Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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I FIELD OF THE INVENTION
This ` invention concerns the polymerizatlon of ethylenic-
a}ly unsaturated polymerizable monomers~susceptlble to frce r~adical
polymerization. Specifically the~invention~concerns novel methods ~
for initiating polymerization of such monomers~and monomer systems ~ -
containing inacti~ve initiators which~lnitiators~may be activated
to polymerize the sy stem.
D~SCRIPTION OF TIIE PRIOR ~IIT
¦ Polymerization of ethy1en1cally uDsaturntecl monomers
may be initiatcd by scveral mcthods wcll k~lown~o tlle ar~. ~ollle
of these include the use of high énergy elcc~tromagnetic radiation
such as gamma r;adiation and x-rays, ultraviole~ llight r2diation,
chemical initiators, and thermal means. Many~polymerizatioll reactio ~s
pend upon the formation of free radicals to~causc the initiatio~
f the polymerization. ;The use of free radical producing agents
~ontaining an acetic acid group has been disclosed in Chambers'
.S~.~3,479,185. The Chambers patent disc10ses or exampl~ the use
of~ a system of N-phenyl glycine or N,N,N~,N',-ethylenediamino
1; ~.
etra~acetio~acid in combination with a 2,4,5-triphenylimidazolyl
dimer aa a photo po1ymerization catalyst. ~
It has now been discovered however that certain
: ~ ituted~aromatic imino diaaetic compounds produce free
ràdiaals and~ provide for excellent and versatile initiators
thout the additional~presence of a dimer.
An add~itional advantage of the initiators of the
en~t lnvèntion is~the1r versatility in that they can cause
polymerlzation in presence or absence of air, oxygen, heat, visible
or ultr~violet;light. ~
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While such sources of radiation energies are therefore not
required, the presence of them as promoters will tend to
increase the activity of the initiator and consequently
the rate of polymerization.
SUMM~RY OF THE INVENTION
According to the invention there is therefore
provided a method of polymerizing a monomer system containing
one or more ethylenically unsaturated compounds su~ceptible
to free radical polymerization which comprises initiating
polymerization by contacting the system with an effective
amount of a dissolved initiator o the formula:
Rl -N~(CH2COOH)2
where Rl is a substituted or unsubstituted aryl radical
provided that the ethylenically unsaturated compounds do
not contain "any group with which all the acid groups of
the initiator will preferentially react chemically" ~as
hsreinafter defined). According to the invention there is
also provided a monomer system susceptible to free radical
polymerization which comprises one or more ethylenically
unsaturated monomers and an initiator comprising a dissolved
compound of the formula Rl -N- (CH2C00~)2 wherein Rl is a
substituted or unsubstituted aryl radical or a salt of said
compound which salt upon acidification will yield said
compound, provided that the ethylenically unsaturated monomers
do not contain any group with which the acid group of the
compound will preferentially react chemically. By aryl is
meant a monovalent radical containing an aromatic ring where-
in the free valence is on a carbon atom of the aromatic ring.
~ESCRIPTION OF THE INVENTION
An important limitation of the process of the
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invention requires that the initiator must be soluble
in at least one phase of a polymerizable system. This
polymerizable system may be an emulsion, suspension or
solution polymerizable system. Often the
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¦initiator is soluble in the polymerizable monorner or monomcrs and
no a~itlonal solvent is rcquil-ed. ~lt~rnativcly in a
polymerizable systcm, whcrc t~e initiator i.s no~ dircctly solublc
in the monomer, thc system n-ust comprise a solvellt such as
for cxamplc, watcr or mcthanol Eor thc initiator. Tllc tcrm
. "dissolved ini-tiator" is therefore meant to include initiators
: dissolved in the polymcrizable monomer and initiators dissolved
in a solvcnt.
The initiating compounds which are useful in thc
proccss of the invention include: ¦
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l-~OOC-CI-I Cll -COOIJ
-. il N- ~ 2 ~- ~ 2
HOOC-CH / Cil -COO~I
, p-methylenedianiline tetraacetic acid
¦ ilOOC-CH
\~ - / ~ CH -COOH
~ ~ ~ 2 m-phenylenediamir.e tetraacetic acid
HOOC-Ci~2 CH2-COOH
l ~ _ l
~Cll -COOil
~C anilinediacetic acid
¦CH ~ ~ -N 2 p-toluidinediacctic acid
3 ~ ~cil2-COoH
Cl~ -COO}I
n-Bu- < ~ -N 2 p-tn-butyl)anilinediacetic acid
Il I
~¦ CH
CH -~ ~ -N 2,4-dimethylanilinediacetic acid
¦ 3 ~ ~CH2-COO
.~ I . I
~CH -COOH
5 ~ -N 2,4-diethy1anilinediacetic acid
-- 5 --
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~ '' OC1l3
C1130- ~ / 2 [(2,4-dimethoxypllenyl)iminoJdiaee~ie acid
C~12COOII I .
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Ho - ~ N~CH2 1~4-hYdro~Yphenyl)iminoJdiacetic ~cid
l ~C~12Coo~
Cl- ~ - N 2 ~4-ehlorophenyl)imino~dlacetie aeid
C112COOII
~C~I COOH
N~ 2 [(1,1'-biphenyl)-4-ylimino]diaeetie
~ ~ C112C0011 aeid
j~ C~ICOOII
~ ~ ~N.~ 2 (2-naphthylimino)diacetie aeid
1 ~ ~ ~ CH2COOH
l l
l ' cil2cooH
. N ~ (l-naphthylimino)diaeetie aeid
~ ~ 12COOI~
2 (~;3Cll;~COOII
[ (4-phcnylmetllylp}lcllyl)ir(lino]diacetic acicl
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C1130 ~ _ N~ 2 [(9-methoxyphenyl)imino]diacetic acid
~ `C' 2C~l l
Preferred initiatin~ compounds are those whercin 1~l has the
~fo110~ing f,rmula: R
¦where R is hyùrogen, a1ky1, a1ko~y, phenyl, ara1ky1, or alkaryl.
Preferred initiators showing high activity are those
containing alkyl or alkoxy substituted aromatic ring c~roup.
Other preferred initiators also having hicJh activity are those
containincJ two aromatic rings.
The initiators useful in the process of the invention
may be prepared by reacting in an aqueous solutian the
corresponding amine component with a slight excess of sodium
chloroacetate at elevated temperatures. During the reaction,
which is usually complete in 2 hours at reflux, the p~1 of the
reaction mixture is carefully controllcd at abou-t 7 by the
addition oE sodium hydroxide. After the reaction is completed
; the product may usually be obtained as the inactive sodium
salt by stripping or alternatively aS anactive precipitate
by acidiflcation such as with hydrochloric acid. In instances
¦1where precipitati~n will not occur after acidification, extraction
procedures may be employed to obtain the product.
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Mc)llon~(r
The unsaturated materials which may be polymeri~ed by
llthe practice of this invcntion are ethylellically unsatura~ed
¦Icompounds susceptiblc to ~rec radical polymcrization. Tllcse
¦compounds include esters, nitrilcs and or~-lnic halo(Jcn compounds
jwhich are cthylenically unsaturatcd compounds of both aromatic and
aliphatic types. ~y way of illustxation, vinyl esters such as
~vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate,
¦and other vinyl esters containing as many as 18 or more carbon atoms
in the acid moicty, may be polymerized in accordance hcrewitll.
Other vinyl derivatives such as vinyl chloride, vinyl
l fluoride, chlorotrifluoroethylene, tetrafluoroethylene, butadicne,
¦ nitroethylene, methyl vinyl ketone, methyl isopropenyl ~etone, buty 11
¦Ivinyl sulfone, vinyl triethoxy silane, ethyl vinyl sulfoxide, styrene,
nuclear substitut~d styrenes including o-methyl, m-methyl,
p-methyl styrene, divinylbenzene, and other related compounds may
alSo be polymerized in accordance hcrewith. Vinylidine
derivatives, viz.~ vinylidene chloride, al~d vinylidene carbonate
respond to this polymerization also.
The acrylates respond particularly well to the tech-
niques disclosed herein and the invention extends to include
acrylates and methacrylates containing up to 18 or more carbon atoms
such as ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl
acrylate, cyclohexo acrylate, cyclohcxo methacrylatc, decyl
I ¦ acrylate, dodecyl methacrylate, methyl methacrylatc, benzyl-acrylate,
tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, methyl
Ichloroacrylate, pentaerythritol triacrylate, neo-pentylglycol
¦diacrylate, ethyleneglycol acrylate phthalate, 2-hydroxypropyl
I ;methacrylate~ 2-hydroxyethyl acrylate and other related compounds
such as acrylamjde, acrylic acid, methacrylic acid rcspolld to
¦treatme;lt set forth hercin.
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¦l Other materials susccptible to the practice hereof
include: acrylonitrile, methacrylonitrilc, 2-chloroacrylonitrile,
lland allyl esters, such as the bisallyl biscar~onate ester of
¦l~diethylene glycol.
¦I Copolymers of the aforementioned unsaturated materials ¦
may be obtained. ~mong the copolymers which may be prepared in
accordance herewith are: copolymers of butadiene, acryloni~rile,
¦¦vinyl acetate, vinylidene chloride, methyl acrylate, and
¦!divinylbenzene with styrene, and one another. Copolymcrs of
butadiene with styrene, butadiene with acrylonitrile, ac~ylic acid
with acrylamide, vinyl acetate ~ith vinylidene.chloride, styrene
with methyl acrylate, and styrene with divinylbenzent:, are
examples of specific copolymers which may be prcpared pursuant to
this invention. Terpolymers prepared in accordance herewith are
~often of special utility, such as those derived from butadiene,
!acrylonitrile, styrene mixtures and other mixtures wherein vinyl
¦lacetate, or methyl methacrylate may be components of the terpolymerl.
Il Preferred monomer systems of the present invention are
¦jthose contailling water soluhle monomers such as acrylamide, diaccto lc
lacrylamide, acrylic acid, methacrylic acid; monomers such as
¦ diethylaminoethyl methacrylate, dimethylaminoethyl mcthacrylate or!
jdimethylaminoethyl acrylate and their derivations such as for example
amine and quaternary ammonium compounds; vinyl monomcr systems
containing unsaturated maleate and fumarate polyesters; monomers
jcontaining acrylate or methacrylate unsaturation either separately
¦or in combination with comonomers such as styrene, methyl methacryl~te
¦lacrylonitrile, vinyl acetate or vinylidene chloride; and latex
forming systems containing butadiene either alone or in combination
rith copolymerizable vinyl monomcrs such as styrene, acrylonitrile,
vinyl acetate or vinylidene chloride.
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The initiators of the invention have differenteffectiveness in different polymerization media, which
may be aqueous or organic in nature. Most of the initiators
are soluble in organic media. However, in aqueous media the
selection of the best initiator is best determined experi-
mentally. In general the least substituted aromatic
diacetic acid initiator is water soluble. As groups are
substituted on the molecules, initiators may lose water
solubility. For example, p-toluidene diacet1c acid was
found soluble in aqueous solutions whereas p- (n-octyl)
anilinediacetic acid was not found soluble in aqueous media.
The ethylenically unsaturated monomers which are
polymerizable according to the method of the invention should
not contain any group with which all the acid groups of the
initiator will preferentially react chemically. For example,
monomer substituents such as for example, amines, isocyanate
or vinyl epoxy groups are highly reactive with the acid
groups of the initiator. Such substituents, i present, will
derivatise the acid groups to amides or esters. While amine
substituents may cause derivation reaction~ which may be
reversible by acidification, substituents ~uch as isocyanate
or vinyl epoxy groups, will cause irreversible reactions
which will permanently diminish or terminate the ability of
the initiators to generate free radicals. By the phrase
"any group with which all the acid groups of the initiator
will preferentially react chemically" is therefore meant
any highly reactive groups which will non-reversibly deriva-
tise all the acid groups of the initiator.
As is well known to those skilled in the art, free
radical polymerization refers to those polymerization reactions
which take place through intermediates having an odd number
; of electrons.
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,ancl, consequently, an unpaired electron. It is these intermediates
¦whieh are generally referred to as free radicals. The free radicalls
¦jare normally cJencrated in one or more of a variety of ways such as
by the decomposition of a chemieal initiator added to the
¦Ipolymerizable mixture or by the application of heat or ionizing
radiation to the composition. If the free radical is generated in
¦the pxesenee of an ethylenieally unsaturated monomer described abov,e,
'the radical will add to the double bond with the regeneration of
another radical. This radical will, in turn, react with another
monomer and in the course of the reaction generate another free
¦radical resultinq in growth of the polymer ehaln through the
laddition of one ehain to another. Free radical polymerization is
¦cleseribed in detail in, for example, the _ncyclo~edia o~ Pol~mer
¦Iseience and Tec}lnology, Vol. 7, pages 361-431, Interseienee
Publishers, 1967, and in the Texthook of l'olymer Scienee, Billmcyer!,
,~Interseienee Publishers, 1962, pages 262-290.
~¦ In addition to growth of the polymer ehaill, several side
¦Ireaetions ean also take plaee during the course of the
olymerization reaetion. One of these, identified as ehain
transfer refers to the transfer of an atom from a moleeule ~o a
¦Ifree radieal in the reaetion mixture. Depending upon the nature of
jthe other material, this ean result in the formation of additional
polymer molecules, the formation of braneh chain polymers, or in
ermination of the polymerization reaetion on a growing raclieal
chain.
¦ Chain transfer agents do not terminate the polymerization
eaetion entirely but merely terminate a growin~J chain ancl allow
the polymerization to start elsewhere. If premature termination
f the growing polymer ehain oeeurs, a reduced molecular weight
results and other polymer properties are achieved. It is, for
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this reason, often desirable to include in a free radical
polymerization system a chain transfer agent which would
funct;on in this manner allowing molecular weight control.
The concentration of the various components utilized
in the production of polymer in accordance with the invention
may be varied over extremely wide ranges and appears to be
not narrowly critical. The concentration of the initiator
is dependent on the activity of the initiator used; the type
and concentration of other components such as solvent and
monomer; and promoters such as heat and light. Although a
concentration range of .01% to 2% is economically preferred
for optimum monomer conversion, under favorable conditions
shown hereafter in the examples, any amounts which are
effective may be used, e.g. initiator concentration of as low
as 0.006% by weight of monomer system and as high as 9% or
more by weight of monomer system may be used successfully.
For example in nonaqueous systems the activity of p-toluidine
diacetic acid is far greater than an initiator having an
unsubstituted aromatic ring such as aniline diacetic acid,
Hence the concentration of a greatly active initiator may be
less than those of less active initiators. In general in the
presence of air, oxygen or other polymerization inhibitor
larger amounts of initiator may be required.
The temperatures used in the practice hereof may
vary widely and are only limited by the freezing and boili~g
point of the polymerizable system. In aqueous systems the
polymerization may be conducted between about 0 and 100C.
Nonaqueous media such as styrene, or isopropyl methacrylate
may allow for polymerization temPeratures as high as about
125C. Other nonaqueous media may allow for polymerization
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temperature of 200C or higher.
The invention does nok exclude the utilization of
~ ~..e~iza'lor. ~-.hl~i~ors, accelerators and molecular
weight modifiers. Any of these may be employed if so
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dcsired. Illhibitors may incllJde any ~ree ra~lical scave~ er.
The polymerization process accorcling to ~he invention mayl
¦occur over a ~ide range of pil. The optimum pll of the polymerizablo
¦systcm will bc affec~cd by ~he stability of the mollolncr ancl the
¦solubility and stability of the initiator.
Ii It has also been discovered that the initiators are
¦¦considerably less active when not substantially in the acid form. I
¦! The activity of the initiator and thus the rate ~f polymerization¦
¦llmay therefore be regulated by adjustment of pll. ~s a further
advantage, the invention therefore provides for a latent polymerizabl~
Isystem by having the initiators present not in the acid form but as
¦the inactive salt, for example, the inactive sodium salt, or amine¦
salt. Such a latent system may thcn be activated by the simplc
adjustment of pll to a point below the neutralization point of the
system. The neutralization point is hereby deined as the pll pOill~
of the polymerizable system at which the initiator becomes active
due to the presence of acid group. In general the lower the pl; of
l~the polymerizable system, the more active the initiator and
; jconversely the higher the pH, the slower the rate of polymerization
¦will be. It should be noted that the neutralization point of the
polymerizable system will vary depending on the specific initiator
¦cmployed.
Il A particular advantage of a latent polymerizable system
¦iis the ability to polymerize a liquid polymerizahle system at any
¦Itime in situ merely by the addition of acid to lower the pl~ of the
¦¦system. For example, in oil recovery operations a water solublc
monomer mixture of sodium acrylate and acrylamide and an inactive I
salt of an initiator may be introduced into an oil bearinc~ formation
las a low viscosity liquid and subsequently polymerized by the
iaddition of acid to activate the initiator to produce a highly
jviscous polymer solution in situ.
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Tlle invention also ~rovides for a polymerizable syst~m
1icontaining additionally a second frce radical polymcrization
j1initiator or catalyst such as a peroxidc systcm to cause postcuring .
The invention is further illustrated by the followin~3
examples in whic1- all parts and percen~acJcs arc by weiyllt unless
¦otherwlse spccified. In the case of the water soluble polymers,
¦the symbol "Ni" represents intrinsic viscosity (i.v.) as measured
in dl/g in a 2N sodium chloride solution at ~5.5C.
\rll~ L~ 1
I A solution of 25 grams of ylacial acrylic acid, 75 grams
¦1of acrylamide and ]00 grams ~istilled water was prepared. To
¦ this monomer solution was added a solution of catalyst consisting
of 0.2 gram p-toluidene diacetic acid and 2.5 grams NaO11, and
87.5 grams distilled water. This mixture resulted in a very light¦
¦tan colored clear solution. The pll was 4.~, the monomer concen-
tration was 20.0~ and the catalyst concentration was 0.20~.
The monomer solution was then poured into a polyethylene
bag, flushed with nitrogen for l minute then sealed with tapc. Tl-
~sample was placed ir. a dark cabinet for 17 hours at room
¦temperature. A rubber gel had resulted. Isolation of copolymer
¦with a methanol-sodium hydroxide solution showed the conversion
of monomers to copolymer to be essentially l00~ complete. The
intrinsic viscosity of the copolymcr was 16.6 dl/cJm when
measured in 2 N NaCl at 2qC.
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.
To illus~rate the wiclc rangc of concclltra~iolls in
wllicll tlle initiators are useful in free radical polymerizations,
p-toluidine diacetic acid was used to initiate a 20% aqueous
acrylamide solution in the presence o air and sunlight at room
temperature. The following Table I shows thc results.
T~Ll. 1
Initiator Ni ~, ~!onomer
I~xaml?le Conccnl:ration % i.v. ConvcLsioll I
2 4 1.6 dl/g ,99
3 2 2.8 dl/cJ 100
4 1 3.8 dl/g 100
0.5 5.~ cll/(J 100
6 0.16 9.0 dl/y 100
7 0.04 ~ little rcac~ion
~ The results of Examples 2 to 7 also indicate that the
; intrinsic viscosity of the polymer is inverscly proportional to
the concentration of the catalyst.
Different initiators were evaluated for their activity
¦ by polymerizing 2 g of acrylamide dissolved in 8 ml of distillcd
water. The following Table II indicates thc results. Irnerc the
indicated light source is sunlight, tlle samplcs wcre exposed to
dlrect sunlight in an open jar at 28C, Whcre the indicated sourcl
is laboratory daylight the samples were stored in a closed jar near
la window und(- an~ient conditions.
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TAB].I II
Concen- Li~ht ~ osure
Example Initiator tration Source Light
8 aniline- z~ sunlic~ht 9 minutes
diacetic acid
9 toluidine- zoO sunlight 45 seconds
diacetic acid
p-l~hcnylcnc 0 5~ sunlight ZO minutes
diaminetetra-
; acetic aci.d
11 2,4-dimethyl- 1.0~ lab. 14 hours
¦ anilinediacetic dayligh~
acid
12 2~4-dimethoxy- 1.0~ lab. 1 hour
anilinediacetic daylight
acid
¦ All of the examples 8-12 produced polymer in th~
I indicated time period.
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~A~ 1 13
To a solution of 2g acrylamidc and 40 mg ~-toluidine
diacetic acid in 8g water wcre addccl 2 drops of a 33% sodium
hydroxide solu~ion. The resulting pll was 9. Thc solution was
cxposcd to sunlight for 80 minutes bu~ failed to ~cl. Thcrcupo
pH was adjusted to 4.5 by addition of concentratcd hydrochloric
¦acid and exposure continued. Gelation was complete within 6
Iminutes. Conversion: 97.5%. The intrinsic visc~sity of thc
Ipolyacrylamide was l~i = 4.6 dl/g in 2N NaC1 at 25.5C.
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¦ To a solution of 2q acrylamide and 8~ water were added
¦20 mg of the sodium salt of p-toluidine diacctic acid. Upon
llillumination with a 300 watt visible light source at 12" for
¦¦1 3/4 hours, no gelation occurred. Thereupon, 20 m~ of p-toluenc j
sulfonic acid were added. The resulting pll was 3. A clear, I
colorless gel formed after 9 minutes of additional exposure ¦ i
indicating the acrylamide had polymerized.
,
EX~LE 15
To a solution of 2q acrylamide and 8g water were added
20 mg of the sodium salt of p-toluidine diacetic acid. Upon
heating at 60C in the dark for over 4 hours, no polymerization
,occurred. Thereupon, 20 mq of p-toluene sulfonic acid were added.¦
The resulting pl~ was 3. Ileating at 60C in the dar~ was
continued. A clear, colorless gel formed in 15 minutes.
E ~ ~LE 16
To a solution of 2g acryl~mide in 4g wa~cr and 49
; ~ methanol were added 40 mg of the sodium salt of p-n-butylaniline
¦diacetic acid. The sample was illuminatcd for 1 1/2 hours with a ¦
¦ 300 watt visiblc light sourcc a~ a dis~allcc oE 12". i~o
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olYnleri~atiotl occurred. 'l'hel:eupon, ~0 sny p-~oluene sul~onie
acid were added. Th~ resulting pll was 3. Fur~her illumination
for ~ minutes resultcd in a eloudy, whi~e gel containin~ ¦
polyacrylamide.
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¦ ~XAMPLF 17
To 2g of a polyoxypropylcnc bisphcnol A fumarate resin
~commereially available from ICI-US Inc. as ATLAC-382-05
¦unsaturated polyester resin) was added 0.3 ml of a solution of
dimethyl~minocthylmethacrylate containinc3 10 mq of
p-n-butylaniline diaeetie aeid. The acid is presumably present as
the amine salt. Tho sample was illuminated ~or 1 1/4 hours with a
30Q watt visible light source at a distanee of 12". A very-sliqht
amount of polymerization oecurred. After addition of 300 mg
I Ip-toluene sulfonie aeid and further illumination, a hard cure
oeeurred within 4 minutes.
EXAMPLE 18
To 2g of polyoxypropylene bisph~nol ~ fumarat~ resin
~as added 0.3 ml of a solution of dimethylaminoethylaerylate
¦¦eontaining 10 mq of p-n-butylaniline diaeetie aeid. The sample
,was heated at 60 overnight in the dark. No eure oeeurred. After
¦addition of 200 mg p-toluene sulfonic acid, the sample cured
~overnight to a hard solid.
¦ EX~LE 19 ¦
To lg polyoxypropylene bisphenol A furmarate resin was
jadded 50 mg of dimethyl-p-toluidine diacetate. The sample was
illuminated for one llour usillg a 300 watt visi~le light source
at a distance of 12". No cure occurred. Thereupon, 50 mg
p-tolucne sulfonic acid were added, illumination continued,
and completo cure occurred witllin 6 minutcs.
* Reg. ~M _ ;8 _ ¦
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¦ EYl~MPL~ 20
Prcparation of m-phcnylenediaminc tet.l^dacet:ic acid
Into a three-neck, round bottom (r.b) flask, equipped
with glass stirrer, reflux condenser, thcrmomcter, and addition
Ifunnel were placed 32.4g (0.3M) m-phenylenediamine dissolved in
¦300 ml water and 203.1g sodium chloroacetate in 300 ml water, and
¦10 drops of a mixed acid/base indicator. The solution was heatcd
¦to reflux and a solution of 48g sodiurn hydroxide in 150 ml water
added dro~)wise so as to maintain the pll betwcen 5 and 8. Re~c~ioll;
was completed within 65 minutes. The reaction mixturc was cooled
and acidified to pH 1 with 120 ml conc. hydrochloric acid. The
formed precipitatc was filtered, washcd with watcr al: pH ~ nd
vacuum dried below 40C. Recovered 49.4g gray solids (mp = 188C,¦
;~N = 7.6).
EXAMPLE 21
Prepar~tion o~ p-(n-butyl)aniline diacetic acid
Into a three-neck r.b. flask, equipped with glass stirrer,
reflux condenser, thermometer, and addition funnel were placed
29.9g (0.2M) p-n-butylaniline; 46.6g (0.4M) sodium chloroacetate
¦ dissolved in a solution of 200 ml water and 45 ml dioxane and 10
¦ drops of a mixed acid/base indicator. The solution was heated to
reflux and a solutlon of 16g sodium hydro;cide in 64 ml water was
added dropwise so as to maintain the pll between 5 and 3 as shown
~¦by the indicator. Reaction was completed within 4 hours. The
! reaction mixture upon dilution with 500 ml water and cooling was
acidified with 43 ml conc. hydrochloric acid. The f~rmed
precipitate was filtered and washed twice with 200 ml of water at
p~l 1.3 and dried under vacuum at 40C. Yield: 41.2g beige solids
(%N = 4.9.)
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I~XAMPLE 2 2
IPreparation of dimcthyl-~-toluidinediaccta~c
I
¦ Into a three-neck r.b. flask, fitted with stirring
assembly, therrnometer, reflux condenser, and a dropping funncl
wcre placed 10.7g (0.1~) p-toluidine, 21.7g (0.2~
methylchloroacetate, 50 ml watcr, and 80 ml dioxane. The
solution was heated to rcflux and 32g of an aqueous solution
containing 8g (0.2~1) sodium hydroxide was added dropwise so as to I
maintain the charge at a ncutral pll. ~ddition was comylctcd
¦Iwithin 1 1/2 hours. The flask was cooled to 5C, and tll~ product ¦
was poured into a 4 1. beaker. Upon addition of 3 1. of water,
a ppt. formed which was discarded. I.xtraction o~ the a-lueous
phase with chloroform and stripping the extract ~ave 24.6g of
¦light-yellow solid.
~ ~XAMPLE 23
¦Preparation of p-mcthylenediallilinctctraacc~ic acicl
¦ Into a three-neck r.b. flask, equipped with glass
¦stirrer, reflux condenser, thermometer, and addition funnel were
placed 29.7~ p-methylenedianiline tO.15M~, and 87.3g sodium
chloroacetate (0.75~1) dissolved in 300 ml distille~ wa~er and 10
¦¦drops of a mixed acid/base indicator. The solution was heated
¦~to reflux and 150 ml of an aqueous solution containing ~a~ (1.2M)
sodium hydroxide added flropwise at a rate so as to maintain the
~pH at 6. Reaction was complete within 2 1/2 hours. The reaction
mixture was poured into a 4 1. beakcr filled with ice water. To
Ithis solution were added slowly and with constant very rapid
; Istirring 60 ml concentrated hydrochloric acid solutioll. Fillally,
JL:dmc I
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I ,......................... I
!
'`` 1097846`
~IIC ~ was broucJIlt to 1.5 wi~!l lN hydrocllloric acid solutio~
precipitate formed. The precipitate ~las filtered and washed twice ¦
¦with 3 l/2 1. and l l/2 1. of cold water whose pll was adjusted to
2. The precipitate was filtered and dried under vacuum, taking
care not to heat the precipitate above 35C. ~ white powder
¦weighing 62g was obtained. Thc product had to be refrlgerated in
¦order to reduce its rate of decomposition. (~ = G.04, ~ Cl = o.l5!,
water = 9 4~ ~ sulfated ash = 0.20~. If the product was kept
refrigerated in the dark and remained stable for more than one
month.
EXAMPLE 24
Preparation of p-toluidinc diacotic acid
l . , Into a three-neck, r.b. flask, equippcd with glass
stirrcr, rcflux conden:cr, thcrmome~cr, and addi~ion funllel wcre
placed 53.5g p-toluidine (0.5 M), and 116.5(J sodium chloroacctatc
dissolved in a solution of 200 ml water and 10 drops of a mixed
acid/base indicator. The solution was heated to re~lux and a
solution of 40g sodium hydroxide in 120 ml water added dropwise
so as to maintain the pll bc~w~cn 5 and 8. l~eaction was complete
within 80 minutes. The reaction mixture upon coolin~ was
¦acidified with 15 ml of conc. hydrochloric acid solution. Thc
¦¦formed precipitate was filtered, washed with water at pll 2, and
¦Ivacuum dried below 40C. Yield: 86g beige solids. (%N = 6Ø)
¦¦ EX~MPL~ 25
¦Preparation of the sodium salt of p- (n-but~l)aniline diacetic acid ¦
¦1 Into a three-neck r.b. flask, equipped with glass
¦Istirrer, reflux condenser, thernlometcr and addition funnel were
placed 29.9g (0.2 M) p-n-butylaniline; 46.6~ (0.4 M) sodium
chloroacetate dissolved in a solution of 200 ml water and 45 ml
IIJL dmc _ l _
:
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dioxane and 10 drops of a mixc~ acid/base indicator. The solution
¦was heated to reflux and a solution of 16~ sodium hyclroxide in
16~ ml water was a~ded dropwise so as to maintain the p~l between
S and 8 as shown by the indicator. Reaction was completed within
,4 hours. The reaction mixture was stripped to dryness to give 50g¦
of the sodium salt of p-(n-butyl)aniline cliacetie acid. Some
sodium chloride impurity may be present in tl-c product.
26
To a solution eontaining 2 gram~ of acrylamide~ 2.0 gralr,s
of sodium ehloride, 40 mg p-toluidine diaeetic acid were added
2 drops of a 33~ sodium hydroxide solution. ~Ihe resulting pll was 9
Tlle solution was exposed to sunligllt for ~0 ;ninutes but failecl to
gel, Thereu~)on, yll was a~justed to 9.5 by addition of eoncentrated
¦hydroehloric aei~ and exposure eontinued. Gelation was complete
¦within 6 minutes. Conversion was 97.56. The molecular weight
Iwas higller than that of a eontrol sample, with no salt added,
Ij as eviclenced by its solution viscosity.
I ~XAMPL~ 27
To a solution o 2 g aerylamide in 7.95 g of water were
added 0.05 ec of a solution eontaininc~ 250 mg of p-toluidine
diacetic aei~ in 100 ml of water. l'he catalyst concentration
base~ on monomer weight was 0. 006o~ The sample was degassed in a
¦viai and kept und~r vaeuum. ~fter illuminatioll with a 300 watt
¦visible light souree at 12" for 25 minutes gelation was observed.
¦A eontrol sample similarily exposed did nGt gel. Conversion 60~.
The intrinsie viseosity of the polyaerylamide was Ni = 19.4 dl/c~
I in 2N NaCl at 25.5C.
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