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Патент USA US2405988

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Patented Aug. 20, 1946
2,405,988
,UNITED STATES PATENT OFFICE
2,405,988
ORGANO-SILICON ESTERS AND MATERIALS
TREATED THEREWITH
Arthur J. Barry, Midland, Mich., assignor to
The Dow Chemical Com
corporation of Michiga11pany, Midland, Mich., a
1
No Drawing. Application December 10, 1943.
Serial No. 513,746
6 Claims. (Cl. 260—462)
This invention concerns certain new organo
silicon esters of organic carboxylic acids, which
esters contain, attached to the silicon atom, an
alkyl or an alkoxy radical having at least 8 car
bon atoms. It pertains especially to such esters
having the general formula:
wherein R in each instance represents a radical
2
and, apparently, with resultant chemical bond
ing of organo-silicon radicals to the hydrophilic
material. The surface of the latter is thereby
modi?ed and is rendered repellent to water.
However, in said copending application it is
taught that the hydrogen halide formed in the
treatment tends to act upon and weaken cellu
losic materials and that in treating the latter
with organo-silicon halides care should be taken
selected from the class consisting of hydrocarbon 10 to remove the hydrogen halide as soon as possible
so as to limit the destructive action which takes
and hydrocarbonoxy radicals and at least one R
represents such radical containing at least 8 car
'bon atoms and selected from the class consisting
of alkyl and alkoxy radicals, R’ represents a hy
place.
I have now found that the organo-siiicon esters
having the general formula hereinbefore men
tioned may similarly be employed for the treat
ment of hydrophilic solid materials to modify
the surface of the latter and render it repellent
is greater than 1, the radicals represented by the
to water. In such treatment the organo-silicon
symbols R may be the same or different and,
esters apparently react chemically with hydroxyl
when n is an integer less than 3, the radicals
represented by the symbols R’ may be the same or 20 groups at the surface of the hydrophilic material
to liberate an organic carboxylic acid and chemi
different. It also concerns the treatment of solid
cally af?x organo-silicon radicals to the hydro
hydrophilic materials with such organo-silicon
philic base member. However, the invention is
esters for purpose of modifying a surface of such
not limited to this theory as to the reason for
normally hydrophilic material to render it re
the result which is obtained. The water-repellent
pellent to water. The invention comprises the re
?lm which is formed at the surface of the base
sultant water-repellent solid products.
member is very thin, and the appearance of the
The organo-silicon esters having the above gen
base member is usually not altered. The water
eral formula vary from mobile liquids to wax
repellent ?lm thus provided on a normally hydro
like solids. They may be hydrolyzed with water
philic base member is absorptive to organic liq
to remove the ester radicals and form organo
uids. Paints, varnishes, lacquers, and the like
silicols which often undergo intermolecular con
usually adhere more ?rmly to such film than to
densation reactions to form viscous liquid or solid
the hydrophilic base member itself; hence, the
products of high molecular weight; or they may be
reacted with hydroxy compounds, e. g. alcohols, 35 latter may advantageously be provided with such
film prior to being painted or varnished.
phenols, or cellulose, to form corresponding al
The organo-silicon esters may be applied to a
koxy-siiicon derivatives of such hydroxy com—
variety of normally hydrophilic solid materials,
pounds. Accordingly, the new organo-silicon
drocarbon radical and n is an integer not greater
than 3. When in the above general formula n
e. g. iron and its alloys, magnesium and its alloys,
esters are useful as starting materials for the
other metals, wool, wood, cotton, or cellulose esters
preparation of a variety of derivatives thereof.
