CA2116569A1

CA2116569A1 - Process for the preparation of organosilicon compounds containing epoxy groups

Info

Publication number: CA2116569A1
Application number: CA002116569A
Authority: CA
Inventors: Christian Herzig; Doris Gilch; Johann Bindl
Original assignee: Individual
Current assignee: Wacker Chemie AG
Priority date: 1991-08-30
Filing date: 1992-08-27
Publication date: 1993-03-18
Also published as: DE59204444D1; DE4128894A1; CN1069980A; WO1993005051A1; MX9204608A; CN1032537C; EP0601008A1; ATE130614T1; EP0601008B1; JPH06505998A; ES2079885T3

Abstract

Organosilicium compounds that contain SiC-bonded organic residues with at least one epoxy group per residue are produced by epoxidizing organosilicium compounds that contain SiC-bonded organic residues with at least one carbon-carbon double bond per residue, with peracetic acid that contains acetic acid and catalytic amounts of strong acid, in the presence of organic solvents and acid-binding substances. The strong acid is bound with an at least equivalent amount of a base before epoxidizing with peracetic acid.
During epoxidizing, 0.4 to 0.8 val acid-binding substances per mole of the total amount of acid, including peracetic acid and acetic acid, are present.

Description

s ` ~
2116.;6~ ~
WO 93~05051 PCT/EP92/01982 Proces~3 for the preparat:lon of organo~ilico~ co~pound~
cont~ining epoxy group~

The in~e~tio~ relate~ to a proces~ for the preparatio~ of organo ilico~ compo~d~ which contain SiC-5 borlded orgarLic radicals having at lea~3t one epoxy groupper radical.
A proce~ for the preparatio~ o~ bicyclic ~erpene oxlra~eM by epox~ datioIl of u~aturated terpe.~ hydro-carbon~ wi'ch a p~raceti~: acid/acetic ac~d mixtur~, which 10 al~o contai~ ~mall amous~ts of ~ulfurlc acid, i~ the prese~cQ of chlori~ated hydro~arbon a~d 0 . 3 to û . 7 mol o a2~ al3cali metal ~:arbo~ate or 0 . 6 to ~ . 4 mol o ar alkali me'cal bicarbonate per mol o acid contellt of the perace'cic acid mixkure i~ }mown from D:E:-A 28 359 40.
15 According to E:xamp~ e 1, c~-pine~Le epoxide i8 obtained in a yield of 93~6 of theory by epoxidatio~ of a-p~s:Lene with peracetic acid i~ the preBe~ce of chlorofQrm and ~3odium c::arboT~ate .
A proce~s for the preparatio~ of epoxidel3, foa:
20 example at-pi~e~e epoxide,~ by epoxidat~orl of thQ olefi~
on whqch they a~e based with perac:~tic a~id containing Rtro~g acid~: i~ t~ preueslce of Bol~e~t~ for example chlorohydrocarbonE~, i8 described ill EP-B 55 3 87 ~or the . . .
: correspondin~: US-A 4,882,442), the ~trong acid, for ~: 25 example ulfuric : acid, being bo~ded with all inorga~ic baze before addition of the peracetia acid to the r~ac-tion mixture,; and the reaction mixture al~o containing, i~ additioIL to the corre~ponding olefi~, 0 . 50 to O . 74 eguivalents o~ acid-bi~ding agent, for example 3-Q ~3odium carbon~te or ~odium bicarbonal:e, per mol of! the total amou~t of peracetic acid ana acetic a~id. According to Example 1, a-pinene epoxide i~3 obtai~ed i~ yields of 9~9~ o~ t~eo~ by u~ing bu fered equilibrium peracetic acid and buf f ~ring 'che acetic acid duri~lg the epoac~ da-tio~, while ac~ording to Com~?ari~o~ Example 1, which wa~
; ~ ~ carried out by the proce~B of DE-A 28 35 940, that i~ to ~;ay t~e acetic acid wa~ buf f ered dur~ng the epoxida'cior~
}~ut ~on-buffered equilibrium perac:etic acid was employed, ~::

2116~6~

- 2 - .
~-pinene epoxide iB obtained in yields of 71%.
A proce~ ~or the preparation of organo~ilicon compound~ in w~ich e~?oxy groupQ or radicalE~ co~taining epoxy group~ are bonded to the ~ilicon atom by mea~ of a ~ilicon-carbon bond, by reaction of organo~ilicon compound~ conta~ny, ~n the molecule, at lea~3t one C=C
group bonded to the Si atom by a Si-C bond with peracid~, ~or e~eample perac~tic aaid, i~ lcnown from DE:-AS 1 061 321 (or the corre~ponding US-A 3, 455, 877) . Acc:ordi~g to 10 Example~ 3 to 6, the epox~ dation r~action~ are carried out with p~racetic acid in the prese~ce G~ ac~d-binding agent~ ~uch a~ ~odlu~ acetate, and the corxe~onding orga~o(poly)siloxane~ ha~ng SiC-bo~ded radical~ co~tal~-ing epo~y groups are obtained i~ yield~, when conv~r~ed, of 18 to 55~ of theory.
The epoxidation of a Yinyl~iloxa~ and an allyl-~ilane with peracetic acid i~ the preQe~ce of an acid-binding agent,~uch as sodium aaetate, i~ d~scribed in E.P. Pluedde~a~n et al., J. Am. Chem. Soc. 81, 2632 (1959~,:gel~1e~ ~partialo8 being obtained in the former ca~e and no epoxy~ilane be~ng obtained in the latter case, ~ince all~ths:allyl group~ ha~e been ~plit off fro~
~: the ~ilicon atom~u~dar the influence of the acid.
: Thare ~waB: therefore the object of pro~iding a :25 proceB~ for the~preparation of organo~ilicon compounds ~: which contain;:SiC-bonded organic radicalR ha~ing at lea~t one epoxy group per radical, in which the organo~ilicon compounds~are:~obta1ned in high yieldæ~ The object i~
achi~ed by the i~Yention. e The invention relates to a proce~ for th~
prepa$ation of organosilicon compound~ which contain SiC-: bonded~-organic rat~cal~ having at least one epoxy group per rad~cal by ~poxidat~on of organo~ilicon co~pound~
which contain~SiC-bonded organic radical~ having at least one carbon-aarbon double bond per radical with peracetic : ac~d which co~tai~8 acetic acid and catalyt~c amou~t8 o a ~tro~g acid, i~ the pre~ence o~ orga2ic ~ol~ent~ and ; a¢id-bi~ding agent~, character~zed in that the Btrong acid i~ bo~ded with at least an equi~alent amount o~ a 2116~69 base before the epoxidation with peracetic acid, and 0.4 to 0.8 egui~alent o~ acid-binding agent per mol of total acid compri~ing peracetic acid and acetic acid i~
employed during the epoxidation.
Solutions of peracetic acid in acetic acid which contain catalytic amounts of ~tron~ acid~, ~uch a~
indu~trial peracetic acid, are preferably u~ed or the epoxidation~ Per~cetic acid i~ preparea by reaction of acetlc acid with hydrogen peroxide ~n the pre~ence catalytic amounts of a ~trong acid. Indu~trial peracatic acid i~ ther~ore a miac'cure of peracetic acid, acetic a~ d, hydroge~ peroxide, water and a ~trong acid.
Sulfuric ac~ d i~ pref erably u~ed aR the ~troag acid, a~d iH pre~erably pre~e~t in amou~ts of 0.5 to 1~ by weight.
Indu~trial peracetic acid ~referably contai~ about 40%
by weight of perac~tic acid and about 45% by weight of acetic aaid, auch a~ ~ 3 obtained from the precur~or~ in indu~trially a~ailable ~oncentratio~.
:~ Examp~le~ o~:ba~e~ which are employed for neutral-ization of the; ~tro~g acid be~ore the epoxidation ar~
alka}i metal and aIkaline earth metal salt~ of ~cetic :~ acid, alkali metal ~ d alkaline earth metal carbo~ate~, alkali metal:~a~d: alkali~e earth metal bicarbonate~ and : alkali metal and alkaline earth metal hydroxide~. Sodium 2S a~etate-:is-preferably:~mployed in the pro e~ accordi~g to the i~ention.~The b~se i~ preferably added i~ solid ~: form.: ~owever, aqueou~ or conce~trated aqueou~ ~olUtio~B
~::: of the base c~an be:employed. 1 to 2% by weight of ~odium :: acetate i9 pre~ferably added.
The bu fered peracetic acid i8 prsferably . employed in the pro6e~B according to the in~e~tio~ i~
ameU~tB~. 0~ to 1.5 equivalent~ of peracetic aci~ per equi~ale~t Q doubl~ bond to be epoxidized.
: : Acid-~indi~g age~ts which are employed for ; 35 neutralizatio~ of the acetic acid duri~g the epoxidatio~
are pref~rably alka}i metal or alkali~ earth me~al carbonate~ or alkali metal or alkaline earth metal bicarbo~a~eG. Sodium carbonate or ~odium bicarbonate iB
: ~ : preferably employed. The acid-binding agent i~ preferably 2.1~ b'.5'-~ ~1 added in ~olid form.
The acid-binding agent ig preferably added in amou~t~ ~uch that the xeaction mixture ha~ a pH of 4 to 7 during the epox~dation. The acid-bindlng agent i~
preferably added in amount~ ~uch that 0.6 to 0.7 equiYa-lent of acid-b~nding agent are present per mol of total acid comprising peracetic acid and acetic acid.
Oxganic ~ol~ent~ which are u~ed ~n the proces~
according to the in~entio~ are preferably aromatic h~drocaxbons, ~uch a toluene, xylene or benzene, or chloroh~drocarbon~, ~uch as methylene chlsridQ, chloro-form, tr~chloroethylene or 1,1,1-tr~hloroeth~no. Th~
organ~c sol~ent i~ preferably:employed ~ amount~ of 80 to 160% by weight, based on the total wslght of the orga~o~i~icon compound employed for the epoxidation.
In the proce 8 according to the i~ention, the organo~ilicon compound to be rea~ted i~ preferably init~ally introduced into the reactio~ ~Qs~el, as a ~olut~on in the organic BOl~eIlt, the acid-bindl~g agent i~ added, the ~;mixture;i stirred ~igorou~ly and the ~: : : : buffered peracetic acid:is ~etered ln.
The~process accordiny to the in~ention i8 prefer-ably carried out at a temperature of 0C to 70~, prefer-ably 20C to 50~, at the pres~ure of the ambie~t 25: ; a~mo~sphere:, that~ to ~ay at about 1020 h~a (ab~olute).
owever, higher or lower préBsure~ can al~o be uYed in the proce~a according to the i~ve~tion.
The reac~ion time in the procesQ according to the in~entio~ i8 ~pre~erably 2 to 24 hour3~
~ 30 For working up the reaction mixture, watar i8 :~ preferably added~in an~amount neces~ary to dis~ol~e the inorgan~c ~alt~. The ~alt~, and alBo the acetic acid, are thu~ pre:ferably~wa~hed:out in agueou~ form a~d remo~ed by pha~s ~eparation. Preferably, the m~xture i~ then wa~hed : 35~ with a~ a ~eous ~olution of a~ i~organic ba~e, Quch a~
odium blcarbo~ats, to remove the la~ trace~ of acid.
T~e orga~c ~ol~ent i~ preferably remoYed by di~tllla-tion. In th~ procedure, water-containi~g ~olUt~o~B can advantageou~ly be dried azeotropically in the ~ame ~li6~S~

pxocess ~tep . Clouding caused ~y inorgani :: salt3 i~
removed7 if appropriate, by filtration.
Orga~o~ilicon c~ou~dEI which co~:Ltal~ SiC-boD.ded organic radical8 hav~ng at lea~t one epoxy group per 5 radical a~d are preferably prepared in the proces~
accordir~g to the i~re~tiorl axe tho~e of ths general ~ormula EaRbSi (OR ) c4- (a+b+c) (I) ~n which R deD,ote~ ide~t~cal or di~x~rLt, op'cis:~ally 10 halogenatQd hydrs~:arbo~ radical~3 ha~ri~g 1 ~o 18 ca~ o~
ato~ per rad~ cal, Rl denoteG identical or diff~rellt, monovale~t hydrocarbon radical~ havi~s7 1 to ô carbo~ atoms per radical and can be ~ 3tituted by a~:L ether oxyg~ atom, 15 l3 d~ote~ ~de~t~czl or dlfferer).t, ~ovalent SiC-bo~ded orga:r~ic radicalJ3 ha~ ing at lea t one epoxy group por radical, a i~ O or 1, o~ a~rQrag~ 0.01 to 1.0, : b i~ 0, 1, 2 ~or 3, on ~rage 0 . 0 to 3 . 0, C! i~ 0, 1,: 2 or 3, o~ av~rage 0.0 to 3.0, and the ~um: a+b+c s 4, O51 aYerage 1.0 to 4Ø
The o rgar~o~ con COmpOU~ldR prepared in the : proc:~ according~ to the in~rention are preferably ~ Lanes or orgarlo (poly) E~iloxanes .
: 25 Orgaao~ilicon compound~ which contairl SiC-bonded organic radi ::al~3: ha~ring at lea~t o~ epoxy gro~l? per radical a~d whi~h are particularly pre erably prepared in the proc~ according.to the inve~tio~ are 3i~an~s o th~
ge~eral- formula : E~aSi(OR )3-d (II) i~ which R, - ~ a~d ~ havs $he msa~ing gi~r~ above for 'che~e radtcala ~ a~d a i8 O, 1 or 2, or oryaxlo~poly) ~iloxaneE of the general formula ~ : :

