CA1071622A - Polyethylenic silicon compounds - Google Patents

Abstract

SPECIFICATIONS OF THE DISCLOSURE: The invention relates to disilanes comprising from 1 to 3 alkenyl groups linked to each silicon atom by a C - Si bond, the silicon atoms of which are linked by an organic residue having functional groups such as ether, thioether, amide, thioamide, ester, thioester, imide, urea, urethane. These compounds are obtained by condensation of a monosilane comprising from 1 to 3 alkenyl group, in particular vinyl or allyl, and a radical comprising an organic function for example a hydroxyl, thiol, amine, ester, carboxylic acid or acid chloride function. , with an organic compound comprising two antagonistic functions. The disilanes according to the invention are very interesting synthesis intermediates in organosilicon chemistry thanks to the presence of olefinic groups.

Description

~ 7.1 ~ 2Z
The present invention relates as products:. .
in ~ ustriels nou ~ waters, polyethic silicon compounds ~ lenic such as those described below.
The compounds according to the inventioll are intermedia-very interesting synthetic res in organosilicon chemistry thanks to the presence of olefinic groups.
They allow access to various polymers, in particular to copolymers with elastomeric properties which are chées, by addi ~ ion of hydrogen silanes on the double bonds 0 ethylenic.
More specifically, the present invention relates to polyethylenic compounds with the formula general (I) ~
(Rl) 3-n (IR 1) 3-n ' (R) n - si - R2 - x - ~ r ~ - xl - R2 '- si - (R') n, (I) in which the various symbols represent:
- n, n ': whole numbers identical or different from 1 to 3 - R, R ': monovalent organic, identical groups or different, comprising an ethyleni- double bond:
that and comprising from 2 to 10 carbon atoms, .- Rl, Rli of identical or different radicals, alkyls ~ ~
straight or branched, substituted where appropriate by - ~.
one or more halogen atoms, or by one or:
several nitrile groups, aryl radicals, alkylaryl radicals; these last radicals aromatics being substituted where appropriate by one or more halogen atoms, - R2, R2 ': divalent radicals, identical or different alkylenes, straight or branched alkylidenes having from 1 to ~ carbon atoms, `;
- X, X ': identical or different divalent radicals made up of, or containing at least one heteroatom:

-1- ~

~ 7 ~
0, S or N; in this case the radicals X, X 'are attached to the raclicals R ~, R'2 via the heteroatom, - r, r ~: identical or diE ~ erent organic radicals; ~
having 1 to 30 carbon atoms taken from groups formed by:
a) divalent radicals: - Gl -, - G'-:.
and b) trivalent radicals: - Gl _, - G'l -- ~: an organic radical chosen from the group consisting of:
killed by :
a) - ~ - C - ~ '- (II) b) - T - X "-T '- (III) ~ j c) - T - X "'/ N- (IV) , ~ ~

\ / ~ R \ / - ~ V); ~
"

in formulas II to V; ..

~ 'represent an oxygen and / or nitrogen atom -R "represents a valential bond or a radical divalent organic ~.

-R "'represents a trivalent organic radical

- 2 ~

:. ~. -, ~; ~ 7 ~ Z

-R ~ "'represellte In ~ adi.ca: organic tretravalent -T, T 'represents the functional groups.
identical or different taken from the group trained by :
- C - 0 -, - C - S -, - NH - Cl - 0 OOO
- NH - C - S - ~ - C - NR3 - ~ - NH - C - NR3 - ~
It 11 11.
o. OO ~ ::
(VI) (VII) ~.
11, VS

it being understood that in formulas (VI) and: ~ -(VII), R3 represents a hydrogen atom, or: ~ -an alkyl radical of 1 to 6 atoms of carbon.
More precisely the various symbols precedents can take the if ~ nifications following:
I - RADICALS R, R '~
These radicals represent an alkenyl group straight or branched substituted if necessary by a QU several halogen atoms, a cycloalkenyl group substituted by the `
if necessary by one or more halogen atoms. In this contextc we can mention the ~ groupelllellts alcényles c] roits or branched having 2 to 6 carbon atoms and possibly su ~> established by one to three atoms of chlorine and / or fluorine than the following groups: vinyl, allyl, 2,2-dichloro vinyl, 1,2,2-trichloro vinyl, propene-2 yl, butene-2 yl, propene-l yl, butene-l yl, methyl-2 propene-l. yle.

~ - 3 -.

. .

) have ~ '? cJ. Ilelllelll: represent a gropelllent ov ~ r ~ -r X ~

~ 2 ~ 3 in which the symbols Xl X2 X ~ represent an atom d hydrogen a straight or branched alkyl group having 1 to 4 calbolle atollles such as radica ~ lx métllyle étllyle and isobutyle a pilényLe grouping; X4 denotes the group Lln OJ men ts orc ~ allosiliciques suitallts - 91 - ~ 51 - O - ~ - 5- - ~ C112) ~

1 ~ 4 R4 icletll: ics or diEEerents represent Utl groupemertt métlly1e p ~ lényle and nl is an integer notllbre equal to 1 2 or 3.

~ 7 ~ ~ 2 ~

De pr ~ fCrcnce ~, T ~ 'represen-ten-t an alkenyl group linen ~ area having 2 ~ 6 carbon atoms II RADIC ~ UX ~ 1 'R1 , They represent more specifically:
- straight or branched alkyl groups having at most 10 ~.
carbon atoms and substituted if necessary by one to four: ~
chlorine and / or fluorine atoms or by u ~ nitrile group, - ~ aryl groups such as phenyl, alkyl groups -Ryles containing from 1 to 4 carbon atoms in the sub ~ -tituant alkyl such as tolyles or xylyles l these aromatiqv.ss radicals ~ both possibly substituted by a ~ four atom ~ of chlorine and / or fluorine.
Among this ~ radicals, mention may be made of the following groupings:
methyl, ethyl, 4,4,4,4-trifluoro bu-tyle, phenyl, p-, m- or o- tolyl, xylyles, p-, m- chlorophenyl, dichloro- ~, 5-phenyl, trichlorophenyl, tetrachlorophenyl, ~ - cyanoethyl, y -cya.no ~:
propyl.
~ e ~ radicals R1, R1 'represent pre ~ erentially a alkyl radical having 1 ~ 5 carbon atoms possibly substituted by 1 to 4 chlorine and / or ~ luor atoms, a radical p ~ enyl. ~

III RADICALS R2 ~ R2 ': I.

These radicals represent a divalen.t radical defined pre-cedation such as ~ that m ~ thyl ~ ne, ethyla.ne, trimethylene, ethylid ~ ne, tetramethylene ~ isopropylidene, methylethylene.
Preferably, R2 and R2 'represent a methylene group ~
or ~ th ~ lene.

These radicals represent ~ entent one of the following groups:

,,; .
.

~ (i 7 ~

linked ~ by the h ~ teroatom to the radicals R2, R'2:
0 -, - S ~, ~ N -, - 0 _ C -, ~ 0 - C _, S ~ C -, _ S -C-R5 represents ~ en-te a hydrogen atom or a right alkyl radical t or branched ayan-t from 1 to 4 carbon atoms ~
X) X ′ preferably represent an oxygen atom or sulfur, a grouping - 0 - C -, - N -gold (R5 represents ~ then entering a hydrogen atom or a methyl radical, ethy ~ e).

V - XADICAUX G, G ':

They represent one of the following groupings:
1) An aliphatic hydrocarbon radical, straight or branched, saturated or unsaturated cycloaliphatic substituted where appropriate by ~ chlorine atoms, a monocyclic or poly- aromatic radical cyclic ~ ub ~ tltué if necessary by methyl or by chlorine atoms. This ~ aromatic radicals can for ~
sea between them of ~ orthocondensed systems or ortho and pericon-. ~ ...
dense 3.
2) A saturated heterocyclic radical ~ in ~ aturated, or aromatic, monocyclic or polycyclic, comprising at least one of the hetero-atoms 0, N, S1 and sub ~ substituted if necessary by radicals methyls.
By the expression ~ ion "polycyclic heterocyclic rsdical", we defines:
- a radical consisting of at least 2 heterocycles containing at less ~ a heteroatom in each cycle and forming between them; ~
sy3t ~ mes ortho or ortho and pericondensed ~.
~ a radical consisting of at least one aromatic hydrocarbon cycle tick or not and at least ~ a heterocycle forming between them ~ ystamos ortho or ortho et periconde.n ~ s.

3) A divalent radical constituted by group linking ments, as defined ~ in paragraphs 1 and / or 2 and linked ~ between them by a valentlel link and / or by at least one of the groups ~ -next ~:
- 0 -, - S -, - N -, - C0 - N _, - C0 -_ C00 ~ I ~ S02 -, - N = ~ N = N
o, o ,, ~ ", In these formulas, R6 and R6 represent an alkyl radical having from 1 to ~ carbon atoms, a cyclohexyl or phenyl radical, R6 can also represent a hydrogen atom. J
Among the radio stations that have just been mentioned G and G ' represent more ~ particularly a) an alkylene radical, alkenyl9 alkenylene, alkenyl-straight or branched lidene ayan-t plus ~ 12 carbon atoms ~, a `~.
radic ~ lc ~ cloalcoylene, cycloalkenylane having 5 to 8 atomea of oar ~
bone dan ~ the cycle.
. By way of illustration, mention may be made of methylene radicals ethylene, ethylidene, cyciohexylan, butylene.
:. b) a phenylene, tolyene or xylylene radical c) a heterocyclic monocyclic radical ~ unsaturated aturated or aromatic and comprising as heteroatom one or more oxygen, nitrogen or sulfur atoms, and containing 4 to 6 atoms .-. in the cgole; heterooyclic radicals can be substituted.
by one or two methyl groupings .A t-itre illustrati ~ we can cite the radicals ~ ui.vants ~ ~ ~ C-~ 07 ~ 2 d) a divine radical ~ t constituted by a chain of two to four groupings as defined in the paragraphs a9 b or c above and linked ~ between them by the bond and / or;
by at least ~ one of the following groupings:
0 - - NH -, - C00 _, - CO ~ S02 -, - N
O
_ CO -, and / or also by an alkyl or alkylene group having 1 to 4 carbon atoms.
A ti-be illu ~ trati ~ we can cite the radicals of formula next ~

CH2 ~ 9 CH2-CH2 ~ ~ -CH2_0 ~, -aH2 ~ CH2 ~;

;, '~, ~ ~ ~ ~ 2 ~ CH2 ~ ~ H2 ~
, , ~ O ~,, ~ S02 ~

e) an aromatic radical consisting of a set of 2 with 3 aromatic carbocyclic and / or heterocyclic rings and for ~
. .
mant between them a system ~ me orthocondensé, this aromatic radical for-before being substituted by ~ methyl group ~
By way of illustration ~ the aromatic cycles are ~ -benzene nuclei ~ and pyridini ~ ues. These radicals are for example . . .
the following Preferably, G and G 'represent a radical alkylene or alkylliaane having 1 ~ 6 carbon atoms 9 a radi ~
cal cyclohexyl ~ ne, a phenyl ~ ne radical, tolylene, xylene, a radical ~ '' ~. ' ~ ~ '7 ~ ~ Z' ~

cal formed by 2 grou ~ ement ~ phenyl ~ nes linked together by a valential link, a methylene group) isopropylidane, u ~
oxygen atom, a group - NH -, - SQ2 - 3 - CO - ~ - CO - NH -VI RADICALS GG ' It ~ more particularly denote a trivalent radical constituted by a ben ~ enene triyl radical, naphthalene triyl, pyridine triyle, a radical of formula ~ E ~ in the ~

which ~ represents ~ a valential bond or deæ groupings alkyl-io lene or alkylidene having 1 to 4 carbon atoms such as methylene, ethylene, isopropylidene or - O ~ ~ CO -, - C ~ O _, _ S02 -, - C0 - N ~
By way of illustration, the following radicals can be included , _ ~, CO ~ ~ CH
-:
: Among the radials that we just mentioned, G1 and G
prefer: erentially a radical ben ~ ènetriyle-1, 2, 4 or a trivalent radioal comprising two linked benzene nuclei between them by a; llen valentiel, a carbonyl group,; suI-; ~
: ~ fone, methylane, or isopropylidene.

VII_RADICA ~ R "~

It ~ ymboli ~ e particularly pleased 1) A hydrocarbon radical ~ aliphatic, straight or branched, ~
cycloaliphatic ~ aturated or unsaturated`substituted ca ~ appropriate by ~
~ chlorine atom ~ a monocyclic or aYomatic radical;
polycyclic whose cycles ~ form systems between them orthocondensed or ortho and pericondensed. ~ -These aromatic radicals can be substituted3 by -8-:.
',; ~.

~ '7 halo ~ dne atomc ~; of ~ radiclux ~ lcoyle ~ having 1 ~ 4 atom ~ of carbon such as ~ ra (lical methylc, e-thyle; radic ~ alc ux-nyle ~ having 2 ~ ~ carbon atoms preferably ~ or ~ ethy- `~
lenic ~; or by one or more ~ their functional groups ~: nitrile, é-ther, urethane, amide, e ~ ter (in particular methylcarboxy and mé-thoxy ~
carbonyl) ~ amine. ~ -:
2 ~ A saturated, unsaturated, or aroma heterocyclic r ~ ~
tick, monocyclic or polycyclic, comprising at least one of heteroatoms 0, N, S, and substituted ca ~ appropriate by ~ radicals meth ~ Jle 9. .
3) A divalent radical constituted by u: n sequence of -:
groupeme ~ ts such as dé ~ inis in paragraph ~ 1 or 2 above ~ and . linked together, by `~ - a valential link :; ~ and ~ or at least one of the following groups ~
0 -, - S -, - N r ~ ~ CO ~ N -, - C0 -, - C00 _, :. R'6 d.
= ~ r - ~ - N = N - ~, - P _.
~ 20 0 0 ... .
,:, ~, i ~ ....
~ In these formulas ~ 6 and R6 'represent an alkyl radical . '':!'~
: ~ having 1 ~ 4 carbon atoms, a cyclohexyl or phenyl radical, ~ R6 can also represent a hydrogen atom. ~. ;
~ - an organic radical containing ~ ilicium such as ~
17 IR7 17. ~:
_ S - t - S - o - ~ - S - (crl2) R7 R ~
~ (C ~ 2) n ~ ~ (CH2) n2 ~ 7 R8 .. ~
: '-9-', ~:, ; .. '' ~ 07 ~ 6; ~ Z

2) n2 ~ Si - O - Si - (CH2) -l7 IR8 - (CH2) n - Si - (CH2) - Si - (~ H2) . R 'R' : l7 IR8 -O - tCH2) - Si - (C ~ 2) n2- Si ~ (CH2) n2 R7 ~ R8 1 10 In this ~ formula ~, n2 represents ~ en-te an integer of 1 ~: 3, R7, R7'j R89 R8 'identical or different ~ represent a group-~; alkyl having 1 to 6 carbon atoms, an alkenyl radical : ~ having 2 ~ 4 carbon atoms ~ preferably a or ~ ethylenic, a phenyl group or a hydrolytic function ~ able chosen in the ~.
group: Rg / E

o - R9, - 0 ~ C - Rg, - N, _ C _ N, ..
Rg '0. Rg' . . ~. .
~ / Rg Rg : - 0 - N = C, .- 0 _ N: .A ~
"\ \. .'`"'' ~ ' Rg 'Rg' ~; .. Rg, Rg 'identical or different ~ represent from ~ groupr ~
alkyl items ~ having 1 ~ ~ carbon atom.
~ ~ Among the radicals that we just mentioned, R "re ~
:. present more ~ particularly . ~. ,.
a) an alkylene, alkylene, alkenyl ~ ne, alkeny ~ radical straight or branched lidane having at most 12 ~ carbon atom ~ e ~ one -10-. '' 1 ~ 7 ~ 62Z

``
radical c ~ cloa'.co ~ ne ~ cycloalkenyl ~ e ayan-t 5 ~ 8 ~ -tomes de bus ~
. ~ bone in the key.
By way of illustration; if it is possible to mention the methylene radicals9 é-thylène, éth ~ lid ~ ne, cyclohexylane, ~ utylène.
b) a radical ph ~ nylene 3 tolyl ~ ne or xylylane sub ~ titrated if necessary by one or more chlorine atoms, groups ~
, nitrile elements ~ amide, amine es-ter (no-ta-mment mé ~ ylca ~ on ~ lGxy and ~ ethoxycarbonyl)., alkoxy ayan-t radicals 1 to 4 carbon atoms ~
bone such as the methoxy radical.
c) an unsaturated saturated monocyclic heterocyclic radical: ~
or aromatic and comprising as a heteroatom one or more oxygen atoms ~ no nitrogen or sov ~ re, and containing 4 to 6 atoms .`
~ in cycle 3 the heter radicals ~ rocycli ~ ue ~ can be replaced :; by one or two methyl groups ~.
As an illustration ~ 3trati ~ we can oi-ter the following radicals ~

. ~ 3 ~ 1 3 -NOT

CH
, 3 -; .
. ~ 20 ~, N -C _ NN -N ~
B-9 ¢ ~ ~ o ~

d) a divalent radi.oal consisting of a chain of:
two ~ four groupings as defined in ~ paragraph $ 3 a, b or . c previous and li ~ $ 3 between them by a link chosen dan ~ le; ~
~. ,.
~ roupe constituted by the valèntiel link, by to the ego: ns one of ~ ~ roupe ~
; ment ~ following ,.; .
! : -i. :. '.
~ ~ O - 7 - NH -, - COO -, - CONH ~, - S02 ~, --N = N ~
~ T -, - CO -, by an alkylene group or ;; ~:
. ~ O; . : ~
alkyliddne having 1 ~ 4 carbon atoms, and by a radical .: -11- ',', ~

~ 7 ~

orgaIliqlle contcnant of ~ il.icium such as:

I IR7 l7 _ If _, - If _ 0 ~, - If ~ (~ H2) n2 R7 R7 ~ 7 ... .
. . :
7 ~ 8:
~ (2) n2 ~ li - 0 - Si - (CH2) _, - R7l R8; ~:
:
.
l7 l8. ~;
2) n2- 1 i - Si - ~ CH2) - - "~

R7 'R8 ! ,::
: 17 18 ~:
,; (CH2) n2 ~ ~ CH2) n2- Si - (CH2), n _, ~

R7 '8 ~:

2) n2 li ~ (CH2) n2 ~ Si ~ (CH2) n ~

R7 'R8 ., I.