40 or others, etc., to modify surfaces of such ma
The organo-sillcon esters provided by the in
terials and render them water-repellent. Ap
vention are especially useful as agents jor the
parently all such hydrophilic materials have re
treatment of solid hydrophilic materials, par
active groups, usually hydroxyl and in some in
ticularly cellulosic materials, to modify the sur
face thereof and render such materials repellent 45 stances amino radicals, at the surface so that in
all such treatments a chemical reaction may oc
to water. In my copending application Serial No.
cur with resultant bonding of organo-silicon radi
513,745, filed concurrently herewith, it is disclosed
cals to the surface of the hydrophilic material
that organo-silicon halides may be applied to and
under treatment. That chemical bonding prob
reacted with the hydroxyl groups at the surface of
solid hydrophilic materials, e. g. metals, glass, 50 ably does take place is evidenced by the fact that
the treated material does not readily lose its
wood, or cellulosic substances, to modify the sur
Water-repellent properties when washed with
face of such normally hydrophilic materials and
solvents for the organo-silicon ester employed in
render them repellent to water. It is also pointed
the treatment.
out that during such treatment a chemical reac
The organo-silicon esters may be applied with
tion occurs with liberation of hydrogen halide 55
particular advantage to cellulosic materials such
2,405,988
as wood, cotton, cellulose acetate, or ethyl cel
lulose, etc., since the organic carboxylic acid
which is liberated by the treatment has little or
no detrimental action on cellulosic materials;
hence. special precautions for rapidly removing
the acid as it is formed are not required. For
this reason, the organo-silicon esters of this in
vention are superior to organo-silicon halides as
agents for treating cellulosic materials to render
nesium bromide with a silicon tetrahallde, e. a.
silicon tetrachloride. Usually an ether is used
as a medium for the reaction. The reactants are
preferably employed in approximately the stoi
chiometric proportions, and the product is puri
?ed by distillation. Alkoxy silicon halides may
be prepared by reacting an alcohol, e. g. octyl
alcohol or dodecyl alcohol, with a polyhalo-sili
con compound such as silicon tetrachloride, sili
10 con tetrabromide, diethyl-silicon dichloride, or
them water repellent.
phenyl-silicon trichloride. Such reaction usu
The requirement that the organo-silicon esters
ally occurs readily at room temperature or below
contain on the silicon atom at least one alkyl or
alkoxy radical having 8 or more carbon atoms is
and may be carried out nearly quantitatively by
heating the mixture, e. g. to 80-l00° C., after the
important, since I have found that the perma
initial vigor of the reaction has subsided. The
nence and durability of the water-repellent film
reactants are employed in proportions such as to
which is formed at the surface oi a. iwdrophilic
replace at least one, but not all, of the halogen
material when the latter is treated with such
atoms of the polyhalo-silicon compound with al
ester is largely dependent on the length of the
koxy groups. For instance, tridodecoxy-silicon
largest allryl or alkoxy radical attached to the
chloride may be prepared by reacting 3 molecular
20
silicon atom of the ester. For instance, a hydro
equivalents of dodecyl alcohol with one mole of
philic material such as cotton may be rendered
silicon tetrachloride and di-dodecyl-dodecoxy
water repellent by treatment with a lower organo
silicon chloride may be prepared by the reaction
silicon compound such as triethyl-silicon ace
of equimolecular amounts oi’ dodecyl alcohol and
tate, triethoxy-silicon acetate, tripropoxy-silicon
di-dodecyl-silicon dichloride. Usually, a solvent
25
acetate, tri-isopropoxy-silicon acetate, tributoxy
such as benzene, ligroin, or petroleum ether is
silicon acetate, or dimethyl-silicon dichloride,
used as a reaction medium and the mixture is
etc., but the water-repellent ?lm which is formed
cooled, e. g. to 10° C. or lower, in the early stages
is readily removed by washing, particularly with
soapy water.
of the reaction.