2~16.~6~

~ ~ E.R3~SiO(SiR2o~(SiREo)~SiR3~E. (III) ,"~
`~` in which R and E have the meaning gi~en above for these radical~, e i~ 0 or 1, m i8 0 or an integer fro~ 1 to 1000 and n i~ 0 or an i~te~er from 1 to 200.
The oxganosilico~ compou~ds prepared in th~
proce~s according to the invention prearably ha~e a ~iscosity of 4 to 10,000 mml~s1 at 25C, p~eferably 4 tc 0 2, 000 mm~ 8-' at 25C.
Ex~mples of ra~icals R ar~ alkyl radical~, ~uch as tha m~t~yl, ethyl, n-propyl, iso-propyl, l-~-butyl, 2-n-butyl, iso-butyl, tert-butyl, ~-pentyl, i~o-pentyl, neo-pentyl a~d tert-pentyl radical, hexyl radical~, such a~ the n-hexyl radical, heptyl radicals, such a~ the n-heptyl radical, octy~ radicals, such a~ the n~octyl radical, and~i!o-octyl radicals, such a~ th~ 2,2,4-~ tr~ethylpentyl radlcal, nonyl radical~, ~uch as the n-: nony~ r~d~cal, decyl radical~, such an the n-decyl ; 20 rad~cal, dodecyl radicals, ~uch aB t~9 n-dodecyl radical, :and~octadecyl~radicals, such a~ the n-oct~decyl radical;
~:~ ; cycloalkyl rad~ calB ~ auch a~ the cyclopentyl, cyclohe ~ l and cyclohep~tyl:radicals and methylcyclohexyl radical~;
aryl radicalu, ~uch a~ the phenyl, ~apht~yl, anthryl aAd phe~anthryl radical; alkaryl radicals, such as the o-, ` : m-~and p-tolyl radicals, xylyl radical~ and ethylphen~l radicals; and~aralkyl radicalQ, 3uch as the benzyl radiaal a~d th~ - and ~-phenylethyl radical. The methyl radical iB preferred.
" Example ~of hal~ogenated radical~ R are halo~eno-alkyl ~r~dical~ uch a~ the 3,3,3-trifluoxo-n-propyl radi~al, tho 2,2,2,2',2',2'-hexafluoroi~opropyl radical : and the hepta~luoroisopropyl radical, and halog~oaryl r dical~, ~uch a~ the o-, m- and p-chlorophenyl radical.
Exa~ples of alkyl radical~ Rl are the methyl, : : ethyl, n-propyl, iso-propyl, l-n-butyl, 2-~-butyl, i~o-butyl and tert-butyl radical. Th2 m~thyl and ethyl radi al are preferred. ~xample~ of alkyl radicals X

2~165~

which are ~ tituted b}r an ether oxygen atom are ~hemethoxyethyl and etho~cyethyl radical.
The rad~cal~ E ha~ring at leaRt one epoxy group, that i~ to ~ay an epoxy group of t:he formula f f 5 are pre~erably built up only from carbon, hydrog~3n a:~d epoxy oxygen atomE~, if appropriate in additio~ ~o e~her oxygesl or carbo:~yl oxyg~n atoms or ~ ~ add~tion to eth~r oxygen ar~d carbonyl oxyger~ atom .
The ~adicals E: are pr~f~rably thoEle o:E th~a 10 forInula 2 ~ \ 3 4 R2C -- CR R - ~IV), R2e ~\~ R3 ~V) or 2 / \ 3 R2 ~ - CR ~ (~

i~ which R2 i~ identical or differe~t a~d denoteE~ a hydrogen atom or a mono~ralent hydrocarbon radical whi~h :~ ~: 15 ha~ 1 'co 10 carbon atom per radical and ean be æubat~ tuted by arl ether oxyge~ atom, ~3 denote a hydroge~ atom or a mo~ovale~t ~ydrocarbon radical which ha 1 to 10 carbon atoms per radical ~d ~a~ be ~ ti'cut~d by at leaE~t o~e ether oxygen ato~, ~: 2 0 R~ denotes a divaler~t hydrocarbo~ radical which ha~ 1 to 12 carbos~ ato~3 per radical and can be ~ tituted by al;
: ~ ~ leaat o~e ether oxygell atom a~d/or by at leaBt o~e carbonyl group, and R5 derlote~ a tr~.~rale~t hydrocarbon radical havi~g 3 to 12 2 5 carbon a'c~m~ per radical .
:E5x~mple~ of hydrocarbon radical~3 R ha~ring 1 to 10 :::

