Note: Descriptions are shown in the official language in which they were submitted.
5~
ALPHA-AMINOMETHYLENE PHOSPHONATE BETAINE MONOM~RS
This application is a division of application serial no. 547,077, filed
September 6, 1987.
The present invention relates to alpha-aminomethylene phosphonate betaine
monomers. In particular, the invention related to monomers having the general
formula:
\ C (CH2~a - N - C~2- CH -(CH2)b- N\ /O- (I)
~i CM
Rl is hydrcgen or methyl;
O O . . .
X is Ic 0, C-~l, or C~2;
~ o o
a is O, 1, 2, or 3, with the condition that vhen X is C-O or ~-NH, that a be
greater than l;
R2 and R3 are independently C1 - C6 alkyl, aryl, benzyl, or cyclohexyl; Y is
hydrogen or hydroxyl:
b is 0, 1, 2, or 3:
1l /OM
Z is Cl - C6 alkyl, aryl, benzyl, cyclohexyl, or CH2-P \
OM: and
~,
M is hydrogen, metallic cation, or~ammonium ion.
:
'''`''i''''' : ~ '
`;
.
-- 2 --
Also disclosed herein are homopolymers of these betaines. Copolymers
thereof prepared with any ethylenically unsaturated copolymeri~able comonomer
are described in the afore-mentioned parent application.
These alpha-aminomethylene phosphonate betaines are useful in a variety of
applications including soil anti-redeposition agents in detergents, chelating
agents for scale inhibition, as crystal modifiers and in oil well drilling
needs.
The monomeric betaines are prepared by the reaction of a compound of the
general structure
R2
R\ / X ( CH2 ) a \ ( II )
C R3
where Rl, X, a, R2, and~R3 are as defined above with compounds of the
following general stFuctures:
Y Z
L--CH2~H--(CH2)~ N\ CM (III) or
C 2 lli
O OM
~ 0 ~Z
CH2 CH( CH2 ) b--N\ /CM
CH2--P ( IV )
Il~
5~
o
where L is halogen or o-S-R4 with R4 ?being alkyl or aryl; and Y, b, Z,
o
and M are as defined above.
The reaction of these compounds is carried out in a suitable aqueous
solvent (usually water or alcohol/water) at a pH of 7-9 and a temperature
of 10-90C. Under such conditions the reaction is substantially complete
in one-half to ten hours, preferably one to five hours. The solution may
be acidified with mineral acid if the acid form of the moncmer, (where M
is hydrogen), is desired.
If bisphosphonomethylchloroethyl amine is used as the ccmpound of
Formula III, the reaction is carried out at a pH of about 7-9 obtained by
the addition of sodium hydroxide, preferably pH 8, and a temperature of
20-60C, preferably about 50C. This reacticn is carried out under
atmospheric pressures and is substantially completed within a period of
about 3 hours. Using this starting materlal, the resulting betaine will
correspond to formula I where y is H, Z is -CH2-PO(ONa)2 and b is O.
In order to prcduoe compounds of formula I where Y is OH, b is 1 or
2, and Z l5 -CH2-PO(OH)2, chlorohydroxypropyl (or butyl)
bisphosphonomethylamine l5 used as the compound of Formula III and the
reaction is carried out at a pH of about 6 to 8, preferably about pH 7,
using the same temperature and other conditions described previously.
Isolatlon~of the monomers is difficult owlng to their hygroscopic
nature. However, these campounds may be isolated by eva~oration of the
., :
2S reaction~solvent to give~a thick syrup. ~The syrup is then lyophilized to
give the~mono~er~in dry form.
- 4 -
Generally, the monomer solution obtained by the above described
reaction is used directly in conventional free radical e~ulsion or
solution polymerization procedures. The betaine monaners rnay be
hcrnopolymerized or copolymerized with up to 99% by weight, preferably at
least 50~ by weight of an ethylenically unsaturated comonner or rnixture
of 03monomers.
Representative ocmoncmers include acrylic or methacrylic acids and
esters thereof with Cl-C18 alcohols; unsaturated carboxylic acids such as
itaconic and maleic acids and esters thereof, (meth)acrylamide and their
N-substituted derivatives, such as N-mono and N-dimethyl, -ethyl,
propyl, and -butyl acrylamide or methacrylamide and N-mono or
diphenylacrylamide; vinyl esters such as vinyl acetate or vinyl
propionate; vinyl ethers such as butyl vinyl ether; N-vinyl lactams such
as N-vinyl pyrrolidinone; halogenated vinyl compounds such as vinyl
chloride and vinylidene chloride or fluoride; alkyl vinyl ketones such as
methyl or ethyl vinyl ketone; diesters such as dimethyl, diethyl,
dipropyl, dibutyl, diphenyl, dibenzyl, and di(phenylethyl) itaconate,
maleate, and fumarate; and polyethyleneglycol acrylate or methacrylate or
polypropyleneglycol acrylate or methacrylate.
Also useful herein are mlnor amounts (e.g., 0.01 to a~out 2%) of
multifunctional crosslinking monomers. Representative of suitable
crosslinkers are those containing a multiplicity of ethylenically
unsaturated units per molecule such as diallyl maleate, triallyl
cyanurate, tetraethylene glycol dimet~yacrylate, hexa-allyl sucrose, etc.
The polymerlzation is initiated by a~free radical initiator such as
peracid~or sâlt ~thereof~, e.g., hydrogen peroxide, sodium peroxide, lithium
peroxide, peracetic~acld, persulfuri,c acid or the ammonlum and alkali
.
- 5 ~
metal salts thereof, e.g. ammonium persulfate, sodium peracetate, lithium
persulfate, potassium persulfate, sodium persulfate, t-butyl peracetate,
etc. Various azo ccmpounds may alco be used, azobisisobutyronitrile, for
example. A suitable concentration of the initiator is frcm 0.05 to lO
weight percent and preferably fram 0.1 to 3 weight percent.
The free radical initiator can be used alone and thermally deccmposed
to release the free radical initiatirg species or can be used in
combination with a suitable reducing agent in a redox couple. The
reducing agent is typlcally an oxidizable sulfur ccmpound such as an
alkali metal metabisulfite and pyrosulfite, e.g. sodium metabisulfite.
If emulsion polymerization procedures are employed, the emulsifying
agent is generally any of the nonionic oil-in-water surface active agents
or mixtures thereof generally employed in emulsion polymerization
procedures. When ccmbinations of emulsifying agents are used, it is
advantageous to use a relatively hydrophobic emulsifyirg agent in
combination with a relatively hydrophilic agent. The amount of
emulsifyirg agent is generally fram 1 to 10, preferably frcm 2 to 8,
weight percen~ of the moncmers used in the polymerization.
The emulsifier used in the polymerization can also be added, in its
entirety, to the initial charge or a portion of the emulsifier, e.g. frcm
90 to 25 percent thereof, can be added continuously or intermittently
during polymerization.
The preferred in'erpolymerization procedure is a mcdified batch
process whereln the major amounts of scme or all the ccmonomers and
emulsifier are charged to the reaction vessel after polymerization has
been initiated. In this manner, control over the copolymerization of
monomers having widely varied degrees of reactivity can be achieved. It
.. .. .
6 - ~ 5 ~
is preferred to add a small portion of the monGmer emulsion initially and
then the remainder of the moncmer emulsion intermittently or continuously
over the polymerization period which can be frcm 0.5 to 10 hours,
preferably from 1 to 5 hours.
The resulting polymeric emulsion or solution contains 10 to 80%,
preferably 30 to 60% solids, by weight. It may be used directly or the
polymer may be recovered in solid form using the procedure described for
isolation of the moncmer or well-known spray-drying techniques. Using the
above described procedure, the polymer is produced at a yield of at least
about 90% conversion.
An alternative method for the production of the betaine polymer
involves first the polymerizaticn of the tertiary amine moncmer with
subsequent quarternization of the polymer with phosphoncmethylamine
reagent. More specifically, these polymers are synthesized by first
polymerizing a monGmer of the general structure
Rl R2
\ C X - (CH2)a N ~ (II)
where Rl, X, a, R2, and R3 are as defined above to give a hGmopolymer or,
if other ethylenically unsaturated comoncners are used, a copolymer. The
resultant polymers can be represented by the general structure:
, ~ .
L5
CH2 ~A ~m (v)
where Rl, X, a, R2, and R3 are as previously defined, n and m are positive
integers, and A i5 a repeating unit derived from one or more ethylenically
unsaturated comonomers. These polymers are then reacted with a compound
10 of general structure
Y ~Z
L CH2 - CH - (CH2)b ~ \ /CM (III)
CH2--P
- OM or
~0 /z
C 2 CH- (CH2)b ~N / CM
2 1I j (rV)
O CM
under conditions analcgous to those previousIy described for the moncmer
preparation.
The resulting derivatized:polymers can be represented by the general
structure
,
'
R _ _ .
(CH2)a (VI)
(I 2)b
/ N
_ /\~ _
MO n _ _
where R , X, a, R , R3, Y, b, Z, M, n, A, and m are as previously defined.
In the latter case, the reagents, reaction conditions and isolaticn
procedures for the quaternization are substantially the same as those
described previously however the yields are in the range of about 50 to
70~ conversion.
Parts and;percentages in the following examples are by weight and
ternperatures in degrees Celsius unless otherwise noted.
EXAMPLE 1
This example lllustrates the preparation of haloalkylaminomethylene
diphosphonic acid from haloalkylamines, ~o~naldehyde and phosphorous acid.
These acids correspond generally to Fonnula III where Y is hydrogen, L is
cblorine and Z is~methylene phosphoic acid. These ccmpounds were made
according to the procedure of K. Moedritzer and R.R. Irani, J. Org. Chem.
31 1603 (1966`i~
g ~'~gl~
A 2 liter flask was equipped with a mechanical stirrer, thermcmeter,
condenser, heating mantle, and addition funnel. Phosphorous acid (164.cg,
2.0 mol), water (300 ml), and 2-chloroethylamire hydrochloride (115.99 g,
1.0 ml) were charged to the flask, and concentrated hydrochloric acid (300
ml) added. The reacticn mixture was brought to reflux ard formula
solution (324.3 g, 37~ solution, 4.0 mol) was added over 1 hour. After
the addition was ccmplete the reaction mixture was refluxed an additional
2 hours. The reaction mixture was concentrated to give a thick syrup.
Ethanol (275 ml) was added to induce crystallization. The prcduct was
. .
filtered and dried to give a white powder. Repetitions of this procedure
resulted in yields of 20S to 240 grams (76-90% conversion).
EXAMPLE 2
This example illustrates the preparation of haloalkylaminoalkyl-
methylenephosphonic acids frcm N-haloalkyl, N-alkyl amines, formaldehyde,
and phosphorous acid. These compounds correspond to Formula III where L
is chlorine, Y is hydrogen and Z is methyl. These ccm~ounds were made
also according to the procedure of K. Moedritzer and R R. Irani, J. Org,
Chem 31 1603 (1966).
A 2 liter flask was equipped with a mechanical stirrer, thermcmeter,
condenser heating mantle, and addition funnel. Phosphorous acid (82.2 g,
1.00 mol), N-2-chloroethyl! N-methylamine hydrochloride (130.1 g, 1.0
mol), ard water (260 ml) were charged to the flask. Concentrated
hydrochloric acid (300 ml) was added slowly. The reaction mixture was
heated to reflux and formuIa solution (153.6 g, 37% solution, 2.0 mol) was
added over l hour. After the addition was ccmplete, the reaction mixture
was held an reflux an additional 2 hours.
...
As noted by Moedritzer and Irani, crystallization cannot easily be
induced. A solution of the product in water (total solution weight 240 g)
gave 4.10 meg of organic chloride per grarn. Conductcrnetric titration of
the product solution yielded three equivalence points, indicating that the
5 prcduct exists as the hydrochloride salt of the amincrnethylene pho.sphonic
acid .
EXAMPLE 3
This example describes a two step synthesis for the preparation of
halohydroxyalkylarnincrnethylenediphosphonic acids frcrn alkenylamino-
10 rnethylenediphosphonic acids, elemental halogen, and water. Theseccrnpounds correspond to Forsnula III where L is chlorine, Y is hydroxyl,
and Z is -CH2-PO~OEI)2. (It will be recognized by those skilled in the art
tha~ during the reaction of the above cosnpounds of Forrnula III where Y is
hydroxyl and L is halogen with the ccrnpounds of Formula II, ccrnpounds of
15 Formula IV wiIl be produced as interrnediates.)
The alkenylamincsnethylenediphosphonic acids were synthesized frcm
alkenylamines, formaldehyde, and phosphorous acid in the manner described
in Example 1.
A S00 rnl flask was equipped with a rnechanical stirrer, condenser, gas
20 dispersion tube, thermcrneter, and water bath. Allylamincmethylene-
diphosphonic acid (lOO.g, 0.408 rnol) and water (100 ml) were charged to
the flask and partial dissolution occurred. Chlorine gas (31.9 g, 0.449
mol) ~was bubbled sub-surface into the reaction mixture through the gas
dispersion tube. ~The temperature during the chlorine addition was
25 coAtrolled ~t 30 C. The~ rFsulting solution of 3-chloro-2-
' '
-
hydroxypropylamincmethylenediphosphonic acid weighed 240 g and contained
1.7 meg of organic chloride per gram. The solution can be concentrated to
yield the product as a white solid, but is generally used directly.
EXP~LE 4
This example describes the preparation of alpha-amincmethylene-
phosphonate betaines from reaction of N-dialkylaminoalkyl acrylamides or
2-substituted acrylamides with the haloalkylaminomethylenediphosphonic
acids of Example 1. This ccmpound corresponds to one of Formula I where Y
is H, Z is -CH2-PO(OH)2, b is O, Rl, R2 and R3 are -CH3, X is CONH and a
is 3.
A 2 liter flask was equipped with a mechanical stirrer, thermcmeter,
condenser, addition funnel, ard a pH probe. 2-Chloroethylaminomethylene-
diphosphonic acid (267.5 g, 1.0 mol) and water (350 ml) were slurried in
the reactor. Dimethylaminopropylmethacrylamide (170.1 g, 1.0 mol) was
15 added portionwise. A solution of sodium hydroxide (120.0 g, 3.0 mol) in
H2O (180 ml) was added to the mixture slowly. The temperature of the
reaction mixture was raised to S0C and the reaction allo~ed to oontinue
for 3 hours, at which time analysis for chloride ion indicated that the
reaction was substantially complete.
~ EXAMPLE S
This example i~llustrates the preparation of alpha-amincmethylene-
phosphonate betaines from reaction of N-dialkylaminoalkyl acrylates or 2-
substituted acryIates with the halohydroxyalkylaminomethlenediphosphonic
~ acids of ExampIe 3. The resulting moncmers correspond to those of Fonmula
I where X is CO2, a is 2, Rl, R2, and R3 are -CH3, y is OE~, b is 1, and Z
is -CH2--PO(OH)2.
:
:
9~
- 12 -
A 2 liter flask was equipped with a mechanical stirrer, thermometer,
condenser, addition funnel, and a pH probe~ 3-Chloro-2-hydroxypropyl-
amincmethylenediphosphonic acid (148.8 g, 0.5 mol) and H2O (150 ml) were
charged to the flask. Dimethylaminoethylmethacrylate (78.5 g, 0.5 mol)
was charged to the flask portionwise. A solution of sodium hydroxide
(60.0 g, 1.5 mol) in H2O (90 ml) was added slowly with stirring. The
temperature of the reaction mixture was raised to 50C and the reaction
mixture stirred for 3 hours, at which time analysis for chloride icn
indicated that the reaction was substantially cc~plete.
EXAMPLE 6
This example illustrates the copolymerization of the betaine moncmer
from Example 4 with acrylic acid in aqueous isopropanol.
A 500 ml flask was equipped with a stirrer, condenser, addition
funnels, heating mantle, and thermcmeter. Isopropanol (910 g) and water
(88 ml) were charged to the flask and brought to reflux. A moncmer charge
of acrylic acid (57.6 g) and a 44% solution of the betaine moncmer from
Example 4 (239.0 g) was added continuously over 3 hours. An initiator
charge of sodium persulfate (3.6 g) dissolved in H2O (16.4 ml) was added
simultaneously with the monomer aharge over 3 hours. After the additions
were o~mplete, the polymer solution was refluxed for 1 hour. The
isopropanol was removei by distillation, then the polymer solution was
cooled and~discharged from the reactor.
This polymer was characterized as follows:
Mw = 45,716
Mn = 3,571 ~ ~
After exhaustive dialysis against water, the polymer was analyzed for
nitrogen and phosphorus content:
, , ,
,
5~
- 13 -
Calculated Observed
%N 5.30 5.93
%P 7.85 7.01
~X~PLE 7
This example illustrates the copolymerization of betaine monomer from
Example 4 with acrylic acid in water with sodium hypophosphite present.
A 2 liter flask was equipped with a stirrer, condénsor, addition
funnels, heating mantle, nitrogen purge, and thermometer. Water (2.62 ml)
and sodium hypophosphite ~38.4 g) were charged to the flask and heated to
10 75C. A moncmer charge of acrylic acid (285.g) and a 30.8% solution of
the betaine monomer from Example 4 (62.11 g) was added continuously over 2
hours. Simultaneously, an initiator charge of sodium persulfate (7.5 g)
is H2O (70 ml) was added over 2 1/2 hours. When the initiator addition
was complete the reaction temperature was raised to 85 and the reaction
mixture stirred for 2 hours. The polymer was then cooled and discharged
from the reactor.
This polymer was characterized as follows: Mw = 2820; Mn = 1280; % P
is 3.81 (calculated) and 2.47 (observed).
~ EXAMPLE 8
This example describes an alternative method Eor the preparation of
polymers containing pendant alpha-amlncmethylenephosphonate betaine
structures frcm polymers containing tertiary amines and haloalkylamino-
methylenediphosphonic acid.
A tertiary amine-containing polymer is prepared as follows: A 500 ml
flask w:s equipped with a stirrer, condenser, thermometer, additicn
funnels, and hot water bath. Isopropanol (70 g) and water (110 ml) were
added~and~brought~to reflux. A monomer solution of acrylic acid (57.6 g),
dimethylaminopropylmethacrylamide (34.0 9), and water (20 ml) were added
:
::
- 14 - ~i7~ 5~
over 3 hours. S~multaneously, an initiator solution of a~monium
persulfate (5. g) in water (25 ml) was added over 3 hours. ~hen the
additions were complete, the polymer solution was held at reflux for 1
hour, the isopropanol removed by distillation, then the polymer solution
cooled and discharged frcm the reactor. The polymer concentration was
adjusted with water to 40%.
The resulting solution (145.5 g at 40~; 0.120 mole polymeric tertiary
amine) was charged to a 500 ml flask equipped with stirrer, thermcmeter,
addition funnel, condenser, and hot water bath. 2-Chloroethylamino-
methylenediphosphonic acid (32.1 g, 0.120 mol) was-added and the
temperature raised to 50C. Sodium hydroxide (132. g, 3.3 mol) in water
200 ml) was slowly added. The mixture was stirred for 3 hours at 50C.
After exhaustive dialysis against water the polymer was analyzed for
phosphorous and nitrogen:
lS Calculated Observed
%N 4.97 5.94
%P 7.32 4.31
EXAMPLE 9
This example illustrate the preparation of polymers containing
pendant alpha-amincmethylene phosphonate betaire structures frcm polymers
containing tertiary amines and haloalkylaminoalkyl methylene diphosphonic
acids in non-aqueous media.
A tertiary amine-containing polymer was prepared as follows: A 2
liter flask was equipped with a stirrer, condenser, thenmometer, additio
funnels, and hot water bath. Ethanol (180.0 g), benzoyl peroxide (3.0 9),
methyl methacrylate (15.0 g) butyl methacrylate (3.0 g), ard dimethyl
aminopropyl methacrylamide (12.0 g) were charged to the flask and heated
to reflux. A monomer solution of methyl methacrylate (135.0 g), butyl
-- 15 --
methacrylate (27.0 g), dimethylaminopropylmethacrylamide (108.0 g) in
ethanol (160.0 g) and an initiator solution of benzoyl peroxide (3.8 g) in
ethanol (105.0 g) were added continuously over 4 hours. After the
additions were complete, the reaction mixture was held at reflux for an
S additional 2 hours. A second initiator solution of t-butylperpivalate
(2.0 g) in ethanol (30.0 g) was added over 1/2 hour and the solution was
then refluxed an additional hour.
The resulting solution (275 g at 36.3~, 0.235 mole polymeric tertiary
amine) was charged to a 1 liter flask equipped with a stirrer, condenser,
thermcmeter, addition funnel, and hot water bath. A solution of N-(2-
chloroethyl)-N-methyl-amino methylene phosphosphonic acid (111.9 g at
47.1% in ethanol, 0.235 mol) was added and the reaction mixture heated to
S0C. Ethanolic potassium hydroxide (144.2 g at 2S%, 0.642 mole) was
added dropwise over 1 hour. The reaction mixture was heated at 50C for l
hour, then cooled.
The resulting polymer was completely soluble in water, in contrast to
the total water insolubility of the parent butyl methacrylate/methyl
methacrylate/dimethylaminopropylmethacrylamide polymer. Dialyzed a3ainst
water, the polymer was analyzed for phosphorus and nitrogen:
Calculated Observed
%N 6.62 5.70
%P 4.89 4.33
Example 10
This example illustrates an emulsion polymerization procedure for the
preparation of polymers containng pendant alpha-aminomethylenephosphonate
betaine structures.
- 16 -
A 2-L flask is equipped with a stirrer, condenser, thermcmeter,
additional funnels, hot water bath, and nitrogen purge. Ethoxylated nonyl
phenol (6.9 g), water (192.0 g) and t-butylhydroperoxide (0.06 g) are
charged to the flask. The pH of this initial charge is adjusted to 4.0
using acetic acid. With agitation a pre-emulsified mixture of ethyl
acrylate (475.0 g), betaine moncmer (Example 1, 38%, li2 g), water (55.0
g), ethoxylated nonylphenol (54.5g), and t-butylhydroperoxide (0.6) is
added at 60 over 4 hours. Simultaneously, a solution of sodium
formaldehyde sulfoxylate (0.6 g) in water (20 g) is added. The resulting
emulsion polymer is coagulated and washed with water. The washed-polymer
is analyzed for phosphorus content.
Calculated Observed
%P 1 . O O . 10
%N 0.44 0.05
_ PLE 11
This example illustrates the preparation of the beta me analog from
dimethylaminopropylmethacrylamide and chloro-hydroxypropyl-bisphosphono-
methylamine.
The procedure of Example 5 was repeated using 288 grams of a 51.7%
solution of chloro-hydroxypropyl-bisphosphonomethylamine and 85 grams of
dimethylaminopropylmethacrylamide with the pH adjusted to 7 with 150 grams
of a 40~ solution of sodium hydroxide.
The resulting betaine (52.3% solids) was used directly in a
polymerization~with acrylic acid using the procedure of Example 3 with 144
grams acrylic acid and 533 grams of the betaine solution.
Analysis of the dialyzed polymer gave~the following:
Calculated Observed
~P 10.3 7.26
%N 6.21 5.57
~:
, . , ' ' '
. .
~ .
