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    • 专利摘要:
    The present invention relates to an organosilicon compound having at least three silicon atoms in units of formula (I). RaSi (NR 1 C = ONR 2 2 ) K (NR 3 C = ONR 4 ) t / 2 YmOn / 2 [(CR 5 2 ) S ] r / 2 (Ⅰ) Here, Y is a unit of general formula (III). -SiR 6 3-pq (NR 1 C = ONR 2 2 ) p (NR 3 C = ONR 4 ) q / w (II) Herein, R, R 1 , R 2 , R 3 , R 4 , and R 5 are each independently the same or different, and are optionally substituted monovalent hydrocarbon radicals having one hydrogen atom or 1-20 carbon atoms. a, k, t, n, m, r, s, p and q have the meaning given in claim 1 under the following conditions. -The sum p + q is ≤3. -The sum a + k + t + m + n + r is 4. The sum m + r is 0 or 1; And The organosilicon compound according to the present invention contains at least one unit of formula (I). T is not zero.
    公开号:KR20000062316A
    申请号:KR1019997005750
    申请日:1997-12-18
    公开日:2000-10-25
    发明作者:오버네터스테판；헥틀볼프강；필스베거에리흐；필루슈도리스；스텝미켈
    申请人:에리히 프란케 ; 칼 하인츠 룀뵈크；와커-헤미 게엠베하；
    IPC主号:
    专利说明:

    ORGANOSIOSILICON COMPOUNDS HAVING UREA GROUPS METHOD FOR PRODUCING SAME AND THEIR UTILIZATION}
    For example, silylated products of urea such as N, N'-bis (trimethylsilyl) urea and derivatives thereof are already known.
    This is mentioned, for example, in US Pat. No. 3,346,609 (GE: published October 10, 1967).
    U.S. Patent No. 3,239,489 (published Monsanto: 1966.3.8) describes a polymer consisting of silane unit-urea unit-hydrocarbon yarns which can be prepared by reaction of diisocyanate with silane acid.
    U.S. Patent 4,959,407 (GE: 1990.9.25) also describes siloxane chains that are blocked by urea units and have up to 10 siloxane units as chain extension.
    The present invention relates to organosilicon compounds containing urea groups linked via Si—N bonds, their preparation and their use.
    The present invention relates to an organosilicon compound having at least three silicon atoms in general units.
    RaSi (NR 1 C = ONR 2 2 ) K (NR 3 C = ONR 4 ) t / 2 YmOn / 2 [(CR 5 2 ) S ] r / 2 (Ⅰ)
    Here, Y is a unit of general formula.
    -SiR 6 3-pq (NR 1 C = ONR 2 2 ) p (NR 3 C = ONR 4 ) q / w (II)
    Here, R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , which are independent of each other, are the same or different in all cases and are one hydrogen atom, and in some cases, a substituted monovalent having 1 to 20 carbon atoms Hydrocarbon radicals.
    a is 0,1,2 or 3,
    k is 0,1,2 or 3,
    t is 0,1,2,3 or 4,
    n is 0,1,2,3 or 4,
    m is 0 or 1,
    r is 0 or 1,
    s is an integer from 1 to 20,
    p is 0,1,2 or 3,
    q is 0,1,2 or 3 under the following conditions.
    The total p + q is ≤ 3,
    The sum a + k + t + m + n + r is 4,
    The sum m + r is 0 or 1,
    The organosilicon compound according to the invention contains at least one unit of formula (I), wherein t is not zero.
    Although represented by formulas (I) and (II), all radicals characterized by the indices a, k, t, m, n, r, p and q are Si-bonded radicals and radicals (NR 3 C = ONR 4 )-, -O- and-(CR 5 2 ) s -may be said to have two Si bonds each time.
    Preferably, the sum k + t + n is not 0 in the unit of general formula (I).
    Examples of hydrocarbon radicals R and R 6 include methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, Or alkyl radicals such as t-pentyl radicals; heptyl radicals such as n-heptyl radicals; octyl radicals such as n-octyl radicals and iso-octyl radicals such as 2,2,4-trimethylpentyl radicals; nonyl radicals such as n-nonyl radicals; decyl radicals such as n-decyl radicals; dodecyl radicals such as n-dodecyl radicals; Octadecyl radicals such as n-octadecyl; Alkenyl radicals such as vinyl and allyl radicals; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals such as phenyl, naphthyl, anthryl and phenanthryl radicals; alkali radicals such as o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; And aralkyl radicals such as benzyl radicals and α- and β-phenylethyl radicals.
    Examples of substituted hydrocarbon radicals R and R 6 include halogenated radicals such as 3-chloropropyl radicals, 3,3,3-trifluoropropyl radicals and 1-trifluoromethyl-2,2,2-trifluoroethyl Hexafluoropropyl radicals such as radicals; 2- (perfluorohexyl) ethyl radical, 1,1,2,2-tetrafluoroethyloxypropyl radical, 1-trifluoromethyl-2,2,2-trifluoroethyloxypropyl radical, perfluor Leusopropylethyl radicals and perfluoroisopropyloxypropyl radicals; N- (2-aminoethyl) -3-aminopropyl radical, 3-aminopropyl radical and 3- (cyclohexylamino) propyl radical and 3- (butylamino) propyl radical and 3- (3-methoxypropylamino) Radicals substituted by amino groups such as propyl radicals; Ether-functional radicals such as 3-methoxypropyl radical and 3-ethoxypropyl radical; Cyano-functional radicals such as 2-cyanoethyl radicals; Ester-functional radicals such as methacryloxypropyl radicals; Epoxy-functional radicals such as glycidoxypropyl radicals; Sulfur-functional radicals such as 3-mercaptopropyl; And radicals substituted with a (poly) glycol group.
    The latter can here be constructed from oxyethylene and / or oxypropylene units.
    Preferred radicals R and R 6 are, in each case independent of each other, hydrocarbon radicals having 1 to 10 carbon atoms and optionally substituted amino and glycidoxy groups bonded to silicon atoms via alkylene radicals having 2 to 6 carbon atoms. There is this.
    Particularly preferably radicals R and R 6 are independent of each other in all cases and are alkyl radicals and alkenyl radicals having 1 to 4 carbon atoms, such as methyl and vinyl radicals, in some cases 3- (2-aminoethylamino) There are substituted amino and glycidoxy groups bonded to silicon atoms via alkylene radicals having 2 to 6 carbon atoms, such as propyl radicals, 3- (cyclohexylamino) propyl radicals or 3- (glycidoxy) propyl radicals.
    In particular, R and R 6 are methyl radicals.
    Examples of radicals R 1 , R 2 , R 3 and R 4 which are identical to hydrocarbon radicals substituted as necessary are examples of radicals R and R 6 described above.
    Preferred radicals R 1 , R 2 , R 3 and R 4 are in each case independent of each other and are hydrogen and hydrocarbon radicals having 1 to 10 hydrocarbon [SiC] atoms.
    Especially preferably, radicals R 1 , R 2 , R 3 and R 4 are independent of each other and are hydrogen or methyl radicals.
    Examples of radicals R 5 are examples above for radicals R and R 6 .
    Preferably the radicals R 5 are hydrogen radicals or hydrocarbon radicals having 1 to 10 hydrocarbons [SiC] as well as amino-functional and fluorine-substituted hydrocarbon radicals.
    Here, R 5 is particularly preferably a hydrogen atom.
    a is preferably 1, 2 or 3,
    k is preferably 0, 1 or 2,
    t is preferably 1, 2 or 3,
    n is preferably 1 or 2
    s is preferably 2,
    p is preferably 0, 1 or 2,
    q is preferably 1 or 2.
    Examples of units of general formula (I) are as follows.
