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Патент USA US3079438

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3,079,428
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metal to form an anion, the conjugate acid of said an:
having
The following
a pKa valueof
examples
at least,16.,
are given to illustrate
the in
vention. Parts mentioned are‘ parts by Weight.
...
'PURE‘ICATION OFORGANIC LIQUIDS
Massimo ,Baer, Longmeadow, and ,Mi'chael'F. Vignale,
,_ s,
_
Fatented ‘Feb, '26,
__ ,,_
,CONTAININGACID’IMPURITIES
.
Spring?eld;_Mass., assignors, top'Monsantp Chemical
‘EXAMPLE I
(Iompany, St. Louis; 70., a 'cnrpoi‘ation of Delaware
N0 Drawing. Filed ()ct.20,~1959, Ser. No. 847,472
6 Claims. (Cl. 260—486)
_ ,A suitable‘reaction
Preper's?qiofi’witying
vessel is chargedAgent
with BTOQparts
.
of
_ This invention relatestorinsoluble polymei'ic anionic
water, followed by addition of. 1 partof'bentonite with
agitation. The'slurry is heated to 65—70f’ ‘C., and}.
‘mixture of 50 parts of. vinyl fluorene, 4O partslof styrene,
materials. More particularly, .the invention relatesytto
.insolublepolymeric anionic materials which are ‘useful
asipiurifying agents for removing acidic impurities from
organic‘liquids.
_
_
.
_
,
v,
'10 parts of divinyl benzene, and'l part of benzoyl peroxide
.
is added thereto. The air in the-vessel is purged with
,Because of the sensitivity of anionic polymerization
nitrogen, and the pressurized vessel contents are heated
at 88+90° C. for '20 hours and then-‘at 1l5—120° C. for
‘systems to acidic, impurities, i.e., proton ‘donors, Which
destroy‘ or consume the growing'chaius and‘ initiator, sol~
vents and monomers to be employed in such polymeriza
12 ‘hours. The batch is cooled anddischarged into a
centrifuge where the suspension is collected 'andwashed
_tion_systems should be substantially, free'of impurities
.Wit hot water.. The polymer beads ,are‘dried in a forged
__dra'ft’air oven for 12 hours at 110-120“ 'C, and washed
aving apKa value lower than that of the monomers to
_'be. polymerized, i.e., impurities which are more highly
_with 'LZ-dimethoxYe'tha‘ne to form substantially pure
acid than the monomers, Many materials known to be
capable‘of reacting with the acidic impurities cannot‘ be
vused to purify the solvents, and monomers, ‘because, in
_ zene
‘A molar
(50':40:l0)‘terpolymer.
solution of sodium
.
naphthalene
.
>
t.
.
(in
v1_,i2:cl_i—
t.
order _to_ be suitable as a, purifying agent in this applica
tion a material must satisfy these general requirements:
‘. (1) _It ,must be capable of removing the acidic inipur
ities without contaminating the solvents and/or monomers
methox'yethane is passed through a ‘column containing
the polymer beads inorder to replace the active hy
drogen atoms of "the vinyl, ?uorenefu'nits withlso'dium.
The effluent from the column, a solution of diliydronaph
beads of cross-linked vinyl ?uoreneéstvreneidivinyl ben
with another impurity which'reacts with anionic initiators,
and
.
,
,
,
,(2) It must be inert to the Iiquid‘beingJpuri?ed, e.g., it
must‘ib'e'incapable of initiating polymerization of ‘the
monomer being-‘puri?ed.
.
,
l
,
thalene and sodium naphthalenein'LZ-dimethoXYethaiie,
.
30
t
tion indicates no further capacity of tthefpolymerlto react
'with'so'dium. The column of beads-is then washed with
I Asiusedvthroughout the speci?cation, terms referring
to acidity shouldjbe understoodas follows‘ in the's‘ense
of the de?nitions derived from the proton-transfer theory
of acids and bases:
,
V,
, t ,
35
.
substantially, all. of the vinyl-fluorenetunits of._.the,'_cross
base, a'base being any substance which, because 'of an
unshared electronpair, can accept a'proton, ,
40
_ (2) Conjugate acid-acid related *to'a‘pa'rticul'ar base
base,
M
;
,
_
.
(3); pKa value—negative logarithm of the dissociation
constant of an acid.
,
,> ,
_._t It will be noted that, whenunderstood in this sense,
the term “acid”_is not restricted to the inorganic, car
lboxylic, and, ,sulfonic compounds conventionally des
ignated as acids, i.e., compounds having low pKa ‘values
ofup to about 10, but also embraces compounds of much
higher pKa value.‘
7
v
t
-
_
.H_O_ne_ objectof this invention is toipr'ovide means for
purifying organic, liquids of acidic'impurities, i.e., im
purities having a pKa value lower than that of the organic
liquid, t
.
_1 'Another object is to provide means for purifying organic
iquids of acidic impurities without contaminating the
liquids with other impurities capable ‘of reacting with
anionic, polymerization initiators.
V ‘.A_ further-‘object is to provide'mean's for purifying
organic liquids of acidic impurities without causing'reao
tion of the liquid being puri?ed. ,
r l
_
t
_ :Th‘e'se and‘other objects are attained by purifying an
organic’ liquid 7 of acidic impurities by contacting the
liquid with an insoluble polymeric anionic material which
isinert .to the liquid, said anionic material being an alkali
metal'salh or'alkaline earth metal salt of an insoluble,
ero‘ssf-linkedpolymer containing anplurality ofunitslcap
‘able "of reacting with an ‘alkali metal or alkaline earth
~LZ-climethoxyethane to remove residual‘sodium naphthal
‘ene and dihydronaphthalene._ The product of thel‘tr'eat
ment is an insoluble polymeric anionic material in which
O. (1‘) Acid-product obtained byiadding ‘a proton‘to a
in‘ being the, product obtained by adding a proton to that
‘is ‘collected in areceiver. The 'treatment'of ‘the, polymer
with sodium naphthalene solution is continued until the
c'onc'entrationoof sodium naphthalene‘in thee?luent solu
linked vinyl ,?uor'ene-styrenejdivinyl ‘benzene’ (50:40:10)
‘ter'polymer
,_ The samehave
procedureIof
been converted
interpolymerizingjmonomers
'to theis'odium‘sjalt,
by suspensionpolymerization to form beads of'a cross
linked polymer and then reacting the beads ,with'an alkali
inetal‘naphthalene to form an insoluble vpolym'eric'anio'nic
material'is used'to' prepare the following salts;
, v
‘T
(1) ‘Sodium salt of a styrene-N,N-dia1lylacrylamide
(80:20)v copolymer in which substantially all of the ac
‘tive hydrogen'atoms ofthe N,N-diallylacrylamide units
have been replaced with sodium,
7
p
t
t v,‘
. (2) :Lithium, salt of a vinyl benz’yl alcohol-divinyl ben
zene (90:10,), copolymer in which substantially'all ‘of the
activehydro'gen atoms of the vinyl benzyl'alcohol units
have been replaced with lithium,
,
’
~ __ _
-
(3), Lithium salt of a styrene-vinyl indene-divinyl ben
Lz'ene‘ (6Q:30:_1O)jt_erpolyn1er in which'substantially ‘all 'of
the activejhydrogen atoms of the Vinyl inderie units have
been ‘replaced with lithium,
'
v
,
.
,
v
,
h ';(4).'Potassium salt of a styrene-vinyl,?uorenedivinyl
benzene (§0:30:l_()),te1'polymer in Whichsubstantiallyall
of‘the active hydrogen atoms of the vinyl ?uorene units
have been replaced with potassium, and
_ H.
,1 ‘(5) Potassium salt ofta p-aminostyrene-styrene-divinyl
il_:enze‘ne__(8"0: l0: l0)‘terpolymer in which substantiallyfall
of the active hydrogen atoms of the p-aminostyrene units
have ‘been replaced with potassium.
EXAMPLE ”II
Puri?cation of Organic-Liquids
‘organic liquids are puri?ed, using the indicated in
acre/res
3
soluble polymeric anionic materials of Example I as puri
tying agents:
Organic liquid
Purifying agent
Benzene ___________________ -_ Na salt of vinyl ?ucrene-styrene-diviny
benzene (50:40: 10) terpclymer.
cross-linking agent may constitute the only polymeric
1,2-dimethoxyethane _______ _- Na salt of styrene-N,N-d1allylacrylam
'
ide (80:20) copolymer.
_
benzene (90:10) copolymer.
component capable of reacting with an alkali metal or
.
Methyl methacrylate ______ __ Li salt of vinyl benzyl alcohol-divmyl
_ _
10 alkaline earth metal to form an anion.
_ _
with which alkali metal or alkaline earth metal is re
Butadiene _________________ __ K salt of styrene-vinyl ?uorene-divmyl
benzene (60:30:10) terpolymer.
acted to form the purifying agents of the invention is
_ _
that they be insoluble, cross-linked polymers containing
Isoprene ___________________ __ K salt of p-aminostyrene-styrene-d1vmyl
'
benzene (80:10:10) terpolymer.
In each case puri?cation is accomplished by passing the
organic liquid through a column of beads of the purifying
agent, andrin each case the effluent from the column is
an unreacted organic liquid substantially free of acidic
impurities.
EXAMPLE
Demonstration of E?ectiveness of Puri?cation
7
However, since the only requirement of the polymers
Styrene ____________________ __ Li salt of styrene-vinyl indene-divinyl
benzene (60:30:10) terpolymer.
4
which in the course of polymerization leave residual un
reacted allyl groups. These cross-linking agents are co
polymerized with one or more monoethylenically-unsatu
rated copolymerizable monomer-s which may, if desired,
also be monomers which, as a chemically-combined unit
of a polymer, contain active hydrogen replaceable with
alkali metal or alkaline earth metal. Alternatively, the
a plurality of units capable of reacting with alkali metal
or alkaline earth metal to form'an anion and that they
have a pKa value at least as high as 16, and since mono
mers capable of contributing such units containing active
hydrogen are already well known, various other poly
20 mers utilizable in preparing the purifying agents will be
obvious to those skilled in the art. The polymers usually
A suitable reaction vessel is charged with half of a
carefully-degassed solution of 100 parts of styrene in 980
parts of 1,2-dimethoxyethane, followed by the addition
with agitation of half of a substantially pure, carefully
degasscd solution of about 0.13 part of sodium naphtha
should contain about l-40%, preferably 5—25%, by
‘weight of units of the cross-linking agent and at least
about 10% by weight of units capable of reacting with
25 alkali metal or alkaline earth metal to form an anion.
l,2-di>methoxyethane, an inert atmos- '
They can be prepared by any suitable polymerization
technique, advantageously by suspension polymerization
of the monomers to form polymer beads, as demonstrated
in Example I, or by impregnating an inert carrier, e.g.,
lens in 20 parts of
silica gel, alumina, calcium sulfate, carbon black, di
phere being maintained in the vessel throughout the re 30 atomaceous earths, clays, etc, with the monomers and
action. The reaction results in a small yield of poly
then polymerizing to form a thin coating of polymer on
styrene.
a large surface of the inert carrier.
The second half of the carefully-degassed monomer
The purifying agents of the invention are prepared by
solution described in the previous paragraph is passed
reacting these insoluble, cross-linked polymers with a
35
through a column of beads of the sodium salt of the vinyl
metal of group IA .or HA of the periodic classi?cation of
?uorene-styrene-divinyl benzene (50:40:10) terpolyme'r
the elements, i.e., with Li, Na, K, Rb, Cs, Mg, Ca, Ba, or
of Example I. The e?luent from the column is charged
Sr, to replace the active hydrogen atoms of the polymer
to a suitable reaction vessel, followed by the addition
with metalrthus forming an insoluble polymeric anionic
with agitation of the second half of the substantially
material. This reaction can be accomplished by contact
40
pure, carefully-degassed initiator solution, an inert atmos
ing the polymer in any suitable manner with a‘ solution
phere being maintained ‘in the vessel throughout the re
or dispersion of the metal in an inert liquid medium or,
action. The' reaction results in substantially quantita
more efficiently, by contacting the'polymer with a solution
tive conversion of styrene to high molecular weight poly
or dispersion in an inert liquid medium of an organo
metallic compound of the metal whose conjugate acid is
styrene.
The present invention relates to novel insoluble poly 45 weaker than that contained in the insoluble polymer. Ad
meric anionic materials and to their use as purifying agents
vantageously, the polymer is reacted with the metal by
for organic liquids containing acidic impurities.
.
contacting it with a solution of an ion-radical adduct,
The insoluble polymeric anionic materials are the alkali
c.g., sodium naphthalene, in a polar solvent ‘such as 1,2
metal salts and alkaline earth metal salts of insoluble,
dimethoxyethane, as demonstrated in Example I.
cross-linked polymers containing a plurality of units capa 50
The treatment of the/polymer with the metal-containing
ble of reacting with an alkali metal or alkaline earth
metal to form an anion, the conjugate acids of said salts
having pKa values of at least 16.
composition is preferably continued until the capability
Exemplary of known polymers which can be reacted
with the maximum number of possible sites for subsequent
of the polymer to react with the alkali metal or alkaline
earth metal is exhausted in order to furnish the polymer
with alkali metals or alkaline earth metals to form the 55
purifying agents of the invention are copolymers of vinyl
toluene, vinyl 'isopropyl benzene, vinyl benzyl alcohol,
peacetylstyrene, p-aminostyrene, vinyl pyridine, ethyl
reaction with acidic impurities contaminating the organic
liquids to be puri?ed. However, this exhaustion of the
capability of the polymer to react with alkali metal or
alkaline earth metal is obviously not required to make the
eniminc, or other polymerizable compound which, as a
polymeric anionic ‘materials effective as’ purifying agents,
chemically-combined unit of a polymer, contains an ac 60 particularly when the polymer contains a large number
tive hydrogen replaceable with alkali metal or alkaline
of units capable of reacting with alkali metal or alkaline
earth metal, or mixtures of such compounds, with one
earth metal. After completion of the treatment of the
or more cross-linking agents such as divinyl benzene, di
insoluble polymer with the alkali metal or alkaline
vinyl toluene, divinyl xylene, divinyl ethylbenzene, diiso
propenyl benzene, trivinyl benzene, divinyl naphthalene,
trivinyl naphthalene, polyvinyl anthracene, etc., and op
tionally with one or more other interpolymerizable mono
mers, e.g., vinyl ethers, styrene, etc.
Other known polymers utilizable in preparing the puri
earth metal, the polymeric anionic material is preferably
65 washed with an inert solvent, e.g., liquid ammonia, to re
move unreacted metal, metal compound, or residue of
metal compound.
The insoluble polymeric anionic materials of the in;
vention are e?ective as agents for purifying organic
tying agents of the invention are copolymers in which 70 liquids of acidic impurities. The invention is particularly
the cross-linking agent, as a chemically-combined unit of
applicable to the puri?cation of organic liquids to be em
a polymer, contains active hydrogen replaceable with
ployed in anionic polymerization systems, e.g., anionical
alkali metal or alkaline earth metal. Such cross-linking
ly-polymerizable vinylidene monomers such as styrene,
agents are, for example, p-diallyl benzene, diallyl mela
vinyl toluene, 0-, m-, and p-methoxy-styrenes, butadiene,
75
mine, N,N-diallylacrylamide, allyl silancs, and the like,
3,079,428
5
isoprene, methyl methacrylate, etc., or solvents such as
benzene, hexane, tetrahydrofuran, 1,2-dimethoxyethane,
What is claimed is:
1. A process for purifying an organic liquid of more
etc., but it can also be applied to the puri?cation of any or
highly acidic impurities which comprises contacting the
ganic liquid which is contaminated by impurities having
liquid with an insoluble polymeric anionic material which
a pKa value lower than that of the liquid.
5 is inert to the liquid, said anionic material being a salt of
Puri?cation of the organic liquids is accomplished by
a metal of the group consisting of alkali metals and al
contacting the liquid with the purifying agent in any suit
kaline earth metals with an insoluble, cross-linked polymer
able manner, advantageously by passing the liquid through
containing a plurality of units capable of reacting with
a. column of beads of the purifying agent, as demon—
said metal to form an anion whose conjugate acid has a
pKa value at least as high as 16.
2. A process as in claim 1 wherein the organic liquid
is an anionically-polymerizable vinylidene monomer.
strated in Examples 11 and 111. After being used to puri
fy an organic liquid, the insoluble polymeric anionic ma
terial can be regenerated by repeating the metal treat
ment used in preparing the purifying agent.
3. A process for purifyirig methyl methacrylate of
Since the various organic liquids which can be puri?ed
more highly acidic impurities which comprises contacting
of acidic impurities by the insoluble polymeric anionic
the methyl methacrylate with a lithium salt of an insoluble,
materials of the invention have varying degrees of reac
crossalinked vinyl benzyl alcohol-divinyl benzene co—
tivity with anionic materials, care must be taken in the
polymer.
choice of a purifying agent for a particular organic liquid
4. A process for purifying styrene of more highly acidic
to insure removal of the acidic impurities without causing
impurities which comprises contacting the styrene with a
undesrable reaction of the liquid. The suitability of a 20 sodium salt of an insoluble, cross-linked vinyl ?uorene
particular insoluble polymeric anionic material as a puri
styrene-divinyl benzene terpolymer.
fying agent for organic liquids can readily be determined
5. A process for purifying butadiene of more highly
by routine experimentation, and in many cases this de
acidic impurities which comprises contacting the butadiene
termination of the suitability of the anionic material is
with a potassium salt of an insoluble, cross-linked styrene~
facilitated by the fact that the reactivity or lack of re 25 vinyl fluorene~divinyl benzene terpolymer.
activity of many of the organic liquids with anionic ma
6. A process for purifying isoprene of more highly
terials of varying pKa values is already known. For
greatest e?iciency in removing acidic impurities, the puri
with a potassium salt of an insoluble, cross-linked p—
fying agent should have as high a pKa value as is con
aminostyrene-styrene-divinyl benzene terpolymer.
acidic impurities which comprises contacting the isoprene
sistent with the requirement that it be inert to the organic 30
liquid being puri?ed.
The invention is particularly advantageous in that it
provides novel insoluble polymeric anionic materials
which, when used as purifying agents for organic liquids,
enable the removal from solvents and monomers of sub
stantially all of the acidic impurities which interfere with
anionic polymerization without contaminating the solvents
35
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,609,387
2,687,383
2,704,770
2,891,916
Basdekis et al. ________ __ Sept. 2,
D’Alelio ____________ __ Aug. 24,
Anspon ____________ __ Mar. 22,
Hwa ________________ __ June 23,
1952
1954
1955
1959
OTHER REFERENCES
and monomers with other impurities which would react
with anionic initiators.
Ion Exchangers in Organic and Biochemistry (1957),
It is obvious that many variations may be made in the 4 O pages 130-156, pages 139, 140, 143, 147, 150-151 par
products and processes set forth above without departing
ticularly relied upon; Interscience Publishers, Inc., New
York.
from the spirit and scope of this invention.
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