(n2 representing an integer of 1 ~ 3, ~ R7 ~ R7'7 R8? R8 ~ ~
aésignant a methyl radical or ph ~ nyle). ; ~:
By way of illustration ~ we can cite the radicals of for ~
!, :: `. ~:`.
1 ~ 20 next mule ~

~. .. ~,.
''"'CH2 ~ ~ - CH2 o ~; ~
'', `.:

: CH = CH `
- CH ~ -CH2 ~; ~ 2 ~ 12- ::
, ",, ~ ',' ~.

~ 3 C ~ NH ~ cH2 ~ 3 NI-I - C ~
oo ~

, ~ S02 ~ NH ~ ~ 12 - (CiEI2). ~ CH ~ - CH2 - OOC ~ C00 - CH2 - CH2 ~; 1 ~ n2 ~ = J ~

: ~ -. ~,,, "'' ~ '''.

1 IH3 CH ~ ~
li ~ 3 0 - (CH2) 3 - Si - O - li - (CH2) 3 -, O ~ ..
CiH3 3 . i ~, ...
e) u ~ radical consisting of a set of 2 to 3 cyclesis.
There r carbocyclic ~ romatic and / or hey-t ~ aromatic rocyciliques or .i. ...
1 no and forming between them an orthocondensé9 system this radical louse ~
- ~ :; before being substituted by methyl groups. .
By way of illustration, the aromatic cyles ~ are nuclei.
benæéniques and pyridiniques. ~ These radicals its ~ for example the ~
the following:

~, "~", ..: ~ i.

S ~ H

~ 0 , ' .: Preferably, R "represents:

~ (17 ~
, '~.
- an alkyl radical having 1 to 8 atoms of ca: rbone, a r3dical CYC1OheXY1ane 9 a phenyl ~ nc 9 toly ~ ne radical, xylyl ~ ne, one.
radical pyri.dyl ~ ne : - a divalent radical comprising from 2 to 4 phenyl ~ nes groups linked ~ between them by a valential bond, an atom of oæyg ~ ne, one of : groupings::

, ^ '¦.
~ ~ ~ CO - t - SO2- 9 - NH -, - P ~, - C0 - NH -, 1 ~ o or by an alkylene or alkylene group having from 1 to

4 carbon atoms, or by an organic radical containing . silicon such as:

R7 R17 17 -:
Si -, Si - O -, - Si - (CH2) n -,.; ~
- R7 t R7 IJ 7 ~.

~: R7 R8 (2) n2 li - 0 - Si - (CH ~
: R71 R8; ~ -~ 20 ~ ~ (~ H2) n2 ~ Si - 0 ~ - Si - (CH2) n2 ç: R7 'R ~

7 18 ~:

(2 ~ n2 ~ Si - (CH ~ n ~ Si - (CH2) 7 ~ 8: ~
~, -.., -lq, -::

~ C ~ 7 ~ Z ~

l7 l ~
- O - (C112) n Si - (C ~ 12) n2- li - (C ~ 12) n2 ~, R7 '8 (n2 representing an integer from 1 to 3, R7, R7 ', R8, R8' ~, denoting a methyl or phenyl radical). . ~.
:,. . ' - a divalent radical comprising 2 alkylene groups having ~, ' ., from 1 to 4 carbon atoms linked to a phenylene group by ~, a valential bond, an oxygen atom or one of the groups:
. '. ~, :: 16.
~ 10 - CO -, - SO2-, - CO - NH -, - ~, - O -, - P -O
"VIII - RADICALS R" and R "" ~
: ~ ~ ",:.
, ........................ R "'and R""are multivalent radicals which,' s; ,, can be '~, 1) A radical h ~ saturated aliphatic drocarbon, ~
: 'branched linear having from 2 to 20 carbon atoms. ; ~
2) A saturated alicyclic hydrocarbon radical or, ~
not having at most 6 carbon atoms in the ring. ,::
3) A ra, r ~ ical heterocyclic saturated or not '.'", ~
containing at least one of the atoms O, N and S.
4) A monocyclic aromatic hydrocarbon radical,.,.
~ or polycycli ~ condensed eu or an aromatic radical ~ polycyclic eu , i "~ to several c ~ clique systems condensed or ~ not, linked between them;` ~
::, by, a valential bond or by an alkylene or alkylidene radical i '.' ,. '~;,,' having from 1 to 4 carbon atoms or by one of the groups.
~ following: '' `, `, - O -, - S -, - N ~ l -, - COO -, - CO -, - CO - NL -, - SO2-, , ". ~ - N- = N -, N = ~ CO - NH - ~ -, - CO - O - ~ - O - CO -, - P ~

OO '' i,. , :. ~., ~,.
, - ',,'.;

; ~

37 3L6 ~ 22 dan ~ which ~ represents a linear or rami alkylene radical.
; ~ fie having less than 13 carbon atoms, a cycloslcoylene radical with 5 or 6 carbon atoms in the ring or an arylene radical mono or polycylic and ~ represents a hydrogen atom ~ ne, a an alkyl radical having from 1 to 4 carbon atoms or a radical.
phenyl ~ n addition, these aromatic radicals ~ can be sub-set up by ~ methyl groups or chlorine atoms.
More specifically R "~ and R""represent ~ entent ~
- a) a linear aliphatic hydrocarbon radical ~ or ~. :
branched having 2 to 10 carbon atoms ~ e.
~: By way of illustration, mention may be made of the following radicals:
-CH2 CH2 ~
~ CH ~ CH \, / C, _ CH2 - CH - CIH ~ CH2 ~ ' CH2 CH2 ';, : ~! b) a saturated or unsaturated alicyclic hydrocarbon radical having ~ ~:

5 ~ 6 atom ~ of carbon in the cycle. ~ -.,, ~ - ..
~ This ~ radicals are for example the following ~

~, ~ ZO '~

, - o) a saturated or unsaturated heterooyclic radical comprising 5 to 6 `- ~
.. atoms in the ring and containing at least ~ one of the atoms 0,; - ~
.l ~ and S
~. By way of illustration, mention may be made of heterocyclic radicals ~ i de ~ ormule ~
:,. , : '~ S
-. .
- d) a monocycllqùe or poly- aromatic hydrocarbon radical;

: -16-, ~ ........ -,. -.,. ~., ....................... ... .... -::
. .

107 ~ 62h . -: ''. '':
- ~ condensed cyclic or a polycyclic aromatic radical r ~
.,; . .
more ~ ieurs systems cycliquas co. ~ dense ~ or not, linked3 between .` them by a bond or an alkyl group or `.
~ lcoylldène having 1 ~ 4 ~ carbon atom such as methyl radicals ~ e, ethylene, isopropylidene, an atom; ~
- oxygen or one of the following groups:
: R6 t ~ -,, I ``
- CO - ~ - CO ~ 2 ~ ~ - CO _ ~ H _ ~ _ P _ -. "~ -, , ~. O ~ ~: "
", ~,:
- ~ 10 For illustration, R "'and R""can represent one of ~ radicals:

SO

Pre ~ erence ~ R "'and ~ R""; ~: are radicals tr1 ~ or ~ tetra ~
valents comprising 1 or 2 benzene nuclei ~ linked between them "` ~
by a valential bond, an oxygen atom, a radioal methylene, isopropylidene, a group:::. ~ .; :
Rg ~: 20 - CO ~ S02 _, P

~ X - FON ~ TIONS '~ and ~
j1 ',. ~ ~, ,, ~ ','"'', ;: T and T 'represent pre ~ erence one of the functions sui ~
~ ;:

~ 7 ~ 6 boasts 3 - C ~ O - ~ - NH - C '-, - NH - C - O -, - NH - C
. Il 11 Il '11 ~
j OOOO '~ ~
~ O: ' , He ',' : NOT -., --C ~ ...
: 11,. ~;:.
O '. .

Among the ~ compounds of formula (I), we claim more party.
~. ~ lO culiarement those for which the various radicals de.ladite for ~
`mule have the following meanings:
- nj n? : an integer equal to 1 ; - R, R ': a linear alkenyl group having from 2 to 6 atoms of carbon R1, R1 ': an alkyl radical having from 1 to 5 carbon atoms ~;
possibly substituted by 1 ~ 4 chlorine atoms ~ .:
., -. -and / or ~ lu ~ r, -a phenyl radical.
R2,: R2 ': ~ a methylene group or ~ thyl ~ ne.
X9 ~: one of the groups ~ u ~ van-ts ~ - 0 - 9 - 5 - ~ - 0 ~ N

R5 represented: entering a hydrogen atom or a radical methyl, ethyl ~
an oxygen atom. -. ~
G, G ': an alkyl ~ ne or alkylidene radical having from 1 to 6 atoms' -:
. . .
- carbon, a cyclohexylene radical, a pheny radical ~
. ~ lene ~ tolylene, xylylene, a radical formed by two phenyl ~ nes groups linked together by a valen-tiel ~ a group ~ ethylene 9 isopropylidene, an atom . 30 of oxygen ~ or a group -: ... ,,.,. :
. . . . ... ... . ... ...

~ 7 ~:; Z2, ~, ~ ~ J ~ 7 - S2 - ~ - CO - ~ - CO NH
- G1 t G1 ': a benzenetriyl radical_1, 2, 4 or a trivalent raaical ~ nt -~; behave two benz ~ nique ~ nuclei linked together by a . ~ link vale: ntiel, a carbonyl group, sul ~ one, mé-thy ~
lane or isopropylidane. . ~
R ~ an alkylene radicsl having 1 ~ 8 carbon atom3, i ~ ;. -a cyclohexylene radical, a phenylene, tolylene radical, xylylene9 a pyridylene radical. ..
a divalent radical comprising 2 ~ 4 groups phenylenes linked together by a valence bond, a.
. oxygen atom ~ ne, one of 9 groupeme ~ t3 next ~
. ~: R ~
,,.: I.:.
- CO - - SO, - N ~ P -, - ~ 0 -; NH -,.; ; .

i or also by an alkyl ~ ne or alkylidene group having 1 ~ 4 carbon atoms, or by a : organic radical ~ containing ~ 11ioium ~ such as ~.

~ X7 'R7 ~ R7 7 ~ 2 7 ~ 1 8 2) n2 ~ ~ jSi - O - Si - (CH2) n ~ ~ ~;

"''''"', ~

. ; '' --lg-- ','' ~ ' ''',,, ~

... ~; `; . . . , ''''".',",:'.'''''.'~.'.' `` '' -` '''.'.'".;'''":''':,:', ; ~ io ~ 6ZZ `:

, ~
R7 IR ~

~ (CE12) n ~ li ~ CE12) n2 1 ~ 2 n2 ~
R7 '8. ~::
'~

, ~, _ o - ~ CH2) n - li - (CH2) n2 li (2) n2 ' R7 '8 (n2 representing an integer from 1 to 3, R7, .R7 ', . R8, Ra ~ denoting a methyl or phenyl radical). ..
- a divalent radical comprising 2 groups ~ alkenes having 1 to 4 carbon atoms linked to a `. `~
phenylene grouping by a valential bond an atom of oxygen or one of the groups: R61.
;. ~ - CO -, - SO2 -, - CO - NH -, - NH -, - C - O, - P -He - J
~ oo. .. -.
~: .` -R "', R"": tri.or ~ tetravalent radlcals with 1 or 2 . ~.
. benzene nuclei linked together by a valential bond,:
an oxygen atom, a methylene radical, isopropyli-; . ~:
d ~ ne, a gro ~ perent : - CO -, - ~ SO2 -, - P -; (R6 'has the meaning given above) ; - R3: this radical occurring in formulas VI and VII.
`denotes a hydrogen atom or a methyl group.

. ~.
;, "~

- 20 ~
, ':

~ L33t7 ~ L ~ Z ~ ~:

- Ts T '~ one of the i'unctions ~ 3ui.v ~ tes ~
C ~ O, - Nl ~ - C -, - NH ~ O -, OO
: -:
O
_ NH ~ C - NE -, - C; '- ~

O

o. ~: -: `` 1, '~. , .. ~ ...

, .

": ~: ~ '~:' , '~:'' :

::
-. -. . . :. ,, .-. ,, ~. ~.

~ '71 ~

By way of illustration5 we will cite the ~ oomposés of formula (I) following:
.

'~ ~

~,.

.; ~ '' '' .
.

~ c ~ W. ~.

, ~: T = ~ = ~

~ ~ ~ = o ~. ", -22 ~;
.. ~,,, . l, ... ..

~ 7 ~ 6 '~

. .
J

. ''''~~'' , `~ ~,,,,;
"''''';~''..''""
.; ~ "~" ~ ':
'.'''',,`":' '''~ ~ ,.''''' , '.,, . ~
~ O -,. : ' ~ = O ~ o y ~ 0 Y

3 0 ~ ~ p ~, ~ N ~ N ' v ~ m ~ vv-- ~ --v ~ v ~
"

vvvc),.:
.

. .
,,, .... .,. .,, -. ~. ... .

~ o ~ 2 ~

o '~ ~ `:

''''"

m DID

op ~, "~
m ~ ~, mN

oo O l ~ ''; -- I ~ v I l = ~

m IO = D ~ = D

~ aN N ~ mN
VV ~
v-- ~ --v ~ ~
It 1l m P ~ vv ~.
- 2 ~ -. , ~.

~ 07 ~ GZ ~
'~,. ;.

,, ~ ,, 1, ''';,~' ,, . ,.
. . . `.
..: .. ' '~ 10.
... ~, .. ~.

v-- o_ ~ ~ T

o 1 ~ 3 ~ 3 0, ~ 3:
20 ~ o = o / \ = oo = ~ = o ~

T

', 25 ~. ~ 7 ~ 62 ~

.,, ~, -. . ~. .
V ~ ~.
o W ''' "~ 10 ~ ~ - ~ ''"' `~ = o ~ w '^ T_o ~ ^ ~

W t ~ Ç3 ¢ ~ V

w_ ~ _ o ~ W ~ ~ ~ y = o '~ IIW _ ~ _W
~ 3 ow ~ W ~

V ~ o = ~ o O ~ V - O
., ~ $ j ~; V = OO-- V ~ '' ^ ~ `` '''~
O '= ~;', -.- ':''' ', ~ ~ V ~ V ~

, ~. . ,,. ,. ~,. . . . .