    1a) Me 3 Si (NH—C═O—NH) 1/2 ; Me 2 Si (NH— C═O —NH) 2/2 ;
    MeSi (NH—C═O—NH) 3/2 ; Si (NH— C═O —NH) 4/2 ;
    1b) Me 3 Si (NMe—C═O—NMe) 1/2 ; Me 2 Si (NMe—C═O—NMe) 2/2 ;
    MeSi (NMe-C═O-NMe) 3/2 ; Si (NMe-C = O-NMe) 4/2 ;
    2) Me 3 SiO 1/2 ; Me 2 SiO 2/2 ; MeSiO 3/2 ; SiO 4/2 ;
    3) Me 3 Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )];
    Me 3 Si [SiMe (NH—C═O—NH) 2/2 ]; Me 3 Si [SiMe 2 (NH—C═O—NH) 1/2 ];
    4) Me 3 Si [(CMe 2 ) S ] 1/2 ;
    5) Me 2 Si (NH— C═O —NH) 2/2 (NH— C═O —NH 2 );
    MeSi (NH—C═O—NH) 2/2 (NH—C═O—NH 2 );
    MeSi (NH—C═O—NH) 1/2 (NH—C═O—NH 2 ) 2 ; Si (NH— C═O —NH) 3/2 (NH— C═O —NH 2 );
    Si (NH— C═O —NH) 2/2 (NH— C═O —NH 2 ) 2 ; Si (NH—C═O—NH) 1/2 (NH—C═O—NH 2 ) 3 ;
    6) Me 2 Si (NH—C═O—NH) 1/2 O 1/2 ; MeSi (NH—C═O—NH) 2/2 O 1/2 ;
    MeSi (NH—C═O—NH) 1/2 O 2/2 ; Si (NH— C═O —NH) 3/2 O 1/2 ;
    Si (NH— C═O —NH) 2/2 O 2/2 ; Si (NH— C═O —NH) 1/2 O 3/2 ;
    7) Me 2 Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═O—NH) 1/2 ;
    Me 2 Si [SiMe (NH—C═O—NH) 2/2 ] (NH—C═O—NH) 1/2 ;
    Me 2 Si [SiMe 2 (NH—C═O—NH) 1/2 ] (NH—C═O—NH) 1/2 ;
    Me 2 Si [SiMe 2 (NH—C═O—NH 2 )] (NH—C═O—NH) 1/2 ;
    MeSi [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═O—NH) 2/2 ;
    MeSi [SiMe (NH—C═O—NH) 2/2 ] (NH—C═O—NH) 2/2 ;
    Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═O—NH) 3/2 ;
    Si [SiMe (NH—C═O—NH) 2/2 ] (NH—C═O—NH) 3/2 ;
    8) Me 2 Si [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 1/2 ;
    MeSi [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 2/2 ; Si [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 3/2 ;
    Here, s is 1-20.
    9) Me 2 SiO 1/2 (NH—C═O—NH 2 ); MeSiO 2/2 (NH—C═O—NH 2 );
    MeSiO 1/2 (NH—C═O—NH 2 ) 2 ; SiO 3/2 (NH— C═O —NH) 2 ;
    SiO 2/2 (NH— C═O —NH 2 ) 2 ; SiO 1/2 (NH—C═O—NH 2 ) 3 ;
    10) Me 2 Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═O—NH 2 );
    Me 2 Si [SiMe (NH—C═O—NH) 2/2 ] (NH—C═O—NH 2 );
    Me 2 Si [SiMe 2 (NH—C═O—NH) 1/2 ] (NH—C═O—NH 2 );
    Me 2 Si [SiMe 2 (NH—C═O—NH 2 )] (NH—C═O—NH 2 );
    MeSi [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═O—NH 2 ) 2 ;
    MeSi [SiMe (NH—C═O—NH) 2/2 ] (NH—C═O—NH 2 ) 2 ;
    Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═O—NH 2 ) 3 ;
    Si [SiMe (NH—C═O—NH) 2/2 ] (NH—C═O—NH 2 ) 3 ;
    11) Me 2 Si [(CMe 2 ) S ] 1/2 (NH—C═O—NH 2 ) 3 ;
    MeSi [(CMe 2 ) S ] 1/2 (NH—C═O—NH 2 ) 2 ; Si [(CMe 2 ) S ] 1/2 (NH—C═O—NH 2 ) 3 ;
    Here, s is 1-20.
    12) Me 2 Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] O 1/2 ;
    Me 2 Si [SiMe (NH—C═O—NH) 2/2 ] O 1/2 ; Me 2 Si [SiMe 2 (NH—C═O—NH) 1/2 ] O 1/2 ;
    Me 2 Si [SiMe 2 (NH—C═O—NH 2 )] O 1/2 ;
    Me 2 Si [SiMe (NH—C═O—NH) 1/2 O 1/2 ] O 1/2 ; Me 2 Si [SiMeO 2/2 ] O 1/2 ;
    Me 2 Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] O 2/2 ;
    Me 2 Si [SiMe (NH—C═O—NH) 2/2 ] O 2/2 ;
    Me 2 Si [SiMe (NH—C═O—NH) 1/2 O 1/2 ] O 2/2 ;
    Me 2 Si [SiMe (NH—C═O—NH) O 1/2 ] O 2/2 ; MeSi [SiMeO 2/2 ] O 2/2 ;
    Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] O 3/2 ;
    Si [SiMe (NH—C═O—NH) 2/2 ] O 3/2 ; Si [SiMe (NH—C═O = NH) 1/2 O 1/2 ] O 3/2 ;
    Si [SiMe (NH—C═O—NH) O 1/2 ] O 3/2 ; Si [SiMeO 2/2 ] O 3/2 ; Si [SiMeO 2/2 ] O 3/2 ;
    13) Me 2 Si [(CMe 2 ) S ] 1/2 O 1/2 ; MeSi [(CMe 2 ) S ] 1/2 O 2/2 ;
    Si [(CMe 2 ) S ] 1/2 O 3/2 ; Where S is 1 to 20.
    14) MeSiO 1/2 (NH—C═O—NH) 1/2 (NH—C═O—NH 2 );
    SiO 2/2 (NH— C═O —NH) 1/2 (NH—C═O—NH 2 );
    SiO 1/2 (NH—C═—NH) 2/2 (NH—C═O—NH 2 ));
    SiO 1/2 (NH—C═O—NH) 1/2 (NH—C═O—NH 2 ) 2 ;
    15) MeSi [SiMe (NH-C = O-NH) 1/2 (NH-C = O-NH 2 )] (NH-C = O-NH) 1/2 (NH-C = O-NH) 2 ;
    MeSi [SiMe (NC═O—NH) 2/2 ] (NH—C═O—NH) 1/2 (NH—C═O—NH 2 );
    Si [SiMe (NH-C = O-NH) 1/2 (NH-C = O-NH 2)] (NH-C = O-NH) 1/2 (NH-C = O-NH 2) 2;
    Si [SiMe (NH-C = O-NH) 2/2 ] (NH-C = O-NH) 1/2 (NH-C = O-NH 2 ) 2 ;
    Si [SiMe (NH-C = O-NH) 1/2 (NH-C = O-NH 2)] (NH-C = O-NH) 2/2 (NH-C = O-NH 2);
    16) MeSiL [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 1/2 (NH—C═O—NH 2 );
    Si [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 2/2 (NH—C═O—NH 2 );
    Si [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 1/2 (NH—C═O—NH 2 ) 2 ; Where s is from 1 to 20.
    17) MeSi [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═O—NH) 1/2 O 1/2 ;
    MeSi [SiMe (NH—C═O—NH) 2/2 ] (NH—C═O—NH) 1/2 O 1/2 ;
    Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═O—NH) 1/2 O 2/2 ;
    Si [SiMe (NH—C═O—NH) 1/2] (NH—C═O—NH 2 ) 1/2 O 1/2 ;
    Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] (NH—C═OH) 2/2 O 1/2 ;
    Si [SiMe (NH-C = O-NH) 2/2] (NH-C = O-NH 2 ) 2/2 O 1/2
    18) MeSi [(CMe 2 ) S ] 1/2 (NH-C = O-NH) 1/2 O 1/2 ;
    Si [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 2/2 O 1/2 ;
    Si [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 1/2 O 2/2 ; Where s is 1 to 20.
    19) MeSi [(CMe 2 ) S ] 1/2 (NH—C═O—NH) 1/2 O 1/2 ;
    MeSi [SiMe (NH—C═O—NH) 2/2 ] O 1/2 (NH—C═O—NH 2 );
    Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] O 1/2 (NH—C═O—NH 2 ) 2 ;
    Si [SiMe (NH—C═O—NH) 2/2 ] O 1/2 (NH—C═O—NH 2 ) 2 ;
    Si [SiMe (NH—C═O—NH) 1/2 (NH—C═O—NH 2 )] O 2/2 (NH—C═OH 2 );
    Si [SiMe (NH-C = O-NH) 2/2 ] O 1/2 (NH-C = O-NH 2 )
    20) MeSi [(CMe 2 ) S ] 1/2 O 1/2 (NH-C = O-NH);
    Si [(CMe 2 ) S ] 1/2 O 1/2 (NH—C═O—NH 2 );
    Si [(CMe 2 ) S ] 1/2 O 1/2 (NH—C═O—NH 2 ) 2 ; Where s is 1 to 20.