21 16S~!~

carbon atom3 per radical apply in their full ~cope to hydrocarbon radicals R~ and R3 ha~ing 1 to 10 carbo~ atom~
per radical. The hydrocarbon radical~ R~ and R3 are pre~erably alkyl radical~ having 1 to 10 carbon atoms per 5 radical.
Examples of di~alent hydrocarbon radicals R~ are linear or branched alkylene radical~ ha~i~g 1 to 12 carbon atoms per radical, ~uch as the m~thyl~ne, ethyl-ene, buty}e~e and octylene radical; cycloalkylene radi-cal~, cuch a~ the ethyl~e cyclohexylan~ radlcal; andarylene radical~, ~uch a~ the phenylenQ, xenylene and tolylene radi¢al.
Example~ of radical~ B o~ the ~onmula IV ara the 2,3-epoxy-3-methyl-butyl radical, 6,7-epoxy-7-meth~l-1~ octyl xad~cal, 3,4-epoxypentyl radical, 4,5-epoxyhexyl radic 1, 3, 4-epoxy-2, 3-di~methyl-butyl radical, 6, 7-epoxyoctyl radical and 4, 5-epoxy-4, 5-dimethyl-hexyl radical, pr~ferred ~xample~ being trialkyl-~ub~tituted : epo~y groupB E1 of the ~ormula :: R2 C.- C~R4' ~IV') : ~ ~ i~ which R2 denote a monovale~t hydrocarbo~ radlcal ha~ sg 1: to lO~ carbon atom~ per radical, preferably an alkyl radical havi~g 1 to 10 carbon atoms per radical, and R~' denotes;~;a;~d1~alent hydrocar~o~ radical ha~i~g 1 to 25 ~ 12 carbon a~o~s pèx radical, preferably a lineax or branched alkylene radical having 1 to 12 carbo~ atom~ per ~: ra~ical.
; Example~ jof epoxy grou~ E1 are th~ 2,3-epoxy-3-methyl-~utyl radical a~d th~ 6,7-epoxy-7-~ethyl-octyl 30 radical, the 6,7-epoxy-7-m~thyl-octyl radical b~ing preferred. Dl~iloxane~ contai~i~g 6,7-epoxy-7-methyl-octyl radical~::are particularly preferred.
: ~ Radical ~ of th~ formula V are preferably cyclic, bicyclic or tricyclic hydrocarbon radical~ ha~i~g ; : 35 3 to 12 ca~bon at~ms and containi~g epoxy groups, preferred radical~ being bicyclic or tricyclic hydro-1~

2 1 ~

carbon radicals E2 containing ~poxy group~, of t~e f or~ula o R C ~

I S' LRJ
I

i~ which R2 and R~ ha~re th~ ~ani~g given abo~ for these radical~ a~d Rs deno~Q~ ~ trl~alent cyclic or bl¢yclic hydrocarbo.
radical ha~rlg 4 to 12 carbon atom~ p~r radical, with th~
pro~ o that the ~ licon atom i8 bonded dirQctly to 'che ring ~ystem.
~3xam~1e~ oiE radi~a}~ E of th~ fo~llla V are c:ycloalkyl radical~ conta~ ni~g ~poxy groupa, ~uch a~ thQ
2~ ~3,:4-~poxy~yclohexyl)ethyl radi~al a~d t~e 5,6;9,10-diepoxycyclodod~canyl radi~al; a~d bicycllc or tricyclic hydrocarbon radical coDtai~i~g epoxy group, ~llch a~ the 2- (5,6-epoxy~orborna~-2-yl)~3thyl rad~cal~ the , 6 - ep4xynorbor~a~- 2 -yl radical and the 3, 4 ~

::
epoxytric~yclot5.2.1.0~ 6~decan-8~9) -yl radic:al (the ri~g Qy~tem here can b~ bonded to the ~ilicoIl atom ~ria the C8 or the C9 atom).
~; 20 A pr~err~d example of th~ radical E of th~
formula ~ iQ t h~ 5, 6-epoxy~orbor~an~ 2-yl radicaI aIld ~he 3, 4 - ~poxytricyc lo t 5 . ~ . 1 . o2 .~ d~s:an- 8 ( 9 ) -yl radi cal .
DiailoxaIles ha~ri~g S, 6-spoxyno~orcLan-2-yl ra~ical~3 or 3, 4~epox~tricYclo t5 . 2 ~1. o2.6~ de~a3a- S (9) -yl radical~ are 25 p~rtlc:ularly ~preferred.
; Exam~les of radlcalR E of the fonnula ~rI are th~
: :~
1, 2 - epoxy- 2 -propyl radical, 1, 2 - epoxybutyl radical ~ 1, 2 -:
epoxy-2~ethy~-propyl radical a~d 2,3-epoxy-3-m~th~ 2-bul:yl radical.
Organo~ilico~ COIDpOU~ldR which co~tai~ SiC-bo~ded organic 2:adical~ ha~ing at lea~ on~ carbo~-ca~on double 21165~9 bond per radical and are pref erably employed in the proce~ according to the i~ention are tho~e of th~
g~neral f onnula AfRgSi (OR ) h4- (~+g+h) (VI I ) 5 in w~ich :R a~d Rl haYe the meani~g giv~n above for th~a radicals, A denotes ideIltlcal or d~ ffere~:Lt mono~ralen'c SiC-bo~ded organic radical~ ha~ring at l~aE~t oIle carbon-carbo~ double bond, f iB O or 1, orl a~rerage 0.01 to 1.0, g ~3 O, 1, 2 or 3, on av~rage 0 to 3, h ~ ~3 0, 1, ~ or 3 ~ o~ ave~ag~ 0 to 3, a~d the aum a I b~c s 4, or~ a~rerage 1. 0 to 4 ., 0 .
Silane~ or organo (poly~ ~iloxa~eEI ars pre ~rably employed a~ orga~o~ co~ com~ound~ he procesl3 ~5 accordirLç~ to th~ i~ventio~.
Th~ orga~oE~lico co~npound~ which corltain SiC-bonded orgarl~:c radicals ha~irlg at l~a~t o~ carbon-car~on double bond per r~dical a~d are part~cular}y pref e~rably employed i~ the proe~e~ according t~ th~ lnvent~o~ ar2 ~il~e~ of the ge:n~ral fonnula AR~Si (~:)R~) 3 ~c (YIII ) i~ which R, Rl a~a A ha~re the me~ni~g gi~re2l abo~e for : ~ theae radical and k iz 0, 1 or 2, or organo (poly) ~ loxane~ of the general fo~ula AlR3 lSiO ~SiR~O) O (SiRAO~ ~SiR3 lA~ (IX~

iR w~ ~h R a~d A halve th6 meaning gi~ren above ~or the~e radicals ~
0 or 1, o i~ O or ~ integer fro~ 1 to lû00 and p iE~ 0 or a~ i~kQger from 1 to 200 .
The xadical~3 A ar~ preferably those o: 'che ~orm~l~