~ 6 ~ 7 ~; 2Z ~
:.
, ~ ~
`;. ~:`
,: .. ':

. _,, ~ ~ ....
C ~ J ~ d `N CU

"~, ', ~`., ~

. ~. , ~.: -.
... .
~, ~ 10 ~, "

NOT

7 \ 7 /

; 20 ~ ~ `~ ~ ~ q V = O,:, i:

o .. ~ 30 p ~

~ ~ ~ V
, V, ..: ~
-27 ~
, ~ ..

~ 2 We can evid ~ ment cite dc ~ analogous compounds ~ to the compound ~
to (24) obtained by rernplaQant the vinyl grouping with a - ~
allyl group. -- ~ The ~ most particularly compounds in-ter ~ 3ants ~:
30nt ceu} ~ in which ~ the ~ 3 nanbreg n and n ~ are identical, the .- ~
radicals and functions R, R1 ~ R2, R3, X, ~, G1 ~ are respectively identical to X ', R'1, R'2, R'3, X', G ', G ~ 3', T ' ~ es preferentially claimed compounds are those of formula (3), (4 ~, (5), (6), (7), (17), (18), (19), (20), (21), 2) ~ (23), (24).
.. ,,,., ~ ~
: ~ '' -:

,; , -PREPARA ~ ION OF COMPONENTS IF ~ ICIES PO ~ YETHYIENIC

~ e ~ compounds corresponding to ~ the general formula (I) can be obtained by a process which co.nsiste ~ Iaire react::
. ~ 1) An organosilicon compound of: Formula (A):
1) 3-n :: - (R) n - Si - R2 - x _ r _ y (A) ~ zo alone or as ~ ooié to an organosllic compound of formula (A ') ~ ~, .: (I 1) 3 ~
~ (R '): rl' ~ Si - R'2 ~ X '- r ~ _ Y ~ (A') ~ ~ `

.: .- with `~ 2) A compound hereinafter called coupling agent ~ ormule (: B) .
1 (B) Dan ~ the formulas (A) and (A '), n, n', R, R ', R1, R'1, R2, R2 t X, X ', r, r ~ have the ~ ~ ignifications already dorLnée3 for the : ..

~ 7 ~ Z2 ::

formula (I):;.
~: Y and Y 'identical or different represent ~ entent one of grouping3 functional 3next ~:
- - ~ OH (VIII) . ~, .. - - SH (IX) N = C - O (X) . _ _ C - Cl (XI) O

- - a - o _ R10 (XII). ~
..:. :
0.

H (XIII) a- o - a - (XIV) O o R ~ ~ the meaning given in ~ formulas (VI) to e ~ t (VII). ~
: R10 ~ represented ~ ente ~ a hydrogen atom, ~ an ayan alccyl radical of ~ -4 atoms ~ of ~ carbo ~ e; such ~ as the ~ methyl radicals, ~ thyle ~
propyl ~ R1o preferably represents a hydrogen atom ~ or a methyl group. ~ r and r 'represent ~
~ - G and G 'when Y and Y' represent the functions ; ~ and / or - G1 and G1 'when Y and Y! represent the function (XIV) ., In formula (B), ~ represents a group - a - or o ~:
one of the radic ~ ux R ", R"', R "" which have the ~ meanings already . ~ data for formulas (III), (IV), (V).
, -~. Tj and ~ 1 'identical or different represent ~ entent an atom 9_ ., :,. ; ,::
. :. . . . .
... . ~.

~ L0 '~ 162Z

``:
chlorine or one of the functions defined for Y and ~ '. ..
represerlte a carbonyl group when '~ 1 and T1' represent a ~ tome of chlorine and a radical R "'9 R""when T1 and '~ 1' represent one or two anhydride functions.
: ~ More precisely, the compounds of ~ ormule (B) respond . . ~
~ to the formula ~
a) CO ~ Cl (~ i?
,, .. ~ o b) '~ 1 ~ R "_ T 1 (2) - ~. 10 o c) T1 ~ ~ "'\ ~ (3 ~ ~ ~

.:. o., ~,:

~ a ~ ~ c ~ ~ 4) ac ~
~:, ......................, oo ~ 20 ~ ~ 'ml coupling agent ~ in play during the syn-thaise i ^ compo ~ é (I) can have two identical ~ or di ~ erent `groupings.
. T1 and T1l which do not have to be reactive one to the other ; in the ~ operating conditions of the sy ~ these deis compo ~ és de ~. formula (I) es compounds (~ 2) and ~ (B3 ~ are cholsis: so that lei ~ onional groups T1 and / or T1 'can react with the ~.
, i - i., ~
~ function ~ Y and ~ .or Y 'carried by the components ~ s (A) and / or ~ A'). . ::
. ~. .
We prefer to choose ~ onotions T1 and T1 '- ~
identical when we mct a matching coupling agent in play ~?
to formula (B2) ~ when we react on the compound (~ i), two compounds . ~.
-30- ~

; ;,,, ~ ,,,, ,,, ~,,, ~ 7 ~ ZZ
(A) and t ~ ') dif ~ erent by their function Y and Y', the latter should be chosen to avoid in the conditions of the reaction, any condensation between them. -`
The choice of groups Tl, Tl ', Y and Y' is easy-determined by those skilled in the art from the nature of the silicon compounds and the coupling agent.
By way of example, the synthesis of the compounds of Formula (I) can be illustrated by one of the reaction schemes-following nels ~

r-lyi- ~ Tl ~ + Yl ~ -r ~ -xl-r2 ~ -si- (r ~) n ~ `' (A) (B2) (A ') ~ ~

. ~ ~, (IRl) 3-n (ll) 3-n ' (R) n-Si-R2-XrTR "-T'-r'-X'-R2'-Si- (R ') n, . : ~
I) ~
, ~, Thus T and R ', ~ and ~' previously defined -result from the reaction between the groups Y, Y 'and Tl, Tl'.
The quantities of reagents to be used depend on of the nature of the reactants brought into contact: they can be neighbors of stoichiometry or deviate from it without inconvenience. ~ ~
Generally we have to react at least two moles of ~ -... , ~
~ compound A (or 1 mole of each compound A and A ') with one mole; ~
.:
of compound B.
Condensation reactions of the compound (s) `I;
or-Jallc) siliciclucs and clu c ~ mposc (U) Sollt c ~ lectuelles seloll les general processes described in the literature and well known:; ~

of those skilled in the art.
'~. '~.
~:,:
',', ~, ,,. ' :,: ,,,. . ,,,.,. ~. , ~.,. . ,,; .

; ZZ
~ eq compo ~ e ~ organosilicon of formula (I) in which ~ 'and T' represent an amide function, are obtained by condensation of a compound carrying an acid chloride function and diun compound dlaminéO ~ a reaction is carried out as a rule ~ -general ~ a temperature compri3e between -20 and 200 ~ and. ~
preferably -10 and 100C One of the following is gradually introduced: ::
reagents in the reaction medium containing the other reagent. We generally operates in a suitable solvent medium consisting of for example with acetone, dimethylacetamide, tetrachloride carbon or their mixtures, in the presence of 9 acid acceptors;
usual hydrochloric. ~ When the reaction is complete, the compounds (I) are -isolated from the reaction medium by any known means. ~
We can also conduct this type of condensation at ~:
:. the interface of two immiscible solvents each containing one of the . reagents and the acid acceptor [NO V. SONN ~ AG _ Chem.Rev. ~
268-29 ~ (1953 ~, J. ZA ~ RI ~ I ~ Y - ~ he Chemistr ~ of Amides (1970) p.73 i;
(Interscience Publishers)]
.
~ es ~ organosilicon compound of formula (I), in which T and ~ 'are es-ters functions, can be irreparable.
~ 20: 90it directly by reaction of a compound with aided group : free carboxylic acid with a hydroxyl group compound, or by transesterification in the presence of the usual catalysts. In this ,,.
de ~ denier cas, one preferably uses the methyl e3ter of the compo ~ é
acid We can also obtain this ~ compounds (I) by reaction.
~ acid anhydrides ~ or acid halides with ~
l corresponding hydroxylated compounds, optionally ~ in the presence of a ... ~; .-.
; ~ hydracid acceptor ~ cf - KIE ~ O ~ E ~ ER Enoyclopedia of Chemical. ~. :
.` ~ echnology - 2nd edition -, 8 313 to 339, NO ~ V. SO ~ N ~ AG - Chem.
.; ~ Rev. 52, 312-321 (1953)]. . ``
~ e ~ organosilicon compounds (I ~ to group ~ imides are ~
: Obte: nu ~ in a manner known per se .heating an acid anhydride with u ~ compound to:. primary amine function so as to give:
; ~ 32 ~
'':, '' ~ s , ~. .
. ... . . .. ... ..

~ ~ 7 directly the corresponding imide. According to another method ~ also known, we can ~ intermediately form the salt d ~ ammonium corr ~ pond.an-t to the diacid and ~ the amine according to 10 9 method 9 uguelle g then cause the cyclisa-tion by heating salt with elimination of water. We can also train interm ~ diarily an amide-acid which will then be dehydrated by heater.
In all cases, the temperature will be chosen in depending on the reagents used.
- 10 In general 7 this temperature e ~ t between 50 and P
200C ~ aes imides training can be conducted av. within; ~;
~ organic solvents or diluents ~ iner-your vis-à-vis the reagents.
~ es organo ~ ilicic compounds ~ (I) with urea groups or urethanes ~ obtained easily from reacti ~ s comprising ~ -;
on the one hand isocyanate groups and on the other hand grou ~ ements amines or hydrox ~ them, operating under the conditions ~
u ~ uelles reaction of lsocyanates with compounds ~ hydrogen active (Cf KIRK OTHMER - Encyclopedia of Chemical ~ echnology 2ame edition - 21, 63 ~ 74). ~ n general the reaction temperature, : ~. .
~ Ariable according to the hydrogen compound acti ~ implemented, e ~ t;
~; between O and 100C and plu9 particularly between O and 50 ~
~ Condensation can be conducted in the presence of catalysts u ~ uels (tertiary amines, ~ metal halides, chloride aluminum, tin chloride, organo ~ ilic compounds, etc. ~.) O -~ reaction can be conducted in mas ~ e or preferably in ~ `~
suspension or solution in an inert solvent vis-à-vis reagents especially vis-à-vi ~ lsocyanates. In this regard, we can use for example ~ aliphatic hydrocarbons, c ~ cloaliphatic, aromatic or ~ their derivative ~ chlorinated, or from ~ ethers -33_ , ~
. ~, , ... ~. . .,, .. ~,, ~ 07 ~ Z
"', ~ GTI ~ S MIS EM ~ UV ~

NA '~ URE D ~ I.'AG ~ N' ~ 'D ~ COUPLA ~ E `~

As an illustration, we can quote among the agents of '~ coupling (~), the following components ~ ~ ~ having two groups . ~ onctionnels ide ~ -tiques ou di ~ erent ~ respondent ~

- the pho ~ g ~ ne. ~ -. ~ 2) ~ the formula ~ 2 a) the ~ dicarbox acids ~ eu ~ and their derivative ~ (esters and chlorides' . 10 acid ~

~ Gum examples of dicarboxylic acids ~ 9 we can cite notably: .-.` - the ~ aliphatic ticks such as: i ~
'~ oxalic acid ..:
: ~ malonic acid '~' succinic acid;
.; ~ glutarlic acid . '~' adipiqve acid -; ~? '~
di ~ ethyl-2 ', 4 adipic acid' pimelic acid ~ .` '';
~ "~ 20 ~ ~ uberic acid '. ~.' the acid has ~ éla ~ que. ~ .. ~. -: ~ `. sebacic acid dodecane.dio acid ~ that.
.- -acid ~ umaric. '~ maleic acid. ". ~:
'methylirnin.odiacetic acid''~' ~
3-dimethylamino acid hexanedio ~ than ~. '. ~;

-3 ~ -~ 6171 ~ Z2 - acids ~ cycloalkane ~ d: icarbox ~ lique ~
cyclohexanc-1,4-dicarboxylic acid dimethylamino-3 cyc] .opentane dicarboxylic acid-1,2 - the aromatic dacids . ~ phthalic acid isopntalic acid terephthalic acid phenylenediacetic acid naphthalenedicarboxyli.que-1,5 acid naphthalenedicarboxylic acid-1,6 . : ~
diphenyldicarbo acid ~ ylique-4,4 ' ~ `.! diphenyldicarboxylic acid-3.3 ' bis (hydroxycarbonyl-4) phenyl oxide ~ -`~ bi oxide ~ (hydroxycarbonyl-3jphenyl ~ 4-dihydroxycarbonyl., 4 'diph ~ nysulfone : la.dihydroxycarbonyl-3,3 'diphenylsul ~ on ~
- pyrimidine acids ~ or imidazoles dicarboxyliq ~ e ~
~ "~ ,,,.,: ~...
; "j ~` We can also use ~ as age-nt ae coupling the chlorides ~ of acidea and the e ~ ters of pre ~ erence methyligues obtained from ~ such ~ dicarboxylic compounds.
i ~ eq diacids used ~ pref ~ rentielleme ~ -t ~ have the following ~: ~ o ~ alic acid; . ; ~
succinic acid. .
- adipic acid . -îfumaric acid .`.
; s ~ _ i ~ ophthalic acid - terephthalic acid : ~ naphthalene dicarboxylic acid-1.5 . ~ r ~ 4,4 'diphenylcarboxylic acid ; ~ 30 ~ diphenylcarboxylic acid-3.3 ' ,::
.,::.
-35 ~

~ ~ 7 ~ 6 ~ Z

b) ~ eg_dl ~ r ~ c ~ ~ r1 ~ Lre__et_c ~ cond ~ i ~ res - hexam thyl ~ nedianline - oc-tam ~ thylanediamine -:
- decamethylenediamine - ~
- 2,5-dimethyl heptamethylenediamine -- bis hexamethyl ~ netriamine - ~ iethylenetriamine - tetraethylenepen-tamine - bis (4-amino cyclohexyl) methane lO - bi ~ (4-amino cyclohexyl) -2,2 propane le.diamino-1,4 cyclohexane :; - m-phenylanedi.am ~ ne ~ p-phenylenediamine .. - m-xylenediamine - p-xylylenediamine benzidine -`
; - Bii ~ tamino-4 phenyl) m ~ thane,.
- bi 9 (4-amino phenyl) -2, - propan ~
l - diamino-4,4` phenyl oxide : ~; 20: - the sul ~ ure of diamino-4,4 'phenyl diamino-494 'diphenylsul ~ one.
~, .. - the diamino-4,4 'benzophenone ~: diamino-4,4i benzanilide; ~.
: ~. 4,4 'diamino phenyl benzoate ; ~, ,, : - - dicarboxy-3 ~ 3 'benzidine ~: ~
~: - bis (p_aminophenyl) -191 phthalane; -;
N, ~ 'bis (p-aminobenzoyl) diamino-4,4' diphenylmethane.
- bi ~ p- (4-amino phenoxycarbonyl) ben ~ ene - bis p- (amino-4 ph ~ noxy) benzene - diamino-1,5 naph-talene - diamino-2,6 pyridi: ne ~ - diamino-6 7 6 'bipyridyle 2,2' ..
, ..::
- ~ 6 ~
, '',:,.:

~ 71 ~; Z '~

- bis (m-amirlophenyl) -2.5 oxadiazole-1,3,4 - bis (p-ami.nophcnyl) -2 ~ 5 oxadiazole-1,3,4 - bi 8 (m-aminophenyl) -2 7 5 thi.azolo (4,5d) thiazole - di (m-aminophenyl) -5t5 'bis (oxadiazolyl 1,3,4) (2,2') - bis (p-aminophenyl) -4.4 bithiazole-2.2 '. : ~
- m-bis (p-aminophenyl-4 thiazolyl-2) benzene the bi ~ (m-aminophenyl) -2,2 'bibenzimidazole-5.5 - diamino-3,5 triazole-1,2,4 - bi ~ (4-amino phenyl) -3 ~ 5 pyridine - bis (4-amino phenyl) methylphosphine oxide - bis (4-amino phenyl) phenylphosphine oxide - N, N 'bi ~ (4-amino phenyl) methylamine; -bi ~ (4-methylamino phenyl) methane - bis (4-methylamino-phenyl) oxide.
- bis (4-methylamino phenyl) -2.2 propane - bi ~ (3-methylamino phenyl) sul ~ one ~ - bi ~ (methylamino) -1S3 benz ~ ne `~ bis (4-methylamino cyclohexyl) methane ~: ~
- N, N 'di ~ -thylhexamethylenediamine `/ 20 - bls (methylamino) -2 ~ 5 oxadiazole-1,3,4 bi ~ (methylamino-3 propo ~ y) -13 2 ethane - (meth ~ lamino-4 phenyl) (amino-4 'phenyl) methane `.
~ ¦ ~ - 4-methylamino benzene oxide and 4-amino benzene oxide -. I - (methylamino-4 phenyl) (amino-4 'phenyl) sul ~ one - ~ - methylamino-1 amino-4 benzene ~ ~
, - 2-methylamino-4-amino toluene:
~,.
- 2-methylamino-5 amino anisole.
- methylamino-3 propylamine - 2-ethoxy-4-methylamino aniline ~ `
; 30 - 3-methylamino-4-benzoylamino aniline ,, _ lt ethylaminoethox.y-3 propylamine - 3-ethylaminoethylmercapto propylamine `~
.
-37- `: ~ ~
":
,. . ,. `. . , - ``
`..