In contrast, the higher organo
The organo-silicon esters 01' this invention are
silicon esters provided by the invention, when 30 preierably
prepared by treating an organo-sili
applied to cotton or other hydrophilic materials,
con halide, having on the silicon atom an alkyl
form a far more permanent and durable water
or alkoxy group containing at least 8 carbon
repellent film which is not readily removed by
atoms, with a metal salt of an organic carboxylic
washing. Furthermore, when, after prolonged
use or extensive washing, the water-repellent film 35 acid and heating the mixture to a reaction tem
perature. Examples of organo-silicon halides
starts to fall, e. g. the hydrophilic base member
which
may be employed as reactants are octyl
becomes wetted in spots, the goods may again
silicon trichloride, decyl-silicon trichloride, di
be rendered uniformly water repellent by drying
octyl-sllicon dichloride, tri-dodecyl chloride, di
and washing them with an organic solvent such
myricyl-silicon dichloride, octyloxy-silicon tri
as benzene, toluene, carbon tetrachloride, ethyl 40 chloride, di-octyloxy-silicon dichloride, tri-octyl
ene chloride, or propylene chloride, etc. It ap
oXy-siiicon chloride, dodecoxy-silicon trichloride,
pears, therefore, that such ultimate failure of the
phenyl-octyl-dodecoxy-silicon chloride, di-dodec
water-repellent ?lm formed by the higher organo
yl-dodecoxy-silicon chloride, dodecyi—myricyloxy
silicon esters oi.’ this invention is not due to de 45 silicon dichloride, etc. In place of the chlorides
struction of the him but, more probably, to a
the corresponding organo-silicon bromides may
change in the orientation of the organo-silicon
be used. Among the various salts of organic
groups at the surface or the hydrophilic base
carboxylic acids which may be used as reactants
member and that the subsequent washing with
are sodium formate, potassium acetate, sodium
an organic solvent causes a re-orientatlon of such
groups so as to again render the treated ma
60
propionate, potassium butyrate. sodium valerate,
sodium crotonate, sodium oleate, sodium stea
rate, sodium benzoate, or sodium cinnamate,
etc. Salts of polycarboxylic acids may similarly
as to the reason for the results obtained. In
be used to form neutral organo-silicon esters
general, the permanence and durability of the
The salt is employed in amount at least
water-repellent ?lms formed at the surface of 55 thereof.
as great as that theoretically required to displace
hydrophilic base members increases with increase
the halogen atoms oi’ the organo-silicon halide
in the number of carbon atoms in the largest
reactant and it preferably is used in excess. Usu
alkyl or alltoxy radical attached to the silicon
ally, two chemical equivalent weights or more of
atom of the organo-silicon ester used in forming
the salt is used per atomic weight of halogen in
such ?lm and the organo-silicon esters contain
the organo-silicon halide reactant. In place of
ing such alkyl or alkoxy group having at least 12
the salts of the carboxylic acids, the free acids
carbon atoms are preferred for the purpose.
may, though somewhat less conveniently, be used
The organo-silicon esters may be prepared by
as reactants. One part by volume or more of an
the reaction 01' a salt of an organic carboxylic
inert organic solvent such as petroleum ether,
acid with a higher organo-silicon halide corre
iigroin, benzene, or toluene, etc., is preferably
sponding to the ester product desired. Methods
employed, per part of the organo-silicon halide,
terial uniformly repellent to water. The inven
tion is, of course, not restricted by this theory
for making organo-silicon halides are well known,
as a medium for the reaction, but the reaction
but, since many of the higher organo-silicon
may be carried out in the absence of such
halides used in preparing the esters are them
selves new compounds, the general methods for 70 medium.
The mixture is heated under re?ux, or in a
making the halides will be mentioned brie?y.
closed container, to a reaction temperature, usu
Alkyl silicon halides, e. g. octyl-silicon trichlo
ally of from 60° to 120° C., for a time su?lcient
ride or tri-dodecyl-silicon chloride, etc., may be
for completion of the reaction. Reaction tem
prepared by reacting an alkyl magnesium halide,
e. g. octyl-magnesium chloride or dodecyl-mag- 75 peratures below or above those Just mentioned
2,406,988
5
6
may be used. The reaction is usually complete
after from 10 to 20 hours oi’ heating at about
100° C. The product is then separated from the
sodium chloride, or other inorganic halide, formed
heating at said temperature was sumcient. The
mixture with an organic solvent such as petro-
vent was added prior to the ?ltration in order to
mixture was then filtered to remove the sodium
chloride formed in the reaction, after which the
solvent was distilled from the ?ltrate to obtain
in the reaction by usual procedure, e. g. ?ltration 5 the organza-silicon ester product as the residue.
