Wacker Chemie Ag Verfahren zur Herstellung von Aminogruppen aufweisenden Organopolysiloxanen

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US3146250A (en) * 1961-10-11 1964-08-25 Dow Corning Nitrogen-containing cyclic silanes, their preparation and hydrolysis
US4528324A (en) * 1982-11-01 1985-07-09 General Electric Company Process for producing RTV silicone rubber compositions using a devolatilizing extruder
JPH07110897B2 (ja) * 1988-01-29 1995-11-29 信越化学工業株式会社 片末端アミノアルキル停止オルガノシロキサン化合物
JP2843620B2 (ja) * 1989-11-29 1999-01-06 東レ・ダウコーニング・シリコーン株式会社 片末端分岐状アミノアルキル基封鎖オルガノポリシロキサン及びその製造方法
US5276123A (en) * 1992-09-03 1994-01-04 Dow Corning Corporation Alkoxy endblocked polydiorganosiloxane and room temperature vulcanizable silicone elastomers made therefrom
DE10051886C1 (de) 2000-10-19 2002-01-10 Consortium Elektrochem Ind Herstellung von aminofunktionellen Siloxanen
DE10137855A1 (de) * 2001-08-02 2003-02-27 Consortium Elektrochem Ind Organopolysiloxan/Polyharnstoff/ Polyurethan-Blockcopolymere

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Title
See references of WO2005087842A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007020568A1 (de) 2007-05-02 2008-11-06 Wacker Chemie Ag Verfahren zur kontinuierlichen Herstellung von Aminoalkylgruppen aufweisenden Organopolysiloxanen

Also Published As

Publication number Publication date
KR100894089B1 (ko) 2009-04-21
KR20060117999A (ko) 2006-11-17
DE102004011992A1 (de) 2005-09-22
CN1930214A (zh) 2007-03-14
WO2005087842A1 (fr) 2005-09-22
JP2007527940A (ja) 2007-10-04
US20070197757A1 (en) 2007-08-23

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