FR2569700A1 - SILYLATION PROCESS OF AROMATIC IMIDES AND PRODUCTS OBTAINED - Google Patents
SILYLATION PROCESS OF AROMATIC IMIDES AND PRODUCTS OBTAINED Download PDFInfo
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- FR2569700A1 FR2569700A1 FR8512626A FR8512626A FR2569700A1 FR 2569700 A1 FR2569700 A1 FR 2569700A1 FR 8512626 A FR8512626 A FR 8512626A FR 8512626 A FR8512626 A FR 8512626A FR 2569700 A1 FR2569700 A1 FR 2569700A1
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- 150000003949 imides Chemical class 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 9
- 238000006884 silylation reaction Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229920000548 poly(silane) polymer Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- -1 Dimethylmethoxysilyl Chemical group 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229940072395 n-butylphthalimide Drugs 0.000 claims description 2
- APOAEMIYHVGWEZ-UHFFFAOYSA-N 4-chloroisoindole-1,3-dione Chemical compound ClC1=CC=CC2=C1C(=O)NC2=O APOAEMIYHVGWEZ-UHFFFAOYSA-N 0.000 claims 1
- 241000238876 Acari Species 0.000 claims 1
- 125000006519 CCH3 Chemical group 0.000 claims 1
- BQLQQEHXQQLKEV-UHFFFAOYSA-N dimethoxy-methyl-trimethylsilylsilane Chemical group CO[Si](C)(OC)[Si](C)(C)C BQLQQEHXQQLKEV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- LIIFSQNIIUNBFT-UHFFFAOYSA-N 2-butyl-4-chloroisoindole-1,3-dione Chemical compound C1=CC(Cl)=C2C(=O)N(CCCC)C(=O)C2=C1 LIIFSQNIIUNBFT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 description 1
- BXHLWHLRFBMRTC-UHFFFAOYSA-N 4-butyl-5-chloroisoindole-1,3-dione Chemical compound C1=C(Cl)C(CCCC)=C2C(=O)NC(=O)C2=C1 BXHLWHLRFBMRTC-UHFFFAOYSA-N 0.000 description 1
- VVQTYZKVZLDUND-UHFFFAOYSA-N 4-chloro-2-phenylisoindole-1,3-dione Chemical compound O=C1C=2C(Cl)=CC=CC=2C(=O)N1C1=CC=CC=C1 VVQTYZKVZLDUND-UHFFFAOYSA-N 0.000 description 1
- DCFSQEWFDPNDPQ-UHFFFAOYSA-N 5-chloro-2-methylisoindole-1,3-dione Chemical compound C1=C(Cl)C=C2C(=O)N(C)C(=O)C2=C1 DCFSQEWFDPNDPQ-UHFFFAOYSA-N 0.000 description 1
- RLXKJHQKSUMZIZ-UHFFFAOYSA-N 5-chloro-2-phenylisoindole-1,3-dione Chemical compound O=C1C2=CC(Cl)=CC=C2C(=O)N1C1=CC=CC=C1 RLXKJHQKSUMZIZ-UHFFFAOYSA-N 0.000 description 1
- XGAGMIKJBSNJGP-UHFFFAOYSA-N C(CCC)C=1C(=C2C(C(=O)NC2=O)=CC=1)Cl Chemical compound C(CCC)C=1C(=C2C(C(=O)NC2=O)=CC=1)Cl XGAGMIKJBSNJGP-UHFFFAOYSA-N 0.000 description 1
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- VIPCDVWYAADTGR-UHFFFAOYSA-N trimethyl(methylsilyl)silane Chemical compound C[SiH2][Si](C)(C)C VIPCDVWYAADTGR-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
PROCEDE DE PREPARATION D'IMIDES SILYLAROMATIQUES CONSISTANT A:A. LA MISE EN REACTION D'UN POLYSILANE REPONDANT A LA FORMULE: (CF DESSIN DANS BOPI) ET D'UN IMIDE HALOAROMATIQUE REPONDANT A LA FORMULE: (CF DESSIN DANS BOPI) EN PRESENCE D'UNE QUANTITE EFFICACE D'UN CATALYSEUR CONTENANT UN METAL DE TRANSITION, ET B. LA RECUPERATION DE L'IMIDE SILYLAROMATIQUE RESULTANT DU MELANGE DE A. APPLICATION AUX COMPOSITIONS VULCANISABLES.PROCESS FOR PREPARING SILYLAROMATIC IMIDES CONSISTING OF: A. THE REACTION OF A POLYSILANE RESPONDING TO THE FORMULA: (CF DRAWING IN BOPI) AND OF A HALOAROMATIC IMID RESPONDING TO THE FORMULA: (CF DRAWING IN BOPI) IN THE PRESENCE OF AN EFFECTIVE QUANTITY OF A CATALYST CONTAINING A METAL TRANSITION, AND B. RECOVERY OF THE SILYLAROMATIC IMIDE RESULTING FROM THE MIXING OF A. APPLICATION TO VULCANIZABLE COMPOSITIONS.