    21) Si [SiMe (NH-C = O-NH) 1/2 (NH-C = O-NH 2 )] O 1/2
    (NH—C═O—NH 2 ) (NH—C═O—NH) 1/2 ;
    Si [SiMe (NH—C═O—NH) 2/2 ] O 1/2 (NH—C═O—NH 2 ) (NH—C═O—NH) 1/2 ;
    22) Si [(CMe 2 ) S ] 1/2 O 1/2 (NH—C═O—NH 2 ) (NH—C═O—NH) 1/2 ;
    Here, s is 1-20, Me is methyl radical.
    Examples of the compound according to the present invention in units of general formula (I) are as follows.
    a) [Me 3 Si (NH—C═O—NH)] [SiMe 2 O] x [SiMe 2 —NH—C═O—NH—] y [SiMe 3 ] X = 0-1000;
    y = 0-500; x + y≥1
    [Me 3 Si (OSiMe 2 ) 4 (NH-C = O-NH)] (SiMe 2 O) X [SiMe 2 -NH-C = O-NH-] y [(SiMe 2 O) 4 SiMe 3 ] where x = 0-1000, y = 0-500, x + y ≧ 1;
    [Me 3 Si (OSiMe 2 ) 4 (NMe-C = O-NMe)] [SiMe 2 O] x [SiMe 2 (NMe-C = O-NMe)] y [SiMe 3 ] where x = 0-1000 ; y = 0-500; x + y ≧ 1;
    [Me 3 Si (OSiMe 2 ) 4 (NMe-C = O-NMe)] [SiMe 2 O] x [SiMe 2 (NMe-C = O-NMe)] y [SiMe 2 O) 4 SiMe 3 ] wherein x = 0-1000; y = 0-500; x + y ≧ 1;
    [Me 3 Si (NH-C = O-NH) 2/2 (NH-C = O-NH 2 )] [MeSi (NH-C = O-NH) 3/2 ] 2 ;
    [Me 3 Si (NH-C = O-NH) 1/2 (NH-C = O-NH 2 ) 2 ] 2 [MeSi (NH-C = O-NH) 2/2 (NH-C = O- NH 2 )] 3 [MeSi (NH—C═O—NH) 3/2 ] 12 ;
    [MeSi (NPh-C = O-NPh) 1/2 (NPh-CO = NPh 2 ) 2 ] 2 [MeSi (NPh-C = O-NPh) 2/2 (NPh-C = O-NPh 2 )] 3 [MeSi (NPh-C═O-NPh) 3/2 ] 12 ;
    [ViSi (NH-C = O-NH) 1/2 (NH-C = O-NH 2 ) 2 ] 2 [ViSi (NH-C = O-NH) 2/2 (NH-C = O-NH 2 )] 3 [ViSi (NH-C = C-NH) 3/2 ] 12 ;
    [MeSi (NH-C = O-NH) 1/2 (NH-C = O-NH 2 ) 2 ] 2 [MeSi (NH-C = O-NH) 2/2 (NH-C = O-NH 2 )] 2
    [MeSi (NH-C = O-NH) 3/2 ] 2 [(NH-C = O-NH) 1/2 (SiMe 2 O) x SiMe 2 (NH-C = O-NH) 1/2 ] y where x = 0-2-; y = o-50;
    [ViSi (NH-C = O-NH) 1/2 (NH-C = O-NH 2 ) 2 ] 2 [ViSi (NH-C = O-NH) 2/2 (NH-C = O-NH 2 )] 2
    [ViSi (NH-C = O-NH) 3/2 ] 2 [(NH-C = O-NH) 1/2 (SiMe 2 O) xSiMe 2 (NH-C = O-NH) 1/2 ] y , Where x = 0-20; y = 0-50;
    b) [MeSi (NH-C = O-NH) 2/2 {SiMe (NH-C = O-NH) 1/2 (NH-C = O-NH 2 )}] 7
    (MeSi (NH-C = O-NH) 1/2 (NH-C = O-NH 2 ) {SiMe (NH-C = O-NH) 1/2
    (NH-C = O-NH 2 )}] 4
    [MeSi (NH-C = O-NH) 2/2 (SiMe (NH-C = O-NH 2 ) 2 }] 3
    [MeSi (NH-C = O-NH) 2/2 (SiMe (NH-C = O-NH) 2/2 }] 2
    [MeSi (NH—C═O—NH) 1/2 (NH—C═O—NH 2 ) {SiMe (NH—C═O—NH 2 ) 2 }];
    [MeSi (NH-C = O-NH) 2/2 (SiMe (NH-C = O-NH) 1/2 (NH-C = O-NH 2 )}] 3
    (MeSi (NH-C = O-NH) 1/2 (NH-C = O-NH) 1/2 SiMe (NH-C = O-NH) 1/2
    (NH-C = O-NH 2 )}] 4
    [MeSi (NH-C = O-NH) 2/2 {SiMe (NH-C = O-NH 2 ) 2 }] 4
    [MeSi (NH-C = O-NH) 2/2 {SiMe (NH-C = O-NH 2/2 }] 2
    [MeSi (NH-C = O-NH) 1/2 (NH-C = O-NH) {SiMe (NH-C = O-NH 2 ) 2 }]
    [SiMe 2 (NH—C═O—NH) 2/2 ] 20 ;
    C) [MeSi {(CH 2 ) 2 } 1/2 (NH-C = O-NH) 1/2 (NH-C = O-NH 2 )] 5
    [MeSi {(CH 2 ) 2 } 1/2 (NH-C = O-NH) 2/2 ] 4
    [MeSi {(CH 2 ) 2 } 1/2 (NH-C = O-NH) 2 ) 2 ]
    [SiMe 2 (NH—C═O—NH) 2/2 ] 10 ′ wherein Me is methyl radical.
    Vi vinyl radical and Pr is phenyl radical.
    The organosilicon compound according to the present invention preferably contains 3 to 1000 silicon atoms, particularly preferably 3 to 300 silicon atoms.
    The organosilicon compound according to the invention in units of formula (I) is preferably a compound with r = 0.
    The organosilicon compound according to the invention in units of formula (I) is particularly preferably a compound with r = m = o.
    The compounds according to the invention can be prepared by several different routes.
    Method A
    The present invention also relates to a process for preparing organosilicon of the present invention by reaction with an organo compound containing chlorine radicals of the following general formula (IV) under the cleavage of urea (derivative) of the following general formula (III) and HCI Is about

    In the general formula, R 7 and R 8 may be the same or different, provided that at least one compound having at least one radical R 8 which is a hydrogen atom is used, and in each case is independent of each other and is R 1 , R 2 , Has the meanings given above for R 3 and R 4 . In addition
    R a SiO n / 2 Y m [(CR 5 2 ) s ] r / 2 Clu (Ⅳ)
    In the general formula of, provided that the sum a + n + m + r + u is 4 and at least one compound of the unit of formula (IV) having at least one chlorine atom per molecule is present, R, R 5 , Y, a, n, m, r and s may be the same or different in all cases, and imply the meaning given above for these symbols, and u is 0,1,2,3 or 4.
    The HCl formed in this reaction is preferably removed.
    Examples of urea (derivatives) used in method A according to the invention include urea, N-methylurea, N, N'-dimethylurea, N-vinylurea, N, N'-dimethylurea, N-phenylurea, N , N'-diphenyl urea, N-ethyl urea, N, N'-diethyl urea, N- (trifluoro propyl) urea, N, N'-di (trifluoropropyl) urea, N- (tri Fluoropropyl) urea, N, N'-di (trifluoropropyl) urea, N-cyclohexylurea, N, N'-dicyclohexylurea, N-benzylurea, N, N'-dibenzylurea , Wherein the element is particularly preferred.
    The compound containing chlorine radicals used in the method A according to the present invention may be a monomeric, oligomeric or polymeric compound, wherein the properties and amounts are of course selected such that the organo compound formed contains at least three silicon atoms. .
    Examples of organosilicon compounds containing chlorine radicals and used in Method A according to the present invention are as follows.
    a) Me 3 Si (OSiMe 2 ) eCl; Cl (SiMe 2 O) eSiMe 2 Cl; MeSiCl 3 ; SiCl 4 , where e is from 0 to 1000.
    b) ViMe 2 Si (OSiMe 2 ) e (OSiViMe) f Cl; Cl (SiMe 2 O) e (SiViMeO) f SiMe 2 Cl; ViSiCl 3 [SiC], where f is from 0 to 100.
    c) PnMe 2 Si (OSiMe 2 ) e (OSiPnMe) f Cl; Cl (SiMe 2 O) e (SiPnMeO) f SiMe 2 Cl; PnSiCl 3 [SiC), where e is from 0 to 1000 and f is from 0 to 100; (Trifluoropropyl) Me 2 Si (OSiMe 2 ) e (OSi (trifluoropropyl) Me) f Cl; Cl (SiMe 2 O) e (Si (trifluoropropyl) MeO) f SiMe 2 Cl; (Trifluoropropyl) SiCl 3 , where e is from 0 to 1000 and f is from 0 to 100.
    d) Cl 3 Si- (CH 2 ) s-SiCl 3 ; MeCl 2 Si— (CH 2 ) s-SiMeCl 2 ; ClMe 2 Si— (CH 2 ) s—SiClMe 2 , where s is 1 to 20; Silicon ethane of general formula Me 6-g Si 2 Cl g , wherein g is 1-6.