or extraction oi’ the product from the reaction
In some instances a further quantity of the sol
leum ether or ligroin followed by vaporization
dissolve the ester product, but usually the quan
oi' the solvent from the product. By such procetity of solvent employed as the reaction medium
dure, a neutral organo-silicon ester may be 010- 10 was suil‘lclent to maintain the product in solu
tained in a concentrated, or substantially pure,
tion. Many of the organo-silicon ester products
form. In some instances, the product may be
thus obtained were further purified by fractional
further puri?ed by fractional distillation under
distillation, but some of the products were of too
vacuum, but many oi’ the organo-silicon esters of
high boiling point to permit distillation without
the present invention are high-boiling compounds 15 the occurrence of decomposition. In all in
which tend to undergo decomposition when fracstances. the products were obtained in a highly
tionally distilled.
concentrated form satisfactory for use in the
The following examples describe a number or
treatment of fabrics or other solid hydrophilic
ways in which the principle of the invention has
materials to render such materials repellent to
been applied, but are not to be construed as 11m. 20 water. The following table names the reactants
iting the invention:
employed in preparing each organo-silicon ester
Emu!“ 1
product, states the molecular proportions in which
they were used, describes the ester product. and
In each of a series of experiments. a higher
states whether the product is distilled.‘ Since
cream-silicon ester was prepared by heating a 25 many of the organo-silicon halides employed in
mixture of a sodium Salt 0! an Organ-l0 carboxylic
acid and a solution of an organo-silicon chloride
in an equal volume or more. usually about 1.5
preparing the ester products are themselves new
compounds, the table includes a statement as to
the kinds and proportions of reactants used in
parts by volume, of petroleum ether. or toluene,
making such halides. The procedures for making
under re?ux at about 100° C. until the forma- 30 the organo-silicon halides have been presented
lion and Precipitation of Sodium chloride was no
in the foregoing general description of the inven
longer observed. In most instances, 16 hours 01'
tion.
Table I
Reactants
Organo-silicon eater product
Organs-silicon halide
Run
No.
Salt
Prepared h-om—
Kind
Name
Moles
Kind
Compound
Tl'ldodeeo
sili-
‘
m... s.
Moles
Moles
sicil ............ ..
1
I inmates...
1* id d
3 imam
‘11-
3 { 20863.3...“
Li
id i‘
SlCh ____________ ._
1
Ti d d
I {Dodecyl alcohol...
3 isodmmmtate"
4
'
3“... Trl-octadecoxy
4 _____ Daillotznghlorlde.
—0C 8 ccoxy-
1 {Sick ____________ __
glcéi‘idecyl
alcohol.
4 ____________ ._
l }
d0
ill "“
4
‘ tugs;
slcli ............
still};._
i1 is“ -------- --
* { may-slim
'
dowry-aroma}
1 gg?fc‘ggyé??‘f;
silicon chloride.
mpmpyl gleam], v
}I imlio ......... --
4 { silicon
deccxy-propoxyacetate.
_
_
.'i__... 0ctadecoxy-do~
6___-_ Di-dodecoly 8115
1
Sick ____________ ..
l }
Dl-dodecyi alcohol
2
1
SIC]; ____________ ..
l }
1
SlCh ___________ ..
Myricyl alcohol."
3
1
SlCli _____ ._
l }
con dichloride.
7“... Dodecoxysilicou
trlchloride.
Dodecyl alcohol...
Tri-myric 10!?
silicon ch orldc.
9___._ Tri-oct loxy sili- }
._
0011 c iOridB-
.
10___. Di-dodeeoxy-iso-
rise-am l
amyl silicon
1
chloride.
Di-phenyl Silicon
phenyl silicon
l
chloride.
Trl-dodecyl slli-
con chloride.
13'
trlehlorldc.
