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Патент USA US2407181

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Patented Sept. 3, 1946 '
2,407,181
UNITED STATES ‘PATENT OFFICE
2,401,181
‘
'
ARTIFICIAL waxes AND GREASES
Samuel Le Roy Scott, Wilmington, Del., asslgnor
to E. I. du Pont de Nemours 8: Company, Wil
mington, Del., a corporation of Delaware
, ‘ No Drawing, Application March 30, 1944,
Serial No. 528.770
8 Claims.
,
(Cl. 260—-2)
.
This invention relates to the reaction of a
2
'
The end of the reaction is indicated by the ces
polymerizable aliphatic monoole?nic hydrocar;
sation of ethylene absorption. When this point
bon with a silicon halide and to novel products
is reached, the reaction mixture is allowed to
cool, removed fromv the reactor, and the mono
meric silicon halide, e. e., silicon tetrachloride,
with any added inert organic solvents which may
resulting therefrom.
This invention has as an object the prepara
tion of wax-like polymeric products from a poly
merizable aliphatic monoole?nic hydrocarbon
have been employed, is removed by distillation.
and a silicon halide.
preparation of wax-like compounds from ethyl
The residue which is an organic material con~
taining silicon and chlorine‘ is greasy to wax-like
ene and a siliconhalide. Other objects will ap
10 in character, usually melting between 85° and
pear hereinafter.
The further object is the
,
a
110° 0., although lower melting products can be
-_
These objects are accomplished by the follow
obtained. ‘The reaction products produced by
ing invention wherein a polymerizable monoole
this reaction have molecular weights of between
?nic aliphatic hydrocarbon of from’ two to four
400‘ and approximately 4000, although slightly
carbon atoms is reacted with a silicon halide of 15 higher molecular weight products can be ob—
not more than twenty-one carbon atoms, having
tained when silicon tetra?uoride is employed. directly attached to silicon at least one halogen
The mixtures obtained by this reaction of the
atom of atomic weight below 90, i. e., selected
silicon halide and the monoethylenically unsatu
from the class consisting of ?uorine, chlorine,
rated hydrocarbon such as ethylene in the ab
‘and bromine.
2,0 sence of a Friedel-Craf-ts catalyst are not readily
The reaction is carried out in the absence'of'a
amenable to separation by distillation or other
Friedel-‘Crafts reaction catalyst and preferably
means into their component parts and the mix
ture can be employed per se, since it is probably
a mixture of functionally similar compounds.
In order that the process may be more fully
in the presence of a catalyst which is effective for
the polymerization of the monoole?nic hydrocar- '
bon and ine?ective in the Friedel-Crafts reac
understood, the following speci?c examples are
given by way of illustration. In the examples,
the parts given are parts by weight.
' tion.
The reaction of the silicon halide with the
polymerizable aliphatic ~monoole?nic hydrocar
bon, e. g., ethylene, to give wax-like products is
carried out in general as follows: A reaction ap
Example I I
paratus, a pressure reactor capable of being
A pressure reactor was charged with 78 parts
heated and provided with a means of agitation,
is equipped with inlet tubes for admitting a gase
of cyclohexane, 30 parts of silicon tetrachloride,
one part of hexachloroethane, and one part of
ous monoole?nic hydrocarbon such as ethylene, a
mercuric chloride. The reactor was flushed with
vent connected to a safety rupture disc, and a 35 nitrogen, closed, and pressured to about 150 at-‘
mospheres pressure with ethylene. The tempera
pressure gauge. The liquid charge, which con’
ture was then raised to 275° C. with a correspond
sists of a silicon halide such as silicon tetrachlo
ing increase in pressure within the reactor to
- ride, and usually small amounts ofa catalyst
(OJ-5%) such as ‘a peroxygen compound, e. g.,
approximately 900 atmospheres. Over a reac
diethyl peroxide, with or without inert organic
tionperiod of 16 hours, the pressure was main
solvents such as ,cyclohexane, is placed in the
tained at 900 atmospheres by occasional injection
of ethylene and during‘this period the total pres
pressure reactor. The reactor is then ?ushed
sure drop was about 175 atmospheres. The re
with nitrogen, closed, the contents agitated by a
suitable means such as stirring with an internal
actor was cooled, ethylene bled off, and the prod
stirrer or by agitation of the reaction vessel, and 45 uct which consisted of a solid suspended in the
ethylene is admitted. ' The pressure of ethylene
cyclohexane was obtained. This solid material
for the reaction with silicon tetrachloride is pref
was ?ltered and dissolved'in benzene, and the
’ erably between 600 and 1000 atmospheres and
benzene solution ?ltered. After ?ltration,‘ the
the temperature‘ at which the reaction is usually
benzene solution was heated to distill the unre
carried out is between 75 and 300° C. Pressures 50 acted silicon tetrachloride'and after about 3A of
of from 20 to'1000 or more atmospheres may be
the benzene had also been ‘distilled, the‘ re
used and the exact pressure and temperature em
mainder of the benzene was removed by steam
ployed-is dependent upon such factorsv as the
distillation and the product ?ltered from the wa
speci?c catalyst employed and properties desired
in the resulting product.
