Note: Descriptions are shown in the official language in which they were submitted.
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
-- 3
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
- 4 -
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~
- 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~
- 7 -
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~!~
-- 8
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
/ 0
:: 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 ~
- 9
carbon radicals E2 containing ~poxy group~, of t~e
f or~ula
o
2 3
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
- 10 -
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
- 12 -
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~
- 14 -
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
- 15 -
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 ~
- 18 -
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~%.
::
~: :