2116~9 R~ C=C~,3 _R4 _ ( X ), R2~ 3 (XI~

R~ C=CP~3 - ( XII ) in which Ra, R3, R4 and Rs hav~ the meaning g~en abovE3 for thes~ radical~.
Exampl~ of rad~cal~ A of the formula X ~re 5 radical~ ~:o~talnirlg a trialkyl~ tituted double boDld, ~uch a~ th~ 3 -~nethyl - 2 -buterlyl radical and the 7 -m~3thyl -6-oct~xlyl r~d~cal; radicals co~tai~Li~g dialkyl-~ubEt~u-ted doubl~ bos:ld~, ~uch a~ the 3-pe~toYlyl radical a~d t~
2,3-dim~thyl-3 butenyl radical; a~d radical~ cc~taisli~g 10 a kermirlal double bo~d, ~uch a~ the 5-hexenyl radical a~d the 9-dece~yl radlcal.
~ xample~ o~ radi~als A o the foxmula XI are ~yclic, bicyc~ ~ d tricy~lic h~drocarbo~ radicalR
co~taini~g doubl~ bo~ds, ~uch a~ cyclohexe~ylethyl radical~ a~d ~orbor~e~yl radicals.
~ :cample~ o radi~aI~ A o th~ formula XII ar~ the propen-2-yl r~diaal, the l-butenyl radical a~d th~
2-methyl-1-prope~yl radica}.
I~ respect o~ the rate o~ reactio~ ~url~g the epoxidation by the proce3~ accordi~g to the invention, it ha~ bee~ fou~d that trial~yl-~ubstituted double bo~d~ are epoxidized faater~than dialky~-~ub~tituted do ~ Ie bo~d~, a~d ~heæe in tu~ are epoxidizRd fa~ter than tenmi~al doubl~ bo~d~ t ha~ furthermore b~e~ ~ound that wit~ the aame olefl~ic radical A, 8ilane8 or di~iloxa~eP react faster ~han organo(poly)siloxa~ , but orga~o(poly)-~iloxa~e~ ~o~tai~i~g epoxy group~ are ~eYerthel~
: obtai~ed in h~gh y~ld~.
. The o~ano~ilico~ compou~d~ which co~tai~ 5~C-3Q bo~ded orga~c radioalR ha~i~g at lea~t o~e car~o~-carbo~
double bo~d: ~r radical are ~repar0d by addîtio~ of die~e~ onto organosilicon co~pound~ co~tai~i~g Si-~onded ~ydrogen atoms i~ ~he pre~e~ce of hydro~ilylatio~

2116~6~9 cataly~ts, ~uch a~ platinum c~mpound~ or platinum com-plexe3. Since ~-ole~in~ react more readily than cyclic or dialkyl- or trialkyl-~ub~tituted olefin in the hydro-~ilylation, the hydro~ily}ation take~ place with the 5 desired ~electi~ity. Vinylcyclohexe~e i~ thu~ hydro-~ilylated on the exocycltc double bond, while the remain-ing cyclic double bond react~ readily with peracetic acid. In the case of 7-methyl-1,6-octadie~, ~mooth hydro~ilylation on the terminal double bond (l-po~ition) and a very rapid epoxidation o~ the trialkyl-~ub~tituted doubl~ bond (6-po~itio~) i~ achie~ed.
Higher poly~er~ can be prepared by conda~ation from the organo~ilicon compound~ which contai~ epoxy groups and alkoxy grou~ and ar~ prepared in th~ proce~
a¢cord~ng to the in~ention.
The organo(poly)~iloxz~e~ which contain epoxy : group~ and are prepared by th~ proce~ according to the i~vention can ~e equilibrat~d with organopoly~iloxane~.
The ~ organopolyBilc)xa2leB with which the organo-:~ 20 polysiloxanes containing epoxy groups can bQ e~ullibrated are pref~rably tho~e ~cho~en from the group com~riE~i~g linear organopoly~iIoxan~ co~taining terminal tri-organo~iloxy~ group~, of the formula R~SiO (SiR~O) rSiR3 i~ which R ha~ the mea~ing given above for thi~ radical : and r i9 0 or an integer ha~ing a ~alue frQm 1 to 1500, linear organopoly~iloxa~e~ contai~ing terminal h~droxyl group~ o the~formula HO(SiR~03~H
~ , in w~ich R ha~ the meaning given above ~or t~iR radical : and is an :integer ha~i~g a ~alu~ from 1 to 1~00, : cyclic organopoly~ilvxane~ of the fo~mula (RlSiO) e ~ in which R ha~ the meaning give~ above for this radical '~

2 1 1 ~

and t i8 an integer from 3 to 12, and copolymers of un~t~ of the formula R~SiO and RSiO3ta in which R ha~ the meaning giYen above for thie radical.
The ra~io of the amount of the organopoly~iloxane employed i~ the eguilibration which i~ optio~ally carried out a~d the orga~o(poly)~iloxane containing epoxy group~
i8 determined m~rely by the de~lr~d co~te~t o~ epoxy groups in th~ organo~olysiloxa~e~ produced by the e~uil~-brat~on optio~ally carried out, aGd by the de~ired a~erage chain length.
Basic catalyBtB which promote th~ equllibratio~
are preferably employed in the equ~libration optionally carried out. Example~ of ~uch cataly~ts ara alkali metal hydroxides, ~uch a~ ~odium hydroxide a~d pota~Gium : hydroxide, trimethylbenzylammonium h~droxide a~d tetra-methylammo~ium~h~drox~de. Tetramethylammonium hydroxid~
i8 preferr~d. :~Basic cataly~t~ ar~ preferably u~ed i~
amount~ of:50 to 10,000 ppm (- parts per mi~lio~ by : 20 weight, preferably 200 to 1,0~0 ppm by we~ght, i~ each ca~e ba~ed on the~otal weight of the organopolysiloxanes :~
:: employed.
~ :The equilibration optionally carried out i~
; ~ ~ preferably carried ~out at lOO~C to 150C at the pre~ure of the ambient;atmo~phere, hat i~ to ~ay~ for example, : at 1020 hPa~(abBolutej. ~f de~ired, hows~er, higher or lower pres~ures:can aluo b~ used. The equilibration i~
optionally carr~ed out in 5 to 20% by weight, ba~ed on the~ total weig~t of th~ organopolyBiloxane~ employed, of : 30 a water-.immiacible 301vent, such a~ toluene. The catalyst can:be rendered inactive before the m~xture obtained i~
the equilibration iB worked up.
The proces~ according to the in~entio~ ca~ be :: carried out batc~w~e, z#mi-continuously or completely conti~uou~ly.
The organo(poly)~iloxa~e~ which contain epoxy group and are prepared by the proce~ accordi~g to the 2116~