    The examples described in a), b) and c) are preferred, and Me 3 Si (OSiMe 2 ) eCl, Cl (SiMe 2 O) eSiMe 2 Cl, MeSiCl 3 and SiCl 4 with e of 0 to 1000 are particularly preferred. When Me is methyl radical, vi is vinyl radical and Pn is phenyl radical.
    In method A according to the present invention, the amount of urea (derivative) is preferably in each case 0.01 to 10 moles per mole of chlorine of the organosilicon compound containing chlorine radicals used according to the present invention. Especially preferably, 0.1-2 mol is used.
    Chlorine-containing organosilicon compounds used by the present invention are also commercially available products such as urea (derivatives) or can be prepared by chemically common methods, for example US Pat. No. 5,473,037 and Europe. Reference is made to the manufacturing method described in patent EP-A 484 959.
    Process A according to the invention can be achieved preferably at temperatures of -80 to 200 ° C, particularly preferably at temperatures of 0 to 80 ° C, and preferably at ambient atmospheric pressure of 900 to 1100 hpa.
    Process A according to the invention is preferably achieved in inert air.
    Herein inert air means oxygen and water free air such as nitrogen or argon air in the sense of the present invention.
    The reaction according to the invention is preferably achieved in the presence of a solvent which is inactive in the reaction participant, such as, for example, perfumes, hydrocarbons, ethers, hydrocarbon chlorides or α, ω-trimethyl silylpolydimethylsiloxanes.
    The solvent used here as necessary is comprehensively preferably free of water or contains up to 0.2 wt% of water.
    When a solvent is used in the method A according to the present invention, preferred solvents are for example benzine, toluene, xylene, chloroform, methylene chloride, trichloroethane, trichloropropane, hexane, heptane, octane, decane, dodecane, petroleum Ethers such as ether, diethyl ether and tetrahydrofuran and optionally substituted hydrocarbons.
    When a solvent is used, the amount thereof is preferably 1 to 1000 parts by weight, particularly preferably 20 to 400 parts by weight, and in all cases relates to 100 parts by weight of chlorine radical-containing organosilicon compound.
    The removal of hydrogen chloride formed in the reaction according to the invention is for example ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, octylamine, dioctyl Achieved by bases such as amines, trioctylamine, nonylamine dinonylamine and trinonylamine.
    The base used in the process A according to the invention is preferably an amine, particularly preferably a tertiary amine such as for example triethylamine or pyridine.
    When a base is used in the method A according to the present invention, the amount thereof is preferably 0.1 to 20 mol, particularly preferably 0.5 to 5 mol, and in all cases of the chlorine radical-containing organosilicon compound used according to the present invention. Associated with 1 mole of chlorine.
    Salts formed by trapping, for example ammonium hydrogen chloride such as triethylammonium chloride, are preferably removed from the reaction mixture, for example by filtration or centrifugation.
    If necessary, the filtrate is removed from the organic solvent optionally used, for example by distillation.
    In a preferred embodiment of process A according to the invention, the chlorine radical-containing organosilicon compound is allowed to react in addition to a mixture of urea (derivatives), optionally a base, and optionally an organic solvent.
    In a particularly preferred embodiment of process A according to the invention, the chlorine-containing organosilicon compound is allowed to react in addition to the mixture base of the urea (derivative) and the organic solvent.
    The salt formed at this time is filtered after completion of the reaction and the organic solvent is separated.
    The components used in the method A of the present invention may in all cases be singular or at least two different forms of the components.
    The chlorine radical-containing organosilicon compounds used by the invention are preferably mixtures of different forms.
    Method B
    Moreover, this invention relates to the manufacturing method of the organosilicon compound by this invention, It is characterized by including the following two steps.
    In the first step, the chlorine radical-containing organosilicon compound in the unit of formula (IV) reacts with the amino compound of formula (V).
    Provided that the sum a + n + m + r + u is 4 and there is at least one compound in units of formula (IV) having at least one chlorine atom per molecule.
    R 9 2 NH (Ⅴ)
    Wherein R 9 is the same or different and has the meaning given to the radical R.
    In a second step,
    The organosilicon compound obtained in the first step is reacted with urea (derivative) of the general formula (III) in the presence of a catalyst, if necessary.
    Provided that at least one compound of the general formula (III) having at least one radical R 8 as a hydrogen atom is used.
    The radical R 9 is preferably a hydrogen atom or an alkyl radical having 1 to 20 carbon atoms. At this time, an alkyl radical having a hydrogen atom and 1 to 4 carbon atoms is particularly preferable.
    Examples of the amino compound [SiC] of the general formula (V) include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, and dipentylamine. , Octylamine, nonylamine, decylamine, coconutfatamine, oleylamine, stearylamine, resinfatamine, cyclohexylamine, benzylamine, phenylethylamine, ethylenediamine, diaminobutane, diaminohexane, aniline, Methylaniline, diphenylaniline, toluidine, chloranyl, nitroaniline and phenylenediamine.
    Ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine and dibutylamine are preferred, and ammonia and Methylamine is particularly preferred.
    The chlorine-containing organosilicon compound in units of formula (IV) is the same as described in Method A, where the properties and amounts are of course selected such that the organosilicon compound formed contains at least three silicon atoms.
    In the first step of the method B according to the present invention, the amino compound of the general formula (V) is preferably 0.5 to 10 moles with respect to 1 mole chlorine of the chlorine radical-containing organosilicon compound used by the present invention. Especially preferably, 0.8-5 mol is used.
    The reaction by the first step of method B of the present invention can be achieved or by a known method.
    Therefore, the reaction of chlorosiloxanes with ammonia or amines is described, for example, in DE-A 29 53 680 and the literature cited therein.
    The elements (derivatives) of general formula (III) are the same as those described for method A.
    In the second step of process B according to the present invention, all these catalysts which have been used so far as catalysts for the reaction of urea with hexamethyldisilazane to produce N, N'-bis (trimethylsilyl) urea are Can be used.
    Examples of these catalysts are described in DE-A 25 07 882, DE-A 25 53 932, DE-A 27 57 936, J.org. Chem, 1982, 47, 3966-9 (Bruynes et al.) And Ullmann Encyclopedia of Industrial Chemistry, A 24, page 34.
    If the catalyst is used in the second step of process B according to the invention, it is preferred, as used in DE-A 25 07 882, wherein (NH 4 ) 2 SO 4 is particularly preferred.
    When the scouring medium is used in the second step of the method B according to the present invention, the amount is preferably 0.001 to 1 part by weight based on 100 parts by weight of the chlorine radical-containing organosilicon compound used by the present invention.
    The first step of method B according to the invention is preferably achieved at a temperature of 0 to 200 ° C, particularly preferably at 0 to 150 ° C.
    The second step of method B according to the invention is preferably achieved at a temperature of 0 to 200 ° C, particularly preferably at 20 to 180 ° C, in particular at a temperature of 40 to 160 ° C.
    The first step of method B according to the invention is preferably achieved under ambient atmospheric pressure, ie under a pressure of 900 to 1100 hpa.
    The second step of method B according to the invention is preferably achieved under pressure between 1 hpa and normal pressure, ie between 900 and 1100 hpa.
    The second step of the reaction according to the present invention is achieved in the presence of a catalyst which is inactive to the reaction participants.
    But that is not desirable. Examples of these are all the catalysts mentioned in connection with Method A.
    In a preferred embodiment of Method B according to the invention, the amine is added to the mixture of the chlorine radical-containing organosilicon compound and the organic solvent in the first step for reaction.
    At this time, the salt generated after completion of the reaction is separated.
    In the second step, if necessary, the mixture is mixed with a catalyst, and urea (derivative) is added to the organosilicon compound obtained in the first step to react.
    The components used in the method B according to the invention are each time a single form of such a component, or at least two different forms of such a component.
    The chlorine radical-containing organosilicon compounds used according to the invention are preferably mixtures of different forms.