Dodecyl di hen-
yi silicolii db}
chloride.
i5..,. Dodecoxy-di-
octyloxysilicon
chloride.
' "
3
-" '
"""""" "
do
'
d0
'“ ‘
4
'
'
‘
,. .do _________ ..
3
l
pggleg'éhk?f?'e‘
Sic!‘
1 {node'c?mniégiitl‘
.
Dina]?
chllorilqe'
' ‘my 5 1”“
1 Ddg’zhl?dgi n
giu‘inl’cmorf me‘
l
1
No.
y
Nearly
colorless
No.
liquid (light tan).
Anearly colorless
N0.
liquid.
Trimyriciloxy sili- A white warlike
No.
'l‘ri~octyloxy sill-
No, 96hr.
con acetate.
solid.
A liquid of light
amber color.
amylsiliconace-
3
phenyl
silicon
Tri-dodecy]
“"do """"" "
1
1 }
-"
.do
- ‘ - '
.
"
2' 5
I ..._do. __
1
1mm
Allquid of brown
reaction
0.
pcrlo
color.
A nearly colorless
No.
liquid.
acetate.
3
2
trichloride.
A ellow liquid.
Dodecoxy-di~
_...do ________ __
Dodccoxy silicon
4
late.
i
Sec-octyl alcohol. .
'
Octadeeoxy-do-
Di-dodccoxy-iso-
2
-° "u
No.
con acetate.
i
immoral’
mm. with de
A soft war of yel-
tri-acetateJ
{
"
Yes
Dl-octadecoxy-
Dodccoxy silicon
‘
4
“'
pale
N .
No.
con diacctateJ
w 7
of
a"
composition.
Trl-octadccoxysil- Awhitewaxol‘M.
icon acetate.
P. 413° C.
8 {Dl-dodeooxy sili—
do
‘ ----------- --
}
D ‘Km’
d l silicon }
l4. ..
1
1 }
dichloride.
gtédlecyl alcohol. , ,
d
'" ' o ****** "
trich oride.
Dodecyl alcohol. _ _
11- -- Dod?c?Xy-di12.. .
silicon
’’’’’ "
legngcgfggs
ill.
2 """"" "do“'"“"'‘
l t
a..."
Liquid
?lii’iltild’é.“
Product
distilled
Description
ISodiumstearate
sill-
3 { con acetate.
6
A liquid of pale
No
yellow color.
Adné'xiuiq
0; iir?' "mdo'm'mm N0‘
" Y 5"“
a
tale
and
CgeHuSiChCCHg.
Dodecyldi- henyl
2 { silicon alienate
(c. F. 0-5560).
Dodecoxy
di-
i [ stearatc.
octyloxy silicon
IProducts believed to contain compounds iormed by loss oi one or more acetate radicals.
A liquid of light
No.
A liquid of tan
No.
tan color.
color.
.
9,405,988
7
8
esters are somewhat more effective and more
Exmu:
stable against the action of soapy water than
are the ?lms formed by treating fabrics with
In each of a series of experiments, a strip of
cotton broadcloth, having a count of 80 x 160
threads per inch, was immersed for 10 minutes
in a solution containing 3 per cent by weight
of the organo-silicon ester named in Table II dis’
solved in a dry-cleaning liquid consisting of a
corresponding alkoxy-silicon esters.