in~entio~ can be u~ed for impregnating fiber~, that i~ to ~ay for textile fini~hing, and can be polymerized cation-ically .
Example 1:
175 g (O.S0 mol) of the addition product of one mol of l t 1 ~ 3,3-tetra~ethyldisiloxane and two mol of 4-~inylcyclohexe~e, 1,3-bis~2-(3-cyclohexe~yl)ethyl~-1,1,3,3-tetram~thyldisiloxane, are di~Rol~ed i~ 450 g of trichloroethylene, and 168 g o ~odium carbonate are add~d. 240 ~ of techn~cal grade perac~tic acid (corre~-pondi~g to 19.2 g of ac~i~e oxygen~, ~n which 4 g of ~odium acetate were di8~01ved ~hortly before th~
addition, are added dropwi8e to the mlxtur~ in the cour~e of one hour, whil~ cooli~g, a~d th~ r~act~on mixtur~ iB
heated at 35C to 40C for a further 6 hours. The non-di~sol~ed ~altB are di~Bol~ed i~ 300 ml of water a~d the : aqueou~ pha e i~ remoYed. The epoxide solution i~ wa~hed ~ twice with ;100 ~l of dilut~ (approxi~ t~ly 2% ~tre~gth~
;~ ~odium bicarboaate ~olut~lo~ each time and then conce~-trated at 100C at lOZO hPa (ab~olute) aad then at 100C
at 5 hPa (ab~olute).~18;7 g (98% of th~ory) o~ a co}orle oil haY~ng a ~i~co~ity of 38 mm~ at:25C are obtained.
The lH-NMR:~pectru~ of the product :l,3-bi~[2-(3,4-epoxy-cyclohexyl)~ethyl3-l,l, 3 r 3-tetramethyldisiloxa~e ~how~ a~
: :: 2:5 epoxide:content~of more than 96~, ba~ed o~ the oIefinic ; double bond~employed. The product ha an epo~y egui~alent weight ~f 197.
xample 2~
; ` 122 g of:tech~ical grade peracetic acid (corre~-ponding to 9~6 g ~f active oxygen) which co~tain~ 1.67%
by weight of aodium acetate are added dropwi~e to a mixture-^ o 95:.5 g ~0.25 mol) of 1,3-bi~(7-meth~1-6-octenyl)-l,l,3,3~-tetr~methyldiRiloxane, w~ich wa~ pre-pared by additio~ of 7-methyl-l,6-octadiene onto 1,1,3,3-:35 : tetramethyldi~iloxane, 200 g o~ tolue~ a~d 84 g of sodium bicarbonate at 25C to 30~C in the cour~e of o~e hour, whil- ~tirring and cooling. The mixture iB ~tirred at the ~ame temperature for a further 4 hours. The ~o~-~: dis~olved alt~ are di~ol~ed i~ 150 ml of wa~er and the 21165~9 aqueouM pha~e i8 remo~ed. The toluene ~olution i~ wa~hed twice with 50 ml of dilute (approximately 2% ~trength) ~odium bicarbonate ~olution each time~ The toluene ik distilled of~ a~d the re~idu~ of ~ol~ent axe removed 5 from the re~idue by di~tillation at 80C and 5 hPa (ab~olute). 103 g (g9% of theory) of a clear, colorle~
liquid ha~ing a viscoaity of 13 mm2 B-l at 25C are obtainf~d. Accordi~g to 'che ~H~ pectrum, the product, 1,3-bi~(6,7-epoxy-7-meth~locSyl) -1,1,3,3-Setram~thyl-disiloxa~e, containa le~ tha~ 1% of the amount of doublebond employed. The product ha~ an epoxide e~uivalent weight of 209.
Examplo 3:
272 g of an olefi~ically unsaturated c~opolymer of tr~methyl3iloxane and 2-(3-cyclohexe~yl)eShylmethyl-nil~xane unit~ having an iodine number of 127 and a Yi~cosity of 133 mm2/s at 25C are initially introduced into the r~action ~e~el together with 600 g of toluene and 252 g o~odium bicarbonatQ. 360 g of peracet~c acid, which contai~s 2:9~g o~ active oxygen and to which 6 g of ~odium ac~tate:ha~ bs~n admixed be~orehand, are added dropwi~e to~thi~ mixture at 35 - 40C i~ the courBe o~
:~ about 1 hour, while stirring thor~ughly. After a further : 18~ hour~ :at the Bame tempsrature, the NaOAc formed i~
:: 25 di~olved ~n 350 ml of water, a~d the organic pka~e i~
wa~hed with~150 ml of 7% strength ~odium bicarbonate : ~olutio~. The water ~till contai~ed in the mixture i~
r~moved under a~ ge~tle vacuum at about 45C, and the toluene i8 then~removed at 80C at 5 hPa (ab~olute3.
236 g of a clear, colorle~ ~ilico~e oil ha~ing a vi~co ity of 840 m~'/~j at 25C are obtained. Compari~o~
o~ the~-Rig~als of residual O
/
C~zCH- proton~ at 5.6 pp~ with the re~ulti~g -CH-C~-proto~ at 3.1 ppm in the lH-NMR spe¢txum ~how~ a co~er-Bio~ o~ 90% of theory7 The product, a~ organopoly~iloxan~
: of tr~methyl~iloxane and 2-(3,4-epoxycyclohexyl)~ethyl-: methyl~iloxane unit~ ha~ a~ epoxide equi~alent weight o~
238. The hydroxyl n ~ er of 0.15 ~howY that le~ than 0.1 mol % of all ~he epoxy groupB formed are opened by ~: :