ter. After drying under reduced pressure at‘100"
55 0., the product, consisting of about 16 parts of
2,407,181 '
3
a soft, tacky wax, was found to contain about“
0.07% siliconnand had a molecular- weight of
about 487 as determined by elevation of the boil
ing point of a benzene solution. The waxy prod
uct melted at about 85° C.
cooled and the ethylene bled oil. The reactor was
then warmed and evacuated to remove unreacted
dimethylsilicon dichloride. There was obtained
seven parts of a waxy product (puri?ed by pre
cipitation from xylene/methanol mixture) which
contained 0.11% silicon and 1.10% chlorine. The
A similar reaction product was obtained when,
’ waxy product melted at 106-l09° C.
in place of the hexachloroethane and mercuric
The above described reaction, between silicon
chloride, 0.4 part of diethyl peroxide was used as
halides and an ole?n can be carried out with
catalyst under similar conditions.
10 any polymerizable aliphatic monoole?nic hydro
Example I!
carbon capable of being polymerized when treated
with a peroxygen catalyst. Although ethylene
A silver lined reaction vessel was charged with
undergoes the reaction with silicon tetrachloride
85 parts of silicon tetrachloride, 0.5 part of po
readily, other monoole?nic hydrocarbons having
tassium chlorate, and 0.1 part of manganese di
oxide. The reactor was swept free of air with a 15 from two to four carbon atoms and which pref
erably have a CH:=CH— (vinyl group) may be
current of nitrogen. closed, and ethylene admitted
used.
to the tube until a pressure of 150 atmospheres
In the process of this reaction there may be em
was obtained. The temperature of the tube was
ployed any silicon halide having at least one
then raised to about 200° C. and additional
ethylene added to bring the pressure to 900 at 20 halogen of atomic weight below 90, i. e., ?uorine,
chlorine or bromine directly .attached to siliconin
mospheres. The reactor was maintained at this
temperature for about 14 hours and ethylene was ' cluding (CrHsO) zslClz, C2H5OS1C13, (CH3) 281012,
SiCh, SizBro, SiBn, SlF4, SlFzClz, Sl(CI-Ia) C13,
occasionally admitted to maintain the pressure
_ SiHClc, S1(CH3)F3, SKGH'!) 2C12, CaHsCHaSiCla,
at about 900 atmospheres. At the end of this
(CuHsCI-Iz) 2S1Cl2,
SiHsCl,
period, the reactor was cooled and the unreacted 25 Si (CrHs) 2012,
(CcHt) aSlF, (CaHt) aSiCl, (C6H5CH2)3S1C1.
ethylene removed. The unreacted silicon tetra
chloride Was distilled from the reaction vessel by
Although the reaction of the present invention
attaching the reactor .to a vacuum line and re
can occur in the absence of substantial amounts
ducing the pressure to about 10 mm. The solid
of a catalyst, it is preferred to use a catalyst
product left within the reactor was rinsed with 30 which is effective for the polymerization of the
water and the water removed by ?ltration. The a
oleflnic hydrocarbon and which is ineffective as a
solid was dissolved in xylene, ?ltered, and meth-'
catalyst for Friedel-Crafts reactions, (1. e., alkyl
anol added to give a precipitate, which was then
ation or acetylation reactions). By way of ex
?ltered from the xylene/methanol mixture. The
ample, the following suitable catalysts may be
product after drying in vacuum consisted of 23 35 mentioned as effective for the reaction between
parts of a waxy material softening at 87° C. and
silicon halides and an ole?nic hydrocarbon such
melting at 104° C. when heated on a copper bar.
as ethylenezperoxygen compounds‘, e. g., diacyl
The product contained 0.55% silicon and 1.22%
peroxides such as acetyl peroxide, dibenzoyl per
chlorine.
oxide, and lauroyl peroxide; dialkyl peroxides
Example III
40 such as diethyl peroxide; other peroxides such as
When a reaction was run in a manner similar
ascaridole, cyclohexanone peroxides; ammonium
persulfate, perborate, and percarbonate; molec
cular oxygen; amine voxides, for example, tri
to that of Example II except that for the potas
sium chlorate manganese dioxide mixture, there
was substituted about 0.5 part of “Chloramine-T"
methylamine oxide; oxygen-containing com
Example IV
dibenzoylhydrazine, hydrazine dihydrochloride;
as catalyst, a product was obtained which softened 45 pounds such as manganese dioxide, perchlorate,
etc.; such metal alkyls as tetraethyllead and
at 85° C. and melted at 104-110‘ C. when heated
tetraphenyllead; ultraviolet light, especially in
on a copper block. This product contained 0.91%
the presence of such photosensitizers as mercury;
silicon and 2.06% chlorine.
-
50 N-halomines, e. g., “Chloramine-T"; and tetra
chloroethane. Combinations of some of these
A stainless steel pressure reactor was charged
compounds with other compounds, for example
with 80 parts of benzene and 0.3 part of benzoyl
with mercuric chloride, are also useful.‘ These
peroxide. The reactor was closed; evacuated. and
compounds or combinations are effective as cata
cooled by “Dry Ice.” There was then added 50
parts of silicon tetra?uoride and the reactor was 55 lysts for the polymerization of ethylene under the
pressured to 600 atmospheres with ethylene. The
conditions of temperature and pressure that are
necessary. In general, these catalysts have been
reactor was heated to 80° C. and ethylene injected
termed “telomerization catalysts" as described in
occasionally to maintain a pressure of 810-960
pending application. Serial Number 438,466. These
atmospheres. A pressure drop of 310 atmospheres
occurred during a period of about nine hours 60 catalysts are usually employed in amounts varying
from about 0.01 to 5.0% by weight as based on
after which the reactor was cooled and the ethyl
the silicon halide present. When molecular oxy
ene and unreacted silicon tetrailuoride were bled
gen is employed as a catalyst, its concentration
off. There was obtained 25 parts of a solid which
should be less than 1000 parts per million as
gave a waxy, brittle film. The solid product con
65 based on the polymerizable ole?nic hydrocarbon
tained 0.14% silicon and 1.2% ?uorine.
Example V
_
A stainless steel pressure reactor was charged
, with 0.5 part of potassium chlorate, 0.1 part of
manganese dioxide. and 25 parts of dimethylsili
con dichloride. Ethylene was introduced and
maintained at 850-950 atmospheres while the re
actor was heated to 198-201° C. At the end of
; nine hours, during which there was a total pres
employed.
,
'
To obtain the polymeric products of this in
vention the reaction is to be carried out in the
absence of a Friedel-Crafts reaction catalyst such
70 as a halide of an amphoteric metal, e. g., alumi
num trichloride, since the reaction in the pres
ence of a Friedel-Crafts type catalyst leads .to low
molecular weight, non-polymeric compounds
containing one unit derived from the silicon hal
sure drop of 105 atmospheres. the reactor was 75 ide and one from the oleilne.
'
2,607, 181
5
6
To obtain a sufllcient' concentration of polymerizable oleflnic hydrocarbon. such as ethylene;
it is necessary usually to employ superatmospheric
.
The wax-like polymeric products of this inven
tion are useful in the preparation of polishes such
as automobile polishes, floor polish, shoe polish,
emulsion floor polish, and other places where
pressure. Although pressures of 20-1000 atmos
pheres can be used for this reaction, the ultimate
pressure limit for the reaction is only that which
the equipment available will stand and accord
ingly pressures higher than 1000 atmospheres
camauba or similar waxes have found employ
ment. These waxes similarly are useful as modi
fiers for lubricating 011. paper coating, and‘im
pregnation as for example as a textile ?nish and
may be used. Pressure is used principally as a
similar applications. The higher molecular‘
means of obtaining su?icient concentration of 10 weight products can be fabricated‘ into self-sup
ole?ns at the temperatures desired. -
porting illms, etc.
‘
.
In a similar manner the temperature for the re
The above description and examples are in
action of silicon halides‘ with the polymerizable
tended to be illustrative only. Any modification
aliphatic monoolefi-nic hydrocarbons ' may be
thereof or variation therefrom which conforms
‘ varied within wide limits and is dependent usually 16 to the spirit of the invention is‘intended to be
upon the catalyst employed. For the majority of
cases, temperatures of 50° to 300° C. are employed.
For such catalysts as those having directly linked
included within the scope of the claims.
What is claimed is:
1. Process for the preparation of greasy to '
oxygen atoms such as the peroxy compounds, the
waxy, silicon-containing, polymeric materials
temperature range is usually 50° to 150° C. For 20 which comprises reacting ethylene with a silicon
halide containing not more than twenty-one car
molecular oxygen, hexachloroethane, chlorate
manganese dioxide mixtures, the temperature re
bon atoms and having directly attached to silicon
quired for catalytic action is usually between 125°
at least one halogen selected from the class con
and 300° C.