Exmu3
A number of strips of cotton broadcloth, having
a count of 80 x 160 threads per inch, were treated
mixture of ethylene chloride and propylene chlo
with dodecyl-di-phenyi silicon acetate, or with
ride. The cloth was then pressed with a ?atiron 10 tri-dodecyl silicon acetate, and the treated fabrics
heated to about 250" C. until substantially free
were pressed with a heated ?atiron, as in Exam
of the dry-cleaning ?uid and thereafter for about
ple 2. However, the different pieces of treated
fabric were then subjected to washing procedures
two minutes to assure reaction of the organo
which were even more severe than those employed
silicon ester on the fabric. Different strips of the
treated cloth were subjected to di?erent kinds 16 in Example 2. One of the washing procedures
was the standard soap and water washing Opera
of washing operations, after which each was
dried, i. e. until substantially free of the wash
tion described on page 170 of the AATCC book of
“Standard Test Methods." Another procedure
liquor, and tested for water repellency by the
involved subjection of a fabric to extraction for
"hydrostatic” method described by Slowinske in
approximately 18 hours in a Sohxlet extractor
Am. Dyestuif Reporter 30 7 (1941). The kinds
while using the dry-cleaning ?uid mentioned in
of washing operations employed in the different
Example 2 as the extractant and then freeing the
fabric of the dry-cleaning ?uid and subiecting it
to said standard washing operation with soap and
tained 0.5 per cent by weight of soap (the hand
soap marketed as Palmolive was used) and (2) 25 water. A third procedure involved extracting a
fabric with the dry-cleaning. ?uid and then sub
subjecting the treated material to extraction for
jecting it to the standard washing operation with
18 hours in a Sohxlet extractor using the above
soap and water, as just described, and next again
mentioned dry-cleaning ?uid, i. e. a mixture of
subjecting it to extraction with the dry-cleaning
ethylene chloride and propylene chloride, as the ?uid for a period of about 18 hours in a Sohxlet
extractant. The purpose of the treatment with
extractor. A treated fabric, after being washed
the dry-cleaning ?uid was to ?nd whether said
by one of these three procedures, was dried and
?uid, which is an excellent solvent for the organo
tested for water repellency by the "hydrostatic”
silicon esters applied to the pieces of fabric,
method mentioned in Example 2. Table III
would extract from the latter the ingredient
causing it to be repellent to water. Failure of 35 names the alkyl silicon esters used for the treat
ment of fabrics in the different experiments and
the dry-cleaning fluid to destroy the water-repel
gives the water repellency of the treated fabrics
lent property of a fabric would be evidence that
experiments are named in the table and are as
follows: (i) a hand wash with water which con
after being subjected to the respective washing
the organo-silicon ester had reacted chemically
procedures just described. The water repellency
with the fabric. The table states the repellency
toward water of each treated fabric in terms of 40 is expressed in terms of the hydrostatic pressure,
in centimeters of water, which the fabric with
the hydrostatic pressure in centimeters of water
which the fabric withstood before leakage ocstood before leakage occurred.
Table III
H10 repellency of treated fabric alter
113,1)?
Orgsno-lillcon am:
am.
D cleaning dsufc‘?mg;
soap and
water
wash
fol wed by
at
water wash
dnmleantng
ma
d
std. soap and warm, ‘as;
1 ____ __ Dodecyl-di-pbenyi-silicon scetsta.
l4
l0
l6
2 .... ..
l0
i0
30
Trl-dodeeyl-sllicon acetate ..... _-
curred during the test of the fabric by the above
mentioned hydrostatic method.
From the above data it appears that the dry
cleaning ?uid has the effect of orienting the or
Table II
H10 repellency of treated fabric after
Rnn
or gene-silicon ester
0'
No wasb- Walling witl
“'8
Elia“???
MP’ ‘me’ cleaning uld
l- _ ._ _
Tri-octyloxy-silicon acetate ______ ._
11
Not tested . _
ill
2___..
Dodecylory-sillcon tri-acetate_-._.
18
1| _________ _.
35
3_._. .
DI-dodecylory-sillcon iii-acetate.--
l0
l6 _________ r-
34
4-.-. .
Tri-dodeeox
-si.llcon acetate ..... . .
19
ll _________ ._
34
5..." Dodeco
-d vphenyl-sllicon acetate
16
Not tested“
24
6__-__
eoyloxy-sillcon acetate...
21
20 ......... __
32
7---“ Dodecyl-di-phenyl-sllicon acetate _
23
Not tested"
34
a-.-“
32
.__..do ..... _.
38
'l‘rl-oc
Tri-dodecyl-silicon acetate _______ _-
From a comparison of Run 4 of Table II with
Run 8 and of Run 5 with Run '7, it will be noted
that the water-repellent ?lms formed on fabrics
gano-silicon radicals at the surfaces of the fabric
so as to increase the repellency toward water.
Other modes of applying the principle of the
by treating the latter with higher alkyl silicon 76 invention may be employed instead of those ex
9,406,988
9
plained, change being made as regards the step
or steps herein disclosed provided the step or
steps set forth by any 0! the following claims or
the equivalent of such stated step or steps be
10
2. An organs-silicon ester having the general
formula:
0
n.si( o-ii-n')...
employed.
wherein R in each instance represents an alkoxy
radical containing at least 8 carbon atoms, R’
1. An organo-silicon ester having the general
represents an alkyl radical, and n is an integer
not greater than 3.
formula:
0
m
3. Tri-octadecyloxy-silicon acetate.
I therefore particularly point out and distinct
ly claim as my invention:
( E
)
as o- —R' 0-‘
wherein R in each instance represents a radical
selected from the class consisting of hydrocar- n
4. An crgano-siilcon ester having the general
iormula:
0
R B1(o g R.)
"
_ "
"“
ban and hydrocarboncxy radical; and at least one
R represents such radical containing at least a
wherein R is an alkyl radical having at least 8
carbon atoms, R’ represents an alkyl radical and
carbon atoms and selected from the class con-
Me an integer not greater than 3.
sisting of alkyl and alkoxy radicals, R’ represents
5. Dodccyl-dl-phenyl-slllcon acetate
a hydrocarbon radical, and n is an integer not an
greater than 3.
6. Tri-dodecyl-sillcon acetate.
ARTHUR J. BARRY.
Disclaimer
2,405,988.—Arthm~ J. Barry, Midland, Mich. ORGANO-SHJCON Esme AND
MATERIALS TREATED Tnannmm. Patent dated Aug. 20, 1946. Dis
claimer ?led June 20, 1951, by the assignee, The Dow Ghemical 00m
pang].
Hereby enters this disclaimer from the scope of said patent: In claim 1,
esters of the formula given wherein the symbol R represents an alkyl radical;
claim 4 in its entirety.
[O?cz'al Gazette July 31,1951]
9,406,988
9
plained, change being made as regards the step
or steps herein disclosed provided the step or
steps set forth by any 0! the following claims or
the equivalent of such stated step or steps be
10
2. An organs-silicon ester having the general
formula:
0
n.si( o-ii-n')...
employed.
wherein R in each instance represents an alkoxy
radical containing at least 8 carbon atoms, R’
1. An organo-silicon ester having the general
represents an alkyl radical, and n is an integer
not greater than 3.
formula:
0
m
3. Tri-octadecyloxy-silicon acetate.
I therefore particularly point out and distinct
ly claim as my invention:
( E
)
as o- —R' 0-‘
wherein R in each instance represents a radical
selected from the class consisting of hydrocar- n
4. An crgano-siilcon ester having the general
iormula:
0
R B1(o g R.)
"
_ "
"“
ban and hydrocarboncxy radical; and at least one
R represents such radical containing at least a
wherein R is an alkyl radical having at least 8
carbon atoms, R’ represents an alkyl radical and
carbon atoms and selected from the class con-
Me an integer not greater than 3.
sisting of alkyl and alkoxy radicals, R’ represents
5. Dodccyl-dl-phenyl-slllcon acetate
a hydrocarbon radical, and n is an integer not an
greater than 3.
6. Tri-dodecyl-sillcon acetate.
ARTHUR J. BARRY.
Disclaimer
2,405,988.—Arthm~ J. Barry, Midland, Mich. ORGANO-SHJCON Esme AND
MATERIALS TREATED Tnannmm. Patent dated Aug. 20, 1946. Dis
claimer ?led June 20, 1951, by the assignee, The Dow Ghemical 00m
pang].
Hereby enters this disclaimer from the scope of said patent: In claim 1,
esters of the formula given wherein the symbol R represents an alkyl radical;
claim 4 in its entirety.
[O?cz'al Gazette July 31,1951]
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