    Method C
    The present invention relates to the preparation of an organosilicon compound by the reaction of a silylated element (derivative) of the general formula (VI) with a chlorine radical-containing organosilicon compound in units of the general formula (IV).
    Provided that the sum a + n + m + r + u is 4 and at least one compound in the unit of formula (IV) having at least one chlorine element per molecule is present.

    Wherein R 7 and R 8 have one of the meanings [SiC] given above for these radicals, z is silly radical and x is 0 or 1.
    Provided that the compound of formula (VI) has no more than two silicon atoms and at least one compound of formula (VI) when x = 1.
    Examples of radical Z are Me 3 Si-, Et 3 Si-, ViMe 2 Si-, PnMe 2 Si-, (H 4 F 3 C 3 ) Me 2 Si-, (H 4 F 3 C 3 ) 3 Si- and Me 3 SiOMe 2 Si—.
    Me is methyl radical, Vi is vinyl radical, Et is ethyl radical and Pn is phenyl radical.
    Examples of the silylating elements (derivatives) used in the method C of the present invention are N, N'-bis (trimethylsilyl) urea, N, N'-bis (trimethylsilyl) -N, N'-dimethylurea and N, N'-bis (trimethylsilyl) -N, N'- diphenyl urea.
    Particular preference is given here to N, N'-bis (trimethylsilyl) elements.
    The silyl urea (derivative) used in Method C of the present invention is a commercially available compound, or can be prepared by conventional methods in silicone chemistry.
    Examples of chlorine radical-containing organosilicon compounds which are units of general formula (IV) and used in the method C of the present invention are those described in connection with the method A, wherein the corresponding organosilicon compound as well as the properties and amounts are at least It is selected to contain three silicon atoms.
    In the method C of the present invention, the silyl compound of the general formula (VI) is preferably a silyl group, preferably 0.1 to 10 mol of chlorine per mole of chlorine radical-containing organosilicon compound used every time according to the present invention. Preferably it is used in the quantity containing 0.2-5 mol silyl groups.
    The reaction according to the invention is preferably achieved at a temperature of 0 to 200 ° C, particularly preferably at a temperature of 20 to 180 ° C, in particular at a temperature of 30 to 160 ° C.
    Method C according to the invention depends on the reaction temperature and the chlorine radical-containing organosilicon compound used, or the silyl urea or urea derivative used, preferably between 1 mbar pressure and ambient atmospheric pressure, i.e. 900 to 1100 hpa. Is achieved in the liver.
    The components used in the method C of the invention are each time a single form of such a component or at least two different forms of such components, and the chlorine radical-containing organosilicon compound used by the invention is preferably a mixture of different forms. .
    The method A of the present invention has the advantage that can be easily achieved, and the preparation of the organosilicon compound according to the present invention is advantageous in terms of time and price only because it is carried out directly without separation of intermediate processes.
    Method B according to the invention has the advantage that the chlorine-free final product is obtained by this process.
    The method C according to the invention is easily achieved and has the advantage of removing the ammonium salt for free use in the product according to the invention.
    The organosilicon compounds according to the present invention are, for example, water, alcohols or silanos through chemical reactions that generally lead to nonvolatile, toxicological and ecologically satisfactory reaction products such as urea or urea derivatives and siloxanes. It has the advantage of permanently and quantitatively removing the same protein compound.
    The organosilicon compounds prepared by or according to the present invention can be used for the most other applications for which the purpose is to remove protein compounds or protein groups, and the compounds according to the invention are particularly suitable for the removal of substances containing OH groups. Do.
    Examples of compounds or groups which can be removed by the organosilicon compounds produced by or according to the invention include, for example, water, alcohols, organic acids, such as carboxylic acids and sulfonic acids, and for example sulfuric acid, sulfonic acids or nitric acids. And a silanol group-containing compound and an inorganic acid having an OH group.
    The amount of the compound according to the invention to be used depends on the amount of protein compound or protein group to be reacted.
    For complete removal, preferably at least one chemical bond between the silicon atom and the urea unit is required for each protein group to be removed from the compound according to the invention.
    The compounds according to the invention are particularly suitable as adducts to organopolysilicon compounds such as, for example, RTV-1-alkoxysilicon compounds in order to enhance storage safety.
    The present invention also relates to organopolysiloxane compounds which can be stored under moisture removal and can be crosslinked at room temperature in order to produce an elastomer under separation of alcohol upon moisture ingress, and are based on the following materials.
    (A) a polydiorganosiloxane having at least two organyloxy radicals in each terminal group,
    In some cases,
    (B) a crosslinking agent of an organyloxy function having at least three organyloxy groups
    In some cases,
    (C) a condensation catalyst containing at least one of the following:
    (D) The organosilicon compound according to the present invention having at least three silicon atoms and in the unit of general formula (I).
    The compounds according to the invention are firm and fluid in use.
    The polydiorganosiloxanes used by the present invention having at least two organyloxy radicals at each end group are preferably of the following general formula.
    (R 12 O) 3-b R 11 b SiO- [R 10 2 SiO] c -SiR 11 b (OR 12 ) 3-b ( iii )
    here,
    b is 0 or 1,
    R 10 is the same or different SiC-bonded hydrocarbon radical having 1 to 18 hydrocarbon atoms, and in some cases a halogen atom, an amino group, an ether group, an ester group, an epoxy group, a mercapto group, a cyano group or a (poly) glycoral radical It is substituted by.
    The latter is then constructed in oxyethylene and / or oxypropylene units.
    And R 11 may be the same or different and has the meanings mentioned for R.
    R 12 may be the same or different and is a hydrocarbon radical having 1 to 18 carbon atoms, interrupted by an oxygen atom, and optionally substituted by an amino, ester, ether, keto or halogen group.
    C is an integer of 10-10,000, Preferably it is 100-3,000, Especially preferably, it is an integer of 400-2,000.
    Examples of radicals R 10 and R 11 are the examples mentioned above for the radicals R.
    The radicals mentioned above as preferred for the radicals R are preferred like the radicals R 10 .
    The radical R 11 is preferably a hydrogen atom, an unsubstituted hydrocarbon radical having 1 to 10 carbon atoms, and a hydrocarbon radical having an amino, mercapto, morpholino, glycidoxy, acryloxy or methacryloxy group.
    The radical R 11 is particularly preferably alkyl radicals and alkenyl radicals having 1 to 4 carbon atoms, especially methyl, ethyl and vinyl radicals, and in some cases silicon atoms via alkylene radicals having 2 to 6 carbon atoms. Substituted amino and greenox groups.
    Radical R 12 is preferably an alkyl radical having 1 to 8 carbon atoms which may be substituted by methoxy or ethoxy groups, with methyl or ethyl groups being particularly preferred.
    Examples of alkyl radicals R 12 are examples of alkyl radicals mentioned above for R.
    The average value of C in general formula (XII) is such that the organopolysiloxane of general formula (VII) is measured at a temperature of 25 ° C. each time, preferably a viscosity of 1,000 to 1,000,000 mm 2 / S, particularly preferably 5,000 to 500,000 It is preferentially chosen to possess a viscosity of mm 2 / S.
    Although not shown in the general formula and not conjectured by the polydiorganosiloxane name, up to 10 mole% of diorganosiloxane units are usually present as impurities, but somewhat difficult to avoid, as R 10 3 SiO 1/2- , It can be replaced by other siloxane units such as R 10 SiO 3/2 -SiO 4 / 2 -unit.
    Where R 10 has the meaning mentioned above for this.
    Examples of the polydiorganosiloxane having at least two organyloxy radicals in each end group (A) and used in the compound of the present invention are as follows.
    (MeO) 2 MeSiO [SiMe 2 O] 200-2000 SiMe (OMe) 2 ,
    (EtO) 2 MeSiO [SiMe 2 O] 200-2000 SiMe (OEt) 2 ,
    (MeO) 2 ViSiO [SiMe 2 O] 200-2000 SiVi (OMe) 2 ,
    (EtO) 2 ViSiO [SiMe 2 O] 200-2000 SiVi (OEt) 2 ,
    (MeO) 2 CapSiO [SiMe 2 O] 200-2000 SiCap (OMe) 2 ,
    (MeO) 2 BapSiO [SiMe 2 O] 200-2000 SiBap (OMe) 2 ,
    (EtO) 2 BapSiO [SiMe 2 O] 200-2000 SiBap (OEt) 2 ,
    Where Me is methyl radical, Et is ethyl radical,
    Vi is vinyl radical, Cap is 3- (cyclohexylamino) propyl radical and Bap is 3- (n-butylamino) propyl radical.
    Polydiorganosiloxanes having at least two organyloxy radicals at each end group and used in the compounds of the present invention can be obtained commercially or for example corresponding organooxysilanes and α, ω-dihydroxypolyorganosiloxanes. It can be prepared by a method known in silicon chemistry by reaction with.
    The crosslinking agent of the organyloxy function used in some cases is described, for example, by German patent DE-A 34 24 206 (Wacker-Chemie GmbH; published February 11, 1988) and in the following general formula US-A 4,801,673. Plain organocrosslinkers known to date, such as silanes or siloxanes having at least three organoxyoxy groups and cyclic silanes.

    Wherein R 13 is a divalent hydrocarbon radical,
    R 14 may be the same or different and has the meanings mentioned for R 12 .
    And R 15 is a hydrogen atom or an alkyl group or an aminoalkyl group.
    In the compound according to the present invention, the organylyl crosslinking agent (B) used in some cases is preferably an organosilicon compound of the following general formula.
    `` (R 12 ) 4-d SiR 16 d (IX)
    Here, R 12 may be the same or different and has one meaning mentioned above.
    R 16 has a meaning given to R 11 or is a hydrocarbon radical substituted by radical —SiR 11 e (OR 12 ) 3-e . Wherein R 11 and R 12 have the above meanings, e is 0,1,2 or 3, d is 0 or 1 and its hydrolyzate.
    The partial hydrolyzate here is a partial homohydrolyzate, i.e., a partial hydrolyzate of one type of organosilicon compound of general formula (IX), and also a partial cohydrolyzate, i.e. at least of the organosilicon compound of general formula (IX) Two different types of partial hydrolysates.
    In the compound according to the present invention, in some cases, when the crosslinking agent (B) used is a partial hydrolyzate of the organosilicon compound of the general formula (IX), a crosslinking agent containing up to six silicon atoms is preferable.
    Examples of radicals R 16 are those described above for radicals R 11 , and hydrocarbon radicals containing 1 to 6 carbon atoms substituted by radicals-SiR 11 e (OR 12 ) 3-e , where e is 0 or 1 R 12 has the above meaning.
    Particularly preferred radicals R 16 are radicals which are particularly preferably described for R 11 , and also hydrocarbon radicals having two carbon atoms substituted by radicals —Si (OR 12 ) 3 , wherein R 12 is ethyl or methyl radicals.
    In the compound according to the invention, the crosslinking agent (B) optionally used is particularly preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyl Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenylphenylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-sia Nopropyltriethoxysilane, 3- (2-aminoethylamino) propyl trimethoxysilane, 3- (N, N-diethyl-2-aminoethylamino) propyltrimethoxysilane, 3- (N, N -Diethyl-2-aminoethylamino) propyltriethoxysilane, 3- (cyclohexylamino) propyltriethoxysilane, 3- (glycidoxy) propyltriethoxysilane, 1,2-bis (trimeth Of the alkoxy functions described above such as methoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane and hexaethoxydisiloxane Partial hydrolysates of organosilicon compounds.
    The crosslinking agent (B) used in the composition according to the present invention is a commercially available product or can be prepared by a method known in silicone chemistry.
    The composition according to the present invention is preferably 0 to 50 parts by weight, particularly preferably 0.1 to 20 parts by weight, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the organopolysiloxane (A). It contains B).
    The composition according to the invention comprises any condensation catalyst (C) which can be stored under the exclusion of water and which can be present so far in the composition crosslinked with the ester at room temperature by the ingress of water.
    In addition, they are for example all condensation catalysts mentioned in German Patent DE-A 38 01 389 such as butyl titanate and organotin compounds such as di-ene-butyltin diacetate and di-ene-butyltin dilaurate. And a silane having at least two monovalent hydrocarbon radicals per molecule, which are bonded to silicon via oxygen and optionally substituted by a yalkoxy group or by its oligomer with diorganotin disylate. Contains reactive products.
    In these reaction products, all valences of the tin atoms can be saturated by oxygen radicals of the "SiOSn" grouping or by organic radicals of the SnC bond 1.
    Preferred condensation catalysts (C) are organometallic condensation catalysts, in particular derivatives of titanium, aluminum, tin, calcium and zinc are condensation catalysts, where dialkyltin compounds and zinc dicarboxylates are particularly preferred.
    Preferred organometallic condensation catalysts include dialkyl di (β-diketo) tartarate salts, dialkyltin dicarboxylates, calcium and zinc dicarboxylates, and US Pat. No. 4,517,337 (GECo., 5, 1985). Butyl Titanium Chelate Compound, published on Jan. 14).
    Examples of particularly preferred organometallic condensation catalysts are dibutyltin diacetate, dibutyltin dilaurate, dibutyltin di (2-ethyl hexanoate) and zincdi (2-ethylhexanoate).
    The composition according to the invention is in all cases preferably condensed in an amount of from 0 to 10 parts by weight, particularly preferably in an amount of from 0.01 to 5 parts by weight, in particular in an amount of from 0.1 to 4 parts by weight, based on 100 parts by weight of the organopolysiloxane (A) It contains the catalyst (C).
    Examples of component (D) used in the composition according to the invention are as mentioned above for the organosilicon compounds of the invention in units of general formula (I).
    Component (D) used by the invention is preferably one of the units of (I) with r = 0, wherein the organosilicon according to the invention in units of general formula (I) with r = mo Compounds are particularly preferably used.
    The composition according to the invention, in all cases, is preferably 0.1 to 30 parts by weight, particularly preferably 0.5 to 20 parts by weight, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the organosilicon polysiloxane (D) is contained.
    In addition to the above components (A, B, C, D), the composition according to the present invention may contain additional substances such as plasticizers (E), fillers (F), adhesion promoters (G) and additives (H) In this case, the additional material may be the same material as used so far in the composition crosslinked under the separation of alcohol.
    An example of a plasticizer (E) is dimethylpolysiloxane blocked at the end by a trimethylsiloxane group, which is a liquid at room temperature and also a high boiling hydrocarbon such as paraffin oil.
    The composition according to the present invention has a plasticizer in an amount of preferably 0 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, particularly 20 to 100 parts by weight, based on 100 parts by weight of the organopolysiloxane (A). E).
    In the example of filler (F), non-reinforced fillings have a BET surface area of up to 50 m 2 / g such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, fluorite, and aluminum-, titanium-, iron-, zinc- Powders of glass and plastics such as oxides or mixtures thereof, barium sulfate, calcium carbonate, gypsum, silicon nitride, hydrocarbons and boron nitride, and polyacrylonitrile powders; As reinforcing fillers, fillers having a BET surface area of 50 m 2 / g or more, such as silicic acid, precipitated silicic acid, precipitated chalk produced by firing, and carbon blacks such as furnace black and acetyrene black, and silicon with a large BET surface area / Aluminum mixed oxides; Fiber fillers include asbestos and artificial fibers.
    Such fillers are hydrophobized, for example by treatment with organosilanes or organosiloxanes or stearic acids or by etherifying hydroxyl groups with alkoxy groups.
    The composition according to the invention is in all cases preferably in an amount of 0 to 300 parts by weight, particularly preferably in an amount of 1 to 200 parts by weight, in particular in an amount of 5 to 200 parts by weight, based on 100 parts by weight of the organopolysiloxane. It contains.
    Examples of the adhesion promoter (G) used in the organopolysiloxane composition according to the present invention include, for example, silanes having functional groups such as aminoalkyl, glycidoxydoxypropyl or methacryloxypropyl radicals, and components containing tetraalkoxysilanes. And organopolysiloxanes.
    However, if other components already have such functional groups, for example siloxanes (A) or crosslinking agents (B), the addition of adhesion promoters can be omitted.
    In all cases, the composition according to the present invention is preferably in an amount of 0 to 50 parts by weight, particularly preferably in an amount of 1 to 20 parts by weight, in particular in an amount of 1 to 10 parts by weight, based on 100 parts by weight of the organopolysiloxane (A). It contains adhesive promoter (G).
    Examples of additives (H) include surface formation such as pigments, dyes, fragrances, disinfectants, antioxidants, electrical properties such as conductive carbon black, composition flame retardants, light stabilizers, and silanes with SiC-linked mercaptoalkyl radicals. Time delay agents, cell generators, for example asodidicarboxamides, thermal stabilizers and thixotropic agents such as phosphate esters according to DE-A 26 23 499.
    The composition according to the present invention comprises in all cases additives (H) in an amount per 100 parts by weight of organopolysiloxane (A), preferably 0 to 100 parts by weight, particularly preferably 0 to 30 parts by weight, in particular 0 to 10 parts by weight. It contains.
    The composition according to the invention preferably contains the following constituents.
    (A) polydiorganosiloxane of the general formula,
    (B) crosslinking agent,
    (C) condensation catalyst,
    (D) One or more organosilicon compounds according to the invention having at least three silicon atoms of the unit of formula (I) and optionally other materials.
    The composition according to the present invention is particularly preferably composed of the following.
    (A) 100 parts by weight of polydiorganosiloxane of the general formula (Ⅶ),
    (B) 0.1 to 50 parts by weight of a crosslinking agent of the general formula (Ⅸ),
    (C) 0.01 to 10 parts by weight of an organometallic condensation catalyst,
    (D) 0.1 to 30 parts by weight of an organosiliconized article according to the present invention having at least three silicon atoms in units of general formula (I),
    (E) 0 to 300 parts by weight of a plasticizer,
    (F) 0 to 300 parts by weight of the filler,
    (G) 0 to 50 parts by weight of the adhesion promoter and
    (H) 0-100 parts by weight of adhesive
    In all cases each component of the composition according to the invention may be a mixture of one form of such composition or at least two different forms of such composition.
    In order to prepare the compositions according to the invention, all components of a particular constituent are mixed with one another according to any procedure.
    This mixing is carried out at room temperature under ambient pressure, approximately 900 to 1100 hpa.
    However, in some cases this mixing is carried out at a high temperature, for example at a temperature of 35 to 135 ° C.
    The preparation and storage of the organopolysiloxanes according to the invention are in fact made under anhydrous conditions.
    Otherwise the composition cures prematurely.
    The general moisture content of air is suitable for crosslinking the compositions of the present invention for the formation of elastomers. In some cases crosslinking is also achieved at temperatures above or below room temperature, for example at −5 to 10 ° C. or at 30 to 50 ° C.
    The present invention also relates to a shaped article produced by crosslinking the composition of the present invention.
    The organopolysiloxane according to the present invention crosslinked for elastomer formation under alcohol separation has the advantage of being characterized by very high storage stability and high speed crosslinking.
    Therefore, the composition according to the present invention exhibits a constant vulcanization characteristic at any point in storage at room temperature for at least 18 months.
    In addition, the composition according to the present invention, the organosilicon compound of the present invention having at least three silicone groups in the unit of formula (I) is already at room temperature with OH groups, in particular alcohol and / or water and / or Si-OH groups Has the advantage of reacting.
    The compound having the OH group in the RTV alkoxy composition then is predominantly water introduced into the composition together with a compounding component such as polysiloxane or filler, and at the endblocking of the OH polymer and with the Si-OH group with the crosslinking agent or Alcohols formed upon the reaction of water, and also Si-OH groups in polysiloxanes and in particular silicic acids which are optionally used as fillers.
    In these reactions, volatile fission products are not released which are advantageously unacceptably ecological or painful due to odors.
    The compositions according to or according to the invention are used in all woods which can be stored under water exclusion or in which organopolysiloxane compositions which crosslink by water inflow to form an elastomer at room temperature can be used.
    The composition according to or according to the invention is therefore intended for use in joints, including vertically extending joints, for example, for similar voids with 10-40 mm inner diameters in buildings, on land transport, ships and aircraft. It is very suitable as a composition, or for the manufacture of protective coatings, for example for the manufacture of windows or for the manufacture of glass or aquarium or vaginal heat glass, and for the surfaces exposed to the repetitive action of fresh water or seawater, and for the production of slip or rubbery elastic forms. It is particularly suitable as a protective coating or an adhesive for joining electrical or electronic devices or as a bonding composition.
    In the examples described below, all viscosities are based on a temperature of 25 ° C.
    Unless otherwise noted, the following examples are at ambient atmospheric pressure, ie about 1000 hpa, and at room temperature, ie about 23 ° C., or at temperatures achieved when the reactants are entrained at room temperature without additional heating or cooling. Made at% relative atmospheric humidity, and all parts and percentage data are related to weight, except in special cases.
    In the following examples the hardness (Shore A, Shore A) is determined according to DIN 53 505-87 / Standard Rod SI (German Industrial Standard) and the following abbreviations are also used in the examples: Me is methyl radical.
    Example 1
    A mixture of 8.8 g of trimethylchlorosilane (0.08 mole) and 20.3 g of trichlorotetramethyldisiloxane (0.1 mole) was added to 10.15 g of urea (0.17 mole), 17.12 so that the temperature of the reaction mixture was kept below 30 ° C. To a suspension of g triethylamine (0.17 mole) and 67 g tetrahydrofuran is added dropwise within 90 minutes.
    After 10 minutes heating at 50 ° C., the formed precipitate is removed by filtration, the precipitate is washed with 300 ml of tetrahydrofuran, the filtrate is combined, and the solvent is then distilled off to remove volatiles.
    The remaining residue is viscous at 90 ° C. and becomes a solid at room temperature.
    OneH-and29The average composition of the product was determined by Si-NRR spectrum [Me3Si (NH-C = O-NH)1/2]2[Me2SiO1/2(NH-C = O-NH)1/2]16 [Me2SiO2/2]9Results in
    Example 2
    Gas phase ammonia is introduced into a mixture of 400 ml of anhydrous toluene and 330 g (about 1 mole) of organosilicon containing chlorine radicals of the average Me 3 Si (OMe 2 Si) 3 Cl until the mixture initiates a basic reaction. .
    The ammonium chloride obtained as a by-product during the reaction is then filtered off and the excess is washed twice with 50 ml of anhydrous toluene.
    Toluene is distilled from the compound toluene solution.
    200 g of clear liquid is left, which is a mixture of siloxaneoxamines by 29 Si-NRR and is consistent with the average formula [Me 3 Si (OMe 2 Si) 3 ] 2 NH.
    A mixture of 170 g of oxylyl siloxane, 0.3 g of ammonium sulfate, and 15 g of urea prepared on the average [Me 3 Si (OMe 2 Si) 3 ] 2 NH was added at 140 ° C. until the end of ammonia evolution. Heated.
    The excess siloxane ylamine was then distilled off and the residue obtained was a fluid having a viscosity of about 9000 mm 2 / S at room temperature.
    OneH- and29The average composition of the product was determined by the spectrum of Si-NRR [Me3SiO1/2]5[Me2SiO1/2(NH-C = O-NH)1/2]2[Me2SiO2/2]4 The same result was obtained.
    Example 3
    51 g of N, N'-bis (trimethylsilyl) urea and 3% dichlorodecamethylpentacyloxane, 64% dichlorododecamethylhexahexanoic acid, 31% dichlorotetradecamethylheptasiloxane and 2% di A mixture of 130 g of chlorohexadecamethyloctaxyoxane was stirred at a temperature of 80 ° C. for about 1 hour.
    The pressure of 500 mbar initially used was finally reduced to about 1 mbar upon reaction, with the result that the byproducts of the reaction were removed.
    By 'H- and 29 Si-NMR spectra, the average composition of the product is [Me 3 Si (NH-C = O-NH) 1/2 ] [Me 2 SiO 1/2 (NH-C = O-NH) 1/2 ] 65 [Me 2 SiO 2/2 ] 338 .
    The distillate contained reaction by-product trimethylchlorosilane and hexamethyldisiloxane in a mass ratio of 13: 1.
    Example 4
    RTV-1-silicone sealing compositions were prepared.
    For this purpose, 48.75 g of α, ω-bis (dimethoxymethylsiloxy) polydimethylsiloxane with viscosity of 1000 mm 2 / s, 32 g of α, ω-bis (trimethylsiloxy with viscosity of 100 mm 2 / S ) Polydimethyldisiloxane, 2 g of methyltrimethoxysilane, 4.5 g of 3-aminopropyltriethoxysilane and 9.5 g of urea radical-containing organosilicon compound prepared in Example 3 were mixed.
    Then, 9 g calcined silicic acid having a specific surface area of 150 m 2 / g measured by the BET method was fused homogeneously into the composition, and 0.25 g of dibutyltin diacetate was mixed.
    Finally the mixture was stirred under pressure of 10-20 mbar to remove the air contained during mixing.
    The tube was sealed with the composition so prepared and stored at 50 ° C.
    Immediately after manufacture and after 2,4,8,12 weeks of storage, the surface formation time is determined by the worm (the time at which the dry surface is formed in the shock), and the hardness of Shore A is determined by the 2 mm thick film. .
    The results are summarized in Table 1.