Description
Comme le montre le brevet des E.U.A. n 2 474 087, on a utilisé desAs shown in U.S. Pat. No 2 474 087, we used
disilanes pour préparer des organosilanes en faisant réagir des composés organiques halogénés, comme des halogénures d'alkyle ou des halogénures d'aryle avec un S halodisilane en présence d'un catalyseur métallique. On disilanes for preparing organosilanes by reacting halogenated organic compounds, such as alkyl halides or aryl halides with a halodisilane in the presence of a metal catalyst. We
trouve un procédé un peu semblable dans le brevet des E.U.A. find a somewhat similar process in the U.S. Patent.
n 3 772 347 qui emploie un disilane halogéné et un chlorure organique comme le chlorobenzène ou le chlorure de butyle No. 3,772,347 which employs halogenated disilane and an organic chloride such as chlorobenzene or butyl chloride
pour produire l'organohalosilane approprié. to produce the appropriate organohalosilane.
La silylation de substrats aromatiques activés avec des disilanes, en employant un catalyseur contenant un métal de transition est moins facile à prévoir. Par exemple, Matsumoto et al, montrent dans JOMC, 85, C1 (1985) , que l'on Silylation of aromatic substrates activated with disilanes by employing a transition metal-containing catalyst is less easy to predict. For example, Matsumoto et al, show in JOMC, 85, C1 (1985), that one
peut facilement silyler du nitrochlorobenzène avec du disi- can easily silylate nitrochlorobenzene with
lane. L'expérience a montré, toutefois, que la silylation lane. Experience has shown, however, that silylation
par du disilane de certains composés aromatiques dicar- by disilane of certain aromatic dicarboxylic compounds
bonylés portant des groupes fonctionnels, et par exemple de bonylates bearing functional groups, and for example
l'anhydride chlorophtalique, n'était pas possible. chlorophthalic anhydride was not possible.