~ 716f ~ Z

- m ~ thylam: ino ~ 6 hexylamine - (methylaDIino-4 cyclohexyl) ~ amino-4 'cyclohexyl) methane : - p-methylaminophenyl ~ 2 amino-5 oxadiazole-1,3,4; -:. - m-methylaminophenyl-2, 5-amino benzo ~ azole - bis (p-amino-phenoxy-3-propyl) -1.3 t-tramethyldisiloxane - bis (2-p-amionphenoxyethyl) -1.3 tetramethyldisiloxane - bi ~ (p-aminophenoxy-2 ethyl, dimethylsilyl: 3-1,2 ethane - 4,4 'diamino azobenzene :: ~ es diamines used preferentially are .. ~,.
. ~ 10 next - hexamethylenediamine.
- bis (4-amino cyclohexyl) -2.2 propane:
,. ~.
: - m-phenylenediamine.
- p-phenylenediamine ~ m-xylenediamine.
~ p-xylenediamine -~ - bis (4-amino phenyl) methane ~ i. . -:
,, ",, L 11 4,4 'diamino oxide phenyl diamino-4,4 'benzophenone ~:
20 :: - diamino-4,: 4 'phenyl benzoate N, ~ 'bi ~ (p-aminobenzoyl) diamino-4,4' diphenylmethane - bl ~ p- (4-amino phenoxy) benzene ~~ - diamino-2,6 pyridine.
; - bis (p-aminoph ~ nyl) -2.5 oxadiazole-1,3,4 ..
.`- bi ~ (p-aminophenyl) -4,4 'bithiazole-2,2';. ~:
diamino-3,5 triazole-1,2,4. ~
,; ~;,. ~ ~,.
o ~ yde bis (4-amino phenyl) -1.3 methylphosphine. . ~.
.lc bis (p-aminophenoxy - 2 ethyl) 1,3 tetramethyldisiloxane - bis (p-aminophenoxy-2 ethyl ~ dimethylsilyl) ~ 1.2 ethane; :
", . 30 c) the diisoc ~ anate ~
; ~ - the dii ~ ocyanato-1,2 proparle . . ~
. ...: ..
: ~ 3 ~
~, ................................................ . .

~ 0716 '~ Z

- 1,2-diisocyanato bu-tane - 1,3-diisocyanato bu-tane - diisocyRna-to-1,6 hexane - 1,3-diisocyana-to-benzene - diisocyana-to-1,4 benzene - 2,4-toluene diisocyanato - 2,6-toluene diisocyanato:
- the diisocy ~ nato-2,4 xylene - 2,6-xylene diisocyanato - 3,3 'biphenyl diisocyanato - diisocyana-to-4 ~ 4 'biphenyl diisocyanato-3,3 'diphenylmethane - aiisocyanato-4,4t diphenylmethane ~ I - dii ~ ocyana-to-4,4 'dimethyl-3,3' diphenyl ,: ~
.. - diisocyanato-4,4 'dimethyl-3,3' diph ~ nylmethane 4,4 'diisocyanato diphenylethane - the dii ~ ocyanato-3,3 'diphenyl ether .
; ~, - tiisocyanato-4,4 'diph ~ n ~ leth ~ r ~ i - diisocyanato-3,3 'diph ~ nylsulfone ~ :.
~ j ~ 20 - 4,4 'diisocyanato diphenyl ~ ulfone ¦ - ia diisocyanato-3,3 'benzophenone - 4,4 'diisocyanato benzophenone - the dii ~ ocyanato-3,3 'dicyclohexylmethane.
: - ~
- the diisocyanato ~ 4,4 'dicyclohexylethane:; ~
;. - diisocyanato-1j5 naph-talene - the dii ~ oc ~ ana-to-4,4 'dichloro-3,3 biph ~ nyle - diisocyanato-4,4 'dimethoxy-3 ~ 3' biphenyl ", ~
.,. ,; -~; The ~ diisocyanates used pre ~ erentially are the `
:. following:
- 1,6-diisocyanato hexane - the dii ~ ocyanato-2,4 tolu ~ ne.
'''' . .

~ 7 ~ 62 ~

- 2,6-tolu diisocyanato ~ ne - the dii ~ ocyanato-2l4 xyl ~ ne - 4,4 'biphenyl diisocyanato - diisocyana-to-474 'diphenylmethane - 4,4 'diphenyl ether diisocyanato -~; - diisocyanato-4 ~ 4 'diphenylsulfone - 4,4 'benzophenone diisocyanato ~ - the dii ~ ocyanato-4,4 'dicyclohexylethane. . ? ~
diisocyanato-1,5 naphthalene ~.

".:

d) ~ _diols and_diphenol ~ ethylene glycol:
- diethylene glycol - triethylene glycol ~;
- t ~ traethylene glycol ~ ~
: `- propanediol-1,3 ~ ~:
., ~ j, ~,, . ~ - propanediol-192:.
- buta ~ ediol-1,4. : ~
. - butanediol-1,3 ~:
~ -I - pentanediol-19 5.
1,4-pentanediol - 1,3-pentanediol . . .,. ~, : - 1,6-hexanediol:. :
.:. - hepta ~ ediol-1 ~ 7 .` ~
; ~ - 2,2-dimethyl-1,3-propanediol;
- octanediol-1,8 'J, ~
~ - dodecanediol-1,12 ~ 3` '.
- ~ - tetradecanediol-3.13 `~
. .
- ethyl-2 octanediol-1,8 : - et ~ yl-3 decanediol-1,10 `~ -- di ~ thyl ~ 3,6 octanediol-1,8.
- diethyl-4 ~ 7 dcanediol-2.9 - ~ 0-. '.' ~ 7 ~ 6Z; ~

butene-2 diol-1,4 - pentene-2 diol-1,5 - hept ~ ne-2 diol-1,7 - butyne-2 diol-174 - cyclohexanediol-1,4 - N-phenyl diethanolamine - 2,2l sulfonyl diethanol - 4,4 'sulfonyl dibutanol - [sulfonyi-bi ~ (propyl 3 sulfonyl)] -3,3 'dipropanol - (p-phenylene dioxy) -2,2 'di ~ thanol ~;
- (p-xylene dioxy) -3.3 'dipropanol ~.
- (p-phenylene di ~ ulfonyl) -4.4 'dibutanol - tp-xylene di ~ ulfonyl) -6.6 'dihexanol. `~
- (biphenylene-4,4 'dioxy) -2,2' diethanol - bis (~ hydroxyethyl) -1,4 cyclohexane - bi ~ (~ hydroxybutyl) -1.4 cyclohexane ":
- bis (hydroxymethyl) -4,4 'biphenyl bi ~ ~ hydroxymethyl) -2.6 naphthal ~ ne - bis (~ -hydroxy-thyl) -1.5 naphthalene - bis (~ -hydroxyethyl) -1.4 benzene - bis (~ hydroxypropyl) -1.4 benzene ~.
- benzyl alcohol (~ hydroxyethyl) -2. ~ -t ~ ethylene glycol rephthalate ``;
~.
: - hydroquinone;
- re ~ orcine - cat ~ chol . - p-xylene glycol:
- 1,4-dihydroxy naphthalene - 1,5-dihydroxy naphthalene `~
30 - 4,4 'dihydroxy biphenyl- ~.
- bis (4-hydroxyphenyl) methane ~.

~ - bi ~ (4-hydroxyphenyl) methyl-phenylmethane i ~:.
. '~; ~. ,, ;, ': ~ -:: ..

107 ~ 6i '~ f ~
``
- bis (hydro ~ .y-4 ph ~ nyl) sulfone - bis (4-hydroxyphenyl) -2g2 propane - bis (hyd ~ oxy-4 ph ~ nyl) tolyl me-thanes ~ ~
;. '.
~ ~ es diols and diphenols u-tili3és preferably are; ~
the following ~:
- ethylene glycol propanediol-1,3 . - 1,4-butanediol . '~.
- pentanediol-1,5 ..
- 1,6-hexanediol . - heptanediol-1,7 ...
.i ~ ...
I - (p-phenylene disulfonyl) -4.4 'dibutanol ~.
.I. - bis (~ hydroY ~ ybutyl) -1.4 oyclohexane .l:
. ~ - bi ~ (~ hydroxyé-thyl) -1,4 benz ~ ne: ~
~,. . .
- hydroquinone. ``
. - resorcinol. ..
: - 1,5-dihydroxy naphthalene. .
4,4 'biphenyl dihydroxy bis (4-hydroxyphenyl ~) methane - s. ~ ::
- l ~ bie ~ hydro ~ y ~ 4 phenylj sullone ~ ld) dlthiols:. ~ -.:.

thane dithlol-1,2:. :
. - 1,2-dithlol propane;
.It - propane dithiol-113 .. - hexane dithiol ~ 1 5 6 - the bu ~ ene-2 dithiol-1,4 .. ::
l'xyxy- ~ dithiol-196 `
~ - p-phenylene dithiol `.; : ^
- bis (~ mercaptomethyl) -1.4 benzene ...: ..
... . ;
- ie bis ~ merc ~ ptoethyl ~ -1.4 benzene:.

-42- ~

- b $ s (y-mercaptopropylj-1 ~ 4 benzene - dimercapto-1,5 naphthalene The dithiols used preferentially are following ~
- hexane dithiol-1 ~ 6 - p- phenylenedithiol ~:
dimercapto-1J5 naphthalene '':; :
e) the a ~ ents of coupla ~ e to ~ different functional rouements:
acid (hydroxy-6) capro ~ that; ~
- decanonic acid (hydroxy-10) - l / acid ~ hydroxy-123 stearic - capro (amino-6) acid ~ that - acid ~ amino-9) nonano ~ that.
- acid ~ amino ~ undécano ~ que .--- acid ~ a ~ ino-12) stearic - ethanolamine - 3-amino propanol I'amino-4 bu ~ anol.
5-amino pentanol .-- amino-6 hexanol ..
amino-6 methyl-5 hex ~ nol ~
amino-10 decanol.
- p-aminophenyl-4 cyclohexanol `
- p-hydroxymethylbenzylamioe - hydroxymethyl ~ 4 aminomethyl-4 'biphenyl - alcohol (pamino3 phenethyl. ~
- N- ~ aminoethyl ~ ~ - ~ hydroxyhexyl aniline ;; :. .
~ amino ~ 4 thiophenol `:
- monothioethglene glycol ~ 43O;

1 ~ 7 ~ 6 ~: Z

: ~ e ~ compo ~ é ~ used ~ preferably ~ have the ~
~ next ~:
- the scide (hydroxy-6) capro ~ that . - capro acid (amino-6) ~ eu - ethanolamine .-p-aminophenyl-4 cyclohexanol : ~.

3) ~ formula B
~; By way of illustration, mention may be made of the compound ~ having an anhydride function and an acid function:
trimellic anhydride; `~
2,3,6-naphthalanetricarboxylic acid anhydride-2: 3 - the anhydride-1 2 of naphthalenetricarboxylic acid-1,2,5.
- 3: 4 anhydride of diphenyltricarboxylic acid-3,4,4 ' 3,4,3 'diphenylsulfonetricarboxylic acid 3: 4 anhydride . ~. ...
3: 4 anhydride of diphenyl ethertricarboxylic acid ~ eu-3,4,4 ' - - 1: 2 anhydride of cyclopentadianetricarboxylic acid-192.4. '~
; - 3: 4 anhydride of benzophenonetricarboxylic acid-3,4,4 ';

: ~ es compound ~ utili ~ és preferentially are the .; ~ sui ~ ant ~:
- trimellic anhydride - ~ - anhydride-1: 2 of naphthalenetricarbo acid ~ ylique-1,2,5 ~ -:
~ - 3: 4 anhydride of diphenyl acid ~ ulfonetrioarboxylic-3,4,3 '. : ~:
: ~ 3: 4 anhydride of diphenyl ethertricarboxylic acid-3,454 '. ~::
- 3: 4 anhydride of benzophenonetricarboxylic acid-3,4 ~ 4 '. : -. "i ~ .., -.:
~ ~ 4) has the formula B4 ~;
Among the dianhydride that can be used, mention may be made of for example the dianhydride 9 ~ next ~:
- the dianhydride of ethylanetetracarboxylic acid ~ 30 of methanetetracarboxylic acid:
i. .
..
~ _4 ~

,; -.,:,:. :: ~. -,. :;

~ 7i6 ~

bu-tarlet acid ~ tracarboxyliquc ~ 1: 2, ~: 4 pentanetetracarboxylic acid-1: 2, 4: 5 pyromellic acid , ................................................. .....................
ben ~ enetetracarboxylic acid-1: 69 2: 3 diphenic acid ~ ltetracarboxylic-2: 3, 2 ': 3'.
diph acid ~ nylté-tracarboxylic-3: 4, 3 ': 4' - ~
diphenylmethane-tetracarboxylic acid-3: 4, 3 ': 4'-; -diphenyl acid ~ 2,2 propanetetracarboxylic-3: 4,3 ': 4 diphenyl acid ~ ulfonetetracarboxylic 3: 4, 3 ': 4' .
diphenyl ether tetracarboxylic acid-3: 4, 3 ': 4': ~
benzophenonetetracarbo acid ~ ylique- ~: 4, 3 ': 4' ~ naphthalenetetracarboxylic acid-2: 3, 6: 7 : ~ naphthalenetetracarboxylic acid-1: 2, 5: 6 naphthalenetetracarboxylic acid ~ 1: 2, 4: 5 Naphthalenity-tracarboxylic acid ~ 1: 8, 4: 5 decahydronaphthalene acid ~ tracarboxylic-1: 8, 4: 5 dimethyl-4,8 hexahydronaphthalene-192,3,5,6,7 tetracarboxylic-1: 2 ~ 5: 6 dichloro-2,6-naphthalenetetracarboxylic acid-1: 8, -;
of the dichloro-2,7 naphthal ae ~ netetracarboxyllic-1: 8 2,3,6,7 naphthalenetetraoarboxylic acid tetrachloro that 1 ~ a ~ 4 5:
- ~ phenanthrenetetracarboxylic acid_1: 10, 8: 9.
I ~ ~ perylenetetracarboxylic acid-3: ~, 9:10 - cyblopentanetetracarboxylic acid-1: 2, 3: 4 cyclohexanetetracarboxylic acid-1: 29 4: 5 pyrrolidinetetracarboxylic acid-2: 3, 4: 5 ~ o pyrazinetetracarboxylic acid-2: 3, 5: 6 thiophenetetracarboxylic acid-2: 3, 4: 5 cyclopentadi acid ~ nyltetracarboxylic `

~ O ~ 2 ~, 3% oxybenzancte-tracarboxylic acid 3: 4, 3 ': 4' azobenæènet acid ~ tracarboxylic-3: 4., 3 ': 4' ~ '''' ~ e ~ dianhydrides utili.sés ~ referentially ~ have the ~
next 3 - the ethylene tetracarboxylic acid dianhydride `~ - ~
pyromelli acid ~ eu diphenyltetracarboxylic acid-2: 3, 2 '3' diphenyl-2,2propane tetracarboxylic acid-3: 4.3 ~ ': 4 ~
diphenylsul acid ~ o-net ~ tracarboxylic-3: 4, 3 ': 4' ~.
diphenyl ether tetracarboxylic acid-3: 4, 3 ': 4' - benzophenonetetracarboxylic acid-3: 4, 3 ': 4' ~.
~ naphthalic acid ~ netetracarboxylic-2: 3, 6: 7 ~ -; cyclopenta acid: net-tracarboxylic-1: 2, 3: 4 ,. . ~,.
, -. ... .
NA ~ URE E ~ PREPAR ~ ION OF ORGANIC COMPOUNDS ~ ICIC ~ (A) (A ') 1) ~ (A) ~ A ') As an illustration, we can cite the ~ compo ~ és ~ uivant ~: `-amino-1 ~ (vinyldimethy ~ ylmethoxy) -4 benzene hydroxy-1, (vinyldim ~ thylsilylmethoxy) -4 benzene mercapto-1, (vinyldimethylsllylmethoxy3-4 benzene ~
~ 20 ~ -: carboxy-1, (viny ~ dimethylsilylm ~ thoxy) -4; benzene - - chloride ~ acid (vinyldimethylsilylmethoxy) -4 benæo ~ that - 1-methoxycarbonyl ~ (vinyldimethyl ~ ilylmethoxy) -4 benzene ocyanato-1, (vinyldlmethyl.sllylmethoxy) -4 benz ~ ne .` `~
. - amino-1, (vinyldimethylsilyl-2, ethoxy) -4 benzane hydroxy-17 (2-vinyldimethylsilyl ethoxy) 4 benzene amino-1, (vinyldimethylsilyl-3 propoxy) 4 benzane; ~
: j - mercapto, ~ vinyldimethylsilyl-3 propoxy) - ~ benzene - amino 1 ~ (vinyldimethylsilylmethoxycarbonYl) -4 benæ ~ ne .` ~:
- carboxy- ~ (vinyldimethyl ~ ilylmé ~ hoxycarbo ~ yl) -4 benæène .`;

- ~ 6-'' .