2~16;~6~

hydroly~
Example 4:
The procedure o Example 2 i~ repeated, with the modification that 70.0 g (0.25 mol) of 96.5% pure (3.5%
of stereoisomer) 1,3-b~A(3-methyl-2-bute~yl)-1,1,3,3-tetramethyldisiloxane ha~ing an allylic C~ double bond are employed instead of 95.5 g (0.25 mol) of 1,3-bi~(7-methyl6-octenyl)-1,1,3,3-tetramethyldi~iloxane. 74.5 g of 1,3-bi~(2 t 3-epoxy-3-m~thylbutyl)-1,1,3,3-tetramethyl-di~iloxane are obtained a~ a colorles~, clear liquid haying a ~i~co~ity o~ 4.2 ~m2~ at 25C. According to the l~_NMR ~pectrum, 94% of the olefi~c double bonda ha~e reacted to form the~epox~de. No product corre~po~d-~: ing to acid hydrolyti~ r~ng-opening or ~plitti~g off of ~5 allylic ~ide chain were found. The product haa a~
epoxide equivalent weight of 162.
Bxample 5:
64 g (0.20~ mol) of 1,3-bi~(5-~orbornec-2-yl)-1,1,3,3-tetra~et~yldi~iloxane, which was prepared by addition of rbor~adiene onto 1,1,3,3-tetrame~hyldi-~iloxane, are mixed with 150 g o toluens and 84 g of odium carbonate. 122 g of tec~nical grade peracetic acid (corre~ponding~to~9.;6 g of actl~e oxygen), which co~tain~
1.67% by weight of;~odium acetate, are added dropwi~e to the mixture ~at 3~0C~ in the course of one hour, while tirring. The~mixture iB ~tir ed at 20C for a further 6 honrs.-The non-dissol~ed Balt~ are di~olYed in 150 ml of water and~ the aqueous pha e i8 removed. The tolue~e olution i8~ wa~hed twice with 50 ml of dilute (approxi-mately 2% ~trength) ~odium bicarbonate 801ution eachtim~.~The toluene i ~removed by distillation at 80C and 5 hPa ~ab601ute). 66 g of 1,3-bia(5,6-epoxynorbo~nan-2-yl)-1,1,3,3-te~tramethyldisiloxane ~re obtained a~ a colorlea~ oil ha~ing a ~i~co ity of 104 m~ at 25C.
35~ The lH-NMR ~pectru~ ~how~ no olefinic proto~s (detection limi~ about 1%). The product ha~ a~ epoxide equi~ale~t :: : . ~ :
~ ~ weight of 17~.

2~716~

Example 6:
The pro edure o~ Example 2 is repeated, with the modlfication that 144 g (0~50 mol) of 7-methyl-6-octenyl-triethoxy~ilane are employed instead of 95.5 g ~0.25 mol) of 1,3-bi~(7-methyl-6-octenyl)-1,1,3,3-tetrameth~ldl-3iloxane. 125 g of 6,7-epoxy-7-methyloctyltriethoxy~
~ilane, which ha~ a ~isco~ity of 4 mm~ at 25C, are o~tained. The 1~_NMR ~pectrum ~how~ a co~er~ion of more than 95%, the ethoxy group~ on the silane bei~g retained.
The B~ la~e ha~ a~ epoxide equivalent weight of 316.
Example 7:
99 g (0.25 mo~) of 1~3-bi~t2-(3~4-epoxycyclo-hexyl)ethyl~-1,1,3,3-tetramethyldi~iloxane ha~ng an epoxide equi~alent weight o 197, tho preparat~on of which ~ described in Example 1, are heated together with 962 g (2.6 mol) of decamet~ylcyclopenta~iloxane at 80C, while stlrring and under a nitrogen atmo~pher~. 3.9 ml of a 25% ~tre~gth~olutio~ of tetramethylammonium hydroxide in metha~ol are then~added to the mixtur~. The mixture i~
~t~rred at 80C;for ~ hour~, a~d then at 150C for o~e ~: hour to deact~ate the Qataly~t. The volat~le con~titu-e~t~ are ~ub~equently remo~ed by di~t~llation at 150C
: a~d S hPa (abBolute), and the r~idu~ i filtered. A
~: ~lear, colorless oil ha~ing a ~isco~ity of 120 mm2~ at : 25 25C :and an epoxide equi~alent weight of 2000 i5 obtained.
Example 8:
69~ g of the organopoly~iloxane of tr~methyl-iloxane~ dimethylsiloxane and 2-~3,4-epo~y~yclohexyl)-`30 ethyl-met~yl~iloxane unit ha~i~g an epoxide equivalent weigh~of ~80~,j the preparation of which i~ described in Example-3, are mixed with 500 ~ (1.35 mol) of decamethyl-cyclopenta~iloxa~e, a~d the mixture i8 hea~ed to 80C, while ~tirring~a~d under ~ nitrogen atmo~phere. 2.1 ml of a 25% ~tr~ngth soIution of tetramethylammo~ium hydroxid~
: i~ methanol:are added to the mixturs at 80C, and the ~ixtur~ ~R ~t~xred at 110C for 3 hour~. A further 1.0 ml o a 25% ~trength ~olution of tetrameth~lammonium ~: : hydroxide in methanol i~ then added, and the mixture i~
, :

~ G ~

0tirred at 110C for 3 hours. The reaction mixture i8 ~ub~equently ~tirred at 150C for one hour to deactivate the cataly~t. ~he volatile con~tituent~ ar~ remo~ed by di~tillation at 150C and 5 hPa (ab~olute), and the re~idue iB filtered. A clear, colorles~ oil having a ~i~c08ity 0~ 5,100 mm~ at 25C and an epoxide e~ui~alent weight of 3,840 ia ob~ained.
Example 9:
402 g of an olefinically un~aturated copolymer of trimet~yl8iloxa~e, dimethyl~iloxa~e and ~7-me~hyl-6-octenyl)-methyls~loxane unit~ having an ~odine ~mbex o~
59.8 and a ~i~co~ity of 117 mm~/~ at 25C are mixed thorouy~ly with 420 g of tolue~e ~nd 176 y of ~odium bicarbonate. 252 g of tschnlcal grade peracetic aci~
15 (corre~ponding to 20 g of acti~e oxygen), mixed with 4.~ g of ~odium acetate, ara metered ln at 35 - 40C in the cour~e of 1. 5 hour~ . The mixture i~ a~lowed to react ~ co~pletely overni:ght, and~245 g of water are then added~
A~tor separation :o~ the phaRes, the tolue~e phaBe i8 : 20 washed wit~ lO5~g~of~7% strength Na~CO3 ~olut~on, and the w~ter ~till contained~therein iB r~moved aS 45C under a light ~acuum.~fter concentrating a~ 80C a~d 5 hPa and ; filtratio~:, 363~ g~of a clear, colorle~ oil ha~ing a co ity of 175 mm~/~ at 25C are obtained. A co~ver~io~
2:5 of 91% of theory ca~ ~e ~een fro~ the 1~_NMR ~pectrum with~the aid of the integral~ for the olefinic proton of the ~tarting material and fo~ the epoxide-bonded proto~
of the product. The result~g organopoly~iloxane of trimeth~l3il0xane,~ dimethylsiloxane and ~7-methyl-6,7-epoxyoctyl)-methyl~iloxane unit~ ha~ an epoxide equiva-lent weight o~ 483 a~t a~hydrolytic rin~-openi~g rate of 1 eQQ than 0.2 mol~%.

::

~: :

Claims

Patent Claims I. Process for the preparation of an organosilicon compound which contains SiC-bonded organic radicals having at least one epoxy group per radical by epoxida-tion of an organosilicon compound which contains SiC-bonded organic radicals having at least one carbon-carbon double bond per radical with peracetic acid which con-tains acetic acid and catalytic amounts of a strong acid, in the presence of an organic solvent and an acid-binding agent, characterized in that the strong acid is bonded with at least an equivalent amount of a base before the epoxidation with peracetic acid, and 0.4 to 0.8 equivalent of acid-binding agent per mol of total acid comprising peracetic acid and acetic acid is employed during the epoxidation.
2. Process according to Claim 1, characterized in that the organosilicon compound which contains SiC-bonded organic radicals having at least one epoxy group per radical and is employed is one of the general formula (I) in which R denotes identical or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical, R1 denotes identical or different, monovalent hydrocarbon radical which have 1 to 8 carbon atoms per radical and can be substituted by an ether oxygen atom, E denotes identical or different, monovalent SiC-bonded organic radicals having at least one epoxy group per radical, a is 0 or 1, on average 0.01 to 1.0, b is 0, 1, 2 or 3, on average 0.0 to 3.0, c is 0, 1, 2 or 3, on average 0.0 to 3.0, and the sum a+b+c ? 4, on average 1.0 to 4Ø
3. Process according to Claim 1 or 2, characterized in that the organosilicon compound which contains SiC-bonded organic radical having at least one epoxy group per radical is a silane of the general formula ERdSi(OR1)3-d (II) in which R denotes identical or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical, R1 denotes identical or different, monovalent hydrocarbon radicals which have 1 to 8 carbon atoms per radical and can be substituted by an ether oxygen atom, E is a monovalent SiC-bonded organic radicals having at least one epoxy group per radical and d is 0, 1 or 2.
4. Process according to Claim 1 or 2, characterized in that the organosilicon compound which contains SiC-bonded organic radicals having at least one epoxy group per radical is an organopolysiloxane of the general formula E.R3.SiO(SiR20)m(SiREO)nSiR3.E. (III) in which R denotes identical or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical, R1 denotes identical or different, monovalent hydrocarbon radicals having 1 to 8 carbon atoms per radical which can be substituted by an ether oxygen atom, E denotes identical or different, monovalent SiC-bonded organic radical having at least one epoxy group per radical, e is 0 or 1, n is 0 or. an integer from 1 to 1000 and n is 0 or an integer from 1 to 200.
5. Process according to one of Claims 1 to 4, characterized in that E is a radical of the formula (IV), or (V) in which R2 is identical or different and denotes a hydrogen atom or a monovalent hydrocarbon radical which has 1 to 10 carbon atoms per radical and can be substituted by an ether oxygen atom, R3 denotes a hydrogen atom or a monovalent hydrocarbon radical which has 1 to 10 carbon atoms per radical and can be substituted by at least one ether oxygen atom, R4 denotes a divalent hydrocarbon radical which has 1 to 12 carbon atoms per radical and can be substituted by at least one ether oxygen atom and/or by at least one carbonyl group, and R5 denotes a trivalent hydrocarbon radical having 3 to 12 carbon atoms per radical.
6, Process according to one of Claims 1 to 5, characterized in that an alkali metal carbonate or alkali metal bicarbonate is used as the acid-binding agent.
7. Process according to one of Claims 1 to 6, characterized in that a chlorohydrocarbon or an aromatic hydrocarbon is used as the solvent.
8. Use of an organopolysiloxane obtained by means of the process according to Claim 1 or 2 or one of Claims 4 to 7, characterized in that the organopolysiloxane thus obtained, which contains SiC-bonded organic radicals having at least one epoxy group per radical, is used, for equilibration, with an organopolysiloxane chosen from the group comprising linear organopolysiloxanes containing terminal triorganosiloxy groups, linear organopoly-siloxanes containing terminal hydroxyl groups, cyclic organopolysiloxanes and copolymers of diorganosiloxane and monoorganosiloxane units.
9. Organosilicon compounds which contain SiC-bonded organic radicals having at least one epoxy group per radical, of the general formula (I') in which R denotes identical or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical, R1 denotes identical or different, monovalent hydrocarbon radicals which have 1 to 8 carbon atoms per radical and can be substituted by an ether oxygen atoms, E1 denotes a 6,7-epoxy-7-methyloctyl radical, a is 0 or 1, on average 0.01 to 1.0, b is 0, 1, 2 or 3, on average 0.0 to 3.0, c is 0, 1, 2 or 3, on average 0.0 to 3.0, and the sum a+b+c ? 4, on average 1.0 to 4Ø
10. Organosilicon compounds which contain SiC-bonded organic radicals having at least one epoxy group per radical, of the general formula (I'') in which R denotes identical or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical, R1 denotes identical or different, monovalent hydrocarbon radicals which have 1 to 8 carbon atoms per radical and can be substituted by an ether oxygen atom, E2 denotes an SiC-bonded radical of the formula (V') in which R2 denotes a hydrogen atom or a monovalent hydrocarbon radical which has 1 to 10 carbon atoms per radical and can be substituted by at least one ether oxygen atom, R3 denotes a hydrogen atom or a monovalent hydrocarbon radical which has 1 to 10 carbon atoms per radical, and can be substituted by at least one ether oxygen atom and R5' denotes a trivalent cyclic or bicyclic hydrocarbon radical having 4 to 12 carbon atoms per radical, with the proviso that the silicon atom is bonded directly to the ring system, a is 0 or 1, on average 0.01 to 1.0, b is 0, 1, 2 or 3, on average 0.0 to 3.0, c is 0, 1, 2 or 3, on average 0.0 to 3.0, and the sum a+b+c+ ? 4, on average 1.0 to 4Ø
11. Organosilicon compounds according to Claim 10, characterized in that they are disiloxanes of the general formula E2R2SiOSiR2E2 (III') in which E2 denotes a 5,6-epoxynorbornan-2-yl radical or a 3,4-epoxytricyclo[5.2.1.02.6]decan-8(9)-yl radical, and R denotes identical or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical.