close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3090781

код для вставки
3,090,771
United States. Patent
Patented May 21, 1963
1
2
and/or
3,090,771
CH1=CHOuH4O CHzCHOHzOH
CHELATING MONOMERS AND POLYMERS
Gaetano F. D’Alelio, South Bend, Ind., assignor, by direct
memo 0 0M):
and mesne assignments, to Dal Mon Research C0.,
which is generalized as
Cleveland, Ohio, a corporation of Delaware
No Drawing. Filed May 12, 1960, Ser. No. 28,559
20 Claims. (Cl. 260-47)
l
cm=ono.H.ooH,oH-orn |
l
l j-N(OH2CO OM>2
This invention concerns new chelating monomers and
polymers and methods for making the new monomers and 10 wherein M is a hydrogen, la lower ‘alkyl or aryl group,
polymers. Broadly, this invention deals with polymeri
zable organic compounds having the formula
‘ an ammonium base, or ‘a metal; and that these monomers
can be polymerized and copolymerized with each other
and with other monomers.
I have discovered further that I can ?rst polymerize or
l
T
15 copolymerize the alkenylaryloxyepoxy-allcane to a poly
mer product having a plurality of repeating
and their polymers containing repeating units of the
formula
structure
.I
IR!
_OH,(I]__
Ar~O-K’—C R_CRQ
20
1
of the
1
Am
0
/
wherein Am is aliphatic aminooarboxyl acid radical
and thereafter react the polymer with a compound pos
bonded through ‘a nitrogen atom, R’ represents hydrogen 25 sessing ‘an active hydrogen and having chelating proper
and ‘methyl, R represents hydrogen and lower alkyl radi
ties, for example, an amino acid, thus:
cals of ‘1 to 6 carbon ‘atoms, K’ is a divalent alkylene
radical of l to 8 ‘carbon ‘atoms in the linear chain between
said valencies and preferably represents a total of no
more than about 16 carbon atoms, Ar represents a di 30
valent aromatic hydrocarbon radical and the chloro and
?uoro ‘derivatives thereof.
Speci?cally, this invention is directed to the syntheses
RI
+ HN(CH2COOM)2 ———>
Ar—-O (OHRMORCR;
\O/
of these new monomers and to polymerization products
obtained by polymerizing a mass comprising these new 35
monomer compounds in the presence or absence of other
polymerizable ethylenic compounds. It is a particular
[
—N (CHzCOOM) 2
object of this invention to prepare soluble and insoluble
polymers having in the polymer molecule a plurality of
The ‘aliphatic aminocarboxylic acids can be represented
repeating units having the formula also given above. It 40 by H-Am wherein Am represents an aliphatic amino
is a still further object of
invention to prepare new
acid radical attached to the hydrogen radical through the
monomeric and polymeric compounds capable of che
nitrogen atom.
lating metal ions and to provide a method .for making
As is well known, the conventional ion exchange resins
such monomers and polymers.
45 are incapable of recovering heavy metal ions ?rom solu
Heretofore, certain chelating monomers containing a
tion containing a higher concentration of lallcali- and
vinyl aryl nucleus have been prepared by reacting a vinyl
aryl benzyl halide with ‘an aminoaoid, and this synthesis
is dependent on the expensive and di?iculty prepared
alkaline-earth ions because such resins function solely by
ion-exchange involving electrovalent bonds, and their
performance is determined by mass action laws.
vinylbenzyl chloride. Another synthesis involves the re
It will be noted that the opening of the epoxide linkage
50
action of chloroacetic acid with vinylbenzyl amine which
. results in a hydroxy group which is hydrophilic in char
is synthesized vfrom the vinylbenzyl halide. A third syn
acter and assists in the wetting ‘of the polymer, especially
thesis is even more expensive, involving the use of vinyl
if it is crosslinked, by aqueous solution of metal cations.
benzaldehyde.
'
Illustrative aromatic groups represented by Ar include,
I have now discovered that chelating monomers having
a vinylaryl nucleus can be prepared from readily available 55
alkenyl aryloxyepoxyalkanes of the formula,
CH1=GR’——Ar-—O (OHR) DOB-CR:
\ /
o
e.g. 1~vinylphenoxy-2,3-epoxypropane
60
OHz=OHCaH40OH:CH—CH2
\ /
O
lllustrative examples of the amino acids, H-—Am, which
by the simple reaction with a compound possessing an
active hydrogen and having chelatin-g properties, for
example, an amino acid, more particularly an imino
acid, e.~g.,
CH¢=CHO¢H;OCH¢Q\H/CH1 + NH(OH;OOOM)2 ——->
O
GHFCHCsEhOCHz?JH-OHaNKlHzCOOM):
OH
65
can be reacted with alkenylaryloxyepoxyallcanes are gly
cine, NHZCHZCOOH; alanine, CH3CH(NH2)COOH;
serine, HOCH2CH(NH2)COOH; cystene
HSCH2CH(NH2) CO OH
70 aminobutyric acid, CH3CH2CH(NH2)COOH; threonine
CH3CH(OH)CH(NH2) COOH; valine
(CH3)2CHCH(NH2)COOH
3,090,771
3
norvaline, CH3CH2CH2CH(NH2) CO OH; isovlaline,
0 H3 C H:
NH:
0-0 0 0H
aforementioned amino acids to give the monomers of this
invention; and the corresponding vinyl polymer behaves in
CH3
the same manner, thus,
methionine, CH3SCH2CH2CH (NH2) COOH; neucine,
(CH3) 2CHCH2CH(NH2)>COOH; norleucine
phenylalanine, CSHSCHZCH (NH2) COOH; aspartic acid
4
polymers of this invention. For example, an alkenylaryl
oxyepoxyalkane reacts readily with HCl to give a chloro
hydrin which in the presence of alkali reacts with the
'
10
NET-CH. C O O H
CH2O 0 0H
glutamic acid
15
NHz
(‘EH-C O O H
(1313: CH2 C O O H
lysine, NH2(CH2)4CH(NH2)COOH; 1,2-diamino pro
pionic acid
20
ITIIEI:
NHzCHnCH-C O OH
aminopimelic acid, HOOC(CH2)4CH(NH2)COOH; beta
aminovaleric acid, CH3CH2CH(NH2)CH2COOH; hy
droxylysine
25
hydroxyethylglycine, I-IOCH2CH2NI-ICH2‘COOH; amino
ethylglycine, NHZCHQCHZNHCHZCOOH; iminoacetic
‘acid, NH(CH2COOH)2; iminopropionic acid
NH (CH2CH2C‘O OH) 2
aminoethyliminoacetic acid
35
NHZ‘CH2CH2N (CH2COOH) 2
Or, the'alkenylaryloxyepoxyalkane can be reacted ?rst
aminopropylirninoacetic tacid
with‘ ammonia or a primary amine to give a substituted
alkanolamine and thereafter converted to an amino acid
in the normal manner with a haloacetic acid or with a
NH2(CH2)3N(CH2COOH)"2
etc., and the derivatives thereof wherein the hydrogen
atoms of the carboxylic groups are replaced by lower
mixture of an aldehyde and an inorganic cyanide, thus
alkyl and aryl groups, ammonium bases, and metals.
NH3
Because of economic reasons the above aminocar
boxylic compounds, H——Am, are preferred but there can 45
be used also 3-aminotyrosine, canavanine, citrul'line, cre
. emu-41in
o
atine, oreat-iniue, cysteic acid, cystine, dibromothyrouine,
3,5-dibromotyrozine, 3,4-dihydroxyphenylalanine, ethio
CHFCH
l
nine, ethionine sulfone, 'glycocyanine, histidine, homo
cystine, hydroxyproline, methylhist-idine, pennicillamine,
pyroglytamic acid, thienylalanine, carboxymethyl aspartic
acid
50
'
oomoonionom
|
l
l
——-NH2
7
CHFCH
CHaCOOH
HN—~CH—COOH
HzCOOH
55
and the corresponding polymer behaves in a similar man
etc., to give the polymerizwable monomers of this inven
ner, e.g.,
tion. Instead of the free acid, or the ammonium bases,
or ‘the metal ‘bases, the ‘lower alkyl or aryl esters of the
aforementioned amino acids [also can be used and the 60
reaction product hydrolyzed to obtain the acid.
Instead of reacting the monomric alkenylaryloxyepoxy
alkanes with an amino acid, I can ?rst polymerize the
alkenylaryloxyepoxyalkanes by vinyl (double bond)
polymerization and‘ react the polymer with the amino 65
acid.
In either case, when either the monomer or poly
mer is reacted with the amino acid and the resulting prod
uct has an amino group still possessing unsubstituted hy
drogen or hydrogens, such compounds can react further
with chloroacetic acid or with glycolic nitrile, HOCHgCN 70
(or its equivalent, an aldehyde and hydrogen cyanide), to
introduce further —CH2COOM groups in the compound.
As is well known the oxirane ring is opened readily by
amines and acids and this behaviour offers alternate,
though not the preferred, syntheses for the monomers and 75
Because of costs and other economic factors, I prefer
3,090,771
5
for the practice of this invention, compounds of the for
naphthyl, ethylphenyl, propylphenyl, butylphenyl, etci
mula
groups.
The ammonium bases de?ned herein for M include the
ammonium radical and various substituted ammonium
II
R’
-| |
(g
~——N—Z
CH1: 0,1140 omoHoH
|
l
I
—
radicals having various substituents thereon, such as alkyl
groups, aryl groups, hydroxyalkyl groups, etc., preferably
_.I
those having no more than about 21 carbon atoms, advan
tageously those having no more than about 10 carbon
wherein Z represents a radical selected from the group of
atoms. Typical examples of such substituted ammonium
radicals include those derived from ammonia, methyl
RI!
—omooorr, —r‘mooom, —CHnOHzOOOM, —OHCOOM
moooM
--(OH:) .Nrv'cmo 0 0M, -€0£{,)N(0H,00 0M):
15
If}!!!a
—(OHQMCH-COOM, —(OHQnCHOOOM
NR]!
moooM
f
N OH 0001
(
2
R’
VI):
I
——CH1 CHCOOM
\
n
-
20
lOH
amine, dimethyl amine, trimethyl amine, ethyl amine, di
ethyl amine, triethyl amine, propyl amine, butyl amine,
dibutyl amine, tributyl amine, trihexyl amine, triheptyl
amine, ethanol amine, diethanol amine, triethanol amine,
isopropanol amine, diisopropanol amine, triisopropanol
amine, methyl diethanol amine, dimethyl ethanol amine,
morpholine, dimethyl benzyl amine, pyridine, ethyl pyri
dine, quinoline, isoquinoline amino pyridine, guanidine,
biguanidine, aniline, methyl aniline, dimethyl aniline, phen
ylene diamine, piperazine, triethylene diimine
CHQCH:
CHa=CCsH4O CHzCHCHg
1 | J
(N-OHzGHz-N)
CHgCHg
wherein M is a member of the group consisting of hydro 25 hydrazine, methyl hydrazine, symmetrical dimethyl hy
gen, lower alkyl and aryl groups, ammonium bases, and
drazine, phenyl hydrazine, amino imidazole, amino di
metals, n is an integer of 1 to 10, R’ represents hydrogen
azines, hydrazino triazines, etc.
and methyl, and R" represents a radical selected from the
Typical metals that can be used in substitution for M
class of hydrogen, lower alkyl radicals, lower hydroxyalkyl
radicals, lower mercaptoalkyl radicals, lower aryl radicals,
30
and —K-COOM.
Some of the compounds of this invention can be repre
l
l
tassium, rubidium, cesium, calcium, strontium, barium,
and the chelate-forming metals as disclosed in “Chemistry
sented also by the following formula:
[OHg=OR'—Ar-O—K'—CRGR2-'| i
in the formulas given herein, include lithium, sodium, po
35
-——~N—K—(NR"-OHR")n'—CO0M
of Metal Chelates,” by Martell and Calvin, published by
Prentice-Hall (1956). Page 182 of this book shows the
periodic classi?cation of chelate-forming metals.
The monomers of this invention can be polymerized
individually or as mixtures with each other, or with 0.1,
preferably 1 percent by weight or more of other vinyl
and vinylidene compounds, such as styrene, alphamethyl
wherein the symbols Ar, K’, R, R’, R", and M are as de
styrene,
vinyl toluene, vinyl xylene, chlorostyrene, bu
?ned above; 11' is 0 or 1; R'" is a group represented by R" 40
tadiene, isoprene, acrylonitrile, methacrylonitrile, meth
and can also be
_I
45
and K is a divalent alkylene group preferably having no
more than about 10 carbon atoms in the chain connect
ing said valencies.
It is preferred that, when n’ is 0, either K represents a
methylene or ethylene group or there is an NR",2 group 50
substituted on a carbon atom of K no farther removed
than two carbon atoms from said COOM group. The
alkylene radical K can have substituted thereon various
acrylate, ethylacrylate, benzylacrylate, methyl methacry
late, ethyl methacrylate, glycol diacrylate, glycol dimeth
acrylate, allyl acrylate, allylmethacrylate, vinyl acetate,
vinyl propionate, diallyl succinate, diallyl phthalate,
maleic anhydride, dimethyl maleate, itaconic anhydride,
itaconic imide, dimethyl itaconate, diallyl itaconate, acryl
amide, methacrylamide, allylacrylamide, hydroxyethylac
rylamide, N-methylene-bis-acrylamide, acetylglycine, vinyl
pyridine, methacrylyllysine, methylvinylketone, acetylam
inophenylethylene, vinylimidazole, 2-isopropenyl-4-iso
propyl ~ 2 - oxazolin - 5 - one, N-vinyl - 5 - methyl - 2 - ox
azolidinone, N-vinyl-pyrrolidone-Z, etc., or they can be
grafted to other polymers containing peroxy groups to
substituent groups, such as —OH, —NRZ, —SH, lower
produce grafted copolymers, as disclosed in my copend
55
alkyl-S— groups, and lower aryl groups, as well as addi
ing application, Serial No. 28,560, ?led the same date
tional —COOM groups. The simpler compounds are
herewith.
'
preferred, generally those derived from amino acids hav
The polymers and copolymers of this invention can
ing no more than about 20 carbon atoms therein, prefer
be prepared in mass, in solution, in suspension, and
ably no more than about 10 carbon atoms, and advan~
emulsion systems, using the accepted initiating systems,
tageously having no more than about two groups selected 60 such as the per compounds that generate radicals, or
from the class consisting of hydroxy and thio groups.
thermally, or with ultraviolet light, or with ionizing
Also, it is generally not any particular advantage to have
radiation, and in some cases, with ionic catalysts, both
more than six groups in the amino acid selected from the
cationic and anionic, e.g., BF3, sodamide, HF, etc.
class consisting of amino and —COOM groups.
The invention is illustrated by the following examples
As used herein, the terms “lower alkyl,” “lower hy 65 which are intended merely for illustration and are not
droxyalkyl,” “lower mercaptoalkyl,” and “lower aryl” are
in any way to be interpreted as limiting the manner in
intended to include such groups having no more than about
which the invention can be practiced. All parts and
10 carbon atoms, such as methyl, ethyl, propyl, isopropyl,
percentages are given by weight unless otherwise speci?ed.
butyl, secondary butyl, amyl, secondary amyl, hexyl,
heptyl, nonyl, decyl, secondary hexyl, secondary nonyl, 70
benzyl, phenethyl, hydroxyethyl, hydroxypropyl, hydroxy
EXAMPLE I
To a mixture of 1000 parts of water, 1500 parts
butyl, hydroxyamyl, mercaptoethyl, mercaptomethyl, mer
CHsOH, 81 parts NaOH in 500 parts water and 133 parts
captopropyl, mercaptoamyl, methylmercaptomethyl, meth
of iminodiacetic acid in a suitable reaction ?ask equipped
ylmercaptoethyl, ethylmercaptomethyl, ethylmercaptoeth
with a stirrer and heating means, there is added slowly
yl, ethylmercaptopropyl, phenyl, tolyl, dimethylphenyl, 75 at 35° C. over a period of two hours, 176 parts of 1-(4
3,090,771,
7
8
tively, in place of the isovaline, there is obtained respec1
tively, monomers corresponding to the formulas
vinylphenoxy)-2,3-epoxypropane, following which the
mixture is re?uxed for 11/2 hour. The methanol then is
distilled from the reaction mixture and 10 parts of de-v
colorizing carbon stirred into the reaction mixture and
the mixture ?ltered. The cooled, v?ltered mixture is acidi
?ed with concentrated hydrochloric acid to ‘a pH of 2—3
and the white crystalline precipitate collected by ?ltration,
dried, and there is obtained a monomer corresponding
to the formula
10'
on,=ono?moomonom I
a
| | 'TmomoooH):
which, an elemental analysis, gives C, 58.20%; H, 6.21%;
N, 4.48%, which values are in close agreement with the 15
theoretical.
Reaction with bromine con?rms the presence of'ole?n
unsaturation.
'
The monomer of this example is characterized further
by its ability to chelate metal ions in solution. The.
metal chelates are prepared by dispersing the sodium or
ammonium derivative of monomer compound in water,
or in an N KCl or NaCl solution and adding the metal
ion in the form of a salt, such as the nitrate, chloride,
which on analyses give values for C, H, and N in close
sulfate, etc., e.g. CuClz FeC12, FeCl3, etc; or the acidic 25 ‘agreement with the theoretical values for these com
monomer compound can be used directly by dispersing
pounds, and which have good chelating, properties for
it in the solution of the metal ions and adding alkaline
metal ions.
'
substances, such as NaOH', KOH, LiOH, NH3, CHSNHZ,
EXAMPLE
VI
7
(CH3)2NH, (CH3)3N,
etc. The mOI1-.
omer of ‘this example forms 1:1, and 2:1 chelates with
The procedure of Example I is repeated using 133 parts
CuH, CO++, Ni++, Fe+++, Fe++, P-b++, as well as a
of vaspartic acid instead of iminodiacetic acid and there is
1:1 chelate with Mn++.
obtained’ a monomer ‘corresponding to the formula
EXAMPLE II
The procedure of Example I is repeated using 117
parts of isovaline and 41 parts of NaOH instead of the
iminodiacetic acid and 81 parts NaOH. There is obtained
a monomer corresponding to the formula
whose chelating properties are similar to the monomer of
40
Example I.
>
'
'
EXAMPLE VII
When 147 parts of glutamic acid are substituted for the
‘aspartic acid of Example VI, there is- obtained a monomer
which on analysis gives C, 65.89%; H, 7.22%; N, 4.78%,
which values are in close agreement with the theoretical. 45 corresponding to the formula
EXAMPLE III
om=orro.n,oomoH-cm I
When 117 parts of valine are used in the procedure
| TNH-CHC 0 OH
of Example H instead of isovaline, there is obtained a
HzCHzCOOH
monomer corresponding to the formula,
50
and when 175 parts of aminopimelic acid are used instead
OH
of the aspartic acid of Example VI, there is obtained a
monomer corresponding to the formula
I
I: onF 0110110011
H 2lCHOH
| “II-on omen,
Ll-1\nzt--onooo12r
CH(CHa)z
which on elemental analysis gives'values of C, 65.9%; 55.
H, 7.19%; N, 4.74%, which are in good agreement
with the theoretical values.
'
or:
CHFCHC¢H4OCHgOH—OHg
I
1
I
——NHCHOO0H
7
CHaCHaCHaQHaCOOH
which has marked chelating properties for metal ions.
EXAMPLE Hi
EXAMPLE VIII
When 117 parts of norvaline are used in the procedure 60
of Example II instead of isovaline, there is obtained a
5 '146 parts of 1-(4-vinylphenoxy) -2,3-epoxypropane are
monomer corresponding to the formula,
reacted with 149 parts of methionine and 41 parts NaOH
in a water-methanol solution according to the procedure
of Example I and there is obtained a monomer correspond
ps5 ing
to the formula
l
which on elemental ‘analysis gives values for C, H,’ and’
N in close agreement with the values of Example IH.
CH¢=CHCaIELgO omen-0H, I
70
,EXAMPLEVV I
When the procedure of Example II is repeated using
,
1
1
V
TNHOHGOOH
CHgCHzSCHa
EXAMPLE IX
‘
When the procedure of Example VHI is repeated using
an equivalent amount of (a) 75 parts glycine, (b) 89
119 parts of hydroxyethyl glycine instead. of methionine,
parts alanine, (0) 103 parts aminobutyric acid, (d) 165. 75 there is obtained a monomer corresponding to theformula;
parts leucine, and (e) 151 parts phenyl glycine, respec
3,090,771
9
.
10
When evaluated by the procedure of Example I, the
monomers of Examples H and XII inclusive are shown
to form metal chelates with heavy metal ions in solution.
a:
H’CHzOH
5
EXAMPLE XIII
181.5 parts of vinylphenoxyglycerylchlorohydrin,
-|
EXAMPLE X
When the procedure of Example VIII is repeated using 10
[OHFOHQEOCEHJHYHLL
_|
104 parts of serine instead of methionine there is obtained
a compound corresponding to the formula
log
OHz=0HC6H40CH:?HCH2J_NHOHCOOH
l _|
HIGH
EXAMPLE XI
(obtained by reacting one mole of 1-vinylphenoxy-2,3
epoxypropane with one mole of concentrated HCl solu
15 tion) are added slowly over a period of 90 minutes to a
re?uxing stirred mixture in a suitable reactor of 133 parts
of iminodiacetic acid, 81 parts of NaOH, 1000 parts of
water and 2000 parts of methanol. After half of the
chlorohydrin has been added, another 40 parts of NaOH
20 in 150 parts of water is ‘added, and the addition of the
chlorohydrin continued until completed, following which
When the procedure of Example I is repeated using
the mixture is allowed to cool to room temperature. The
121 parts of cystene instead of iminoacetic acid there
is obtained a compound corresponding to the formula
I:
mixture is then extracted with four separate portions of
30 parts of chloroform. The mixture then is acidi?ed with
—-|
25 concentrated hydrochloric acid to a pH of 2-2.5 and
CHFCHCDH‘O CH’OHCH, !
——0H
the crystalline solid separated by ?ltration and recrystal
———-NHOHCOOH
lized from water.
l
|
.
'
'
_
sponding to the formula of the monomer of Example XII.
HgSH
30
EXAMPLE XII
'
There is obtained a monomer corre
EXAMPLE XIV
163 parts of
The procedure of Example I is repeated using 292 parts
of divinylbenZene-monoepoxide 75 parts of glycine, and
41 parts of NaOH and there is ,obtained a monomer cor-
responding to the compound
I:
-|
CH _OHC H 0 CH CHOH——
:a 4
“1 | 2_|_NH,
35
_|
(a)
om=onotmoongrllnom |
| (frH2OHOHgOCgH4GH=CH:
CHnCOOH
(obtained by treating 1-vinylphenoxy-2,S-epoxypropane
which functions as a crosslinking agent as well as a chelat
ing compound. By using the corresponding aminoacids,
the following monomers ‘are made in a similar manner.
with ammonia), 144 parts of dimethyl maleate and 300
parts of ethyl ether are mixed and stirred for 150 hours
at room temperature, followed by the addition of 50 parts
45 of concentrated hydrochloric acid. The ether layer is
separated, dried with anhydrous sodium sulfate and re
(0)
l
lo
[onponosmoomonom
I N'
I l J
L
cm-on-ooon
(c)
l0
onFonotmoomonon, |
0_|'
N
| omonomommon=om
CZHg-GHC O OH
1(d)
_l
N
|
L
053-0-000H
2H:
(s)
r
l-OH H0—
onponctmoomomlm, ]
_|
N
|
L
CHOOOH
HzCOOH
3,090,771
1I
7
12
of lysine instead of isovaline, and there is obtained a
monomer corresponding to the formula
?ltered. Evaporation of the ether yields the ester,
l
..
CHFCHCuHgO 0112011011, |
l
I
[onponotmoomonom
I
NH’
I | TNH(CH:)iCHCO-OH
—-NHCHO o 0 CH3
CHzGOOOHa
which :can be used directly as a monomer and thereafter
and when the monomer is treated with 3 moles of chloro
saponi?ed, or it can be saponi?ed directly. 150 parts of
acetic acid according to the procedure of Example XV,
this ester is re?uxed with 300 parts of water containing
or with 3 moles of glycolonitrile according to the proce
60 parts NaOH for 4 hours, following which it is acidi?ed 10 dure of Example XVI, there‘ is obtained the monomer
to a pH of 2.5 with concentrated hydrochloric acid and
corresponding to the general formula
~ .
on cooling, the precipitated monomer is ?ltered and dried.
l
There is obtained a monomer corresponding to the for
lOH
.
l' l TN-omomomomorrooon
omoo OH
15
CH3=CHCuH4OCHrCHCHz
|
I I -——NHOHCOOH
EXAMPLE XIX
Fifty parts of distilled water, 0.5 part of hydroxy
omooon
apatite (0.005 to 0.2 micron size), 0.01 part of sodium
EXAMPLE XV
To a solution containing 120 parts of chloroacetic acid,
20 dodecylbenzenesulfonate, 2.5 parts of commercial divinyl
benzene (50% DVB) and 45 parts of 1-vinylphenoxy-2,3
100 parts of NaOH, 1000 parts of water is added 163 parts
of
momoooro;
om=onotmoomorrom |
mula of the monomer of Example VI,
epoxypropane, 0.2 part of benzoyl peroxide are mixed
in a suitable reaction ?ask'and stirred for 15 hours at
90° C. and there is obtained a crosslinked copolymer
.
25
having the repeating unit,
and the mixture heated at 80-90‘? C. for 30-45 minutes.
A small amount of decolorizing carbon is added and the
solution is ?ltered, then acidi?ed with concentrated hy 30
0
drochloric acid to a pH of 1.9-2.2, followed by concen
EXAMPLE XX
trating the solution to 60-70% of its original volume
under reduced pressure. The slurry is ?ltered and the
Fifty parts of distilled water, 0.5 part of hydroxyapatite
(0.1 to 0.2 micron), 0.005 part of sodium dodecylben
crystals dried.
'zenesulphonate, 0.1 part 2,2’-azobisisobutyronitrile and
There is obtained a monomer corre
35 50 parts of l-vinylphenoxy-2,3-epoxypropane are mixed
sponding to the monomer of Example I.
in a suitable quantitative yield of a fusible polymer having
EXAMPLE XVI
the repeating unit,
The monomer of Example XV can be prepared also
by reacting the substituted ethanolamine in the presence
of alkali with glycolonitrile (or its equivalent formalde 40
hyde and an alkali cyanide) as follows: a mixture of
163 parts of
which is soluble in such solvents as acetone, chloroform,
1
——-OH
etc.
l I ——NHn
[onporrotmoomonom
I.
_|
.
EXAMPLE XXI
45
1000 parts of water, 80 parts of NaOH in a suitable con
tainer is heated to 7 0~80° C. and 82 parts of 70% aqueous
solution of glycolonitrile is added slowly over a 3-4 hour
To 1000 parts of water is‘added. 25 parts-of
'l
CHFCHCdLOCIEhCHCHz |
I l —~N(CH:OOOH):
period. After all of the ammonia has been expelled, the 50
solution is concentrated to 60-70% of its original volume,
‘and the solution maintained at 90-92" C. for 4 days while
treated with a little decolorizing carbon, ?ltered, acidi?ed
to a pH of 2~2.5, and the monomer separated by ?ltration
exposed to ultraviolet light. There is obtained a precipi
tate which corresponds to the polymer having
'
and dried.
55
EXAMPLE XVII
-omon
The procedure of Example I is repeated using 176 parts
of aminoethyl~aminoacetic acid instead of the iminoacetic
C6H400H1CHOH1 |
‘acid and there is obtained a monomer corresponding to
the formula
V
60 groups.
om=onoemoomonom I
I
Tumcmnmomo 0 0H):
and when this is treated with chloroacetic acid according
to the procedure of Example XV, or with glycolonitrile ac
cording to the procedure of Example XVI, there is ob
tained the monomer corresponding to the formula
—o
om=onotmo 0111011011, |
I
I
-——NCH2CH2N(CH:COOH):
CHZGOOH
EXAMPLE XVIII
.
-—N(on,oooH),
.1
Using the method of Chaberek and Martell (J. Am.
Chem. Soc., 74, 5052 (1952) ), the disassociation constants
-_-o
|
|
-
as determined qualitatively are about k1=4.58 X 10-4 and
k2=6.68><10-1°. The polymer turns blue upon the addi
tion of a solution of cupric chloride, leaving the water
phase ‘colorless. Using the procedure described by I.
Bjerrum (“Metal Amine Formation in Aqueous Solu
tion,” Publisher Haase and Son, Copenhagen, 1941) it
is determined that the polymer forms both 1:1 and 2:1
70 chelates, whose stability constants are approximately
K1=5.78><109 and K2=1.55><l06. The polymer'also
forms chelates with ferric chloride corresponding to 1:1,
1:2, and 1:3 chelates below pH values of 8.6 and the
stability constants of these chelates are approximately
The procedure of Example II is repeated using 154 parts 75 K1=1.26><101°, K2=4.60>< 107, and K3=8.09><104.
3,090,771
13
.
EXAMPLE. XXII
A mixture of 35 parts of
.I
[onponoirno OHaOHCHz |
| | TNOHzOOOH
14
,
.
and there is obtained 47.5 parts of a crosslinked poly
meric ester which is suspended in '500 parts of 5% sulfuric
acid and heated to re?ux temperature for 24 hours to
hydrolyze the ester groups. There is obtained a chelat
-
ing polymer having properties similar to that of Ex
ample XXV.
EXAMPLE XXVII
A mixture of 28 parts of
100 parts of water, ‘containing 4 parts NaOH are heated
to re?ux and 50 mg. of sodium persulfate added and the
heating continued at 90° C. for 24 hours, following which
.1
is added ‘another 50 mg. of sodium persulfate in 200 parts 10
of water and the heating continued for an additional 24
hours. There is obtained a crosslinked polymer gel which
| l TNHOH?OOoC/iH5
is washed with 2000 parts of water. The washed polymer
(the ethyl ester of the monomer of Example V(a') ), 52
is then added to 2000 parts of dilute sodium hydroxide and
15 parts of styrene (approximately 1:5 mole ratio of mon
[onponoemo omonom |
the mixture heated, cooled, ?ltered, washed with 5000
omers), and 0.35 part of benzoyl peroxide in 200 parts
parts water, and dried. There is obtained a crosslinked
of benzene are re?uxed for eight hours and there is ob
tained a copolymer solution which is concentrated under
reduced pressure and the polymer washed with meth
polymer having the repeating unit,
anol. Hydrolysis of the copolymer with sodium hydrox
ide produces the sodium salt of the copolymer which on
acidi?cation with acid produces the copolymer acid. In
a similar manner other ratios of the two monomers from
100:1 to 1:100 can be copolymerized. Also, instead of
styrene substituted styrenes, such as the methyl styrenes,
the dimethyl styrenes, the chlorostyrenes, etc., may be
used to produce the corresponding copolymers.
EXAMPLE XXVIII
whose chelate stability constants for copper are approxi- 30
mately K1=2.37><105 and K2=4.36><104.
EXAMPLE XXIII
26 Parts of
l
A mixture of 25 Parts of
om=onoimoomzlznoH%_NHOHICOOH
‘I
on
_
o
.
“
>
[ FOHCGH' ] H<|3H2~I— (OHzCOOH):
35 and 81
parts of acrylamide are added
to 175 parts of
'
.
.
Water and the pH adjusted to 5.5 with NaOH. To this
—'
solution is added 0.4 part of 2,2'-azobisisobutyronitrile
and 10 parts of
and the mixture heated to 70° C. for 10 hours. The re
onponoomoomonomlon
]
‘
'
HO-El ongonomoo?monpon
:r—N'—T
>'
" '
HQCOOH
are polymerized by the procedure of Example XXII and
there is produced a resinous copolymer which chelates
sulting copolymer is precipitated with acetone, rewashed
with acetone, ?ltered, and dried, and the isolated copoly
with the metal ions of Fe++, Fe+++, Co++, Ni++, Cu++,
Pb++, Mn++, Sr++, and Mn+++.
mer forms good chelates with copper and other chelate
50
EXAMPLE XXIV _
forming metals. Instead of the approximately 1:1 ratio
used above other ratios varying from 1: 100 to ‘100:1 can
be used to prepare chelating copolymers.
A mixture of 14 parts of iminodiacetic acid, 15 parts
of 1-vinylphenoxy-2,3-epoxypropane polymer of Example
EXAMPLE XXIX
XX, and 500 parts of dioxane are stirred at room tem
'1000 parts of polyethylene granules are irradiated in
perature for .12 hours and 5 parts of tributyl amine added, 55
air at room temperature with a cobalt 60 source to‘a
following which the mixture is heated for 12 hours at
dose of 15 magareps and then immersed in a 50% mix
70—80° C. and at the end of that period 2000 parts of
ture of
water are added slowly. The solid chelating polymer
is separated, dried, ‘and has properties similar vto the
polymer of Example XXI.
I
'
60
EXAMPLE XXV
The procedure of Example XXIV is repeated, using
J
the divinylbenzene-vinylphenoxyepoxypropane copolymer
and heptane and heated at 60—70‘’ C. until the increase
of Example XIX instead of the polymer of Example XX. 65 vin weight of the polyethylene is about 25%. The poly
mer is then hydrolyzed at 80° C. in a 10% NaOH alcohol
There is obtained a crosslinked copolymer having chelat
solution and there is obtained a graft copolymer having
ing properties similar to the polymer of Example JOHII.
chelating
proper-ties similar to the polymer of Example‘I.
EXAMPLE XXVI
The procedure of Example XIX is repeated ‘using 70
EXAMPLE XXX
divinylbenzene and
An aqueous solution of 2-vinyl phenolate is prepared
from 120 parts of 2-viny1 phenol, 42 parts sodium hy
—o
CHnZCHCaH4O omorrom |
droxide, and 400 ml. water. This solution is added with
stirring over a period of 1 to 1.5 hours to 102.6 parts
l i TNHCHO O 0 CH3
H700 0 CH3
75 of epichlorohydrin at 60° C. and stirred for an addi
3,090,771
16
15
_tional~hour at 80-85° C. The resulting solution‘ com
prises.
'
_
-
a
-
l
.
CHg=OHOuH4OGH1CHCHz
\o/
CHaCOOH
While certain features of this invention have been de
which can be used as such,'or the water can be removed
scribed in detail with respect to various embodiments
by evaporation at reduced pressure. Alternately, the
‘thereof, it will, of course, be apparent that other modi
aqueous solution can be extracted with ?ve ZOO-part por
?cations can be made within the spirit and scope of this
tions of ethyl ether; ‘the ether removed by'evaporation
invention and it is not intended to limit the invention .to
10
leaving an oily residue which is distilled at 1 mm. pres
the exact details shown above except insofar as they are
sure to separate the epoxy compound from a small quan
de?ned in the following claims.
tity of l-(2-vinylphenoxy)-2,3-propanediol. When 3- or
4-vinyl phenol are used instead of 2-v-inyl phenol in the
above procedure, the corresponding glycidyl ether is ob
tained.
-
'
.
The invention claimed is:
1. A compound having the formula
Similarly, when the isopropenyl phenols, or 15
when the vinyl or isopropenyl cresols are used, the cor
responding alkenyl aryloxyepoxyalkanes are obtained.
When, instead of epirchlorohydrin, there is used other
haloepoxyalkanes, such as, for example, 1-chloro-2,3
wherein R’ is a radical ‘selected from the class consisting
of hydrogen and methyl radicals; R is a radical from
epoxybutane, 1-chloro-3,4-epoxybutane, 2-chloroV-3,4
the class consisting of hydrogen and alkyl radicals of
epoxybutane, l-chloro-Z - methyl-2,3-epoxypropane, 1
no more than 6 carbon atoms; Ar represents a divalent
lbromo-2,3-epoxypentane, 2-chloromethyl - 1,2-epoxybu
aromatic radical selected from the class consisting of
divalent aromatic hydrocarbon radicals and the chloro,
ethyl-2,3-epoxypentane, 4-chloro-2 - methyl-2,3-epoxypen
25 and ?uoro derivatives thereof; K’ is a divalent alkylene
tane,
1-bromo-4-rnethyl - 3,4 - epoxypentane, v l-bromo-4
lane, 1-chloro-2,3-epoxypentane, 1-chloro-2,3-epoxyoc
Itane,
l-chloro-Z-methyl - 2,3 - epoxyoctane,
radical of at least 1 and no more than 8 carbon atoms
1-iodo.-2,3
in the linear chain between said valencies; and Am rep
epoxydecane, etc., then the corresponding alkenylaryl
epoxyalkane is obtained.
EXAMPLE XXXI
resents an aminoacid radical selected from the class con
30
sisting of aliphatic aminoacids, ‘the metal and ammonium
salts and lower alkyl and lower aryl esters thereof, said
Am radical having the valence bond 'of’said formula
A number of the foregoing procedures are‘repeated
using an equivalent weight of a di?erent epoxy compound
attached to an amino nitrogen in said radical, having no
ing products.
of the formula
more than about 20 carbon atoms therein and having an
in place of that of the original example. The following
table lists the original example and the respective epoxy 35 amino group no farther than 2 carbon atoms away from
a carboxylic group.
compound used. Table H lists the corresponding result
2. A polymer having a plurality of repeating units
Table I
40
Example
repeated
Epoxy compound
Ar—0—-K’—lOR(l)R2_I] A
-—
wherein R’ is a radical selected from the class consist
1-(4-lsopropenyl-2-Me-phenoxy)-3-4-epoxybntane.
1-(4-vinylphenoxy)-3,4-epoxybutane.
2-(4-vinylphenoxy)-4,5-epoxypentane.
2-(éwinyl-Q-Cl-phenoxy)-6,7-ep0xyoctane.
1-(4-viny]naphthoxy)-2,3-epoxypropane.
1-(vinyl-diphenyloxy)-2,3-epoxypropane.
m
ing of hydrogen and methyl radicals; R is a radical from
45 the class consisting of hydrogen and alkyl radicals of
no more than 6 carbon atoms; Ar represents a divalent
aromatic radical selected from the class consisting of
divalent aromatic hydrocarbon radicals and the chloro,
and ?uoro derivatives thereof; K’ is a divalent alkylene
50 radical of at least 1 and no more than 8 carbon atoms
in the linear chain between said valencies; and Am rep
Table II
(Va) ‘
resents an aminoacid radical selected from the class con
(b)
sisting ofraliphatic aminoacids, the metal and ammonium
‘salts and lower alkyl and lower aryl esters thereof, said
Am radical having the valence bond of said formula at
tached’ to an amino nitrogen in said radical, having no
'
OH
more than about 20’carbon atoms therein and having
oHFoHmmo-oHmrncH-om
|
1 ——NHCHCOOH
J
11200011
(c)
an amino group no farther‘ than 2 carbon atoms away
60
from a carboxylic group;
'
.
3. A process of preparing chel'ating compounds which
comprises the step ofreacting an aminoacid'compound
with an alkenylaryloxyepoxyalkane of the formula
lOH,
wherein R' is a radical selected from the class consisting A
of hydrogen and methyl radicals; R is a radical from the
class consisting of hydrogen and alkyl radicals ofv no
J
(a
l
HzCOOOH:
0 more than 6 carbon atoms; Ar represents a divalent aro
matic radical selected from the class consisting of divalent
aromatic hydrocarbon radicals and the chloro, and ?uoro
derivatives thereof; and K’ is a divalent alkylene radical
of at least 1 and no more than 8 carbon atoms in the
linear chain between said valencies; said aminoacid com
3,090,771
17
18
pound being selected from the class consisting of amino-
10. A compound having the formula
om=onoumoonqonclzm_i_.____N______{
] l L| ontonomootmoihone
omooort
acids and the metal and ammonium salts and lower alkyl
11. A compound having the formula
and lower aryl esters rthereof, said aminoacids having a 20
12. A polymer having a plurality of repeating units
hydrogen atom on an amine group therein, having no
having the formula
more than about 20 carbon atoms {therein and having an
amino group no farther than 2 carbon atoms away from
a carboxylic group.
4. A compound having the formula
_QH2CH_
loH
CsH4OCHzCHGHg |
25
_l
CHFOHCeHm omoHomT
l l TNwH’COOH)’
.
5. A compound having
the formula
| TN(OH2COOH)Q
h 1.3. Ahpoflymer1 having a plurality of repeating units
30
avm
e
g
3-011 CH:
_CH’CH‘
oHFoHoeHm OHzCHCHz |
1 | TNH—C—COOH
oHeoH,
lOH
CgH4OCH2CHCHz |
35
6. A compound having the formula
—I
OH
H
H OHCH
l
l TNHCHzOOOH
14. A polymer of claim 2 having at least 0.1 percent
-—
by weight of a polymerizable monomer
having
at least
.
.
[UHF Ca 400 2| 1 al_NH_oHoooH
J
ormu a
011mm),
one CHFCI-K group copolymerlzed therein.
40
15. A polymer of claim 2 having at least 1 percent
by weight of divinyl benzene copolymerized therein.
7- A c°II1P°11nd having the 'fmmula
_| OH
16. A process of claim 3 in which the amino-acid is
iminodiacetic acid.
17. A process of claim 3 in which the aminoacid is
CH,=CHOEH4OCHQCHCH3T
_
1
TNHoHeoooH
45 isovaline.
18. A process of claim 3 in which the aminoacid is
8. A compound having the formula
glycilm
-|
19. A process of claim 3 in which the aminoacid is
CHz=CHCnH4O CHzCHzCHOHzTOH
1
aspartic acid‘
J-NHOHGOOH
50
011100011
9- A compound having the formula
loH
CHFCHCBHQCHCHWH‘EHYLNH(GEMMCHQCOOH),
Ha
._|
20. A process of claim 3 in which the aminoacid is
alamne
References Cited in the ?le of this patent
55
UNITED STATES PATENTS
2,850,481
D’Alelio _____________ __ Sept. 2, 1958
2,860,160
Sundberg et al _________ __ Nov. 11, 1958
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 032 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа