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Патент USA US3100766

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United States Patent 0 ice
3,100,761
7 Patented Aug. 13, 1%63
1
2
3,100,761
organometallic compound and salt of transition element.
Such disadvantages of the systems of the art are ‘avoided
in the process of the present invention.
POLYMERIZATION PROCESS WITH A CATALYST
SYSTEM OF METAL HALIDE AND ORGANO
MAGNESIUM COME'OUND
By the process of this invention, polymerization of es
ters of acrylic and methacrylic acid and of acrylonitrile
cor methacrylonitrile is effected with organo magnesium
to ROlllH & Haas Company, Philadelphia, Pa, a cor
compounds as polymerization initiators to give useful
poration of Delaware
polymers of controlled molecular Weights with certainty
No Drawing. Filed July 24, 1953, Ser. No. 750,563
and with uniformity of results. Since these compounds
15 Claims. (Cl. 260-88/7)
act anionically, they avoid the effects and side reactions
10
Robert P. Fellman, Levittown, William E. Goods, Yard
ley, and Frederick H. Gwens, Croydon, Pa., assignors
which are sometimes troublesome from the use of per
This invention concerns a process for polymerizing es
oxidic initiators. Furthermore, many of the polymers
produced by the process of this invention possess prop
perties which differ from those obtained in other ways,
ters of acrylic or methacrylic acid, acrylonitrile, and
methacrylonitrile. According to this process, boron tri
iluoride or a chloride, bromide, or iodide of speci?c
metals is mixed with monomer to be polymerized, where 15 particularly from those of free-radically polymerized prod
cts, or of polymers formed with the above-noted hetero
by a complex of said ?uoride or a said chloride, bromide,
catalysts. In some cases, the process of this invention has
or iodide and a monomer is formed, and the monomer
surprising and useful stereospeci?c effects. The process
is surprisingly effective and yields clear polymers which
carrying the complex is polymerized in inert organic
solvent under the influence of an organic magnesium
compound.
‘
It was found by Lebedeva and Vaynrub‘ (J. Gen.
20 produce no turbidity in solutions.
‘
It is known that Grignard reagents can be formed not
only from reacting an organic chloride or bromide with
Chem. 22, 1974), that methyl methacrylate and isopropyl
magnesium in ether, but also by adding magnesium chlo
magnesium bromide react to lead to the dimethyl ester
ride or bromide to a dihydrocarbon magnesium com
of a,a’-dimethyl-ot-isobutylglutaric acid. Apparently such
Grignard reagents add 1,4 to the starting ester followed 25 pound.
by addition of the product to a second molecule or“ this
ester. When the organo magnesium complex is decom
posed, as with Water, the ?nal dimethyl ester is formed.
These authors later reported that methyl acrylate reacts
with isopropylmagnesium bromide to give dimethyl tat-iso 30
butylglutanate. On the other hand, methyl methacrylate
and methylmagnesium bromide reacted to give a mixture
of dimethylisopropenylcarbinol and methyl sec-‘butyl lce
tone, such products depending upon 1,2-addition.
Furthermore, Landler reported that, when he treated
methyl meth-acrylate with butylmagnesium bromide, there
Thus, results ‘were variable and un
to give corresponding Grignard reagents. It is of inter
est to note that di-‘hydrocarbon magnesium compounds
often fail to initiate polymerization and are variable in
their actions on vacrylic esters. Their action, however, is
with magnesium chloride or bromide. Nor is the action
of Grignard reagents. improved by addition thereto of
‘magnesium chloride or bromide.
In ‘fact, there vare speci?c salts which form complexes
of low molecular weight of the order of 10,096 to 20,000‘;
Attempts on our part to polymerize methyl methacryla-te
and other acrylic esters with Grignard reagents showed
that sometimes addition polymers could be obtained vand
at other times they did not form. Even when polymers
resulted, they were of low molecular weight and had no‘
apparent utility.
pound. It is known that a diarylmiagnesium or dialkyl
magnesium reacts with magnesium chloride or bromide
35 not improved or made more certain by direct reaction
was ‘a small amount formed of some polymeric material
‘ ‘certain.
We have found great differences which depend upon
whether one of the metal halides as herein de?ned is
added to the monomer or to the organo-magnesium com
with the designated monomers and .then polymerization
‘is greatly improved under initiation with organ-o-magne-ii
‘slum compounds. Yet these same salts, when added 6.1-.
r‘ectly to the organo-magnesium compounds destroy ini
tiator action. This situation is in sharp contrast with the‘.
45 ‘preparation of initiators used,‘ for example, for polym~
Processes have ‘been proposed for polymerizing ole?ns
in which the polymerization catalysts are formed by re
acting an organometallic compound and a salt of a tran
erization of u-ole?ns.
- .
’
Yet it has been found‘that when a chloride,'bromide, or
iodide of beryllium, magnesium, calcium,‘ strontium,
barium, zinc, cadmium, or aluminum or boron triiluoride
the catalysts used are formed from an organo‘aluminum 50 is dissolved in monomer, whereby a complex is formed,
controlled polymerization of monomer can then be ini
compound and a salt of a metal from periodic groups IV
sition metal. For example, in Belgian Patent 533,362,
to VI, While in Belgian Patent 534,888, reaction products
of organo magnesium or zinc compounds and salts of
metals of groups IV to V1 are used as catalysts. Metal
salts from group VIII may be used in the same way.
These catalysts are primarily heterogeneous, for the re
action of organo metallic compounds and such salts gen
erally gives a solid. This may be formed or held in sus
pension or it may be separated. Thus, in this type of
catalysis, it is necessary to deal with heterogeneous catal~ 60
ysis and with the difficulties ensuing therefrom. Appli
tiated with an organo-inagnesium compound.
Effective organo-magnesium compounds may be repre
sented by the formula
where'R is alkyl, cyclo-alkyl, varalkyl, aryl, alhoxyaryl,
alkenyl, \aralkenyl or alkynyl, and Y represents chlorine,
bromine, iodine, or a group de?ned by R. Iodine is less
useful as Y than are chlorine ‘and bromine. Preferably,
the alkyl groups have two to twelve carbon atoms, al
cation of the above systems to methyl methacrylate and
though larger alkyl groups may be used, ‘and the alkyl
other acrylic esters can bring about polymerization as
groups are primary or secodary, including such typical
might ‘be expected, but results are variable and di?‘lcult
groups as ethyl, propyl, isopropyl, butyl, isobutyl, sec
to control, as might also be expected from the nature of 65 butyl, amyl, isoamyl, sec-amyl, neopentyl, 2,-ethylbutyl,
the catalysts. Conversions are low. Molecular weights
heptyl, Z-ethylhexyl, octyl, nonyl, decyl,‘ or dodecyl. The
tend to be low and variable. Separation of such catalysts
cycloalkyl groups may be simple cyclopentyl or cyclohexyl
has proved to the a most serious problem and the pres‘
or ‘hydrocarb‘on-substituted cycloalkyl' groups, such as
ence of catalyst in polymer may seriously interfere with
methylcyclopentyl, methylcyclohexyl, butylcyclchexyl,
properties. Whether sterecspeci?city develops in the poly 70 octylcyclohexyl, or cyclohexylcyclohexyl. The various
mers from- such esters appears to depend more upon the
total system than upon the catatlyst formed by reacting
other cyclic groups that may go along with these alicyclic
groups include dicyclopent'anyl, menthyl, or isobornyl.
8,100,761
3.
4
. A variety of useful groups comes within the aralkyl
The monomers which can be used in the process of this
designation, including benzyl, or-methylbenzyl, methyl
invention are acrylic or methacrylic esters or'nitrile, 1.e.,
benzyl, dimethylbenzyl, butylbenzyl, phenylbenzyl, d1
phenylmethyl, triphenylmethyl, ?uorenyl, or naphthyl
methyl.
acrylonitrile and methacrylonitrile. These can form a
complex with the salt added thereto. The alcohol res1~
dues forming the esters are those free from functional
groups which can react in the Zerewitinofl test. They
'
Aryl vgroups are frequently used in organo-magnesium
compounds. 'They include the simple phenyl group‘ and
‘comprise alkyl, alkenyl, alicyclic, including cycloalkyl and
alkylphenyl groups, such as tolyl, xylyl, ethylphenyl,
terpenyl groupsyaralkyl, aryl, comparable groups having
butylphenyl, diamylphenyl, tert-octylphenyl, or methyl~
one or more ether link-ages, and tertiary amino-substituted
tert-octylphenyl. Such groups as methoxyphenyl, ethoxy 10 groups. More speci?cally useful alcohol residues form
phenyl, or butoxyphenyl are likewise of interest. Other
ing acrylic esters are methyl, ethyl, propyl, isopropyl,
typical useful substituted phenyl groups are cyclohexyl
butyl, isobutyl, sec-butyl, tert~butyl, hexyl, octyl, nonyl,
phenyl, biphenyl, and n-aphthyl.
dodecyl, cetyl, stearyl, and higher alkyl groups, allyl,
methallyl, crotyl, undeoenyl, dodecenyl, and oleyl, cyclo
‘Also effective are unsaturated hydrocarbon groups,
whet-her ethylenically or acetylenically unsaturated, such 15 pentyl, cyclohexyl, methylcyclohexyl, butylcyclohexyl,
as ally], crotyl, undeoenyl, dodecenyl, ethynyl, butynyl, , cyclohexenyl, benzyl, phenylethyl, phenylpropyl, butyl
hexynyl, phenyle’thynyl, or cinnamyl.
=benzyl, cyclopentyl, dicyclopentyl, dicyclopentanyl, iso
bornyl, terpenyl, phenyl, xylyl, tolyl, butylphenyl,
As is well known, Grignard reagents are available
through reaction of organic halides and magnesium.
methoxyethyl, ethylthioethyl, ethoxyethoxyethyl, ethoxy
Simple groups on the magnesium may be replaced by other 20 propyl, ' ethoxypropoxyethyl, benzoxyethyl, cyclohexoxy
ethyl, phenoxyethyl, phenoxyethoxyethyl, octoxypropyl,
groups, as for example,
octoxybutyl, dimethylaminoethyl, 'diethylaminoethyl, di
methylaminopropyl, morpholinoethyl, pipeiidinoethyl,
pyrrolidinoethyl, thenyl, or tetrahydrofurfuryl.
v
25 e The acid portion of the ester may be from acrylic acid,
methacrylic acid, or a thiolacrylic \acid.
While usually a single monomer is polymerized, there
may also be formed copolymers ‘from two or more esters
of acrylic acid or from two or more esters of methacrylic
The (ii-hydrocarbon magnesiums are also known and
any of the above groups may occur in these.
acid with the proviso that the comonomers used in each
class are quite similar in their rates of polymerization;
While it
has been said that RMgX compounds, Where X is chlorine
or bromine, and RzMg compounds show about the same
reactions and differ essentially only in rates of reaction,
. It has also been found that vinyl sulfones can be polym~
erized in the same way and amides which have two unre
active N-substituents.
'
these two kinds of organo-magnesium compounds by
The proportion of monomer to solvent may vary from
themselves may have quite different actions in polymeriza 35 one percent or less up to about 50% of the resulting mix
tion. Yet they both provide the same sort of polymeriza
ture. Suf?cient solvent should be present to .maintain
tions when a complex of monomer and a de?ned salt is
?rst formed and used in thev polymerization.
Examples of speci?c magnesium compounds are di
ethyl-, dibutyl-, dioctyl-, didodecyl-, dibenzyl-, dicyclo
the polymerizing mixture in a mobile, ?uid state.
The ratio of initiator [to monomer may be considerably
It depends in part upon the choice of organo
40 varied.
hexyl-, diallyl-, di-1-hexynyl-, di-phenyl-, ditolyl-,. or di(bi
magnesium compound, upon the choice of metal halide,
phenyDmagnesiums and chlorides, bromides, or iodides
,of ethylmagnesium, ‘butylrnagnesium, hexylmagnesium, l
the molecular weight desired for the polymer. In the
‘hexyny'lmagnesium or phenylethynylmagnesiurn, Z-ethyl- '
lower range of ratios of initiator to monomer, relatively
highermolecular weights are obtained._ Practical dit?
.oulties' determine the minimum ratios, since traces of
upon the monomer to be polymerized, and also upon
hexylrnagnesium, n-octylmagnesium, dodecylmagnesium,
benzylmagnesium, butylbenzylrnagnesium, cyclopentyl
vmoisture or chance admission‘ of air into the reaction
vessel may consume initiator. Even so, polymers of high
molecular weight form but in reduced conversions.
magnesium, cyclohexylmagnesium, phenylmagnesium, ‘bi
phenylmagnesium, diphenylmethylmagnesium, triphenyl
methylmagnesium, ?uoroenylmagnesium, octylphenyl
The practical limits of organo-nragnesium compound
magnesium, allylmagnesium, or Grignard reagents in
are between about 0.1 and 10 mole percent based on the
which the organic group contains :a heteroatom as 2
total monomer. The preferred range is from 1 to 5
pyridinylmagnesium bromide, 4-tri?uoromethylphenyl
mole percent.
magnesium bromide.
.
.
p
The amount of a salt which is complexed with monomer
The presence of an inert ‘organic solvent at least for 55
depends in part upon the amount of organo-magnesium
the monomer is highly desirable. In the absence of such
compound used. The ratio of salt to said compound may
solvent polymer forms around initiator and polymeriza
vary
from about 0.5 mole of salt per mole of said com-,
tion may fail to proceed. The solvent may be one which
pound up to about 2 moles per mole. The optimum
primarily dissolves the monomer, or it may lbe one which
ratios will depend upon monomer, choice of initiator, and
dissolves both monomer and polymer. By inert solvent
is here meant one which does not react with the magne
slum compound under conditions of polymerization. The
vtypes of organic compounds which thus react and those
which do not are well known. Useful solvents include
aromatic hydrocarbons, such as benzene, toluene, xylene,
and aromatic naphthas ror distillates, petroleum distillates
60
the kind of polymer desired, including its molecular
weight.
.
It has beenfound that the above de?ned salts form
complexes with the above de?ned monomers. While mon
omer is present in a polymerizing system in excess of such
65 salt, the complex nevertheless exists and it has been pos
sible to prepare and isolate typical vcomplexes. These
can be demonstrated by shifts in the infrared absorption
spectra and by separation and analysis of product. The
carbons such as dichloroethane, trichloroethane, poly
use of these complexes leads to higher conversions and/
chloropropanes, methylene dichloride, and carbon tetra 70 or
higher molecular weights than when the initiators are
chloride, and dry others, such as diethyl ether, dibutyl
used alone.
ether, the dimethyl or diethyl ethers of ethylene glycol,
It is essential that complex be formed with the monomer
tetrahydrofuran or tetrahyd-ropyran. 'The solvent or mix-‘
before initiator be mixed with the system. If desired, a
ture of solvents should be selected to maintain the reaction
de?ned metal halide and at least su?icient monomer to
mixture liquid at the temperature of polymerization.
75 provide the complex may be ?rst mixed, then this mixture
.of which petroleum ethers, ,n-heptane, n-octane, and
solvent naphthas are typical examples, chlorinated hydro
3,100,761
5
.
6
.
is‘combined with the organo-magnesium compound, 1and
are placed in a reaction vesselequipped with a mechanical
the resulting mixture is mixed with more monomer. A-l
stirrer, thermometer, additional tunnel, and inlet and out
let tubes -for nitrogen gas. One neck of the vessel is cov
ered with a rubber serum bottle cap. Anhydrous, oxy
te'rnatively,.-all of the monomer and de?ned metal salt are
mixed together ‘and this mixture and organo-magnesium
compound are combined. Solvent is supplied before the
gen-free nitrogen is passed through the‘ toluene for two
complex,’ initiating organo-magnesium compound, and
hours to remove dissolved oxygen ‘and to displace air
monomer are combined so that polymerization occurs in
from the apparatus. ‘ The reaction vessel is immersed in
the presence of solvent. ,The order of mixing complex,
an ice bath,_.and 7.2 parts of a 2.82 M solution of di
phenylmagnesium in diethyl ether is introduced by means
initiator, and monomer is not critical.
'
'
'
‘
_ . ‘ fPolymeriza-tions ‘ are, carried out‘ within‘, ‘the general 10 of a hypodermic syringe ‘inserted through the serum b:ot— .
tie cap... When ‘the temperature of the reaction mixture
range of about -90° C; to about 50° C. The tempera
tures used will depend upon the initiator system,‘ the ‘ reaches 3° C, an oxygen-‘free solution of 4.1 parts of
magnesium bromide in 52.0 parts of methyl methacrylate
monomer, the solvent, theidesiged nature of the polymer, '
is ‘added during one-half minute. A vigorous, exothermic‘
reaction occurs, and'the temperature .ofwthe reaction
including‘ molecular Weight, molcular weight distribution,
branching,
‘otherlfa'ctor‘s.
,
I
,
.
15
-‘
-In the range of temperature above about 40 °- C. there
is a tendency for the polymers to becomebranched. Art
.mixture rises‘ to 11° C; ‘ Stirring and cooling in the ice '
.‘ bath are continued for ‘sixteen hours. Two parts of
sence of moisture; While dry, oxygen-free nitrogen is
commonly used, ‘an inert atmosphere may also be supplied
' polymer ‘is Washed with ‘dc-ionized water‘ and dried. There
is obtained 42.6 parts of poly(methyl methacrylate) hav- ‘
lFhB‘yjl‘OV/‘CSt temperatures, conversions may be low in a ‘j methanol are added :to terminate the polymerization, and
the viscous reaction mixture is poured into ten volumes of ‘
given time? ‘ A preferred temperature range is from —‘80°
C. to ‘about 0°. C., for in this range, ‘side reactions are at 20. vigorously agitated low boiling petroleum ether. Solid
a ‘minimum, branching of the polymer chain is avoided; ‘ polymer forms. It is separated, washed with petroleum
ether, and dried. The dried polymer‘ (47.5 parts) is
and the molecular size‘can be well controlled’ and in‘.
puri?ed by suspending it for three hours in a mixture of
general reproduced.
_
90 parts of sulfuric ‘acid, 300‘, parts of methanol, and ~
The polymerization reactionistbest carried out in‘ an
inert atmosphere and preferably in the substantial ab 25 2700 parts of Water. The slurry then ‘is ?ltered, and the
ing an intrinsic viscosity in chloroform of ‘2.08 dl./g.
'_ by helium, argon, methane, or hydrogen.
This corresponds to avmolecul‘ar weight of 625,000.
‘It will be realized that both oxygen’ and moisture re
act with organo-magnesium compounds and the amount so
‘of these present or introduced must/be less than equiv
alentto the amount of such compounds. Desirably, oxy
geniand/or‘moisture should be less than ten mole percent,
with reference to the organo-magnesium compound used. '
in place of the ‘above solution. Well regulated polymer
ization ensues. Thirty-six parts by ‘a polymer, with, a‘
molecular weight of 220,000 is isolated.‘ Similarly, ‘use
of only 1.84 parts of magnesium bromide in. the same
35.
Polymer may be obtained-in a crudetorm, as the non
‘
‘ In a similar experiment, 7.36 parts of-MgBrZ are em
ployed as a solution in 52 partsof methyl methacrylate
amount of methyl methacryla-te producesj23.l8 parts of
volatile residue on evaporation of solvent and monomer
by heating under reduced pressure. When the polymer is
polymer having ‘alrnolecular weight of 380,000.
formed in a solvent for both monomer and polymer, poly- ;
rner can be separated by precipitating polymer with a n0n~
Forlexarnple,‘ a benzene ‘solution of polymer.
solvent.
tially
‘Byway
equivalent
ofncomparison,‘
results are‘there
obtained.
may be mixed
_
7.2'parts~
.
may be ‘mixed with methanol. The polymer precipitating
may be separated, washed, and dried. If a solvent only
.for the monomer is used during polymerization, polymer
nesium bromide. This mixture is supplied to ‘a toluene
‘ separates. us formed.
desired.
‘When this procedure ‘is carried out at 40° C, essen
of diphenylmagnesium and 7.36 parts of anhydrous mag
solution of 52 ‘parts of ‘methyl methacrylate.‘ There is
_
The
‘mixture is
‘warmed to; 12° C. and stirred .at 0° to 12° C. for 205
“nouevidence of ‘any vigorous reaction.
lit can be washed ‘and dried if so
.
hours. , The reaction mixture is, worked up as above. A
' small ‘amount of a lowpolymer is ‘obtained. ‘It ‘ vhas al
Any salts or magnesium compounds in the polymers can ~
be ‘removed by treating precipitated‘ polymer with‘ an
molecular weight ‘of less than 1000. '
acid solution. .Also, the polymerirnay berediss‘olved‘in a‘ '
solvent‘rand precipitated‘ from the solution by mixing with
In place ‘of diphenyhnagnesium used above, ‘there may’
50 be used with likee?’ect a bis(alkylphenyDmagnesiuin.
' The‘ precipitated or powdered ‘polymers are useful as
The alkyl group io‘r groups may be niethyhiethyl,ipropyhi‘
molding powders. The'?rm to hard polymers may be
‘mixed, as‘on‘rolls, with ‘about ‘0.5% of 'a lubricant,‘ such
"-as' stearic acid, and about 0.21% ofra“ light stabilizer, such
ci?c examples. The cyclohexylphenylgroup may beused
_'a
non-‘solvent.
)
i
‘a
,
.
H
.
p
_
.
isopropyhbutyl, tert-butyl, 'or'tert-octyl‘,‘by-way of spei ,
, in exactly thesame'way and the biphenyl, group is also
‘useful and very effective", The same ‘polymerization
obtained.
bis(methoxyphenyl)magnesium ‘or his
\‘as sa1ol,»and the mixture granulated, if‘ydesiredr‘being
screened to remove‘?nes‘ andpartioles‘coarser thaniabout I
l8.meSl1j,(U.S. sieve series). ‘
_
.
_'
(ethoxyphenyl)magnesium;‘ In every‘ case for good, suc
, They‘may be dissolved in organic solvents to provide
lacquers. .They may be used as coatings for metal, wood,
, cessful polymerization, the salt, here ‘magnesium bromide, 1 ~
paper, cloth, leather, {and the like ‘and yas'ladhesives and
binders. ‘This product is useful in .injection molding.
60 erized, ‘ and there ‘are mixed organoe’magnesium compound? ‘
is separately complexed with the acrylic ester to be polym‘J ‘
V
‘ Optionally, theJgranul-ated m‘ixture‘mayhe ‘pelletized be- ‘7 p
fore molding.
and the complex in monomer.
‘
‘
>
r
‘ "
_ ‘Example 2
In theseqapplications‘ advantage‘ may be'take'npf the . .
‘To a reaction ‘?ask'equipped as in Example 1, there is
‘peculiar properties which are possessed by polymers 65 charged‘
1000 parts by volume of anhydrous toluene;
formed under the‘ in?uence of the initiator-complexsys
The
toluene
is freed of dissolved‘ oxygen by bubbling
tem herein described ‘and utilized. These properties in
clude those‘ imparted by stereo regularity, which‘ may ‘ through it, for three hours,_a stream of anhydrous oxy
lead to two dimensional order or even to the three dimen
gen-free nitrogen. The reaction vessel is'immersed‘ in
sional order which is characteristic of crystalline lattices. 70 an ice bath, and 7.5 parts by volume ‘of a 2.82 M solution
of diphenylmagnesium is added by means of a hypo<
‘In the illustrative examples which ‘follow parts are
dermic syringe inserted through the serum bottle cap.
by weight unless otherwise designated.
When the temperature of the reaction mixture reaches
Example 1
2.5° 0., there is added them the addition funnel 49.8
One thousand parts by volume of anhydrous toluene 75 parts of a solution prepared by mixing 100 par-ts of
3,100,761
r
'
7
8
.
methyl methacrylate and 5.3 parts of anhydrous alu
minum chloride. The reaction mixture rapidly becomes
After eighteen hours 2 parts of methanol are added,
and the reaction mixturev is poured into 10 volumes of
petroleum ether. The polymer is {collected on a ?lter,
very viscous, and the temperature rises to 11° C. After
two and one-half hours, two parts of methanol are added
dried, and washed witha mixtureot sul?uric acid, water,
to terminate the reaction. The polymer is precipitated
by pouring the reaction mixture into 10 volumes of
5
and methanol as described in Example '1. There‘ is ob-‘
tained 37.8 parts of pure poly(methyl,methacrylate) hav
vigorously agitated low-boiling petroleum ether. The
ing a molecular weight of 168,000. 3 i‘
.'
Here, for purposes of comparison, the magnesium:
under reduced pressure. This'product is freed of inor
iodide is mixedwith the diphenylmagnesiiim solution and
garlicimpurities by suspending it for three hours in a 10 this mixture is added to the toluenesolution of methyl
mixture of 90 parts of concentrated sulfuric acid, 2700' > ‘ methacrylate under the-‘same conditions as above. No
solid which separates is collected on a ?lter and dried
' V
parts‘ of water, and 300 parts of methanol. The slurry
then is ?ltered, and ‘the solid is. washed with water and
polymer is obtained.
_ Eat-abet; 5;
dried. There is obtained 37.5 parts (78.1% yield) of
poly(methyl methacrylate) having an ‘intrinsic. viscosity
V V
' To a reaction. ?askl'equipped as described in Example .
of 1.55 d-l./g. in chloroform, corresponding to a‘ viscosity ’
1 there is charged, 1000 ‘parts, of anhydrous toluene.
average molecular weight of 430,000. , .
. In a separate experiment it was found that the addition 1 "
'Nitrogen is bubbled through the, solvent for two hours
of aluminum chloride to the solution of diphenylmag
to remove dissolved oxygen a‘nd'ito purge the apparatus‘.
nesiumywithout'?rst forming the aluminum chloride 20 The contents of the flaskv are cooled to j—70° C. by
immersion in a solid carbon dioxide-acetone bath,. and
7.1 parts of a 25.3 M solution of "dibutylma-gnesium in
a polymerization initiator.
diethyl ether are introduced.
"
"
J ‘
There is added from the addition funnel a solution
Example 3
.
monorner complex, produces a mixture tot-ally inactive as
' of 1.8‘parts of rifreshlydiused zinc chloride'in 57 pants
To a reaction vessel equipped with a mechanical stir 25 of dry, oxygen-free methyl methaorylate. The'tempera
rer, addition funnel,’ thermometer, serum bottle cap, and.
ture' of the reaction- mixture immediately vrises to -66°
'a tube for admitting nitrogen is charged 1000 parts by,
volume-of anhydrous,
oxygen-free toluene. Nitrogen is
,
C., and the viscosity, increases markedly. After eighteeen‘
hours the polymer isvprecipitated and, washed as de
bubbled through the toluene for two hours to remove dis
scribed in Example 1. Forty-six parts of poly(methyl
methacrylate) having a viscosity’, average. molecular
solved oxygen and to displace air' from ‘the apparatus.
The reaction ?ask is immersed in an ice bath, and 9.2
,
parts of a 2.17 M solution of diphenyhnagnesium is in
troduced by means of a hypodermic syringe inserted .
throughithe serum bottle cap.
,
_weight of 198,000 are obtained. .
' In'an otherwise similar experiment a solution of 5.4
parts of cadmium bromide in 50 parts of methyl meth
‘
acrylate is added to the initiator solutionv After wash
With the'temperature of the reaction mixture at 2° C., 35 ing and drying there is obtained '35 parts of poly(methyl
a solution of 5.3 parts of anhydrous aluminum bromide
methacrylate) having» a viscosity average molecular
._ in 50 parts of‘ methylmethacrylate ‘is’ added through
weight of 37,000.
7
~
the addition tunnel. The temperature rises to 8° C.
Again, for purposes of comparison, the same amount ‘
'5
vStirring is continued for 18-hours,.then the viscous mix- -
of cadmium bromide and idibutylmagnesium in solution
ture is poured slowly into 7 volumes of petroleum ether. 40 are mixed and this mixture is applied to (the methyl‘ meth
The solid polymer is collected on a ?lter and dried under
acrylate solution as above. No polymer results. ' ‘
reduced pressure. 1 iuri?cation is ‘accomplished by stir
Once -. again, for purposes of comparison, the same‘
ring for three hours, in suspension in amixture of 90
amounts of zinc chloride and dibutylmagnesium are mixed’
parts of tie-ionized water. The polymer is isolated by, " and this mixture is applied to the methyl methacrylate
?ltration, and is washed with water and‘ dried. I There is
obtained,30.6:parts (66.5% yield) of poly(methyl meth- '5 solution in_ toluene. No- polymer can be (found. ’ '
'5 acrylate) having an intrinsic viscosity (chloroform) of Y
Example 6.
1.1.34 dL/gr _ This ‘corresponds to a viscosity average
molecular ‘weight of 360,000.
'
Oneathousand parts by y'oiume of anhydrous toluene
.7 In anotherwise similar experiment, a' solution of 4.1’ 50 are placed in' a reaction vessel-equipped as described in
pants of aluminum. iodide in'50 parts of methyl meth- ' Example 1. Fi‘fty 'parts'i of - Imethyl methacrylate
_
are '
, ‘- acrylate/is added to the initiator solution. ‘After isola'i"
added,’ and nitrogen is bubbled throughthe solution to
~‘ tion and puri?cation there is obtained 38.7 parts (80.6%)
remove dissolved oxygen and to purge the "apparatus of
of"poly(methylmethacrylate) having a viscosity aver
age ‘molecular ‘weight of 1,525,000.‘
'
‘
a air. ‘Boron '?uoridewgas.-(1._3\6parts) is added, and the
'
55
mixture iscooled to 3? C._by immersing theflask'in an.
t
_ Nine parts iby'volurne'of a 2.17 M has}. ofdiplienyl
. ‘Comparison experimentsfin which‘the aluminum bro-v ~ 1 ice'tluth- ~
mide is mixed ldirectly'with'the :dip‘henylmagnesium solu- ’
r tion andv this mixtureis added to the toluene solution of
' magnesium in diethyl ether is introduced'by means of a
, methyl methacrylateldemonstrate thatthis'mixture fails
hypodermic ' syringe. Theternperature of the reaction
tov initiate'polymer ‘formation. Likewise, a mixture of 60 mixture immediately. rises to-13“ C.,-,and there 'isfa
' v the aluminum iodide vwith the idiphenylrnagnesium tails
to bring about polymerization.
,
‘
_
Example 4’
rapid increase inllviscosity. After 1.25. hours, 72 partsv
of methanolI are added, and the'polymer. is precipitated
by pouring the viscous reaction mixture into 10 volumes
of petroleum ether. The polymer'is separated, dried,'and
A
‘One thousand parts by volume of toluene are placed 65 puri?ed by the washing procedure described in Example
1. x'Iihere is obtained'40‘.4 parts of poly(methyl meth-.
in a reaction vessel equipped as in Example 1, and the
a'crylate) having an intrinsic viscosity of 2.13 dL/g.
contentsof the ?ask are-cooled to 1° C. by immersion
in chloroform, corresponding to a molecular weight of
- in an ice bath. Nitrogen is bubbled through the solvent,
and 9.5 parts by volume of a 2.11 M solution of diphenyl
650,000.
.
In place of gaseous boron ?uoride, there may be used
magnesium is added under anaerobic conditions. Fifty
an equivalent amount of boron ?uoride etherate. In.
parts of ‘a methyl methacrylate solution prepared from
6 parts of anhydrous magnesium iodide and 50 parts of
such an experiment, there is obtained 37.0 parts of
the‘ monomer’ then is introduced from the addition tun
polymer having a molecular weight of 710,000. '
nel. The temperature rises rapidly to 9.5 ° C., then slowly
In experiments for the sake of comparison, there are
mixed the above quantities of boron tr-i?uorideand di
subsides.
'
'
,
i
3,100,761
10
‘
minum chloride and 48 parts of methyl methacrylate is
added to the Grignard solution. After purification of
the product there is obtained 36.2 parts (75.4%) of
phenylmagnesium in solution. This mixture is added to
the monomer solution and the above procedure is followed.
No polymer results.
As shown above, essentially the same result is obtained
Whether boron ?uoride itself is ‘added directly to the mono—
mer, tor the boron tri?uoride is ?rst complexed. The
polymer having an intrinsic viscosity in chloroform of
1.18 dl./g., corresponding to 1a molecular weight of 308,
etherate used above was formed by dissolving boron tri
The above quantities of the various materials are used,
but for purposes of comparison, the magnesium. bromide
is mixed with the solution of phenylmagnesium bromide
000.
fiuoride in diethyl ether, the resulting solution being then
added to the monomer.
.
.
Instead of diethyl ether as the substance to form a 10 and the general procedure otherwise followed. The reac- .
tion mixture fails to become very viscous and only a small
coordinated complex with boron tri?uoride, there may be
amount of polymer can be separated. It is of very low
used ‘other complexing substances which are free of reac
tive hydrogen (as may be determined in the ZereW-itino?
molecular weight.
test), and which do not consume all of the organo~mag
nesium compound to he added. Thus, there may be used
to form complexes other ethers such as diisopropyl ether
When the aluminum chloride is mixed with the Grig
n‘ard reagent and the mixture applied to the toluene solu
tion of methyl methaorylate, no polymer can be ob
tained.
Example 9
One‘ thousand parts by volume of anhydrous toluene
and di-n-butyl ether or methyl acetate, ethyl acetate, ethyl
propionate, acetone, or methyl ethyl ketone.
Example 7
To a reaction vessel equipped as described in Exam
20 are charged to an apparatus as described in Example 1.
After ?ushing the equipment with nitrogen, the ?ask is
ple 1 is charged 1000 parts by volume of anhydrous n
immersed in ya solid carbon dioxide-acetone bath. When
the contents of the ?ask have reached a temperature of
heptane. Anhydrous, oxygen-free nitrogen is bubbled
through the solvent for one hour, and the contents of the
?ask are cooled to —70° C. by-imrnersion in a solid 25‘ —-70° C., 12.0 parts of a 2.40 M solution of n-butylmag
. nesium chloride in diethyl ether is added by means of a
carbon dioxide~acetone bath. Seven parts of a solution
hypodermic syringe inserted through the serum bottle cap.
of dibutylrnagne-sium (2.90 M) in diethyl ether is added,
From the addition funnel, a solution of 3.68 parts of an
followed by a solution pf 4.1 parts of anhydrous mag
hydrous magnesium bromide in 100 parts ‘of de-oxygen~
nesium bromide in 50 parts ‘of oxygen-free methyl meth
vacrylate. The temperature rises to ~—65° C. and a ?nely 30 ated methyl methacrylate is introduced. A rapid, exo
thermic polymerization occurs, and the temperature rises
divided white solid begins to separate.
to ~58° C. before subsiding. After sixteen hours, 2 parts
After two hours the slurry is ?ltered, and the solid
of methanol are added to terminate active chain ends.
polymer is re~suspended in a mixture of 90 par-ts of sul
The polymer is isolated by pouring into 10 volumes of
furic acid, 300 parts of methanol, and 2700 parts of de
rapidly
stirred petroleum ether. The solid product is sep
ionized Water. This suspension is stirred for three hours
arated and‘ dried, and is puri?ed by the washing procedure
‘described in Example 1. There is obtained 84,2 parts
of poly(methyl methacrylate) having a viscosity average
and then ?ltered. The solid poly(methyl methacrylate
(43.7 parts)), possesses a viscosity average molecular
, weight of 186,000.
‘
molecular weight of 220,000.
In place of n-heptane there may be used, with the same
'
Example 10
result, diethyl ether or 1,2-dimethoxyethane.
Instead of the addition of the magnesium bromide di
rectly to the monomer, it is ?rst added to the dibutyl
magesium solution and the above procedure then followed.
There is only a slight rise in temperature. Some polymer
Two hundred parts by volume of toluene are placed in
‘1a ?ask equipped with a stirrer, addition funnel, thermom
is separated, but the yield is less than ‘obtained above,
and the molecular weight of this polymer is considerably
Nitrogen is bubbled through the toluene for one hour, and
7.2 parts‘of a 2.82 M solution of diphenylmagnesium in
diethyl ether is added by means of a hypodermic syringe.
lower.
eter, .and ‘inlet and outlet tubes for nitrogen. One neck
of the ?ask is‘ covered with a rubber serum bottle cap.‘
.
In place of the di-n-butylmagnesium used above, there
may be substituted other dialkyl m-agnesiums from diethyl
magnesium upwards. The larger dialkylmagnesiums have
50
the advantage that they are less sensitive to traces of
moisture than diethylmagnesium, dipropylmagnesium, or
dibutylm-agnesium, and are more soluble in para?inic hy
drocarbons which may be used as solvents.
7
To a reaction ?ask equipped as in Example 1, there
bromide in 56- parts of isopropyl methacrylate is in
troduced from the ‘addition funnel. A vigorous, exother
mic reaction takes place, and the temperature of the re
‘ action mixture rises to 25° C. before subsiding. A rapid
55
Example 8
‘ The solution is cooled to 2° C. by immersion of the ?ask
in an ice bath. A solution of 4.0 parts of magnesium
increase in viscosity is noted. After one hour, 200 parts
of methoxyethanol are added, and the insoluble material
is removed by ?ltration. The ?ltrate is stripped of sol
is charged 1000 parts by volume of anhydrous toluene.
After ?ushing of the apparatus with nitrogen, the contents
vent under reduced pressure, and the residual solid is
bath. With a hypodermic syringe, 15.1 parts by volume
methacrylate) having an intrinsic viscosity of 0.175 dl./ g.
washed with deionized water and dried in a vacuum oven
of the ?ask are cooled to 3.5 ° C. by means of an ice 60‘ at 60° C. There is obtained 37.9 parts of polytisopropyl
of a 1.32 M solution of phenylmagnesium bromide in
diethyl ether is added, followed by a solution of 4.42
parts of anhydrous magnesium bromide in 55.4 parts of
oxygen-free methyl methacrylate. A vigorous, exotherm
ic reaction occurs, and the reaction mixture rapidly be
comes extremely viscous.
.
The polymeric product is isolated by slowly pouring the
in chloroform.
Instead of dissolving magnesium bromide in an acrylic
ester, it’ may be dissolved or dispersed in an organic sol
vent such as an other and the mixture with ether added
65 to the acrylic ester.
Example 11' '
Twenty parts of stearyl methacrylate and 2 parts of
reaction mixture into 10 volumes of petroleum ether. The
anhydrous magnesium bromide are placed in a flask
solid which separates is collected on ‘a ?lter, dried, and 70 equipped with ‘a stirrer, thermometer, and‘ inlet and out
freed of inorganic impurities by the washing procedure
let tubes for nitrogen. One neck of the ?ask is covered
described in Example 1. There is obtained 31.5 parts
with a rubber cap. Toluene (250 parts) is added, and
(70.5%) of poly(methyl methacrylate) having a viscosity
the resulting solution is cooled to 3° C. One part of a.
average molecular Weight of 690,000.
2.86 M solution of diphenylmagnesium in diethyl ether is
In a similar experiment, a mixture of 2.7 parts of alu 75 introduced by means of a hypodermic syringe; the tem
3,100,761
11
12
perature of the reaction mixture rises to 6° C. before
Example 15
subsiding.
_
‘
.
To a ?ask equipped with a mechanical stirrer, thermom
eter, ‘addition funnel, and inlet and outlettubes for nitro
gen is charged 680 parts by volume of anhydrous toluene.
., After sixteen hours, the viscous solution is poured into
10 volumes of methanol. The solid which separates is
collected on a ?lter and dried. It is puri?ed, by suspen
sion, for two hours at room temperature in a mixture of
Dry, oxygen-free nitrogen is bubbled through the toluene
for one hour to remove dissolved oxygen and to purge
30 parts of concentrated sulfuric acid, 100 parts of meth
the
apparatus of air. Seven and one-half parts by volume
anol, and 900 parts of water. The dried polymer (16.7
of a 2.82 1M solution of diphenylmagnesium in diethyl
parts, 83.5%) displays an intrinsic viscosity in benzene
ether is added, and the contents of the ?ask are cooled
of 0.165 dL/g.
10 to —-70° C. by immersion in a solid carbon dioxide
. In a similar experiment, a solution of 2 parts of an
acetone bath.
hydrous magnesium bromide and 20 parts of stearyl meth
A solution prepared from 285 parts of isopropyl acry
acrylate in 250 parts of, puri?ed n-octane is ‘treated with
late and 7.9 parts of a 2.54 M solution of anhydrous
2 parts of 2.16 M solution of di-'n~butylmagnesium in di
magnesium ‘bromide in diethyl ether is introduced from
ethyl ether. A very viscous solution of poly(stearyl meth
15 the addition funnel.
acrylate) results.
-
An exothermic reaction occurs.
After being stirred for 16 hours at ~75” C. the reaction
Example 12
mixture is poured into 10 volumes of vigorously agitated
A mixture of 30 parts of benzyl methacryl-ate (B.P.
petroleum ether. The polymer which separates is col
76—77° C. at 1.2 mm), 3 parts of anhydrous magnesium
lected on a ?lter and dried in a vacuum desiccator. It is
bromide, and 300 parts of toluene is placed in an appara 20 freed of inorganic impurities ‘by suspending for two hours
tus of the type described in Example =11. The apparatus
in ‘a mixture of 90 parts of sulfuric acid, 300 parts of
is ?ushed with nitrogen and the contents are cooled to
3° C. by means of a solid carbon dioxide-acetone bath.
methanol, and 2700 parts of white, granular poly(iso
propyl acrylate) having an intrinsic viscosity of 1.45 ‘dl./ g.
A solution of 2.812 M diphenylmagnesium (7.2 parts by
in chloroform solution. This corresponds to a molecular
volume) is introduced by means of a hypodermic syringe. 25 Weight of 550,000.
'
'
'
The temperature of the reaction mixture rises to 12° C.
Substitution of 10.2 parts of a 2.3 M solution of mag
before subsiding. After sixteen hours, 2 parts of metha
nesium iodide in diethyl ether for the magnesium bromide
used above produced 194 parts of poly(isopropyl acrylate)
of a viscosity average molecular weight of 420,000. Sim
nol are added to terminate the reaction, and the viscous
solution is poured slowly into 10 volumes of methanol.
The solid is freed of organic impurities by the washing
procedure described in Example 11. There is obtained
21.7 parts of poly(benzyl methacrylate).
Example 13
'In an experiment similar to that described in Example 1
a solution of 4.1 parts of magnesium bromide in 60 parts
ilarly, use of an equivalent amount of anhydrous mag
nesium chloride dissolved in the monomer provides a high
conversion to p0ly(isopropyl acrylate)>of 390,000 molec—
ular weight.
In place of the toluene used above as the solvent, there
35 may be used n-heptane of other paraf?nic hydrocarbon.
Equivalent ‘conversions and molecular weights are ob
tained.
of oxygen-free dimethylaminoethyl methacrylate is added
The above procedure is followed but the ratio of initia
to one thousand parts by volume of anhydrous toluene
tor to monomer is increased sixfold and the ratio of mag
nesium bromide is held about the same. The polymer
thus obtained in about a 65% conversion has a molecular
containing 7.2 parts of 2.82 M solution of diphenyl
magnesium in diethyl ether. A vigorous exothermic re
action occurs and the temperature of'the reaction mixture‘
risesrapidly to 9° ‘C. Stirring and cooling in the ice bath
weight of 40,000. When the ratio of initiator to mon
are continued for 18 hours. Two parts of methanol are
- other is 2 mole percent, the resulting polymer has a mo
added to terminate the reaction, and the ‘viscous reaction 45 lecular Weight of about 85,000, While With ratios providing
one mole percent and 0.25 mole percent, the products
mixture is poured into 10 volumes of vigorously agitated
have a molecular weight of about 177,000 and 400,000
petroleum ether. The polymer which separates is puri?ed
respectively.
by dissolving in benzene and reprecipitating from petro
Example 16
leum ether. There is obtained 54 parts of poly(dimethy1
aminoethyl methacryla-te) .
50
One thousand parts by volume of' anhydrous toluene
In a similar experiment a'>68% conversion of ?—ethoxy
are placed in a reaction ?ask equipped as described. in
ethyl methacrylate to polymer is obtained.
Example 1. Nitrogen is passed through the solvent for
one hour to remove dissolved oxygen and to purge the
Example 14
apparatus. The contents of the reaction ?ask are cooled
To a reaction ?ask equipped as in Example 1 there is 55 at —70° C. by immersion in a solid carbon dioxide
charged 500 parts by volume of carefully puri?ed tetra
acetone bath and 7.5 parts by volume of a 2.82 M solution
of diphenylmagnesium in diethyl ether is introduced. A
hydrofuran. Dry nitrogen is bubbled through the solvent '
solution of 2.7 parts of anhydrous aluminum chloride in
for-three hours to remove dissolved oxygen and to purge
57 parts of isopropyl acrylate then is added. After 18
the apparatus of
With the solvent at roomltempera
‘cure. a solution of 3.25 parts by volume of a 2.82 M 60 hours, 2 parts of methanol are introduced to vterminate
the reaction. The product is isolated by precipitation of
solution of diphenylmagnesium in diethyl other is intro
the reacting mixture in 10 volumes of petroleum ether.
duced by means of ‘a ‘hypodermic syringe. To the result
After puri?cation by the procedure described in Example
ing (solution is added 66 parts of n~butyl methacrylate con
16, there is obtained 41 parts of pure poly(isopropyl
taining 2.1 parts of anhydrous magnesium bromide. A
vigorous reaction occurs and the temperature of the re 65 acrylate) having a viscosity average molecular weight of
104,000.
'
action mixture rises rapidly to 43° C. before subsidiug
In an exactly analogous experiment, a solution of 2.7
again to room temperature. Stirring is continued at noom
parts of anhydrous aluminum chloride in 73 parts of tert
temperature for 18 hours, then two parts of methanol are
1butyl acrylate is added to a solution of diphenylmagne
added to terminate the reaction.
The polymer is isolated by treating the reaction mixture 70 sium in anhydrous toluene at -70° C. After puri?cation
there is obtained 52.4 parts (71.8%) of poly(tert-‘butyl
. . with 10 volumes of petroleum ether in ‘a Waring Blendor.
acrylate) having a viscosity average molecular weight of
, The polymer that separates is collected on a ?lterrand freed
130,000.
of inorganic impurities as described in Example 1. There
is obtained 52 parts (78.7%) of poly(n-buty1 methacry
late);
'
Example 17
75
To a reaction vessel equipped as described in Example
3,100,761‘
13
14' .
0.48 dl./ g. corresponding to a molecular weight of 132,
1 is added one thousand parts of anhydrous oxygen-free
toluene. The flask is immersed in a solid carbondioxide
acetone bath and 7.3 parts by volume of a 2.82 M solu
tion of diphenylmagnesium in diethyl ether is introduced
500.
‘
Poly (tert-butyl acrylate) having a‘ molecular weight of
160,000 is obtained in a 43% conversion by an exactly
by ‘means of a hypodermic syringe. With the contents of e: analogous reaction. In another similar experiment, poly
(isobiornyl acrylate) of 210,000 molecular weight is ob
the ?ask at ~~60a C. there is added a solution of 1.36
parts of boron ?uoride gas in 57 parts of isopropyl
acrylate. A vigorous exothermic reaction occurs and the
tained in 95% yield.
,
‘ .
.
..
- ‘It has been observedthat in the-‘polymerization of esters
of acrylic acid it is distinctly/desirable to perform the
viscosity of the reaction mixture increases rapidly. Stir- 1
ring at —60° C. is continued for 18 hours, then two parts 10 polymerization between .—-20° and ‘—90° 0, since‘ then
side reactions, which are possible in the case of the esters
of methanol are added to terminate the reaction.‘
of acrylic acid, are kept at a minimum.
The viscous reaction mixture is poured slowly into 10
volumes of petroleum ether. The polymer is separated
Example 20
land collected on a ?lter, dried, and freed of inorganic im
purities by the procedure described in Example 16. There 15 One thousand parts by volume of anhydrous toluene is
placed in an apparatus of the type described in Example 1.
is obtained 36.5 parts (66.3%) of poly(isopropyl acrylate)
Nitrogen is bubbled through the solvent for one hour to
‘remove dissolvedoxygen and to purge the apparatus. A
having an intrinsic viscosity in benzene of 0.90 dL/g This
corresponds to a viscosity average molecular Weight of
2.82 M solution of diphenylmagnesium in diethyl ether
approximately 300,000. Similarly, poly(isobutyl acrylate)
isipiiepared in 74% conversion. This polymer possesses a 20 ]( 11.3 partsby-volume) is added by means of a hypo
viscosity average molecular weight of 360,000.
‘ dermic syringe and the contents of the ?ask are cooled to
~60° C. by-immersion in a solid carbon dioxide-acetone
‘
For purposes of comparison the above amounts of ma
terials are used, but the boron triiluoride is added directly
to the diph‘enylmagnesium solution and the mixture is
used. No polymer‘is obtained.
bath.‘ 'Iloi-the cooled solution is added 53 parts of acrylo
‘nitrile containing 6.2 parts of ‘anhydrous. magnesium bro
mide.‘ Stirring of the reaction mixture is continued for
18 hours. The reaction mixture is then poured into 10
Example 18
volumes of vigorously agitated petroleum ether. The
polymer which separates is collected on a ?lter, dried, and
i To a reaction vessel equipped as described in Example
‘1 is charged 1000' parts of anhydrous toluene, The solvent
is freed ‘of dissolved oxygen by bubbling nitrogen through
puri?ed as described in Example 1. There is obtained
30
it for one hour. Seven parts of a 2.82 M solution of .di~
phenylmagnesium in diethyl ether is‘ added, and the con- .
tents of the flask are cooled to ——60° C. by immersion in
19.7 parts of polyacrylonitrile having an intrinsic‘viscosity
j of 0.117 dl./ g. in dimethylformamide.
This identical reaction carried out at 3° C. produced
, 24.6 parts (46.4%) of polyacrylonitrile.
Repetition of theiabove procedure with substitution of
of. “de¢oxygenated methyl acrylate containing 4.0 parts of 35 an equivalent weight of methacrylonitrile, likewise leads‘
anhydrous magnesium chloride are added rapidly.‘ The‘
to‘ useful polymers with molecular weight similar to those
temperature of the. reaction mixturerises to
shown above.’
‘ _ i ,
_
i
‘
a solid carbon dioxide-acetone bath. Forty-seven parts
before subsidin‘g.
.
, >
.
> By way ofcomparison the above amounts of diphenyl
:‘imagnesium' in‘diethyl ether and magnesium bromide are
, slowly into 10 volumes of petroleum ether, and the rub 40 ?rst‘mixed and this mixture is applied to. the ‘toluene
bery‘polymer which separates is isolated and dried. There
‘ solution of acrylonitrile. No polymer is obtained. _
‘is obtained 19.7 parts of poly(methyl acrylate). The poly
After eighteen hours the viscous ‘solution is poured
We
mer is purified by dissolving in 200 parts of acetone and
precipitating in 2000. parts of deionized water.
claim:
,
.
i
e
1. A process for preparing a polymer from at least one
monomer from the classconsisting of acrylonitrile, meth
In an exactly analogous experiment, a 35% conversion‘ 45 acrylonitrile, and esters‘ of acrylic acid and of methacrylic
acid and an alcohol, the non-hydroxyl portion-of which
propyl acryl‘ate and methyl thiol acrylate are produced in ' is free of groups having reactive‘hydrogen as determined
conversions of 46 and 73%, respectively, .by polymeriza- ’ by the Zerewitinoff test, which comprises ?rst mixing to
gether under substantially anhydrous conditions and be
- tions‘ similar to that described above.
fore organo-magnesium compound is introduced a said
.50
‘
Examplei19
monomer‘ and apmemben‘of the class oonsistingof boron,
‘ ' Toaalreaction flask equipped‘, as‘ described‘in Example 1‘ .7 ' l .tri?uoride, beryllium chloride, beryllium bromide, beryl
‘ of ethyl acrylate to polymer is obtained. Polymers of n
. there. is‘ charged 250 parts by volume of anhydrous :tolu
:e‘ne. Nitrogen is bubbled-through the‘ toluene‘: for one
hour ‘to remove dissolved oxygen‘ ‘andrt‘o purgelthefap
‘paratus of air, and 2.5 parts by volume of phenylmagn‘e
‘sium ‘bromide is introduced‘ by means of a hypodermic
syringe‘ inserted through a rubber cap covering one neck
lium‘iodide,‘ magnesium chloride, magnesium bromide,
‘ magnesium‘ iodide,‘ calcium chloride,‘ calcium bromide,
calcium iodide, strontium chloride, strontiumjbromide,
strontium" iodide, barium chloride, barium bromide, bar;
ium iodideyzinc chloride, zinc bromide, zinc iodide, cad
mium chloride, cadmium bromide,cadmium ‘iodide, alu
. mersing the ?ask in a solid carbon dioxide-acetone bath. 60
minurniichloride, aluminum bromide, and ‘aluminum io
“.dide, the‘ saidymember being mixed in apropo‘rtion of 0.5
_ »A solution of 3.5 parts of anhydrous magnesium .bro- ‘ _
to 2.0imoles [thereof per mole of said monomer, whereby
of the?ask. .The solution is cooledto —_60"v C1 by im
mide in 34.5 parts of cyclohexyl acrylate isde-oxygen‘ated ‘ ‘ ‘ a‘preformed complex is formed from saidmember in said‘
“Wltl'i‘a' stream of nitrogen, and then addedrapidly from
, the ‘addition funnel. The resulting solution is'maintained
monomer, and then bringing together under substantially
anhydrous and anaerobic conditions at a temperature
at ~60” C. ‘for sixteen‘ hours, during which time‘ the vis 65 from -—~90° C. to 50° C. and in admixture with an organic
cosity‘ increases markedly. The product is isolated by‘ ' solvent inert to organo-magnesium compounds the mon
omer containing said preformed complex and 0.001 to 0.1
precipitation of the reactiongmixture in 3500 parts of
mole of an organo-magnesium compound per mole of
methanol. The solid which separates is collected on a
said monomer, said organo-magnesium compound being
?lter, dried, and suspended ina mixture of 30 parts of con
‘
centrated sulfuric acid, 100 parts of methanol, and 300 70 of . the formula
parts of water. This slurry is stirred at room temperature
for three hours and then ?ltered. The polymeric solid is
wherein R is one of the class consisting of alkyl, cyclo
washed'with de-ionized water and dried in a vacuum desic
alkyl, aralkyl, aryl, alkoxyaryl, alkenyl, aralkenyl, and
cator. There is obtained 25.1 parts (72.8%) of poly(cyclo
alkynyl groups, of at least two carbon atoms and Y is‘ a
hexyl acrylate) having an intrinsic viscosity in benzene of 75 member'of the class consisting of chlorine, bromine, io
3,100,761
15
1b
dine, and a substituent de?ned by R, whereby monomer is
converted to polymer.
2. A process for preparing a polymer from at least one
monomer from ‘the class consisting of acrylonitrile, meth
acrylonitrile, and esters'of acrylic acid and of methacrylic
acid and an alcohol, the non-hydroxyl portion of which is
free of groups having reactive hydrogen as determined by
the Zerewitinoii test which comprises ?rst mixing to
gether under substantially anhydrous conditions and be
fore organo-magnesium compound is introduced a said
acid and an alcohol, the non-hydroxyl portion of which is
monomer and a member of the class consisting of boron
free of, groups- having reactive hydrogen as determined by
tri?uoride, beryllium chloride, beryllium bromide, berylli- '
um iodide, magnesium.chloridermagnesium bromide, mag
under substantially anhydrous conditions, and before or
nesium iodide, calcium chloride, calcium bromide, calcium
gano-magnesium compound is introduced a said monomer 10' iodide, strontium chloride, strontium bromide, strontium
and a member of the class consisting of boron tri?uoride,
iodide, barium chloride, ‘barium bromide,.barium iodide,
beryllium chloride,rberyllium bromide, beryllium iodide,
zinc chloride, zinc bromide, zinc iodide, cadmium chloride,
the 'Zerewitino? test, which comprises ?rst mixing together
magnesium chloride, magnesium bromide, magnesium io
dide, calcium chloride, calcium bromide, calcium iodide,
strontium chloride, strontiumv bromide, strontium iodide,
cadmium bromide, cadmium iodide, aluminum chloride,
' aluminum bromide, and aluminum iodide, the said mem
15 ber being mixed in a proportion of 0.5 to 2.0 moles there
barium chloride, barium bromide, barium iodide, ‘zinc
‘chloride, Zinc bromide zinc iodide, cadmium chloride,
of per mole of said monomer, whereby a preformed com
plex is formed vfrom said-member in said monomer, and
then bringing together under substantially anhydrous, and
cadmium bromide, cadmium iodide, aluminum chloride,
anaerobic conditions (1) the monomer containing said
preformed complex, (2) an organic solvent inert to or;
gano-magn-esium compounds, and (3) 0.01 to 0.05 mole of
' aluminum bromide,’ and aluminum iodide, the said mem
ber being mixed in a proportion of 05 to 20 moles there 20
of per mole ‘of said monomer, whereby a preformed com
plex is formed from said member in saidmonomer, and,"
then mixing under substantially anhydrous and anaerobic
conditions (1) the monomer containing said" preformed
complex, (2) an organic solvent inert to origano-‘mag 25
nesium compounds, and (3), 0.001v to 0.1 mole of an
an organo~magnesium initiator per mole of said monomer,v
holding the resulting mixtureibetwee‘n -—80° C. and 0° C.
while polymer forms, andwseparating said polymer, the
said organo-magnesium compound being of the formula
’
organo-magnesium initiator per mole of vsaid monomer,
holding the resulting mixture between —90° C. and 50°
R—Mg—Y
wherein R is one of the class consisting of alkyl, cyclo
alkyl, aralkyl, aryl, alkoxyaryl, alkenyl, aralkenyl, and
C, while polymer forms, and separating said polymer, the
alkynyl groups of at least tworcarbon atoms‘and Y
is a member of the vol-ass consistingof chlorine, bromine, .
said organo-magnesium initiator being of the formula
iodine, and-a'substituent. de?ned by R.
V
_ ,
5. A process for preparing pelt/(methyl methacrylate)
' wherein R is one of the class consisting- of alkyl, cyclo
~talkyl, aralkyl, aryl, alkoxyaryl, alkenyl, aralkenyl, and
which comprises ?rst mixing together under substantially
alkynyl groups of at least two carbon atoms and Y is a 35 anhydrous conditions and before organo-magnesium com
'member‘of the class consisting of chlorine, bromine, io
dine, {and ‘a substituent de?ned by'R. ’
.
1 3. A process for preparing a polymer'from at least
one monomer from the class consisting of ,acrylonitrile';
methacrylon-itrile, and esters of acrylic acid and of meth 40
acrylicr'acid 'and‘an alcohol, the non-hydroxyl portion of
which is‘jfree of groups having reactive hydrogen as de
termined by the Zerewitinoif test, which comprises ?rst
mixing ‘together under substantially anhydrous ‘conditions
pound is introduced methyl ‘methacrylate and a member of
the class consisting of boron tri?uoride, beryllium chloride, ‘
berylliunrbromide, beryllium iodide, magnesium chloride,
magnesiumbr'omide, magnesium iodide, calcium chloride,
calciurntbromide, calcium iodide, strontium chloride, stron
tium bromide,‘strontium iodide, barium‘chloride, barium
‘bromide, barium iodide, zinc chloride, Zinc bromide, zinc
iodide, cadmium chloride, cadmium bromide, cadmium io
dide, aluminum chloride, aluminum bromide, and alumi
said'monomer and a member of the class consisting of
num iodide, the said member being mixedin a proportion
of 0.5 to 2.0 moles thereof per moleof said methylmeth
barium iodide, zinc chloride, zinc bromide, zinc iodide, ‘
. organo-magn'esium compounds the methylmethacryla-te .
and'before organo-magnesium compound is introduced a
acrylate, whereby ‘a preformed complex is formed from'
boron‘ tri?uoride, beryllium chloride, ‘beryllium bromide,
said member in said methyl methacry-latqfthen bringing
beryllium iodide, magnesium chloride, magnesium bro
mide, magnesium iodide, calcium chloride, calcium bro ’ together under substantiallyjanhydrous and anaerobic _
mide,,;calcium iodide, strontium chloride,- strontium bro— 50".7 conditions at a temperature from v-—90" C. to 50° C. and ,
in admixture with an organicsolvent which is‘ inert to" ,1
mide, strontiumiodide, barium chloride, barium‘ bromide,
cadmium chloride,‘ calinium bromide, cadmium viodide,
laluminum ‘chloride, aluminum‘brornide, andalu'rn'inumf
lodide, thesaid member being mixed in aprop'ortion
of .0.5i'>moleltoj,2.0t moles‘ per moleof. said monomer,
whereby 'alypreformed'complex'is formed from said mono
‘containing said preformedcomplex and 0.001\ to .0'.'1"ino_le ,
of Van prgano-magnesium compound per mole of $211.5
methyl methacrylate, said organo-ma-gnesium compound
being "of the formula
‘
_
’,
V
V V
V
‘
R-—Mg'—Y‘
_..
rner in said monomer, then bringing together under. sub
whereinR‘is one of the class consisting of-alkyl, cycloal
stantially‘ianhydrous and anaerobic conditions at‘ a temper
hyl, 'aralkyl, aryl, ‘alkoxyaryl, alkenyl, aralkenyl, and
ature from ~90° C} to 50°' C. and‘ in’ admixture with
an. organic solvent- which is inert to organo-magnesium 60 alkynyl groups of at least two carbon atoms and Y ‘is a a
' compounds, the monomer ‘containing said preformed ‘com
plex and 0.0l'to 0.05 molefof an organo-magnesium com
pound per'moleof said monomer, whereby- polymer. is
formed,‘ and separating said polymer, said organo-magnesi
um compound being of the ‘formula
> '
i
member of the class consisting of chlorine,‘ bromine, joy 7
, dine, iand'ta substituent ‘de?ned by R, whereby ‘polymer ;is a
formed.‘ '7
j
,,
-
f
f
plexing member is magnesium bromide and the'organo
magnesium compound ‘is diphenylmagnesium. ' _
‘i "7,. A process for preparing poly(isopropyl methacryl
‘wherein ‘R is one of the class consisting of alkyl, cyclo
ate) which comprises ?rst mixing together under, sub
alkyl, aralkyl, aryl, ‘alkoxyaryl, alkenyl, ,aralkenyl, and
stanially iandhydrous conditions and before organ-o-mag
alkynyl groups of at least two carbon atoms and Y is 70 nesium compound is introduced isopropyl methacryla-te
a member of the class consisting of chlorine, bromine, io
and a memberof the class consisting of boron tri?uoride,
dine, and a substituent de?ned by R. I
beryllium chloride, beryllium bromide, beryllium iodide,
magnesium chloride, magnesium bromide, magnesium
c
4. A process :for preparing a polymer from at least one
monomer from the class consisting of'acrylonitrile, meth
‘
6. A process according to claim 5 in which the com- ‘
iodide, calcium chloride, calcium bromide, calcium iodide,
acrylonitrile, and esters of acrylic acid and of 'methacrylic 75 strontium chloride, strontium bromide, strontium iodide,
.
3,100,761
17
.
18
barium chloride, barium bromide, barium iodide, zinc
chloride, zinc bromide, zinc iodide, cadmium chloride,
cadmium bromide, cadmium iodide, aluminum chloride,
preformed complex is formed from said member in said
tert-butyl acrylate, then bringing together under condi
aluminum bromide, and aluminum iodide, the said mem
ber being mixed in a proportion of 0.5 to 2.0 moles
‘ perature from -90° C. to 50° C. and in admixture
thereof per mole of said isopropyl methacrylate, whereby
a preformed complex is formed from said member in
said i-sopropyl methacrylate, then bringing together under
nesium compounds the tert-butyl acrylate containing said
tions substantially anhydrous and anaerobic at a tem
with an organic solvent which is inert to organo-mag
preformed complex and 0.001 to 0.1 mole of an organo
magnesium compound per mole of the tert-butyl aory~
late, said organomagnesium compound being of the
substantially anhydrous and anaerobic conditions at a
temperature from —90° C. to 50° C. and in admixture 10 formula
with an organic solvent which is inert to organo-mag
nesium compounds the isopropyl methacrylate contain
wherein R is one of the class consisting of alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl, alkenyl, aralkenyl, and
organo-magnesium compound per mole of the isopropyl
methacrylate, said organo-magnesium compound being of 15 alkylnyl groups of at least two carbon atoms and Y is a
member of the class consisting of chlorine, bromine,
the formula
ing said preformed complex and 0.001, to 0.1 mole of an
R--Mg--Y
iodine, and a substituent de?ned by R. _
12. A process according to claim 11 in which the
complexing agent is aluminum chloride and the organo
wherein R is one of the class consisting of alkyl, cyclo
alkyl, aralkyl, ‘aryl, alkoxyaryl, alkenyl, aralkenyl, and
magnesium compound is diphenylmagnesium.
alkynyl groups of at least two carbon atoms and Y is 20
13. A process for preparing poly(cyclohexyl aorylate)
a member of the class consisting of chlorine, bromine,
iodine, and a substituent de?ned by R.
which comprises ?rst mixing together under substantially
anhydrous conditions and before organo-magnesium com
pound is introduced cyclohexyl acrylate and a member
plexing member is magnesium bromide and the organo
25 of the class consisting of boron tri?noride, beryllium chlo
magnesium compound is phenylrnagnesium bromide.
ride, beryllium bromide, beryllium iodide, magnesium
9. A process for preparing poly(isopropyl acrylate)
chloride, magnesium bromide, magnesium iodide, calcium
8. A process according to claim 7 in which the com
which comprises ?rst mixing together under substantially
Ianhydrous conditions and before organo-magnesium
chloride, calcium bromide, calcium iodide, strontium
chloride, strontium bromide, strontium iodide, barium
chloride, barium bromide, barium iodide, zinc chloride,
zinc bromide, zinc iodide, cadmium chloride, cadmium
bromide, cadmium iodide, aluminum chloride, aluminum
bromide, and aluminum iodide, the said member being
compound is introduced isopropyl acrylate and a mem
ber of the class consisting of boron trifluoride, beryllium
chloride, beryllium bromide, beryllium iodide, magne
sium chloride, magnesium bromide, magnesium iodide,
calcium chloride, calcium bromide, calcium iodide,
mixed in ‘a proportion ‘of 0.5 to 2.0 moles thereof per mole
strontium chloride, strontium bromide, strontium iodide, 35 of said cyclohexy-l acrylate, whereby a preformed com
barium chloride, barium bromide, barium iodide, zinc
plex is formed from said member in said cyclohexyl acry
chloride, zinc bromide, zinc iodide, cadmium chloride,
late, then bringing together under substantially anhydrous
cadmium bromide, cadmium iodide, aluminum chloride,
and anaerobic conditions at a temperature from >—90°
aluminum bromide, ‘and aluminum iodide, the said mem
C. to 50° C. and in admixture with an organic solvent
ber being mixed in a proportion of 0.5 to 2.0 moles there 40 inert to organo-magnesium compounds the monomer con
of per mole of said isopropyl aorylate, whereby a pre
taining said preformed complex and ‘0.001 to 0.1 mole
formed complex is formed from ‘said member in said
of ‘an organo-magnesium compound per mole of said
isopropyl iacrylate, then bringing together under substan
monomer, said organo-magnesium compound being of
tially anhydrous and anerobic conditions at a tempera
ture from ~90” to 50° C. and in admixture with an 45
the formula‘
organic solvent which is inert to organo-magnesium com
pounds the isopropyl acrylate containing said preformed
wherein R is of one of the class consisting of alkyl, cyclo
complex and 01.001 to 0.1 mole of an organo-magnesium
alkyl, aralkyl, aryl, allcoxyaryl, alkenyl, aralkenyl, ‘and
compound per mole of the isopropyl acrylate, said organo
alkynyl groups of at least two carbon atoms and Y is a
magnesium compound being of the formula
50 member of the class consisting of chlorine, bromine, io
wherein R is one of the class consisting of alkyl, cyclo
dine, and a substituent de?ned by R.
14. A process according to claim 13 in which the com
plexing member is magnesium bromide and the organo
alkyl, aralkyl, aryl, talkoxyaryl, ralkenyl, aralkenyl, and
magnesium compound is phenylmagnesium bromide.
alkynyl groups of at least two carbon atoms and Y
15. A process for preparing poly(aorylonitrile) which
comprises ?rst mixing together under substantially an
is a member of the class consisting of chlorine, bromine,
iodine, and a substituent defined by R.
hydrous conditions and before organo-magnesiurn com
pound is introduced acrylonitrile and a member of the
10. A process ‘according to claim 9 in which the com
plexing member is magnesium bromide and the organo
magnesium compound is diphenylmagnesium.
.
11. A process for preparing poly(tert-butyl acrylate)
which comprises ?rst
together under substantially
‘anhydrous conditions and before organo-magnesium
60
class consisting of boron trifluoride, beryllium chloride,
beryllium bromide, ‘beryllium iodide, magnesium chlo
ride, magnesium bromide, magnesium iodide, calcium
chloride, calcium bromide, calcium iodide, strontium chlo
ride, strontium bromide, strontium iodide, barium chlo
compound is introduced tert-butyl acryla-te and a mem
ride, barium bromide, barium iodide, zinc chloride, zinc
ber of the class consisting of boron tri?uoride, beryllium 65 bromide, zinc iodide, cadmium chloride, cadmium bro
chloride, beryllium bromide, beryllium iodide, magnesium
mide, cadmium iodide, aluminum chloride, aluminum
bromide, and aluminum iodide, the said member being
chloride, magnesium bromide, magnesium iodide, cal
mixed in a proportion of 0.5 to 2.0 moles thereof per
cium chloride, calcium bromide, calcium iodide, stron
mole of said acrylonit-rile, whereby a preformed com
tium chloride, strontium bromide, strontium iodide, blar
ium chloride, barium bromide, barium iodide, Zinc 70 plex is formed from said member in said tacrylonitrile,
then bringing together under substantially anhydrous and
chloride, zinc lbromide, Zinc iodide, cadmium chloride,
anaerobic conditions at a temperature ‘from —90° C. to
cadmium bromide, cadmium iodide, aluminum chloride,
aluminum bromide, and aluminum iodide, the said mem
ber being mixed in a proportion of 0.5 to 2.0 moles
50° C. and in admixture with an organic solvent which
is inert to organo-magnesium compounds the acryloni
thereof per mole of said tert-butyl acrylate whereby a 75 trile containing said preformed complex and 0.001 to 0.1
- 3,100,761
.
mole of Ian organo-magnesium compound being of the
‘
formula
R—Mg—-Y
wherein R is ‘one of the class consisting of alkyl, cyclo
alkyl, aralkyl, aryl, alkoxyaryl, 'alkenyl, aralkenyl, and 5 '
Marks _______________ __ Aug. 24, 1954
Findlay ______________ __ Aug. 5, 1958
566,713
FOREIGN PATENTS
Belgium ______________ ‘Apr. 30, 1958
Beaman: Journ. Amer. Chem. 800., vol. 70, pages
dine, and a substituent de?ned by R.
2,687,395
2,846,427
.
True-tt _- _____________ __' Aug. 11, 1959
Nowlin et a1. _________ __ Oct. 27, 1959
OTHER REFERENCES
alkynyl groups of at least two carbon atoms and Y is a
member of the class consisting of chlorine, bromine, io
References Cited in the ?le of this patent
UNITED STATES PATENTS
‘2113
2,899,415
2,910,461
3115-3118 (1948).
1
Landler: Recueil des Travaux des Pays-Bas, v01. 68,
pages 992-998 (1949).
<
Schildknecht: “Polymer Processes,” vol. 10 of High
Polymer Series, published 1956, by Interscience vPub
lishers, page 221.
'
I
'
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