.
sisting of ?uorine, chlorine, and bromine, at 50—- '
Inert diluents such as isooctane, cyclohexane, 25 300° C. and a pressure of at least 20 atmospheres,
any catalyst present being a polymerization cat
benzene or similar aliphatic, cycloaliphatic or
aromatic hydrocarbons may be employed. It is
alyst ineffective in the Friedel-Crafts reaction.
preferred to use low boiling solvents which can
2. Process for the preparation of greasy to
waxy, silicon-containing, polymeric materials
readily be removed by distillation of the reaction
mixture. The reaction should be carried out‘ 30 which comprises reacting ethylene with silicon "
under anhydrous conditions to avoid hydrolysis
tetrachloride at 50-300° C. at an ethylene pressure ,
of the silicon halides. The compounds resulting
of at least 20 atmospheres, any catalyst present
from the polymerization of ethylene with silicon
being a polymerization catalyst ineffective in the
halides, e. g., silicon tetrachloride, are wax-like
Frieder-Crafts reaction.
materials having molecular weights between 400 35
may be obtained by adjustments in the propor- ‘
3. Process for the preparation of greasy to
waxy, silicon-containing, polymeric materials
which comprises reacting ethylene with silicon
tions of silicon halide and catalysts employed, and
tetrachloride at 50-300° C. at an ethylene pres- I
and 4000 although higher molecular weight values
‘
in choice of temperature and pressure, 1. e., the
sure of at least 20 atmospheres, any catalyst pres
concentration of olefin employed. In general, the 40 ent being a potassium chlorate-manganese diox
ide catalyst.
molecular weight .of the polymeric material is
increased by increasing the pressure, 1. e., increas
4. A greasy to waxy, silicon- and halogen-con
ing the relative concentration of ethylene. The
molecular weight is also increasedv by decreasing
the reaction temperature and/or decreasing the
catalyst concentration. Materials of higher
average molecular weights, e. 8-, up to15,000 may '
taining, polymeric product of the reaction, at 50
300° C. and a pressure of at least 20 atmospheres,
of a silicon halide containing not more than
twenty-one carbon atoms having‘ directly at
tached to silicon at least one halogen selected
. from the class consisting of ?uorine, chlorine, and
be obtained when silicon tetrailuoride is used. .It
is probable that small amounts of polymers of
bromine, with ethylene, any catalyst present being
ethylene are also formed during the silicon halide 60 a polymerization catalyst ineffective in the
ethylene reaction.
The products obtained by the above described
reaction are different from monomericaddition
Friedel-Crafts reaction.
'
5. A ‘greasy to waxy polymeric product of the
reaction, vat 50—-300° C. and a pressure of at least
products of silicon halides with an'ethylenically
_ 20 atmospheres, of silicon tetrachloride with eth
unsaturated hydrocarbon and also differ in 66 ylene, any catalyst present being a polymeriza
molecular weight and other properties from the
tion catalyst ineffective in the Friedel-Crafts re
polymerizable products of ethylene or other‘
action.
a
6. A greasy to waxy polymeric'product of‘the
absence of the silicon halide. It is probable that
reaction, at 50—300° C. and'a pressure of at least
there are produced in this reaction compounds 60 20 atmospheres, of silicon tetrachloride with eth
ylene, any catalyst present being potassium
of the general formula A<CH2CH2>11B in which n
monoole?nic hydrocarbons when prepared in the ,
is a plural integer and A and B together form a
silicon halide. In the case of the reaction em
chlorate-manganese dioxide catalyst.
7. Process. which comprises adding ethylene to
a reaction charge consisting of silicon tetrachlo
ploying ethylene and silicon chloride the product
comprises reaction products of the formula 66 ride, potassium chlorate and manganese dioxide
at a temperature of about 200° C. and maintain- ,
Cl(CHzCH2)nSiCla where n is a plural integer.
ing a pressure of about 900 atmospheres by the
Some of the halogens of such compounds are
addition
of further ethylene for about fourteen
probably removed when the reaction product is
hours.
'
subjected to mild hydrolysis, for example as dur
8. A waxy material containing silicon and chlo
ing puri?cation. ‘This type of reaction is called
rine softening about 8'7‘’- C. and melting vabout
"telomerization” and has been described inpend
104‘? C. obtained by the process of claim 7.
ing application, Serial Number 438,468. .
'
SAMUEL LE ROY SCO'I'I‘.
Certi?cate of Correction
‘
v
Patent No.‘_ 2,407,181.
Seiitember a, 1940.
SAMUEL LE ROY SCOTT
It is hereby certi?ed that error appears in the Yrinted speci?cation of the above
numbered atent requiring correction as follows: Co umn 4, line 22, for “(CH|),SiC1,"
read (0H, )pS’iOlz; and that the said Letters Patent should be read with this correction
therein that the same may conform to the record of the case in the Patent O?ice.
Signed and sealed this 19th day of November, A. D. 1946.
‘ [m]
_ LESLIE FRAZER,
-
_
First Assistant Oommissioner of Patents.
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