    Comparative Example 1
    The process described in Example 4 was repeated except that the urea radical-containing organosilicon compound was not used.
    This result is summarized in Table 1.
    Example 5
    Instead of the 9.5 g of urea radical-containing organosilicon compound prepared in Example 3, the process described in Example 4 was repeated except that the 6.3 g of urea radical-containing organosilicon compound prepared in Example 2 was used. .
    His results are summarized in Table 1.
    Example 6
    Instead of the 9.5 g of urea radical-containing organosilicon compound prepared in Example 3, the process described in Example 4 was repeated except that the 2.8 g of urea radical-containing organosilicon compound prepared in Example 1 was used. .
    His results are summarized in Table 1.
    Table 1
    Example After manufacture after 2 weeks 4 weeks later 8 weeks later 12 weeks later SFT Shore A SFT Shore A SFT Shore A SFT Shore A SFT Shore A 4 9 minutes 20-25 5 minutes 22-23 6 minutes 23-24 6 minutes 20-25 4 minutes 19-22 Comparative Example 1 5 minutes 25-27 >24 hours n.m. n.c. n.m. n.c. n.m. n.c. n.m. 5 12-17 minutes 20 〈6 minutes 20-25 3-6 minutes 20 5 minutes 18-22 4-5 minutes 20 6 40 to 45 minutes 10-15 50-60 minutes 9-12 45-50 minutes 11-14 45-55 minutes 10-13 40-50 minutes 11-15
    Legend:
    SFT = surface formation time
    n.c. = No crosslinking after storage in air for 7 days
    n.m. = Not measurable
    Example 7
    A dish containing 5 g of water was placed in a drier at normal pressure in indoor air, and a second dish containing 100 g of urea radical-containing organosilicon compound prepared in Example 1 was added.
    Changes in humidity in the dryer, ie water content of the atmosphere, were observed.
    Humidity is at initial 65%
    -35% after 1 day,
    After 18% 2 days,
    -5% after 5
    -0% after 10 days,
    Was reduced.
    The urea radical-containing organosilicon compound was converted into urea and polydimethylsiloxane.
    Example 8
    Example 7 was repeated except that 5 g of metanole was used instead of 5 g of water.
    After 10 days, methanol was not detected in the atmosphere.
    The urea radical-containing organosilicon compound here is urea, trimethylmethoxysilane and the series MeO- (SiMe 2 O) n SiMe 2 -OMe, where n = 0,1,2,3,4,5,6 or 7 Is converted to a homologue of.
    The urea-containing organosilicon compound according to the present invention is a sealant for empty spaces having an inner diameter of 10 to 40 mm for all joints and aircrafts, and is used for coating to protect sliding, rubber elastic formations, and insulation of electric and electronic devices. It is suitable for use as adhesives for solvents, and the industrial applicability has a very big advantage.
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] In the unit of the general formula,
    RaSi (NR 1 C = ONR 2 2 ) K (NR 3 C = ONR 4 ) t / 2 YmO n / 2 [(CR 5 2 ) S ] r / 2 (Ⅰ)
    The organosilylcone compound characterized by having three equatorial silicon atoms,
    Where Y is a unit of general formula.
    -SiR 6 3-pq (NR 1 C = ONR 2 2 ) p (NR 3 C = ONR 4 ) q / 2 (II)
    Wherein R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independent of one another, are the same or different in all cases and are optionally substituted monovalent hydrocarbons having 1 hydrogen atom or 1-20 carbon atoms .
    a is 0,1,2 or 3,
    k is 0,1,2 or 3,
    t is 0,1,2,3 or 4,
    n is 0,1,2,3 or 4,
    m is 0 or 1,
    r is 0 or 1,
    s is an integer from 1 to 20,
    p is 1,2 or 3,
    q is 1,2 or 3; However, it has the following conditions.
    -The sum p + q is ≤3,
    -The sum a + k + t + m + n + r is 4,
    The sum m + r is 0 or 1 and
    The organosilicon compound according to the invention contains at least one unit of general formula (I), wherein t is not zero.
    [2" claim-type="Currently amended] The method of claim 1,
    r is 0, The organosilicon compound characterized by the above-mentioned.
    [3" claim-type="Currently amended] The method of claim 1,
    An organosilicon compound, wherein r = m = o.
    [4" claim-type="Currently amended] An organosilicon compound as described in claim 1 is prepared by a reaction between a urea (derivative) having a general formula (III) and an chlorine radical-containing organosilicon compound having a unit of the general formula (IV) under HCl separation. How to.

    R a SiO n / 2 Y m [(CR 5 2 ) s ] r / 2 Clu (Ⅳ)
    In the formula (III), under the conditions under which at least one compound of the formula (III) having at least one radical R 8 as a hydrogen atom is used, R 7 and R 8 are the same or different, and all Are independent of each other, have the meanings given above for R 1 , R 2 , R 3 and R 4 and in formula (IV), the sum a + n + m + r + u is 4 and at least 1 per molecule Under the condition that at least one compound in units of formula (IV) having 2 chlorine atoms is present, R, R 5 , Y, a, n, m, r and s are the same or different in all cases and these symbols Has the meaning given above, and u is 0,1,2,3 or 4.
    [5" claim-type="Currently amended] In the first step, under the condition that a total of a + n + m + r + u is 4 and at least one compound in units of the general formula (IV) having at least one chlorine atom per molecule is present, Reaction of a radical-containing organosilicon compound with an amino compound of general formula (V), and in the second step, at least one compound of general formula (III) having at least one radical R 8 as a hydrogen atom is used. On the condition that, in some cases, the reaction between the organosilicon compound obtained in the first step and the urea (derivative) of the general formula (III) in the presence of a catalyst is provided. Process for preparing organosilicon compound.
    [6" claim-type="Currently amended] Under the conditions that the compound of formula (IV) contains 2 or less atoms and contains at least one compound of formula (VI) (where χ = 1 is used), R 7 and R 8 are added to these radicals. Siyl element (derivative) having one of the meanings [SiC] given above, wherein Z is silyl radical and x is 0 or 1, and a sum of a + n + m + chlorine radical-containing organo in units of general formula (IV) under conditions where r + u is 4 and at least one compound in units of general formula (IV) having at least one chlorine atom per molecule is present A method for producing an organosilicon compound as described in claim 1, wherein the compound is reacted with a silicon compound.

    [7" claim-type="Currently amended] Moisture is stored by exclusion and crosslinking at room temperature to form an elastomer under alcohol separation by moisture influx.
    (A) a polydiorganosiloxane having at least two organyloxy radicals in each end group, optionally
    (B) a crosslinking agent of an organyloxy function having at least three organyloxy groups
    In some cases,
    (C) a condensation catalyst containing at least one of the following:
    (D) an organosilicon compound according to the present invention having at least three silicon atoms and in the unit of general formula (I)
    Organopolysiloxane composition, characterized in that.
    [8" claim-type="Currently amended] A formed body formed by crosslinking a composition as in claim 7.
    [9" claim-type="Currently amended] Use of an organosilicon compound as in claim 1, characterized in that for removing the fortin compound or protein group.
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    同族专利:
    公开号 | 公开日
    CZ232999A3|1999-11-17|
    US6218498B1|2001-04-17|
    RU99115893A|2004-03-20|
    NO993179L|1999-08-23|
    NO993179D0|1999-06-25|
    DE19654556A1|1998-07-02|
    KR100323308B1|2002-02-06|
    AT199156T|2001-02-15|
    SK87799A3|2000-03-13|
    WO1998029418A1|1998-07-09|
    ID19408A|1998-07-09|
    RU2165426C1|2001-04-20|
    TW406084B|2000-09-21|
    PL334255A1|2000-02-14|
    JP3241391B2|2001-12-25|
    EP0948501B1|2001-02-14|
    ES2154481T3|2001-04-01|
    AU727551B2|2000-12-14|
    EP0948501A1|1999-10-13|
    HU0000454A2|2000-06-28|
    AU5759598A|1998-07-31|
    CA2274030A1|1998-07-09|
    BR9714437A|2000-03-21|
    JP2001501969A|2001-02-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-12-27|Priority to DE19654556A
    1996-12-27|Priority to DE19654556.0
    1997-12-18|Application filed by 에리히 프란케 ; 칼 하인츠 룀뵈크, 와커-헤미 게엠베하
    2000-10-25|Publication of KR20000062316A
    2002-02-06|Application granted
    2002-02-06|Publication of KR100323308B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE19654556A|DE19654556A1|1996-12-27|1996-12-27|Organosilicon compounds containing urea groups, their preparation and their use|
    DE19654556.0|1996-12-27|
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