La présente invention repose sur la découverte que, contrairement aux anhydrides aromatiques halogénés, on pouvait facilement silyler d'autres composés dicarbonylés aromatiques portant des groupes fonctionnels, comme des The present invention is based on the discovery that, unlike halogenated aromatic anhydrides, other aromatic dicarbonyl compounds carrying functional groups, such as
imides aromatiques halogénés, et par exemple, un chloro- halogenated aromatic imides, and for example a chlorinated
phtalimide, avec des polysilanes. La présente invention phthalimide, with polysilanes. The present invention
concerne donc la synthèse d'imides silylaromatiques confor- therefore concerns the synthesis of silylaromatic imides according to
mément à l'équation suivante: Rl(i)nSi(R1)2R + XR 3 cat R(R1)2SiR2 NR n 2 according to the following equation: R1 (i) nSi (R1) 2R + XR3 cat R (R1) 2SiR2 NR n 2
R1 R1R1 R1
R' R1R 'R1
il Ihe I
1-1I 11-1I 1
+ R -(Si)n1 Si-R,+ R - (Si) n1 Si-R,
R' RR 'R
dans laquelle X représente un halogène, R représente un radical monovalent choisi dans le groupe constitué par X, l'hydrogène, des radicaux alcoxy en C(1-8)' des radicaux hydrocarbonés en C(1.3) et des radicaux hydrocarbonés en C(1.13) substitués, R est choisi parmi R, -0- et -S-, et lorsque R1 représente -0- ou -S- ou une der leurs combinaisons, R1 peut former des groupes de liaison -SiOSi- et -SiSSi-, R2 représente un radical organique aromatique trivalent en C63) R3 est choisi parmi les radicaux hydrocarbonés monovalents en C(6.13)' et les radicaux hydrocarbonés monovalents substitués en C(113), et n représente un nombre entier compris entre 1 et 50 inclus. La présente invention met au point un procédé de préparation d'imides silylaromatiques répondant à la formule : o R(R)2SiR2 "NR3 wherein X is halogen, R is a monovalent radical selected from the group consisting of X, hydrogen, C (1-8) alkoxy radicals, C (1.3) hydrocarbon radicals, and C (C) hydrocarbon radicals ( 1.13), R is selected from R, -O- and -S-, and when R1 represents -O- or -S- or one of their combinations, R1 may form -SiOSi and -SiSSi linkers, R2 represents a trivalent organic C63) radical R3 is chosen from C (6.13) monovalent hydrocarbon radicals and C (113) substituted monovalent hydrocarbon radicals, and n represents an integer between 1 and 50 inclusive. The present invention provides a process for the preparation of silylaromatic imides having the formula: R (R) 2 SiR 2 "NR 3
OO
25697G025697G0
- 3 -- 3 -
qui comprend: (A) la mise en réaction d'un polysilane répondant à la formule: R1 (2) RI-(Si-) -Si(R1) R 1n 2 R1 et d'un imide haloaromatique répondant à la formule, Il which comprises: (A) reacting a polysilane having the formula: R1 (2) R1- (Si-) -Si (R1) R1n2R1 and a haloaromatic imide of formula II
(3) XR2/ *-R3(3) XR2 / * -R3
CC
en présence d'une quantité efficace d'un cata- in the presence of an effective amount of a
lyseur contenant un métal de transition, et (B) la récupération de l'imide silylaromatique résultant du mélange de (A), transition metal-containing lysate, and (B) recovering the silylaromatic imide resulting from the mixture of (A),
1 2 31 2 3
sachant que, dans les formules R, R1, R2, R3, n et X knowing that, in the formulas R, R1, R2, R3, n and X
sont tels qu'on les a définis précédemment. are as previously defined.
On peut citer, par exemple, parmi les radicaux que peuvent représenter R et R1 dans les formules (1) et (2), l'hydrogène, un halogène, comme les groupes chloro, bromo; des radicaux alcoxy en C(1_8), et par exemple, les groupes méthoxy, éthoxy, propoxy; des radicaux alkyles en C(1_8), Examples which may be mentioned, among the radicals which R and R 1 may represent in formulas (1) and (2), are hydrogen and halogen, such as chloro and bromo groups; C 1 -C 18 alkoxy radicals, for example methoxy, ethoxy, propoxy; C (18) alkyl radicals,
comme les radicaux méthyle, éthyle, propyle, butyle, pen- such as methyl, ethyl, propyl, butyl,
tyle; les radicaux aryles et les radicaux haloaryles comme tyle; aryl radicals and haloaryl radicals as
les radicaux phényle, tolyle, xylyle, naphtyle, chloro- the radicals phenyl, tolyl, xylyl, naphthyl, chloro
phényle; les radicaux alcényles comme les radicaux vinyle, phenyl; alkenyl radicals such as vinyl radicals,
allyle, les radicaux haloalkyles comme le radical trifluoro- allyl, haloalkyl radicals such as the trifluoro-
propyle, etc. On peut citer, par exemple, parmi les radicaux que peut représenter R2 dans les formules (1) et (3), OC, O, 9, etc. On peut citer, par exemple, parmi les radicaux que peut représenter R3 dans les formules (1) et (3), les radicaux alkyle en C(1_8) et les radicaux aryle en C(6.13) que peut représenter R. propyl, etc. For example, among the radicals that can represent R2 in the formulas (1) and (3), OC, O, 9, etc. Examples of radicals that may be represented by R 3 in formulas (1) and (3) include C (1-8) -alkyl radicals and C-aryl radicals (6.13) which R. may represent.
On peut citer, par exemple, parmi les imides halo- For example, among the imides halo
aromatiques répondant à la formule (3), le N-butyl chloro-3 phtalimide, le N-butyl chloro-4 phtalimide, le N-phényl chloro-3 phtalimide, le N- phényl chloro-4 phtalimide, etc. On peut citer parmi les polysiloxanes répondant à aromatic compounds corresponding to formula (3), N-butyl-3-chlorophthalimide, N-butyl-4-chlorophthalimide, N-phenyl-3-chlorophthalimide, N-phenyl-4-chlorophthalimide and the like. Among the polysiloxanes answering to
la formule (2), l'hexaméthyldisilane, le chloropentaméthyl- formula (2), hexamethyldisilane, chloropentamethyl-
disilane, le dichloro-l,2 tétraméthyldisilane, le trichlo- disilane, dichloro-1,2-tetramethyldisilane, trichlo-
ro-1,1,2 triméthyldisilane, le tétrachloro-l,l,2,2 diméthyl- ro-1,1,2-trimethyldisilane, tetrachloro-1,1,2,2-dimethyl-
disilane, l'hexachlorodisilane, le méthoxypentaméthyl- disilane, hexachlorodisilane, methoxypentamethyl-
disilane, le diméthoxy-l,2 tétraméthyldisilane, l'éthoxypen- disilane, dimethoxy-1,2-tetramethyldisilane, ethoxypen
taméthyldisilane, le diéthoxy-l,2-pentaméthyldisilane, etc. On peut citer, par exemple, parmi les catalyseurs contenant des métaux de transition que l'on peut employer tamethyldisilane, diethoxy-1,2-pentamethyldisilane, etc. For example, among the catalysts containing transition metals that may be employed
dans la mise en pratique de la présente invention, le palla- in the practice of the present invention, the pallet
dium, Pd/C, du tétrakis(triphénylphosphine)palladium, du dichlorure de bis-(benzonitrile)palladium, du dichlorure de bis(triphénylphosphine)palladium, etc. dium, Pd / C, tetrakis (triphenylphosphine) palladium, bis (benzonitrile) palladium dichloride, bis (triphenylphosphine) palladium dichloride, and the like.
Lorsqu'on parle d'une quantité efficace de cataly- When talking about an effective amount of catalytic
seur contenant un métal de transition, cela signifie que containing a transition metal, this means that
l'on peut utiliser de 0,01 à 0,10 partie de catalyseur con- 0.01 to 0.10 parts of catalyst can be used.
tenant un métal de transition, exprimée par rapport au poids holding a transition metal, expressed in relation to weight
du composé halodicarbonylé répondant à la formule (3). halodicarbonyl compound of formula (3).
Dans la mise en pratique de l'invention, on fait réagir l'imide haloaromatique répondant à la formule (3) et le polysilane répondant à la formule (2) en présence d'une - 5- quantité efficace d'un catalyseur contenant un métal de In the practice of the invention, the haloaromatic imide of formula (3) is reacted and the polysilane of formula (2) in the presence of an effective amount of a catalyst containing a metal of
transition, telle qu'on l'a définie précédemment. L'expé- transition, as defined previously. The experi-
rience a montré que l'on pouvait obtenir de bons résultats en mettant en oeuvre la réaction dans une atmosphère gazeuse inerte, par exemple dans de l'azote, de l'argon ou d'autres gaz rares. Les proportions d'imide haloaromatique et de polysilane peuvent beaucoup varier. On recommande toutefois d'utiliser une quantité suffisante de polysilane pour avoir au moins deux atome-grammes de silicium par mole d'imide It has been shown that good results can be obtained by carrying out the reaction in an inert gaseous atmosphere, for example in nitrogen, argon or other noble gases. The proportions of haloaromatic imide and polysilane can vary widely. However, it is recommended to use a sufficient amount of polysilane to have at least two gram atoms of silicon per mole of imide
haloaromatique.haloaromatic.
On peut utiliser un solvant organique inerte, et par exemple le toluène, l'anisole, le xylène, le mésitylène, An inert organic solvent can be used, for example toluene, anisole, xylene, mesitylene,
pour faciliter la réaction entre le polysilane et l'halo- to facilitate the reaction between polysilane and halogen
génure aromatique. On peut employer des températures de 110 C à 300 C. On peut recueillir l'imide silylaromatique voulu par des techniques classiques comme la précipitation par addition d'un solvant non polaire, et par exemple l'hexane, puis la filtration et l'élimination du solvant aromatic genius. Temperatures of 110 ° C to 300 ° C can be employed. The desired silylammatic imide can be recovered by conventional techniques such as precipitation by addition of a non-polar solvent, for example hexane, followed by filtration and removal. solvent
sous vide.under vacuum.
Les imides silylaromatiques de la présente inven- The silylaromatic imides of the present invention
tion sont utiles comme promoteurs d'adhérence pour les com- are useful as adhesion promoters for
positions vulcanisables à température ambiante et comme vulcanizable positions at room temperature and as
intermédiaires pour la préparation des anhydride silylaroma- intermediates for the preparation of silylaromatous anhydride
tiques correspondants comme un dianhydride bis(dicar- corresponding dianhydride bis (dicarboxylic) di-
boxy-l',2' phényl)-l,3 disiloxane par des procédés d'hydro- boxy-1 ', 2'-phenyl) -1,3-disiloxane by hydrogenation methods.
lyse alcaline classiques.alkaline lysis classics.
Dans les exemples suivants, toutes les parties In the following examples, all parts
sont exprimées en poids.are expressed in weight.
Exemple 1Example 1
On a chauffé au reflux sous atmosphère d'argon une solution de 20 ml de toluène contenant 1,26 gramme (5,62 millimoles) de N-n-butylchloro-4 phtalimide et 2,0 grammes (1,12 millimole) de diméthoxy-l,2 tétraméthyldisilane et 40 milligrammes de tétrakistriphénylphosphinepalladium. La solution chauffée au reflux est devenue jaune d'or puis 6- rouge foncé. Au bout de 48 heures de chauffage au reflux, on a laissé refroidir le mélange puis on l'a débarrassé de son A solution of 20 ml of toluene containing 1.26 grams (5.62 millimoles) of 4-n-butylchlorophthalimide and 2.0 grams (1.12 millimoles) of dimethoxy-1 was refluxed under an argon atmosphere. , 2 tetramethyldisilane and 40 milligrams of tetrakistriphenylphosphinepalladium. The solution heated to reflux became golden yellow then 6 dark red. After 48 hours of refluxing, the mixture was allowed to cool and then discarded.
solvant organique. On a ensuite purifié le résidu en, ajou- organic solvent. The residue was then purified by adding
tant 30 ml d'hexane anhydre. On a séparé le résidu par filtra- tion puis on a éliminé le solvant sous vide. On a obtenu du diméthylméthoxysilyl-4N-n-butyl-phtalimide en un rendement de 83 %. On a encore confirmé l'identité du produit par analyse chromatographique en phase as much as 30 ml of anhydrous hexane. The residue was filtered off and the solvent removed in vacuo. Dimethylmethoxysilyl-4N-n-butyl phthalimide was obtained in 83% yield. The identity of the product was further confirmed by chromatographic analysis in phase
gazeuse-spectrométrie de masse.gas-mass spectrometry.
On a soumis le matériau à une chromatographie sur gel de silice en utilisant de l'hexane comme éluant ce qui a provoqué l'hydrolyse du méthoxysilane formé initialement en le bisimide correspondant répondant à la formule: The material was subjected to chromatography on silica gel using hexane as eluent which caused the hydrolysis of the initially formed methoxysilane to the corresponding bisimide having the formula:
OO
le Othe O
I! HI! H
C41H9 ?13 3 NC4H9C41H9? 13 3 NC4H9
.CHCH 3 3.CHCH 3 3
O OO O
Ce bisimide est utile comme promoteur d'adhérence de compositions de silicone vulcanisables à température ambiante. This bisimide is useful as an adhesion promoter for vulcanizable silicone compositions at room temperature.
Exemple 2Example 2
On a répété le procédé de l'Exemple 1, excepté que l'on a utilisé 0,2 gramme de N-méthyl chloro-4 phtalimide, The procedure of Example 1 was repeated except that 0.2 gram of N-methyl-4-chlorophthalimide was used.
0,37 gramme de diméthoxy-l,2 tétraméthyldisilane et 40 mil- 0.37 grams of dimethoxy-1,2-tetramethyldisilane and 40 mil-
ligrammes de (Ph3P)4Pd. On a chauffé la solution en Ligraphs of (Ph3P) 4Pd. The solution was heated
agitant pendant 15 heures pour obtenir du N-méthyl(diméthyl- stirring for 15 hours to obtain N-methyl (dimethyl)
méthoxysilyl)-4 phtalimide en un rendement de 55 %. methoxysilyl) -4 phthalimide in 55% yield.
7-7-
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64730184A | 1984-09-04 | 1984-09-04 | |
| CA000570203A CA1327044C (en) | 1984-09-04 | 1988-06-23 | Silylation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| FR2569700A1 true FR2569700A1 (en) | 1986-03-07 |
Family
ID=25671959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8512626A Withdrawn FR2569700A1 (en) | 1984-09-04 | 1985-08-22 | SILYLATION PROCESS OF AROMATIC IMIDES AND PRODUCTS OBTAINED |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6183191A (en) |
| CA (1) | CA1327044C (en) |
| DE (1) | DE3531466A1 (en) |
| FR (1) | FR2569700A1 (en) |
| GB (1) | GB2164040B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4730055A (en) * | 1984-09-04 | 1988-03-08 | General Electric Company | Method for silylating aromatic imides and silylimides made therefrom |
| DE3715313A1 (en) * | 1986-09-02 | 1988-03-10 | Gen Electric | IMIDOPOLYSILOXANES AND METHOD FOR THEIR PRODUCTION |
| KR900006209B1 (en) * | 1987-05-19 | 1990-08-25 | 히다찌가세이고오교 가부시끼가이샤 | Process for producing 1,3-bis(dicarboxyphenyl)-disiloxane derivative or dianhydride thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2163579A1 (en) * | 1971-12-15 | 1973-07-27 | Dow Corning |
-
1985
- 1985-05-20 GB GB08512737A patent/GB2164040B/en not_active Expired
- 1985-08-22 FR FR8512626A patent/FR2569700A1/en not_active Withdrawn
- 1985-09-03 DE DE19853531466 patent/DE3531466A1/en not_active Withdrawn
- 1985-09-03 JP JP60193272A patent/JPS6183191A/en active Granted
-
1988
- 1988-06-23 CA CA000570203A patent/CA1327044C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2163579A1 (en) * | 1971-12-15 | 1973-07-27 | Dow Corning |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0547549B2 (en) | 1993-07-19 |
| GB8512737D0 (en) | 1985-06-26 |
| GB2164040B (en) | 1988-10-05 |
| CA1327044C (en) | 1994-02-15 |
| DE3531466A1 (en) | 1986-03-13 |
| GB2164040A (en) | 1986-03-12 |
| JPS6183191A (en) | 1986-04-26 |
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