~ L ~ 7 ~ 22 - amino-1, (vinyldimcthylsilylm6thylthio) -4 benzane thoxycarbonyl-l, (vinyldimethyl ~ ilylmethyl-thio) -4 benzene - 1-ethoxycarbonyl, (vinyldimethylsilylmethylthiocarbonyl) -4 benaeene.:
- ethoxycarbon ~ l-1, (v ~ lyldimCthylailylméthylthio, thiocarbon ~ 4 benzene - vinyldimethylsilylmethoxy-4, amino-4 'diphenylm ~ thane - vinyldimethylsilylmethoxy-4, chlorocarbon; yl-4 'diphenylmethane ; - vinyldimethylsilylmethoxy-4, amino-4 'diphenyl ether - vinyldimethylsilylmethoxy-4, methoxycarbonyl-4 'diphenyl ether - vinyldimethylsilylmethoxy-4, amino-4 'diphenylsulfone ~ ~
~ `lO - vinyldiméthylsilylméthoxy-4, amino-4 'bipényle ~ ~.
- vinyldimethyl9ilymethoxy-4, hydroxy-4 'biphenyl -, -- - vinyldimethylsilymethoxy-4, chlorocarbonyl-4 'biphenyl : l - amino-1 ~ (allyldimethylsilylmethoxy) -4 benzene . - amino ~ butene-1 yle), dimé-thylsilylméthox ~ ~ 4 benzene : ~ amino-1 ~ (methyldivinylsilymethoxy) -4 benzene r - amino-1 ~ E-trichloro-1,2,2 vinyl) dimethylsilylmethoxy ~ -4 benzene : - amino-19 (vinyldiphenylsilylmethox; y) -4 benzene ~ ~.
; il - amino-1, [vinyl bi ~ (3,4-dichloro phenyl) silylmethox ~ -4 benæene . II. . ... ...
~ l _ amino-1, (methylphenylvinylsilylmethoxy) -4 benzane `.
- amino 1 (methyl, y-cyanopropylvinyl ~ ilylmethoxy) -4 benz ~ ne Lp_aminophenyl, N-vinyldimethylsilylmethyl, methylamine:
- ~ -p-ethoxycarbonylph ~ nyl, ~ -vinyldiméthyl9ilylméthyl, methyl ~ mine ; ~ - e ~ ter ethyl aclde (vinyldiméthylsilylméthoxy) -4 butan ~ que ^
! .-:; `:
. - vinyldimethyl9ilylmethoxy-4 butylamine; `
_ amino-3, (vinyldimethyl9ilylmethoxy) -5 pyridine .- ~.
ethoxycarbonyl-3 (vinyldimethyl9ilylmethoxy) -5 pyridine - amino-1 ~ ~ dimethylvinylsiloxy) dimethylsilylmethox ~ -4 benzane _ aminomethyl-19 vinyldiméthyl9ilylméthoxy-4 benzane ~. ~
. ~ - hydroxymethyl-1, vinyldiméthylsiiylméthoxy-4 benzane; :;
,, .. .30 - e ~ r ethyliqle of acid (vi ~ yldimét: hyl ~ lylméthyl) i ~ 2 thioglycolic - amino-1 ~ (methyl ~ trifluoropropylvinyl ~ ilylmethoxy) -4 benzene `;
- acid anhydride (vinyldimethyl9ilylmethoxy) -4 phthalic ~; :
:. . . .
.-47-, -,. . . .. ..

1 ~ 17 ~; Z ~
.
2) ~ ~ ~ -The processes for obtaining the compounds ~ (A) and (A ') 90nt ~; ~
identical ~ For the purpose of ~ impli ~ ication of the presentation, we will not do.; ~
., reference to compound (A) may of course all of these principles .- defined for (A) are valid for (A ') ~:
~ organosilicon compounds (A) can be obtained ~
according to a process which involves reacting ~ a) an organo ~ osilicique compound (C) comprising a groupemen-t :. chloroalkyl and having as forml71e (C) (11) 3-n (R) n - Si - R2 -Cl (C) ~ with .v ~ b) a compound of formula (D) : ~ z - x _ r _ Y (D) In formulas (C) and (D), R, R1, n, X ~ r and have ~ the meanings already given ~ data ~
Z represents: a hydrogen atom ~, an alkali metal ~ or an ammonium group ~ of ~ ormule t ~ 20 ~ - R; 1- representing a ~ groupemerlt alkyl having ~ of 1 : 4 carbon atoms such as: methyl and ethyl groups, isobutyl.
~ when X represents:; an oxygen atom :, an atom of .1 ~ 30ufre or a carboxy group ~ ate or thiocarboxylate Z est ! "'', '~ ~ preferably an atom ae ~ sodium, or of potasslum or: of lithium, ~
~: or an ammcnium group [R11) 3N ~. By ccmmodité the salt ~ s.
. ~ alkalines and ~ els of tsrtiary amines ~ acids ~ or ~ phenols; ~
'''~:

; - ~ 8 ~
'~'':

lOt; ~ j, 2Z ' have been repre ~ ent ~ s by a formula me-ttant in oellvre connections covalent. It goes from 90i that these compounds can be ~ put in ~; ~
sou ~ work ionic form - ~ when X represents a group - N - ~ Z is preferably gal at H. 11 As we have just seen the process according to the invention - ~
consi ~ te ~ ~ react by mi ~ e contac-t a compound ; organosilicon with chloroalkyl group, with a compo ~ e such ~ as phenate, carboxylate, thiocarboxylate, thiolate or amine. ~ e ; lO compo ~ é amino can be optionally used in the form of 90n.
hydrochloride. ;
; ~ ~ e groupingY e ~ t an inert grouping within the framework of `~
i condensation7 and should not be likely to react with the chloroalkyl group of the silicon derivative or with the group Z - X -~ a nature of radicals Y is easily deduced by skilled in the art from the nature of compounds (C) and (D) We can therefore directly obtain the compounds (A? By `~;
~; ~ condensation of organosilicon compounds ~ groups chloroalooyl ~ (C) and compounds Z - X - ~ - (D) may ~
obviously get ~ from such ~ compound (A) by condensation of ~
; oomposed ~ organosilicon (C) and compounds Z - X - ~ ~ Y1 (D1) ~ in which Y1 is easily transformable into Y by a step `, additional success ~ nt ~ Ia condensationt As examples, we can transform selo ~ the ~ methods classics of organic chemistry, nitro derivatives (D1) in . ~ ..
amino derivatives (D) or corresponding isocyanato ~ (D), the derivatives metallics of hydroxylated or mercaptan oomposés in alcohols and thiols corre ~ pondantes ~ les d ~ rivées cyanés en amines, aldehydes . .
in alcohols, the metallic ~ el ~ of carboxylic acid ~ en acid function, e ~ ter or acid chloride, _99 ~

.. ~
'~

, ..,. ,, ...: ... ,,., ... .. ~, -.,. ;

~ 07 ~ 62Z ~

The function Y1 is chosen according to the nature of the ; cQposts (C) and (D) . ~ As an indication, when Z - X represents a group containing an alkali metal atom or a group quaternary ammonium, Y or Y1 can be one of the groupings ~ following functional:
- N02 ~ H ~ - COO ~
,.,. "
.l 3 ~ ',, ~ i (M representing a 30dium atom of potassium or ae lithium).
~ when Z - X represents ~ ente an amino group, the -group Y or Y1 can be O
.,. .. -.
~,,, ~. ., e ~ compo3és orga-nosiliciques (C) peuven ~ e-tre o ~ required according to the ~ general methods of obtaining organosilicon derivatives ~
roupements chloroRlcoyles ~ We usually prepare oet effect ~ of ~ s chloroalcoylchlorosilanes that o ~ tran ~ elm ~ by ~ magnesian synth in the ~ oomposés ~ organo ~ iliciques ét ~ ylènes ~
`~`; - ~ corresponding, These method3 are for example . ~ 20 described ~ in Eaborn's treaty: Organosilicons compounds p. 379 - 381 (1960) ~
; For purely illustrative purposes, one can cite among the Gomposed ~ organosilicon (C) the following components vinyldlmethylchloromethyl ~ ilane allyldimethylchloromé-thylsilane - - me ~ hyldivinylchloromethylsllane:
. - vinyldiphenylchloromethyl ~ ilane - allyldiphenylchloromethylsilane - vinyldim.éthyl-n chloroéthylsilane ..:
- vinyldimethyl, n-chloropropylsilane ~ 50-'',;''.'., ~

, ...,,. ... . . ,. -. . ,,. ; . .

- butene-l yl dimethylchloromethylsilane - 1,2,2 trichloro, vinyl dimethylchloromethylsilane - vinylmethylphenychloromethylsilane - ~ -cyanopropyl, vinylmethylchloromethylsilane - tetramethyl-1,1,3,3, vinyl-3, chloromethyl-l disiloxane The compounds of formula (D or Dl) can be -amino compounds such as: p-ethoxycarbonylphenyl methylamine, o ; p- nitrophenylmethylamine ~ N-methyl ~ amino-4 ~ nitro-4 ' diphenylmethane; or also alkaline salts, or amine salts tertiary carboxylic or thiocarboxylic acids such as:
; the ethyl monoester of tetephthalic acid, the monoester bis (hydroxycarbonyl) methyl -4 ~ 41 diphenylmethane ~ acid ; p- or m-nitrobenzoic acid p-nitrothiobenzo ~ that.
These compounds (D or Dl) can also be ~ - ~
alkali alcoholates or thiolates such as the salts of the compounds following ~
methyl p-hydroxybenzoate; p ~ hydroxynitrobenzene; hydroxy - 4, nitro ~ 41 diphenylmethane, hydroxy-4, nitro-4 'diphenyl ether, mercapto-4 ethyl benzoate, mercapto-49 nitrobenzene, mercapto-4, aminobenzene; the ethyl ester of thioglycolic acid, the ester hydroxy acid ~ 4 butano methyl ~ that.
Condensation reactions of the organosilicon compound (~) and of the compound ~ D or Dl) are carried out according to the methods `
general described in the literature and relating to reactions of nucleophilic substitution using a compound i ~
:.
organosilicon ~ chloroalkyl group LEaborn: organosilicon ~
compounds p. 393 ~ 411 ~ 412 ~ 413 (1960) and American patents i` ~ -; 2,783,262, 2,783,263, 2. ~ 33.802]. "'t' ~`. ''"'' The condensation reaction is generally performed ~ a temperature between 0 and 150C and ~ 0 7 preferably elltre 20 ct 100C by introducing ~ progressive ant ~ ent one ~ ~
re ~ active3 c ~ ans the reaction milleu containing the other reagent,. :
: 0n op ~ re in general in a solvent environment consti-killed by the ~ alcohols , .- such ~ as me-thanol or ethanolS the ~ solvent ~ polar ~ aprotic,; ~
. ~ such as N-methylpyrrolidone, dimethylformamide, le ~
dimethylacetamide, hex ~ methylphosphotriamide ,,, or also:. -organic ethers, such as methyl glycerol of diglycol, La r ~ action completed, the compounds (A) are isolated from the medium ~ :.
., ~ -. .
reaction by any known means such as by di ~ tillation ..:
.
or crystalli ~ tion ~ reacted. . ~ ~

, ':' , ... ... ..

:.

,, i ;, i ~. j ,. .
", '''.

~ '', -: '' '"''', ~ ~

: ~ '-' ~ .. ,, -52:

, ~,. :: ~,. . ...
.. ... . . . .

~ 6Z ~
UTI ~ IS ~ '~ `ION ~ FS ~ RODUI'.rS DE ~ IINVENrION
.es unsaturated organo ~ ilic compounds (I? are very interesting products in organosilicon chemistry By addition of a ~ dihydrogenopolydimethylsiloxane ~: they give block copolymers such as those having the ,. , `recurring patterns on - ~
: - r :
o 7 ~

'~ ~ 20 v, ~ o 3 ~ ^ ~ q On ~ yæ ~
r ~ r ~
vl II t-. ~ 53 ~ ~

Z
These copolyrn ~ res ~ b: locs are elastom ~ re ~ sili--Thermoplastic cones, fuses. They can replace before-tagging in many applications, the elastomers res-usual licones by sui. ~ e of their greatest ease of setting in use, due to their thermoplastic character ~
,:, .-.

`~.

.,; ~ - ~
""'~

.. :( .-'''''': ~:
. ',: ~. ~.
, "',' ~:
,,: -. .

, ::, ~, .
- ..:
. ' . ':
... ..
,. ''''',''. ~: '~. ~. , :: ~

; 54 ~ ~; .
'. '~

~ 716 ~ JZ

: ~ e ~ e ~ e.mple ~ ~ u: i follow ~ l; illu ~ tren-t llinvention ~ X ~ IP- ~ E 1 ~
.
: 1) ~ a-tion of c_mpo ~ (3) In a ball] .on three pipes of 250 cm3 fitted.
; mechanical agitation, an ascending refrigerant, pouring bulb and a thermometer, llen ~ emble being maintained under a dry nitrogen atmosphere, we load 10.35 g of dlamino ~
~; tvinyldimethylsilylmethoxy) -4 benzene, 5905 g triethylamine and .: 50 cm3 of carbon tetrachloride, .-: lO ~ e reaction medium, 30U9 stirring, e ~ t cooled `~
.. at -4C A solution of 5 ~ 22 g of terephthaloyl chloride dan3 17 cm3 of acetone qul est.
`en ~ uite casting reguliaremen-t for 27 minutes during the additlong. ~
the temperature is maintained between -4 and ~ 2C ~. We lai ~ se e.ncore `~`
. the reaction medium under ~ orte agi-tation for 1 H 30.
Then, the mass reactio ~ nelle e ~ t poured dan ~ 100 ~;
cm3 of water: the precipitate formed is drained, washed with 4 times ~ 40 cm3 of a water / acetone mixture drained again with PUI9 dried at 110C under . reduced pre ~ sion (5mm ~ g).
~ We received am ~ l 12 ~ 90 g of a product whose point : of fusion (Eo ~ ler) is 315C.
We perform on the isolated product, the anal ~ se ~ ...
next 9 centeslmale analysis ~ - G ~ = 66.09 l H% - 6.5 .:, ~. ~;, l . N% - 5.06.
- ~ pectre ~ i ~ = the ratio of vinyl group protons and `
aromatic proton is consistent with theory.
,. . . ,,. ~:
- ~ IR pectre =. we observe the different absorption bands ~ following:
,.,. ~ '' `.

-55 ~
., - ~.

. ~. ... ,.,: -:, ... . .

716Z; Z

':

Si-C ~ Cll2 1010 and 950 cm 1 Si-CH3 1250 - 830 cm ~ l:
NH 3280 cm 1 .: CO 1640 Cm 1 . ~ ~ -O CH2 1230 and 1110 cm 1 2) Preparation of amino-l (vinYldiméthYl ~
silylmethoxy) -4 benzene (a) The starting reaction is synthesized in the manner `next. -64.4 g of sodium p-nitrophenate are dissolved in 203 g of N-methylpyrrolidone and introduced this solution into ~ -a ball. After heating to 90, poured in 13 minutes 53.8 g of dimethylvinylchloromethysilane and add 10 cm3 of N-methyl-pyrrolidone. The reaction mixture is maintained at around 100 ~; ~ for 20 hours, filter sodium chloride and distill the N-methylpyrrolidone under reduced pressure. The reaction mass-residual nelle is dissolved in ether and the solution is washed;
tion ethereal with an aqueous solution of sodium carbonate. ~ `~
After dlstlllation of the ether we obtain 91 g of a prodult 2 ~ yellow ~ crista111sant à 34. ~ ~ Centesimal analysis ~ get analysis infrared show that it is nltro-l (vlnyldimethyl ~
silylmethoxy) -4 benzenes. ~ -We prepare; e another quantity of the latter compound ~ er; ~
according to the same operating mode. ~ We then carry out the reduction tion of the nitro derivative. ~;
:. ~:.
: OD introduced into a flask 775 g of chlorides, 700 g of hydrochloric acid (d = 1.19 ~, then flows between 30 and 45 ~ in 50 minutes a solution of nitro-l (vinyl ~
dlmethylsilylmethoxy) -4 benzene containing 118.5 g of derivative nitrated and 150 cm3 of ethanol.

The reaction mass is maintained for 2 hours ~ "~
to 45. After cooling, the tin tetrachloride is filtered, '..

~ 7 ~ 62Z

wash ~ e ~ u, neutral ~ e ~ using sodium hydroxide solution c ~ centr ~
and filters the pr ~ ci.pi-te ~ ormé. This precipitate is di ~ ou dan ~ un excess ~ of ~ oude After 9 extraction with ether and elimination of ether by evaporation, we get a ~ rec-ti ~ ication a fraction ~ Ebo 8: 115-117 of 79, ~ g dlamino-1 (vinyldiméth ~ lsilylméthoxy) -4 `~ ~.
'. benzane.

EXEMP ~ E 2 -1Q) ~ 5 ~ c 9Y 9 ~ ee9 ~ (4) . ~ lO In a three-balloon ~ tubing3 of 500 cm3 equipped ~ as in Example 1 ~ 6595 g of diamino-4.4 '' are loaded.
~ diphenylmetha-ne dissolved in 350 ml of anhydrous chloroform and. : ~
74 g of triethylamine.
~ ~ e reaction medium, with stirring is cooled to; .` .....:
.. 0C, We pour in 1 Il 30, 168 g of acid chloride i ; p- (dimethylvinylsilylmethoxy) benzo ~ that Dura-nt the addition, the ; ~ l temperature e ~ t maintained ~ O ~ 1C. .
. ~ ~ a ~ olution is then drained with stirring dan ~ 400. ~ ~:
cm3 of water. The organic layer is separated which is washed with 3 ~ ois.
; ~ 00 cm ~ of water, chilled on a-nhydrous magnesium sulphate then evaporated constant weight.
.; I: We obtain 219 g of a crude product which is treated with ~:
. ~ 10 g of carbon black and recrystallized from 500 cm3 of ethanol ~.
. ab ~ olu.
- ~ On i ~ ole thus 171 g of N ~ N'-bis ~:
.: [p- (vinyld1méthylsilylméthoxy) benzoyl] diamino -4 ~ 4 'diphenylmethane ~
~ whose melting point is 154 C ................................... ~ .
: Is carried out on the isolated product, the analy ~ es. ~
; : ~
', following l; e 9 ;. . '' ~ 57-,, '~:
:: -, ~. , ", .... ~

~ Q7 ~:; Z2 :, ~
~ hundred analysis ~ tlalc:
C% 69.90 ~ -H ~ 0 6.76 N% 4.58 If% 8.7 ~ -NMR spectrum = in accordance with formula (4).
~ - do ~ age of ~ free amino functions - this assay is negative.
, j ~ 2) Pre, p ~ ration of acid chloride p- ~ dim ~ eth ~ lvin ~ ylmethoxy) benzo ~ que (b) 10In a flask we introduce 760 g of p-hydroxybenzoate methyl, 850 cm3 of ~ -methylpyrrolidone and flows between 82 and 100 ~;
, `in 2 ~ 20 min a methyl solution of ~ odium methylate prepared from 960 g of methanol and 115 g of sodium. We eliminate in ~ followed by methanol distillation and flowing between 108 and 128, ~ ~
in 1 H 5 min 672 g of vinyldimethylchloromethylsilane ~ ~ -After di ~ tillation of ~ -methylpyrrolidone, we ~, `resumes the dlstillation pellet with 2000 cm3 of cyclohexane ~ lava ~ ,, with water and corrects methoxy-carbonyl-1 (dimethylvlnylsil`ymethoxy) -4 benzene. 1136 g of lme fraction are thus obtained ~ bo 1 110-113 don ~ the melting point is 25.5.
By treatment of methoxycarbonyl-1 ~ -(dimethylvinylsilylmethoxy) -4 benzene ~ using ~ me solution 30ude containing 100 g of souae ~ 250 g of water and 1000cm3 of methanol, , ~
preparing the sodium salt of p- acid (dimethylvinylsilylmethoxy ~
~ well ~ o ~ that.
, ~ After ~ acidification of a solution containing the salt of ~ odium p- (dlmethylvinylsilylmethoxy) benzo acid ~ that, we i ~ ole after ~ filtration a white product melting at 118 and . . ...
corre ~ laying ~ acid p- (diméthylvinylsilylméthoxy) benzo ~ que.
We introduce dan ~ a balloon 354 g of acid,; `
previously prepared ~ and poured in 4Q min, between 28 and 29, 357 g thionyl chloride. ~ the reaction mass is then heated ~
-, -5 .

~ 1: 17 ~ L62 ~

and maintained for 1 hour at 102 ~. By rec-tifica-tion we get a Ebo 1 fraction: 126-127 of 344 g corresponding to chloride of llacid p- ~ dimethylvinylsilylmé-thoxy ~ benzo ~ que.

EXAMPLE _3 _ Preparation of the compounds (~) In a 500 cm3 three-pipe flask equipped as ~ `
e ~ example 1, 41.4 g of amino ~ 1 (vinyldimethylsilymethoxy) -4 are loaded;
benzene prepared according to the procedure described in example 1 and 100 cm3 of cimethylformamide containing 0.02% water. -i lO We chau ~ fe the reaction medium, with stirring at 60C
and 21.8 g of pyromeIiq ~ -e anhydride are gradually added over 20 minutes, -in small ~ 3 g reactions.
~ A clear yellow solution of the compound (17) is obtained.
Stirring and heating are maintained at 60C for `
`; another 1 hour and 30.6 g of acetic acetic acid are added in 5 minutes pu ~ s is poured in 5 min, 6.2 cm3 of pyridine At the end of addition of pyridine ~ a yellow precipitate is formed. We prolongs the heating ~ 1 H 45, the temperature being maintained .,. ~. -between 60 and 70C
~ `20 ~ pr ~ re ~ stiffening, we filter the precipitate ~ é formed and we wash it with 4 times 40 cm3 of acetonel and wring it out and dry it around 11 ~ C, sou ~ pres ~ reduced ion (25 mm Hg) for 8 hours ~ ~ -50.2 g of ~ raw product are collected and recri ~ talli ~ e i a reaction of 45 g which is dissolved at the boil in 2000 cm3 of -. ~ dimethyl ~ ormamide ~
43.1 g of yellow crystals are obtained which melt at 380C.
with decompo ~ ition.
We perform the recrystallized product ~, the analyzes following ~
; 30 - centered analysis ~ imale ; `C% 64.42 H% 5960 N% 4.79 ~ ~ 7 ~ ~ 2 - 9l ~ Cctre IR
. CO 17 ~ 5 - 1725 cm ~
Si-C ~ I = CH2 1010 and g60 cm 1 . ~ Si- (~ I3) 2 860 and 800 cm 1 : - chroma-tography in thin layers (aCM) = we obtain by chromatography on a plate of silica, the eluent being a mixture . ethyl acetate (90%) and ben ~ ene (10%), a pot of R ~ = -, 62.
', .,. . . ~ ~. .
E ~

- 10 P ~ ation of the compound ~ (5):
~ In a balloon ~ three tubes of 500 cm3 equipped as ^; ~ Example 1, 41.4 gd are loaded ~ amino-1 (vinyldimethyl ~ lylmethox ~
`` Benzene synthesized as. ~ Example 1 and 50 cm3 of dimethyl ~ ormamide.
`` '' I. . .
Stirred and poured slowly over 30 min a solution of.
25 g of 4,4 'diisocyanato diphenylmethane dan ~ 75 cm3 ~, .` dimethyl ~ ormamide During the addition ~ we maintain the temperature of the reaction medium between 7 and 13a.
Then the heating is extended to 20-22 ~ for ~ hours.
~: ~ a ~ colorless solution is then poured with stirring into 400 cm3: ~
, - ,.
;: 20 iced distilled water. Apra ~ 2 hours ~ of decan-tation, we filter .: the precipi.té which is then washed with 5 ~ ois 75 cm3 of water.
We get 54 g of crude product which is purified by . dis ~ olution in 200 cm3 of dimethyl ~ ormamide and treatment with 200 , . ~ cm3 of acetonite.rile has ~ in to cause precipitation. We re ~ stiffness ~.
~ the mixture for 2 hours in an ice bath and one ~ iltre the precipitate which e ~ -t then washed with 300 cm3 of acetonitrile ~ e ~ and dried at 1 ~ 0C ~ or ~ 1 mm Hg for 8 hours.
: ~ We collect 53 g of white product which melts ~ 280C with decomposition.
30 We realize ~ e ~ ur the product precipitates the ~ analysis ~ following-you ~.
'--60- ~

.

- centGsimal analysis C ~ 66 9 65 II% 6.65 N% 8.42 - IR specter -NH 3300 cm ~ 1 -CO 1665 cm 1 Si_CH = CH2 1010 and 960 cm 1 Si- (CH3) 2,830 cm 1 ~ ~ -~ O_CH2 1220 cm 1 . '~'' - C ~ CM = a spot of Rf - 0.87 is obtained, the dilution solvent ~ both a mixture of chloro ~ elm (96%) and methanol (4%).
. ~.

. ., , i.
~ u com ~ daring (6) i.
In the previous apparatus ~ demmen-t described dan ~ Example 1, ~ -6.36 g of ethylene glycol terephthalate and 30 cm3 of pyridine.
This solution is refrolded to 5C and charged in 12 min, ~
in small ~ fractions, 12,974 g of acid chloride p- (dimethylvinylsilylmethoxy) benzo ~ that synthesized as in example ; I 2.;
~ i ~ a te ~ temperature of the reaction mixture s ~ rises to 10C in 1 end of casting. We gradually increase the heating of the solution which deYient limpid towards 76C and one for ~ uit the heating ~ -at 110C for 3 hours. ;; ~
The mixture is cooled ~ stirring OU9 ~ It is formed ~
abundant precipitate of pyridine hydrochloride which is filtered, washed with 2 times 5 cm3 of anhydrous pyridine and then drained. ~ this filtrate is poured with stirring into 300 cm3 of ice water. After one hour decantation on ~ iltre the precipitate which is then washed ~ by 300 cm3; ~
-61 ~
'': ':'"

~ 7 ~ ~ Zz of water, wrung and dried ~.
We obtain 16.4 g of white crystals melting ~ 70C which are then recrystallized ~ from 100 cm3 ~ 'isopropanol. After filtration and drying, 14.6 g of melting white cries are obtained at 72-74C.
Is carried out on the recrystallized product ~ analyzes ~ following:
- centesimal analysis C% 62 ~ 76 ~;
H% 6.53 . ~,.
If% 7.69 ! _ IR spectrum at 1739 and 1710 cm ~ 1 ; ~ O-CH2- 1250 cm 1 ~;
5i-CH = CH2 1020 and 965 cm 1 `I If CH3 830 cm ~
~ ~ - a ~ c ~ M ~: a spot of R ~ = 0.44 is obtained, the eluent being benz ~ ne.
,: j ~ -.ExA ~ æIE- 6 - `~

~ Dan ~ the apparatus previously deviated from Example 1, 20 g of amino-1 (vinyld1methylsilylmethoxycarbonyl) -4 are loaded ', 1: ~. :.:.
~ benzene, 8.6 g of triethylamine and 50 cm3 of acé ~ one.
Is loaded into the pouring bulb, a solution of; ~
8.8 g of terephthaloyl chloride dissolved in 100 cm3 of acetone which is then poured dan ~ the reaction medium maintained ~ 35C
After addition of 11 cm3 of terephthaloyl chloride solution, It forms a white precipitate. '' ~ n continues the run which lasts 1 hour and 15 minutes.
The reaction mixture is then brought to the boil and ....
it is maintained for 1 hour at a boiling point, i.e. 58C.
~ after cooling, the precipitate is filtered on;

.: ~ ,. :

-6 ~ - ~

7 ~ 6Z ~
..
fried glass t ~, then ~ this pr ~ c-Lpity e ~ -t washed with 5 times 50 cm3 of water, e ~ sore then dried 4 H at 100C gOU3 25 mm pre ~ sion.
21.2 g of product are thus collected. - ~
I, the filtrate is precipitated by 500 cm3 of water which still makes it possible to obtain 3.57 g of product. -We recrystallize 10 g of product from the `
first filtration in 250 cm3 of chlorobenz ~ not allowing - ~
to obtain 8.9 g of pearly crystals identified as ~, both the N ~ N ' bis p- ~ (vinyldimethylsilyl) methoxycarbonyl) phenyl ~ terephthalamide f; - 10 and whose melting point is 260C.
~ We perform the purified product, the analyzes ; following ~
centesimal analysis C% 64.38 -H% 6.06 N% 4.97; ~
',. ~, If% 9, 1, ' ,, i; :.
i - RM spectrum ~: in agreement with the ~ ormule (7).
- IR spectrum 20 ~ ~ CO ~ (conjugated ester) 1700 cm 1- ~;
~, ~ CO (secondary amide) 1665 cm 1 l NH 3350 cm ~
;;, `C ~ NH 1530 om ~
If CH 1250 ~ cm ~ 1 Si-CH - CH2 1010 cm 1 and 955am ~
isub ~ titution ~ aromatic and Si ~ (~ H2) 2 830-850 cm 1 2) ~;
`~ benz ~ ne ~ c) Is introduced into a balloon 102? 8 gd ~ acid p-aminobenzo ~ that and 500 cm ~ of N ~ methylpyrrolidone was introduced, ~
25 after dissolution 60.7 g of triethylamine.

~ 716Z'Z

Dan ~ the mela ~ lge door ~ 130 we sink then ~ in 3 hours 67 ~ 4 g of vinyldîméthylchlorométhyl ~ ilane. May-ntient 21 ~ 130 hours and filter after re ~ roidis ~ ement 64.8 g of hydrochloride triethylamine.
The N-methylpyrrolidone is separated by distillation and takes up the distillation residue with 200 cm of ether and then washes with an aqueous solution of solium carbonate. ~ n separates the ether ~
by di ~ tillation and after rectification obtains a fraction Ebo 35: 153-154 of 78.8 g corresponding to amino-1 (vinyldimethylsilylmethoxycarbonyl) -4 benzene. ~ e IR spectrum, the dosage of amino groups and centesimal analysis ~ have agreement with formula (c).
~ 'amino -1 (vinyldimethylsilylmethoxycarbonyl) -4 benzane crystallizes ~ 30C, , 1) Pr ~ par, atio, n du com, posed ~) , ~, In a 100 cm3 three-tube flask fitted as in Example 1, 4.25 g of bis (p-aminophenoxy-3 prop ~ 1,3 tetramethyldi ~ ilogane 1, ~ 84 g of ~ 20 tri ~ thylamine and 50 cm3 of acetone. -- - We load into the dropping funnel, 4.63 g of chloride ~
of p- (dimethylvinylsilylmethoxy) benzo ~ that prepared according to the, ~
operating mode of lle ~ example 2 and 30 cm3 of acetone.
, We aglte and reProidit the mixture r ~ action at 3C, Then poured in 15 min ~ chloride olution of acid. ~ at temperature ~ 'raises to 6a at the end of casting.
; Then the reaction medium is heated to 50C and maintains this temperature for 1 hour. ~ `
After cooling the reaction mixture e ~ t poured sou ~ stirring in a liter of water. ~ The precipitate formed is ~ illiterate, washed with 100 cm3 of water and then dried.
'~

, ..,. . -. . . ,,. -. . . .

7.43 g of a crude product is obtained.
6 g of this compound are recrystallized from 200 cm 3 of methanol.
5 ~ 1 g of a whitish solid are collected, the melting point is 145C.
By elementary analysis, we dose 3.25% nitrogen and '. 7 ~ 53% hydrogen.
We obtain by CCM, a single spot of Rf = 0.74, the eluent being a mixture of toluene (90%) and ethyl acetate . 10 ~ 10%) o ~, 2) ~ ~
tetrameth2 ~ disilo ~ donkey (d) -The coupling agent is synthesized in this way;
next :
In a 250 cm3 three-tube flask fitted with a mechanical agitation, a coolant, a dropping funnel and .,:. .:, a ther ~ ometer, the whole being maintained under a nitrogen atmosphere, 66 g of dallyloxy-4 nitrobenzene and 0.07 cm3 of a solution are loaded ``
alcoholic chlorophatinic acid containing 30 mg platinum / cm3. ; ~
i: `-. ~ ~
25 g of ~ - 1,3-tetramethyldihydrogeno disiloxane and one begins to flow; ~, ~
S cm3 in the reaction medium with stirring and at temperature ambient. ~ nsuite the reaction mass is heated to 100C and;
the casting is continued: the temperature rises sharply towards 200C ~ The reaction mass is cooled down to 130C and maintained; ~
; ::
this temperature for 30 min.
After cooling, a viscous mass is obtained which is poured with stirring into 2000 cm3 of ethanol.
~:, A precipitate is formed which is filtered and dried.
18.8 g of a compound melting at 80 ° C. are obtained.
which we perform the following analyzes ~

: ':'. , ::.: ~
:,. ... .
65 ~

N02 1510-1330 cm Si-CH3 1250 cm 1 ~ 0 CH 1265 cm 1 If ~ 0 1080 cm 1 ~ ~
RNN spectrum: conform ~ theory ~ -The reduction of the nitro group is carried out in the manner following :
; It is loaded into a stainless steel autoclave of 125 cm3 ~ 10 g of ~;
previously prepared compound, 50 cm3 of ethyl acetate and 0.2 g of - 10 ADAMS platinum at 83.6 ~ O in platinum.
The autoclave is purged with nitrogen. We send in the ,: ~
reaction medium maintained at room temperature of hydrogen -under pressure of 50 bars ~ After 15 minutes, the pressure drops ~ `
: ~ ,! at 28 bars and the initial pressure is restored.
.,. ,., ~
After 35 min, heat ~ 55C for 1 hour.
After cooling the autoclave ~ a ~ suspension of the catalyst which is then separated by filtration.
- The solvent is evaporated off under reduced pressure.
9.15 g of an amine liquide are collected which titers 0 ~ 0392 amine function by assay with perchloric acid.
Obtained by TLC on silica plate ~ the solvent , ~.
~ of elution being acetate of ~ hyle, a spot of Rf = 0.34.

; EXAMPLE 8 Preparation of comE ~ daring (20).
In a 500 cc 3-pipe flask fitted with a mechanical agitation, a thermometer, a condenser, a;
pouring funnel and dune nitrogen inlet pipe ~ on place 45 g tO, l N) of bis (4-amino-41-benzamido-phenyl) methane, then 250 ~ cm3 of N-methyl pyrrolidone.

: ' .::

~ 7 ~ 6 '~ Z

~ an ~ la ~ u ~ pen ~ ion pfiteuse thus obtained and maintained between 5 and 10C, pour in 1 H 51 g (0.2 M) of acid chloride (dim ~ thylvinylsilylmethoxy) benzo ~ that previously heated to -~ 50C
~ has known ~ pen ~ ion dissolves progressively.
~ a brown reaction solution is maintained for 2 hours ~ additional with stirring ~ room temperature Precipitate the reaction medium in 1.5 1 of vigorously stirred ice water ~ e beige precipitate is filtered pui ~ lav ~ with water.
By solubilization of the hot cake in the ~; ~
dimethylformamide, filtration ~ hot then cooling of iltrate, 74 g of light beige crystallized product are obtained.
~ E product thus prepared has a melting point of 315C.
Its spectrum in ~ ra-red presents the characteristic bands of compound of formula (20) By layer chromatographic analysis thin we con ~ tate ~ ue this product is free of impurity ~. ~ 'analy ~ e centesimal on carbon, the hydrog ~ i ~ ne and ai ~ ote gave the `~ following results:.
,, ... . .-:
C% - 70J19 .. `. ~" -~% - 5 ~ 97, N ~ o = 6.42 E ~ EJLPIE ~
Pr ~ R ~ on com ~ daring ~ (21) ~ ans the device used ~ e ~ example 8 we load 20 g ~ 0.05 mol) of bis terephthalate ~ 4-amino phenyl) and 75 cm3 of: ''! ~, ' methyl pyrrolidone. ~ the solution obtained is maintained at 5-10C `~
~ tandi ~ ~ we add in 1 hour a solution of 25.5 g (0.1 mole) ae `` ~ i ~ acid chloride p- (vinyldimethylsilylmethoxy) be ~ zo ~ que aans i 25 cm3 of Nm ~ thylpyrrolidone. Then maintain 3 ~ I at 20C
~ 0 after which we add 500 cm3 of water ~ stiff in the middle r ~ action. ~ n obtie-nt thus a precipitate ~ yellow which one ~ separates by filtration pui ~ -wash ~ ur filter ~ e pr ~ cipit ~ is in ~ uite dissolved ~ in the . '~' - '.,''' ~ .`.

.,:,. ., -. . ,,,. :. ~,,;

: lQ7: ~ 62 '~

dilllethylformamide hot and the solution is filtered and then filtrate cooled to 20C. This way we get a product white crystallized whose weight is .27.5 g after drying under vacuum until constant weight. ~, This product has a melting point of 301C and has - an infrared spectrum conforming to that of the compound of formula "(21). It does not contain impurities and the centesimal analysis,;, ~
elements C, H and N provided the following results:
C% = 66.65 , 10 H% = 5.65 - ~ N% = 3.41;
EX ~ MPLE 10 -Compound preparation (22) , ~ In the device described in Example 8, we load ~
24 g (0.1 mole) of 4-amino-4'-amino benzoate, phenyl 100 cm3 of N-methylpyrrolidone, A suspension is obtained which is maintained between 5,; ~
and 10C while adding a solution of 51 g in 1 hour (0.2 mole) p- (vinyldimethylsilylmethoxy) acid chloride benzoic acid in 50 cm3 of N-methylpyrrolidone. We maintain the ~ ~;
reaction solution 2 hours at 20C after the end of the casting , ~. .
; then it is added to 800 cm3 of ice water with stirring. It is , thus forms a precipitate which is filtered and then washed with water on ~ filter. The precipitate is dissolved in hot dioxane, the, ~
- filtered solution and the filtrate cooled to 20C. We thus obtain ~ - ~
, ^ ~ 56 g of a white crystallized product free of impurities, point ~;
213C fusion and whose infrared spectrum conforms to ... ~. . ~.
that of the compound of formula (22). The centesimal analysis of ~ elements C, H, N gave the following results: ~
,, 30 C% = 66.59 ~, H% = 6.18, N ~ = 4.04 - 68 -, ~ 07 ~

; EXAMPLE 11 -Compound preparation (23) ".
~ In the device described in example 8, we load:
. ~:
21.6 9 p-phenylenediamine 200 cm3 of N-methylpyrrolidone The solution is cooled to 5-10C and added in 1 - ~ hour a solution of 102 g-p-acid chloride (vinyldimethyl-~,. '. -:
silylmethoxy) benzoic acid in 100 cm3 of N-methylpyrrolidone.
The contents of the flask are then brought to 60C and ~ ~
maintained 1 hour at this temperature. ~ -The hot reaction solution is a ~ outée to 1 1 ice water, with stirring. We obtain a beige precipitate which is separated by filtration, washed with water and then dissolved in `~
hot dioxane. `~
This solution is filtered, then the filtrate is `i ~ cooled to 20C. `-; ~
~ We obtain a white-colored crista] precipitate which we ~;
. ~ ~
~ filter and dry to constant weight. We isolate in this way ~
`1 ':, ... .
83.5 g of a product with a melting point of 255C, free of impurities; ~
20 ~; and whose infrared spectrum conforms to that of the compound ~
of formula (23).
The centesimal analysis of the elements C, H and N gave - ~;
the following results ~
C% = 65.13 % = 6 ~ 75 N ~ = 5.25 XIMPL ~ 12 1) P ~ separation of the compound of formula (24) :, ~ -. ~. . ,. -.
In the device described in Example 8, we load:
19.8 (0.1 mole) of 4,4 'diamino diphenylmethane 150 cm3 of chloroform ::.: :: .- -23 9 of kriethylamine.

..
5, ' , ~ :. - -:: -, :: ~:,,.:::::,,:.
:; -,. :. ,,: -, "::... ~., -.". .,,. ,. . ~.

~ 37 ~ L6Z2 We cool the contents of the flask to 4C then add in 1 hour 50 minutes a solution of 53.5 g (0.2 mole) of p- (divinylmethylsilylmethoxy) benzoic acid chloride in 100 cm3 of chloroform.
the reaction mass is then washed three times with 60 cm3 of distilled water, then the chloroform is removed by; ~
distillation. The residue ~ obtained is recrystallized from ethanol absolute. 60.5 g of a white product are thus obtained free of impurities, melting at 142C, the resonance spectrum of which ^
-; 10 nuclear magnetic conforms to that of the compound of formula ^
(24).
The centesimal analysis of this product gave the ~ following results `~ C% = 70.66 H% = 6.69 N% = 3.95 If% = 8.31 2) Preparation of the acid chloride p- (divinylmethylsily, ~ methoxy) benzo'i ~ e ~ in a c1e 500 cm3 balloon equipped with an agi-mechanical ration, a light bulb, a coolant -:, -ascending, thermometer and heater, Orl charge:
`~ 91.5 g (0.6 mole) of methyl p-hydroxybenzoate ; ~ 100 cm3 of methanol The contents of the flask are refluxed and added 40 min a solution of 24 g of NaOH in 200 cm3 of methanol. - ~
.: ... :.
Then methanol is distilled off and ~ 200 cm3 added of N-methylpyrrolidone. We bring the contents of the balloon to 113-, ~ 30 127C and adds 88 g of methyldivinylchloromethylsilane. We i maintain 1:30 in these conditions.
:. ~,.
,.
~ - 70 -, ':

~ ~. ,.:

1. ~? 7 ~

La N-nlé tlly 1., ~? Yr ro: li (k ~ lle es t ensu i te Chasée par .- ~ listi.1 Ia ~: ioll. I, e resi (read is taken ~ ar 250 C1113 (cyclohexane e ~ ce ~ te solut ~

``.
, : `:
~ .` ;, ':
.. ~ ".

~, ~
'''':
,, `,:
'~:

.

. ~, .,:.
., '~ ~
~:
~ :, ,,. :
I ' :
.
'' :
,.

~ 137 ~ 62 '~

is ensui-to laltee ~ l'eal ~ pUi9 clistillate. We i ~ ole cle ce ~ açon 146 g of a product having the following 9 characteristics:
Eb - 0.5 mm Hg 125 - 130C
: ~ ~ 8C:
D
. n 20 1.532 .:
;! '' . '',: ~ d 20/4 19Q525 and whose centesimal analysis is as follows : C% = 63.07 = 6 ~ 94 . 10 If% = 1097:
vinyl% = 20.6 ~ e infrared spectrum corresponds ~ pond ~ that of p- (di ~ i ~ ylmeth.ylsilylmethoxy) methyl benzoate.
By treatment of 105 g of p ~ (divinylmethyl3ilylmethoxy). .:
~ `methyl benzoate with a solution of 20 g of NaOH in 50 cm ~ -of water and 200 cm3 of methanol the acid solium salt is prepared . p- (di ~ inylmethylsilyimethoxy) beni ~ o ~ that After acidification, we isolates by ~ iltration a bla product ~ c ~ 98 g) of melting point ..:
104G with a hundred ~ esimal composition and the following 2 ~ ~ H ~ I ~ 62 05 If ~ o = 10,: 56 vinyl ~ o - 21:, 24 identi ~ ié as ~ both p- (divinylmethyl ~ ilylmethoxy) benzo acid ~ as ..;
, not a word : : . ~
i ~ In the device: previously described, 74.5 g of `- the acid obtained above and added in 15 min 71.5 g of chloride;. ~ ~`
thionyle. (0.6 mole) between 25 and 28C.
has my reactionary ~ is in ~ uite maintained ~ reflux ,. . . . .
. for 1 hour .
: ~ 30 P ~ r distillation, 74 g of a passing fraction are obtained.
between 117 and 120 ~ under 0.06 mm of mercury. This product has been -71 ~

-,. . . ..

107162 '~ ~

identified as 17acid chloride p- (divi ~ ylmethyl ~ ilylmethoxy) benzo ~ that. Its melting point and 22C.
;.

. ,, .-,, '.''; ~ -, '' `:.:
., ~; ''~;'-'i ~,,. ":
,,. , '~

:. ' ~ '. ':''::.

A ~

~ `~ -. ',:.'' ~ 72-:

Claims (45)

The embodiments of the invention, about which an exclusive right of property or privilege is claimed, are defined as follows: 1. Polyethylene silicon compounds having as their general formula (I) in which the various symbols represent:
- n, n ': whole numbers identical or different from 1 to 3, - R, R ': monovalent organic groups, identical or different with an ethylenic double bond and comprising from 2 to 10 carbon atoms, - R1, R1 ': identical or different radicals, straight alkyls or branched substituted where appropriate by one or more halogen atoms or by one or more groups nitrile pements, aryl radicals alkylaryl; these latter aromatic radicals being substituted if necessary by one or more atoms halogen, - R2, R2 ': identical or different divalent radicals alkyl-lenes, straight or branched alkylidenes having from 1 to 4 carbon atoms, - X, X ': divalent radicals, identical or different, consisting of, or containing at least one heteroatom:
O, S or N; in this case the radicals X, X 'are rat-stained with radicals R2, R'2 via the heteroatom, - 1, 1 ': identical or different organic radicals having from 1 to 30 carbon atoms taken from groups formed by:

a) divalent radicals: - G -, - G '-and trivalent radicals: - - .alpha. : an organic radical chosen from the group cons-titled by:
at) (II) b) (III) vs) (IV) d) (V) in formulas II to V:
-B, B 'represent an oxygen and / or nitrogen atom -R "represent a valential bond or a radical divalent organic -R "'represents a trivalent organic radical -R "'represent a tetravalent organic radical -T, T 'represent functional groups identical or different taken from the group trained by:

, (VI) (VII) it being understood that in formulas (VI) and (VII) R3 represents a hydrogen atom an alkyl radical of 1 to 6 carbon atoms. 2. Organosilicon compounds according to claim 1 characterized in that they correspond to the general formula (I) in which the numbers n and n 'are identical, the radicals and functions R, R1, R2, R3, X, G, G1, .beta., T are respectively identical to R ', R1', R2 ', R3', X ', G', G1 ', .beta.', T '. 3. Organosilicon compounds according to claim 1 characterized in that they correspond to the general formula (I) where n = 1 4. Organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which R, R 'represents a straight alkenyl group or branched substituted where appropriate by one or more atoms;
halogen, a cycloalkenyl group substituted where appropriate by one or more halogen atoms, a group of formula:

the identical or different symbols X1, X2, X3 representing a hydrogen atoms, a straight or branched alkyl group having from 1 to 4 carbon atoms, or a phenyl group; X4 desi-glove one of the following organosilicon groups;

; ;
R4, R4 'identical or different representing a group methyl or phenyl and nl being an integer equal to 1, 2 or 3. 5. Organosilicon compounds according to claim 1, 2 or 3, characterized in that they correspond to the general formula rale (I) in which R, R 'represent an alkenyl group straight or branched having 2 to 6 carbon atoms, substituted the optionally with 1 to 3 chlorine and / or fluorine atoms. 6. Organosilicon compounds according to claim 1, 2 or 3, characterized in that they correspond to the general formula rale (I) in which R, R 'represent an alkenyl group linear having from 2 to 6 carbon atoms. 7. Organosilicon compounds according to claim 1, 2 or 3, characterized in that they correspond to the general formula line (I) in which Rl, Rl 'represent:
straight or branched alkyl groups having at least plus 10 carbon atoms substituted if necessary by 1 or 4 chlorine and / or fluorine atoms or by a nitrile group, aryl or alkylaryl groups comprising 1 to 4 carbon atoms in the alkyl substituent; these radi-aromatic cals being substituted if necessary by 1 to 4 atoms chlorine and / or fluorine. 8. Organosilicon compounds according to claim 1, 2 or 3, characterized in that they correspond to the general formula rale (I) in which Rl, Rl 'represent an alkyl radical having from 1 to 5 carbon atoms substituted where appropriate by 1 to 4 chlorine and / or fluorine atoms, or a phenyl radical. 9. Organosilicon compounds according to claim 1, 2 or 3, characterized in that they correspond to the general formula rale (I) in which R2, R2 'represent a radical chosen from the group consisting of methylene, ethylene, trimethyl thylene, methylethylene, ethylidene, tetramethylene and isopropyli-not. 10. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which R2, R2 ′ represent a methylene group or ethylene. 11. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which X3 X 'represent one of the following groups vants linked by the heteroatom to the radicals R2, R2 ' - O -, - S -, , , R5 representing a hydrogen atom or a radical straight or branched alkyl having 1 to 4 carbon atoms. 12. Organosilicon compounds according to claim 1 2 or 3 characterized in that they correspond to the general formula (I) in which X, X 'represent one of the following groups before:

- O -, - S -, R5 representing a hydrogen atom or a radical methyl, ethyl. 13. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which G, G 'represent a radical chosen from the group formed by.
a) - straight and branched aliphatic hydrocarbon radicals satiated, saturated and unsaturated cycloaliphatics, substituted if necessary by chlorine atoms; monocyclic aromatic radicals and polycyclics substituted, where appropriate, by methyl radicals or by chlorine atoms, the aromatic radicals, forming if necessary between them orthocondensed or ortho systems and pericondensed, b) saturated, unsaturated and heterocyclic radicals aromatic, monocyclic and polycyclic, comprising at least one heteroatoms, O, N, S and substituted where appropriate by methyl radicals, and c) divalent radicals formed by linking groupings as defined in paragraphs a) and b) and linked in-be them by a valential link or a group chosen in the group made up of the following groups:
-O-, - S -, , - CO -, , - CO -, - COO -, - SO2_, - N = N -, it being understood that in these formulas, R6 and R6 'represent a alkyl radical having from 1 to 4 carbon atoms, a radical cyclohexyl or phenyl, R6 possibly representing an atom hydrogen. 14. Organosilicon compounds according to claim 1 2 or 3 characterized in that they correspond to the general formula (I) in which G, G 'represent a radical chosen from the group made up of:
a) the alkylene, alkylene, alkenylene radicals, straight or branched alkenylidene having at most 12 carbon atoms ne and cycloalkylene radicals, cycloalkenylene having 5 to 8 carbon atoms in the ring, b) phenylene, tolylene or xylylene radicals, c) saturated monocyclic heterocyclic radicals, unsaturated or aromatic and comprising as a heteroatom, one or______________________________________________________________ several oxygen, nitrogen or sulfur atoms and containing 4 to 6 atoms in the ring; which heterocyclic radicals are substituted where appropriate by one or two methyl groups, d) divalent radicals constituted by a chain from two to four groupings as defined in paragraphs a, b and c and linked together by a bond chosen from the group constituted by the valential link, the following groupings:

- O -, -NH-, - COO -, -CONH -, - SO2 -, , - CO - -N = N -, and alkylene and alkylidene groups having from 1 to 4 atoms of carbon; and e) the aromatic radicals constituted by a whole from 2 to 3 carbocyclic and / or heterocyclic aromatic rings and forming between them an orthocondensed system, these radicals aromatics being substituted where appropriate by groups methyls. 15. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which G, G 'represent a radical chosen from the group consisting of alkylene or alkylene radicals having from 1 to 6 carbon atoms, the cyclohexyene radical, the radicals phenylene cals, xylene xylene, the radicals formed by two phenylene groups linked together by a valential bond, the methylene, isopropylidene, oxygen, and - NH -, - SO2 -, - CO -, - CO-NH - groups. 16. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which G1, G1 'represent a trivalent radical chosen from the group consisting of benzene triyl radicals, naphthalene triyl, pyridine triyl, the radicals of formula E in which E represents a valence bond or a group chosen from the group constituted by the groups al-coylene and alkylidene having from 1 to 4 carbon atoms, the atom oxygen and the following groups; - CO -, - COO -, - S02 -, - CO-NH -. 17. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which Gl, G1 'represent a radical chosen from the group consisting of the benzenetriyl radical -1, 2, 4 and the radicals trivalent cals comprising 2 benzene rings linked together by a valential bond, a carbonyl, sulfone, methylene group or isopropylidene. 18. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which R "represents a radical chosen from the group consisting of a) straight, aliphatic hydrocarbon radicals and branched, cycloaliphatic, saturated and unsaturated, substituted where appropriate by chlorine atoms; aromatic radicals monocyclic and polycyclic whose cycles form between them orthocondensed and ortho and pericondensed systems, these radi-aromatic cals being substituted where appropriate by atoms halogen, by alkyl radicals having from 1 to 4 atoms of carbon, by alkenyl radicals having 2 to 4 carbon atoms bone, or by one or more nitrile, urea-thane, amide, ester, amine and ether, . b) saturated, established and heterocyclic radicals.
aromatic, monocyclic and polycyclic, containing at least one of the heteroatoms, O! N, S and substituted where appropriate by methyl radicals and c) divalent radicals constituted by a chain groupings as defined in paragraphs a) and b) and linked between them by a link chosen from the group consisting of:
- a value link - the following groups:

- O -, - S -, , , - CO -, - COO -, - S02 -, - NN - , R6 and R6 'representing an alkyl radical having from 1 to 4 atoms of carbon, a cyclohexyl or phenyl radical, R6 representing where appropriate a hydrogen atom, -and organic radicals containing silicim of form-mule:

, , , , , , , it being understood that in these formulas n2 represents a number integer from 1 to 3, R7, R7, R8, R8, identical or different represent-feel an alkyl group having from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 4 carbon atoms, a group-phenyl or a hydrolyzable function chosen from groups:

and Rg, Rg, identical or different, represent groups alkyls having 1 to 3 carbon atoms. 19. organosilicon compounds according to claim l, 2 or 3 characterized in that they correspond to the general formula (I) in which R "represents a radical chosen from the group consisting of:
a) the alkylene, alkylene, alkenylene, al- radicals straight and branched cenylidene having at most 12 carbon atoms, and cycloalkylene radicals having 5 to 8 carbon atoms in the cycle, b) the phenylene, tolylene and xylylene radicals if necessary killed by one or more chlorine atoms, by nitrile, amide, amine, ester groups or by al- radicals coxy having from 1 to 4 carbon atoms, c) saturated monocyclic heterocyclic radicals, unsaturated and aromatic and comprising as a heteroatom, a or more nitrogen or sulfur oxygen atoms and containing 4 with 6 atoms in the ring, the heterocyclic radicals being the if necessary substituted by one or two methyl groups, d) divalent radicals constituted by a chain from two to four groupings as defined in paragraphs a, b and c and linked together by a bond chosen from the group formed by a value link or a group chosen from the group made up of the following groups:
alkylene and alkylidene elements having from 1 to 4 carbon atoms, and organic radicals containing silicon of formula:

, , , , n2 representing an integer from 1 to 3, R7, R7 ', R8, R8 ′ denoting a methyl radical where phenyl, and e) radicals consisting of a set of 2 to 3 aromatic carbocyclic and heterocyclic aromatic rings or not and forming between them an orthocondensed system, these radicals aromatics being optionally substituted by groups methyls. 20. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which R "represents a radical chosen from the group consisting of:
- alkylene radicals having from 1 to 8 atoms of carbon, the cycohenxylene radical the phenylene radicals, toly-lene, xylylene and the pyridylene radical, - divalent radicals comprising from 2 to 4 groups phenylenes linked together by a valential bond or a group chosen from the group consisting of the oxygen atom, the groups-following:

- CO -, -SO2-, - NH -, , - CO-NH -, the groups alkylene or alkylidene having i to 4 carbon atoms, and organic radicals containing silicon of formula:
, , - O -, (CH2) n2 -, - (CH2) n2 , - O - , - (CH2) n2 -, - O - (CH2) n2 , - O - , - (CH2) n2 - O -- (CH2) n2 , - (CH2) n2 , - (CH2) n2 -, - O - (CH2) n2 , - (CH2) n2 , - (CH2) n2 - O -n2 representing an integer from 1 to 3, R7, R7 ', R8, R8' desi-generating a methyl or phenyl radical, - divalent radicals comprising 2 alkyl groups-lenes having from 1 to 4 carbon atoms linked to a phenyl group lene by a valential bond or a grouping chosen in the group constitutes by the oxygen atom and the groups:

- CO -, - SO2 -, - CO-NH -, - NH -, -? -O -, . 21. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which R '''and R "" represent a radical chosen from the group made up of:
a) saturated aliphatic hydrocarbon radicals linear and branched having from 2 to 20 carbon atoms, b) saturated or unsaturated alicyclic hydrocarbon radicals having at most 6 carbon atoms in the ring, c) heterocyclic radicals, saturated or not, containing having at least one of the atoms O, N and S, and d) aromatic, monocyclic hydrocarbon radicals and condensed polycyclic and polycyclic aromatic radicals ques to several cyclic systems condensed or not, linked between them by a valential link or a group chosen from the group consisting of the alkylene and alkylene radicals having from 1 to 4 carbon atoms and the following groups:
- O -, - S -, - NH -, - COO -, - CO -, - CO- NL -, - SO2 -, - N = N -, - N =? -, - CO - NL - .DELTA. -, - CO - O - .DELTA. - O - CO -, in which .DELTA. represents a radical chosen from the group consisting of linear and branched alkylene radicals having less than 13 carbon atoms, the cycloalkylene radicals at 5 or 6 carbon atoms in the ring and the mono- arylene radicals or polycyclic and L represents a group chosen from the group consists of the hydrogen atom, the alkyl radicals having 1 to 4 carbon atoms and the phenyl radical, these aromatic radicals ticks being substituted where appropriate by methyl groups or chlorine atoms. 22. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which R '''and R "" represent a radical chosen from the group constitutes by:
a) saturated aliphatic hydrocarbon radicals linear and branched having from 2 to 10 carbon atoms, b) saturated alicyclic hydrocarbon radicals or not having 5 to 6 carbon atoms in the ring, c) heterocyclic radicals, saturated or unsaturated, comprising with 6 atoms in the ring and containing at least one of the atoms Y, N and S, d) aromatic, monocyclic hydrocarbon radicals and condensed polycyclic and polycyclic aromatic radicals than to several condensed cyclic systems or not, linked between them by a valential link, or a group chosen from the group consisting of alkylene and alkylidene groups having 1 to 4 carbon atoms, the oxygen atom and the groups following:

- CO -, - COO -, - SO2 -, - CO - NH -, . 23. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which R '''and R "" represent a radical chosen from the group made up of:
- tri or tetravalent radicals comprising 1 or 2 benzene nuclei linked together by a valence bond, the atom oxygen, methylene, isopropylidene, and - CO -, - SO2 -, and . 24. organosilicon compounds according to claim 1, 2 or 3 characterized in that they correspond to the general formula (I) in which T and T 'represent one of the functions following:

-? - O -, - NH-? -, - NH -? - O -, - NH -? - NH -, . 25. Compound according to claim 1 characterized in what it responds to is:

26. Compound according to claim 1, characterized in what it responds to is:

27. Compound according to claim 1 characterized in what it responds to is:

28. Compound according to claim 1 characterized in what it responds to is:

29. Compound according to claim 1 characterized in what it responds to is:

30. Compound according to claim 1 characterized in what it responds to is:

31. Compound according to claim 1 characterized in what it responds to is:

32. Compound according to claim 1 characterized in that that it meets the formula:

33. Compound according to claim 1 characterized in that that it meets the formula:

34. Compound according to Claim 1, characterized in that that it meets the formula:

35. Compound according to claim 1 characterized in that that it meets the formula:

36. Compound according to claim 1 characterized in that it meets the formula:

37. Compound according to Claim 1, characterized in that that it meets the formula:

38. Process for the preparation of poly- silicon compounds ethylenics having the general formula (I) (I) in which the various symbols represent:
- n, n ': identical or different integers from 1 to 3, - R, R ': monovalent organic groups, identical or different with an ethylenic double bond and comprising from 2 to 10 carbon atoms, - R1, R1 ': identical or different radicals, straight alkyls or branched substituted where appropriate by one or more halogen atoms or by one or more groups nitrile pements, aryl radicals alkylaryl; these latter aromatic radicals being substituted if necessary by one or more atoms halogen, - R2, R2 ': identical or different divalent radicals al-coylene, straight or branched alkylidene having 1 to 4 carbon atoms, - X, X ': divalent radicals, identical or different, made up of, or containing at least one heteroatom:
O, S or N; in this case the radicals X, X 'are attached assigned to radicals R2, R'2 via the heteroatom, identical or different organic radicals having from 1 to 30 carbon atoms chosen from the group consisting of:
a) divalent radicals: - G -, - G '-and trivalent radicals: , -? : an organic radical chosen from the group continued by:
a) (II) b) - T - R "- T '- (III) VS) (IV) d) (V) in formulas II to V:
- .beta., .beta. ' represent oxygen or nitrogen atoms - R "represents a valential bond or a radical divalent organic - R "'represents a trivalent organic radical - R "" represents a tetravalent organic radical - T, T 'represent functional groups identical or different taken from the group consisting of:

, , , , it being understood that in formulas (VI) and (VII), R3 represents has a hydrogen atom an alkyl radical from 1 to 6 carbon atoms, characterized in that we make react:
a) an organosilicon compound of formula (A) (AT) alone or combined with an organosilicon compound of formula (A ') (AT') with b) a coupling agent of formula (B) T1 -? -T1 '(B) in which - n, n ', R, R', R1, R1 ', R2', R2 ', X, X',?,? ' have them meanings given previously.
- Y and Y 'identical or different represent one of the following functional groups:
- - OH (VIII) - - SH (IX) - - N = C - O (X) _ (XI) - (XII) - (XIII) - (XIV) R3 to the meaning given for formulas (VI) and (VII) R10 represents a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms, -? represents a group , the radicals R "

R "', R""which have the meanings given for the formulas (III), (IV), (V), - T1, T1 'identical or different represent an ato-me of chlorine or one of the functions defined for Y and Y '. 39. Process for the preparation of organosilicon compounds according to claim 38 characterized in that Y and Y 'represent have one of the following functions:
- OH, - N = C = 0, R10 representing a hydrogen atom or a methyl group, R3 denoting a hydrogen atom. 40. Process for the preparation of organosilicon compounds according to claim 38 characterized in that T1 and T1 ' represent one of the following functions.
-OH, - N = C = O, R10 representing a hydrogen atom or a methyl group R3 denoting a hydrogen atom. 41. Process for the preparation of organosilicon compounds according to claim 38 characterized in that the agent coupling is a compound of formula T1 - R "- T1 '(B2) 42. Process for the preparation of organosilicon compounds according to claim 41 characterized in that T1 is identical to T1 '. 43. Process for the preparation of organosilicon compounds according to claim 38, characterized in that the coupling is a compound of cheese:

(B3) 44, Process for the preparation of organosilicon compounds according to claim 38 characterized in that the agent coupling is a compound of formula:

(B4) 45. Process for the preparation of organosilicon compounds according to claim 38 characterized in that one does react at least 2 moles of compound A with one mole of compound B.