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Патент USA US2405971

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2,4053%
> Patented Aug. 20, 1946
f'fU'N-prgp STATES PATENT OFFICE
' 2,405,971
1 HAIDGENATED roLxEmLENE’
, S Ambrose McAlevy, Kennett Square, Pa., assignor'
‘
‘_ to _E. I. du Pont de Nemours & Company, Wil
' mington, vDeL, a corporation of Delaware
.
. hlo Drawing- Application March 23, 1943.
.
‘Serial No. 480,211
f “1 Claim. (01. 260-94),
This invention relates to an improved process
used in the description and claims to reierto the
for the halogenation of; polymers from organic
compounds containing “mono‘ole?nic unsatura
polymers , from ethylene alone and also to the
tion, and is more-particularly,related'to an im
telomers of the above kind.
,
' In accord with this invention the polymers are
modified ethylene ‘polymers, interpolymers and
Proved processyfor the chlorination ofpolymers
from ethylene
-An object of
dissolved or suspended in‘ an organic solvent, pref
erably one which is substantially inertjand then
treated with an oxychloride of carbon ‘or sulfur,
in the presenceof light, with or without‘ the aid
the presentginventlonis to provide‘
I
_
_
an improved process for the halog'enation of ‘poly;
mers, derivedfrom ‘organic compounds having
monoole?nic unsaturation _ and which contain at
least one replaceable hydrogen-per structuralunit
10 of a catalyst, re. 2., a heterocyclic compound con
taining- annular nitrogen. Alternatively, the 're-'
and molecular weights in excess of‘ 300. Another
object is to provide-aprocess tor the chlorination
-.action may be catalyzed by the use, in lieu‘ of ‘light, .
of .monoole?nqpolymers; which , have, molecular
- oyl peroxide. The amount of catalyst either used '
of a peroxide catalyst such, for example, as benz
weights in excess o_f1'_300.“_ (Still another object is, 15 withlight or employed in the alternatereaction
to provide an improved process forchlorinating
can vary from 0.01 to 10% on the weight of the
oxychloride, generally the amount which has been
polymers » from, ethylene, ‘which- have I molecular
weightsinexcess of,--300.§,1,0ther' objectsand 'ad- ‘ found to give satisfactorily ‘good results is from
vantages of, the invention lwil'llhereinafter appear.
The polymers from ethylene which are halogen
ated in accord , with, this . invention include the
about 0.10 to 2%. ,.
20
In carrying out the invention by one practical
method, a solution or suspension ,of'the desired
solid to’ semi-solid ;high_,_mQ1ccular weight sub
stances ofa polymelic naturewhich are obtained
polymer and, if desired, acatalytic amount of a
heterocyclic compound containing annular nitro
(1),, by the. polymerizationtof l ethylene alone as .
gen, e. g., pyridine, is‘ charged into a ?ask ?tted
described in U. S. Patents 2,153,553 andv 2,188,465, 25 withv a re?ux condenser, a stirrer with a suitable
(2). by the polymerization of ethylene with other
seal to prevent escape of solvent, a thermometer,
polymerizable organic compounds, as described in
U.-S. 2,200,429, (3) bycontacting ethylene alone
and an oxychloride inlet. The reaction mixture
or in admixture with anotherpolymerizable or
C., with agitation, exposed‘ to a source of actinlc
is then heated,‘ preferably to between 50 and 130°.
ganic compound with molecular oxygen, a pcr-oxy, 30 light, and they oxychloride added portion-wise.
compound, a hydrazine or hydraziniumcompound
After completion of the reaction the chlorinated
or an amine oxide anda normally liquid, substan
polymervis isolated by means well known to the
tially inert reaction mediumI at a temperature in
art.
,
,
.
‘
'
The oxychlorides of carbon or sulfur ‘that may
therange of ,40f't0 400‘? C. andat a pressure in
excess of atmosphericxpreferably in‘ the range of 35 be used include phosgene, (C0012); oxalyl chlo
50 to 3000 atmospheres, or, (4,), ,by. reacting ethyl
ride, (C_0Cl)z; sulfuryl chloride, (SOzClz); and,
thionyl chloride, SOC12. In general, at least half
ene with a telogen to give, telomers; as described
a mole of the oxychloride is used for each hydro
in Jthecopending application Of Hanford 8: Joyce,
gen tov be replaced in the polymer. As a rule,
S.‘ N. 438,466, ?ledhprllllo, 1942,,an'd in, the co
pending application of; Hanford ,8: Roland, S. N. 40 however, it is advantageous to increase the
471,028, ?led January 1:1943.
I
e
-
The polymers of ethylene alone are either semi
amount of the oxychloride to one mole.
_
As a sourceof actinic, light there can be used
a high wattage tungsten ?lament light, a mercury
solid or solidat normal temperatures, correspond
vapor light, sunlight, carbon arc, ultraviolet lamp,
in composition substantially to (CI-12):, and have
molecular weights in excess of 1000. The proper-, 45 infrared lamp, or monochromatic light.
The apparatus may be of glass, enameled ves
ties of the polymers of ethylene with other‘ poly
sels, or corrosion resistant alloys.
merizablev organic. : compounds . vary depending
‘If desired the process may be carried out as a
> upon the nature oirethe polymerizable organic
compound and the composition of the polymer, ‘ continuous operation, for example,‘ vby injecting
The properties .of thetelorners depend inter alia 50 the oxychloride into a hot solution of the polymer
upon such factors as the nature of the telogen and
its reactivity, relative concentrations or telogen
and ethylene, temperature employed in the telom
erization, and nature of the catalyst.
?owing through an illuminated tube.
Suitable solvents include carbon tetrachloride,
tetrachloroethylene, tetrachloroethane, hexa
chloroethane, and the like. In place of these
The expression “polymers from ethylene” is” chlorinated aliphatic hydrocarbons there can be
9,400,071
3
4
used benzene, nitrobenzene, etc. If a low boiling
solvent is used it is desirable to conduct the chic
rination under pressure for this raises the boiling
point of the solvent and maintains the product in
solution.
The peroxide catalyst that may be used in ac
cord with the alternate procedure includes hydro
gen peroxide, persucclnic acid, lauroyl peroxide,
tetralin peroxide, urea peroxide, butyryl peroxide,
acetyl peroxide, diethyl peroxide, the alkali metal l0
and alkaline earth metal peroxides, or mixtures
. thereof.
Generally the products obtained from the poly
.
sulfuryl chloride and 40.5 parts of chlorine are
added and the mixture heated under re?ux, in the
light of a 800-watt tungsten ?lament, electric
lamp, at approximately"l'l° ‘C, for 60 minutes.
The reaction mixture is drawn on, drowned in
1500 parts of methanol to precipitate the chlori
nated polymer and after .decantation and ?ltra
tion the methanol is removed by treatment with
steam. The product analyses 47% chlorine and
0.56% sulfur.
.
The melt viscosity herein described is deter
mined by the following procedure. An aluminum
cylinder of %" internal diameter open at the top
is ?tted at the bottom with an 8 mm. steel disk
mers of ethylene alone are rubbery, flexible, and
tough with higher tensile strengths than the orig 15 containing at its center a 2.1 mm. ori?ce. The
cylinder and disk are heated to a temperature of
inal polymers. At 20 to 25% chlorine content the
190° C. and the product to be tested introduced
materials are tacky. The tensile strength of the
and heated to the same temperature. Above the
products increases very rapidly with increase in
surface of the product a piston heated to 190° C.
chlorine content. Above 30% chlorine, the sof
tening points reach the range of those of the 20 and ?'“ in diameter is superimposed and upon
it a weight is placed giving a. combined weight of
original polymers. The chlorinated polymers
from ethylene are in most cases soluble in arc
2.16 kilograms. The weight of product ?owing
matic hydrocarbons, in chlorinated aliphatic hy
drocarbons and in organic esters at ordinary tem
from the orifice in grams per minute is the meas
ure of the melt viscosity.
peratures.
25
Variation in the chlorine and the sulfur content
of the halogenated polymer is possible. It has
been foundv that if sulfur dioxide is introduced
Example 2.-25 parts of solid ethylenepolymer
having a melt viscosity of 0.1, is added to 500 parts
of carbon tetrachloride and the ‘resulting mixture
heated and stirred to effect solution. 57 parts of
sulfuryl chloride and 0.2 part of benzcyl peroxide »
throughout the reaction sulfur content of the re
sulting chlorinated polymer can be increased up 30 are added and the resulting mixture heated under
re?ux at a temperature of approximately 77° C.
to from 5 to 10%. It is likewise possible to aug
for 90 minutes. The carbon tetrachloride, sul
ment the chlorine content of the chlorinated poly
furyl chloride, and hydrochloric acid are steam
mer by introducing chlorine throughout the re
distilled from the reaction mixture, the reaction
action. Furthermore, both gases may be intro
duced if an increase in the sulfur and chlorine 35 product is separated. dried on a rubber mill and
is analysed. It contains 30.9% of chlorine with
content over that obtained by a given concentra
tion of the oxychloride is desired. Variation in . substantially no sulfur.
Example 3.—Fifty parts of a polymer of ethyl
the sulfur content of the product is also obtained
ene, having a melt viscosity of 0.1, is dissolved in
by the use of suitable reaction temperatures. In
general, the sulfur content of the product varies d0 1000 parts of carbon tetrachloride and to the solu
tion there is added 120 grams of sulfuryl chloride.
inversely, with reaction temperature over the
The resulting mixture is heated under re?ux and
range 10° to 80° C. It is often convenient to lower
irradiated during the reaction with a type H-4
the reaction temperature when the reaction is
only partly complete, for in the intermediate
ranges of chlorine content (10 to 35%) the resin
is su?lciently soluble, in carbon tetrachloride, to
permit lowering the temperature without precipi
100-watt mercury vapor lamp. After 140 minutes -
the product is steam distilled, and milled. It con
tains 34.4% of chlorine.
Example 4.—Eight parts ofan ethylene polymer
(average molecular weight 25,000-30,000) is dis
solved in 480 parts of boiling carbon tetrachlo
When phosgene is employed as the oxychloride
the reaction is partly one of chlorination, but in 60 ride, and one-half part of pyridine is added to
the solution. As the re?uxing solution is stirred
runs of 24 hours’ duration introduction of small
and is illuminated, 99 parts of sulfuryl chloride is
amounts of carbonyl groups into the resin occurs,
added drop-wise over a period of 70 minutes. The
and an infusible, insoluble product results.
tation occurring.
'
mixture is stirred for 2 additional hours. The
When the product of reaction between an oxy
chloride and an oleilne polymer‘is soluble in the 55 product precipitates out as a soft tally-like co
agulate. The carbon tetrachloride is decanted oil’,
reaction mixture, the. following procedure may
and occluded solvent, sulfuryl chloride, and hy
drogen chloride are removed from the product by
chloride and hydrogen chloride present after the
hot-water wash on a rubber mill. The dried prod
reaction may be removed by simple steam distilla
tion and the product, subsequently washed and 60 uct is ?exible and tough and is soluble at ordinary
temperatures in hydrocarbons and organic esters. '
dried on a mill, such as is used in compounding
It softens at 115° C, to 118° C. and contains 44.1%
rubber, or contrariwise the product dissolved in
be used for isolating it. y The solvent, excess oxy
benzene, carbon tetrachloride, dichloro di?uoro
of chlorine and 2.6% of sulfur.
Example 5.—Ten parts of the ethylene polymer
described in Example 3 is dissolved in 486 parts
of hot tetrachioroethylene, and one-half part of
pyridine is added. As the solution is stirred and
is maintained at 100° to 110° C., it is exposed to
actinic light, and 117 parts of sulfuryl chloride is
added slowly over a period of 90 minutes.‘ Stir
ring is continued-for 45 additional minutes. No
weight.
precipitate separates out, and the solution is
Example 1.—Twenty-i1ve parts of a polymer of
steam distilled to remove solvent, sulfuryl chlo
ethylene, having a melt viscosity of 0.1, is dis
ride, and hydrogen chloride.v The chlorinated
solved with heating in 500 parts of carbon tetra
chloride. Into the resulting mixture 15 parts of 7s polymer is washed and dried on a mill. It is
ethane, methylene chloride or other suitable sol
vent is precipitated therefrom by an aliphatic
alcohol or other liquid miscible with the reaction
medium employed but which is a non-solvent for
the chlorinated polythene produced.
The following examples illustrate preferred em
bodiments of the invention in which parts are by 70
2,405,971
5
tough, ?exible, and soluble at ordinary tempera
tures in hydrocarbons and organic esters. It
softens at 115° to 117° C. and contains 53.4% of
Example 10.-A solution of 15 grams of solid
ethylene polymer and 3 grams benzoyl peroxide
break. The original ethylene polymer is insoluble
The resulting resin. is somewhat similar to the
in 300 cc. benzene is kept saturated with phos=
gene at a temperature close to the'boiling point
chlorine and 0.7% of sulfur. A solvent-cast ?lm
3 mils thick has a tensile strength of 4,600 pounds 5 of the solvent. This mixture is irradiated with
per square inch and an elongation of 276%‘ at
a 300 watt tungsten ?lament lamp for 24 hours.
in cold solvents, and a solvent-cast ?lm 4 mils
ethylene polymer in appearance, but is infusible
and insoluble.
thick has a tensile strength of 1,580 pounds per
10
square inch and an elongation of 8% of break.
In place of the polymer set forth in the above
Example 6.—Ten parts of the ethylene poly
examples there can be used any polymer derived
mer of Example 3 is dissolved in 405 parts of hot
from an organic compound containing monoole~
tetrachloroethylene and one-half part of pyridine
?nic unsaturation and which contains at least one
is added. During the reaction the solution is il
replaceable hydrogen per structural unit, said
luminated with actinic light and is stirred vigor 15 polymer being further characterized by having a
ously at 100° to 105° C. Fifty parts of sulfuryl
molecular weight of at least 300. ‘ Speci?c exam
chloride is added over a period of 80 minutes.
ples of polymers which can be used in the prac
The solution is steam-distilled to remove the sol
tice of this invention include vinyl acetate, poly
vent and impurities. The product is washed and
vinyl chloride, polystyrene, polymethylacrylate,
dried on a rubber mill.
It is a soft rubbery ma
terial, containing 21% chlorine and only a trace
of sulfur, and soluble in hydrocarbons at room
20
polymethyl methacrylate, etc., the polymers of
vinyl chloride with either vinyl acetate, fumaric
esters, maleic esters, or vinylidene chloride; the
‘ polymers of ethylene with amylene, styrene, stil
. Example 7 .—Twenty parts of the ethylene poly
bene, vinyl acetate, methacrylic esters, ethyl
mer of Example 1 is dissolved in 960 parts of 25 itaconate, diethyl citraconate, diethyl maleate, di= boiling carbon tetrachloride, and 1 part of pyr
ethyl fumarate, acrylic esters, vinyl chloride, vinyl
idine is added. The re?uxing solution is illum
?uoride, chlorotri?uoroethylene, vinylidene ?uo
inated with actinic light, and 109 parts of sulfuryl
ride, vinylidene chloride, tetra?uoroethylene,
chloride is added slowly over a period of 90 min
maleic anhydride, vinyl butyl ether, eta; poly
utes. Stirring is continued for 30 minutes. The 30 mers of vinylidene chloride with acrylonitrile,
' temperature and in warm butyl acetate.
coagulated precipitate is placed in boiling water
vto remove solvent and impurities. After drying
in the air overnight the product is dissolved in
methylene chloride and the solution shaken vig
orously with powdered sodium bicarbonate to re
move last traces of hydrogen chloride. The so
methacrylic esters, tetra?uoroethylene, vinyl
chloride, etc., and methyl methacrylate, styrene,
or vinylidene chloride.
The products may be removed from the reac-
tion mixture and puri?ed by means already de
scribed or the reaction mixture may be injected
dium bicarbonate is removed by centrifugation
at the bottom of a vessel containing boiling water,
and decantation. Clear, colorless, transparent
whereupon the solvent and impurities will ?ash
?lms may be cast from the resulting solution. A
off or dissolve and the puri?ed polymer may be
?lm 1.’! mils thick has a tensile strength of 3549 40 skimmed off the top of the water. If the prod
pounds per square inch and an elongation of
uct is still in solution it may be precipitated from
308% at break. The product contains 41.4%
solution with alcohol or any liquid miscible with
chlorine and 3%’ of sulfur.
the solvent but not itself a solvent for the poly
Example 8.—To 5 parts of a liquid propylene
mer. The polymer may then be redissolved in
polymer having a. molecular weight of 318 is
a suitable solvent and similarly reprecipitated any
added approximately 0.’! part of pyridine, the
desired number of times. Drying may be' carried
mixture is stirred and irradiated with a 500 watt
out in the air or in a vacuum oven at a slightly
Mazda lamp while adding 5 parts of sulfuryl chlo
ride during a period of 15 minutes. The irra
elevated temperature.
diation is continued for an additional 45 minutes
and the reaction mixture is then poured into 500
parts of a 30% aqueous sodium hydroxide solu
tion. The product is extracted with ether and
dried over magnesium sulfate. The solvent is re
in wrapping ?lms, in coating and waterproo?ng
moved at reduced pressure, and the product is,
obtained as a yellow liquid. Upon analysis it is
found to contain 18.4% chlorine and no sulfur.
Example 9.—To a solution of 30 grams chloro
polythene (having a chlorine content of 30.3%)
in 500 cc. 0614, 30 grams oxalyl chloride is added,
and the mixture irradiated for three days at ‘17°
A process of chlorinating a polymer from eth
ylene having a molecular weight of at least 300
The chlorinated products are applicable for use
fabrics, as protective liners for acid or base con
tainers, in lacquers for wood, cement, or metal, as gaskets and washers, etc.
I claim:
1
'
obtained by polymerizing ethylene at a tempera
ture between 40 and 400° C. under pressures be
tween 350 and 3000 atmospheres and in the pres
ence of a catalyst selected from the group con
sisting of oxygen and peroxy compounds which
by means oi’ a mercury vapor lamp. The prod
comprises reacting the said polymer in solution
uct, which is’isolated by steam distillation of the
in carbon tetrachloride with sulfuryl chloride in
the presence of benzoyl peroxide and at a tem
solvent, contained 34.3% 01, 56.77% C, and 8.86%
B. This analysis shows that the predominating 65 Denture between 50 and 130° C.
1
reaction which occurred was chlorination.
AMBROSE McALEVY.
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