U.S. patent application number 14/354614 was filed with the patent office on 2014-10-09 for vinyl monomers having chelating functionality.
This patent application is currently assigned to ROHM AND HAAS COMPANY. The applicant listed for this patent is Dow Global Technologies LLC, Rohm and Haas Company. Invention is credited to Scott Backer, Allen Bulick, Joseph Manna, Cynthia Rand, Jia Xie.
Application Number | 20140303397 14/354614 |
Document ID | / |
Family ID | 47178352 |
Filed Date | 2014-10-09 |
United States Patent
Application |
20140303397 |
Kind Code |
A1 |
Backer; Scott ; et
al. |
October 9, 2014 |
VINYL MONOMERS HAVING CHELATING FUNCTIONALITY
Abstract
The present invention provides novel polymerizable monomers
having chelating functionality and processes to make them. In
particular, the novel monomers are ethylenically unsaturated
aminocarboxylates and are prepared by reacting ethylenediamine
triacetic acid or its salt with an ethylenically unsaturated
monomer. The ethyleneically unsaturated monomer may be a
polymerizable vinyl monomer selected from (o-, p-, m-)DVBMO, allyl
glycidyl ether, and glycidyl (meth)acrylate.
Inventors: |
Backer; Scott;
(Philadelphia, PA) ; Bulick; Allen; (Lansdale,
PA) ; Manna; Joseph; (Quakertown, PA) ; Rand;
Cynthia; (Sanford, MI) ; Xie; Jia; (Lake
Jackson, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Global Technologies LLC
Rohm and Haas Company |
Midland
Philadelphia |
MI
PA |
US
US |
|
|
Assignee: |
ROHM AND HAAS COMPANY
Philadelphia
PA
DOW GLOBAL TECHNOLOGIES LLC
Midland
MI
|
Family ID: |
47178352 |
Appl. No.: |
14/354614 |
Filed: |
October 31, 2012 |
PCT Filed: |
October 31, 2012 |
PCT NO: |
PCT/US2012/062670 |
371 Date: |
April 28, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61553595 |
Oct 31, 2011 |
|
|
|
Current U.S.
Class: |
560/222 ;
562/564 |
Current CPC
Class: |
C07C 227/18 20130101;
C07C 229/16 20130101; C07C 229/30 20130101 |
Class at
Publication: |
560/222 ;
562/564 |
International
Class: |
C07C 229/30 20060101
C07C229/30; C07C 227/18 20060101 C07C227/18 |
Claims
1. An ethylenically unsaturated aminocarboxylate monomer having the
following general Structure I: ##STR00019## wherein X.sup.1,
X.sup.2 and X.sup.3 are each, independently, hydrogen or a mono- or
polyvalent cation and the total charge on the monomer is zero; and
one, and only one, of R.sup.1 and R.sup.2 is an --OH group, and the
other is a polymerizable arm comprising a vinyl group and derived
from one or more ethylenically unsaturated monomers.
2. The ethylenically unsaturated aminocarboxylate monomer according
to claim 1, wherein the polymerizable arm is derived from a (o-,
p-, m-)DVBMO monomer and has the following structure: ##STR00020##
Wherein R.sup.3 is a polymerizable ethylenically unsaturated group
located at the ortho-, para-, or meta-substituted position of the
benzene ring.
3. The ethylenically unsaturated aminocarboxylate monomer according
to claim 2, wherein R.sup.3 is --CH.dbd.CH.sub.2.
4. The ethylenically unsaturated aminocarboxylate monomer according
to claim 1, wherein the polymerizable arm is derived from an allyl
glycidyl ether monomer and has the following structure:
##STR00021##
5. The ethylenically unsaturated aminocarboxylate monomer according
to claim 1, wherein the polymerizable arm is derived from a
glycidyl (meth)acrylate monomer and has the following structure:
##STR00022## wherein R.sup.3 is hydrogen or --CH.sub.3.
6. The ethylenically unsaturated aminocarboxylate monomer according
to claim 1, wherein the mono- or polyvalent cation is at least one
cation selected from the group consisting of: Na.sup.+, K.sup.+,
NH.sub.4.sup.+, organic ammonium ions, Ca.sup.2+and Mg.sup.2+.
7. A process for preparing the ethylenically unsaturated
aminocarboxylate monomer according to claim 1, comprising reacting
ethylenediamine triacetic acid or its salt with an ethylenically
unsaturated monomer.
8. The process according to claim 6, wherein the ethylenically
unsaturated monomer is a polymerizable vinyl monomer selected from
the group consisting of: (o-, p-, m-)DVBMO, allyl glycidyl ether,
glycidyl (meth)acrylate, and mixtures thereof.
9. The process according to claim 6, wherein said reacting step
occurs in the presence of a phase transfer catalyst.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to novel polymerizable
monomers having chelating functionality and methods to make them.
In particular, the novel monomers are ethylenically unsaturated
aminocarboxylates and are prepared by reacting ethylenediamine
triacetic acid or its salt with an ethylenically unsaturated
monomer, such as a polymerizable vinyl monomer.
BACKGROUND OF THE INVENTION
[0002] Synthetic detergents typically consist of a dispersant, a
builder, and other miscellaneous ingredients such as brighteners,
perfumes, anti-redepositon agents and enzymes. The dispersant
typically comprises a surfactant and functions to separate dirt,
soil and stains from fabric and other substrates. Polyacrylates are
well known and commonly used dispersant compounds. The builder
binds with and forms a complex with metal cations, such as calcium
and magnesium ions found in "hard water," which otherwise interfere
with the dispersant activity. Such binding and complex formation is
also commonly referred to as "chelating" and compounds capable of
such interaction with metal ions are known as "chelating
agents."
[0003] Phosphates are excellent chelating agents, which is why they
were historically used as builders for detergents. However, large
amounts of phosphorus were released to streams, rivers, lakes and
estuaries, even after wastewater treatment. In natural water
bodies, phosphorous acts as a fertilizer, increasing growth of
algae and aquatic weeds, which depletes oxygen available for
healthy fish and aquatic life, whose numbers then decrease.
Consequently, most jurisdictions have limited or banned the use of
phosphates in detergents.
[0004] In the search for phosphate substitutes, amino carboxylate
compounds have been found to be effective chelating agents and,
therefore, useful as builders for laundry and automatic dishwashing
detergents. For example, U.S. Pat. No. 3,331,773, teaches
preparation of water soluble polymers having chelating
functionality by grafting water soluble chelating monomers onto
water soluble polymers. Diethylenetriamine, ethylenediamine
tetraacetic acid, and other polyalkylene polyamine polyacetic acids
are identified as examples of chelating monomers suitable for
grafting onto water soluble polymers.
[0005] U.S. Pat. No. 5,514,732 also describes contact lenses made
from water insoluble polymers having chelating functionality. The
polymers are made from aminopolycarboxylic acids with a
polymerizable olefinic group, as well as a hydrophilic monomer and
one or more crosslinking monomer.
[0006] U.S Patent Application No. 2008/00262192 describes an
water-soluble polymer having a high chelating performance and clay
dispersancy which is made by polymerizing an amino group-containing
allyl monomer derived from adding an amine compound, such as
iminodiacetic acid (IDA), to an allyl monomer, such as allyl
glycidal ether (AGE). Also according to U.S Patent Application No.
2008/00262192, the amino group-containing allyl monomer may be
polymerized with other polymerizable monomers including, without
limitation, unsaturated monocarboxylic acid monomers.
[0007] U.S Patent Application No. 2009/0082242 discloses a
phosphate free dish washing liquor comprising exfoliated nanoclay,
a clay-dispersing polymer, as well as other components including
known chelating agents such as nitrilotriacetates (NTA), ethylene
diamine tetra acetate (EDTA), propylene diamine tetraacetic acid,
(PDTA), ethylene diamine N,N'-disuccinic acid (EDDS) and methyl
glycine diacetic acid (MGDA), or their salts.
[0008] The present invention provides novel polymerizable monomer
compounds which are water soluble and have chelating functionality,
as well as polymers made therefrom which shall be useful in aqueous
systems for scale inhibition, soil removal, tea destaining,
particulate dispersion and metal ion binding.
SUMMARY OF THE INVENTION
[0009] The present invention provides an ethylenically unsaturated
aminocarboxylate monomer having the following general Structure
I:
##STR00001##
wherein X.sup.1, X.sup.2 and X.sup.3 are each, independently,
hydrogen or a mono- or polyvalent cation and the total charge on
the monomer is zero; and one, and only one, of R.sup.1 and R.sup.2
is an --OH group, and the other is a polymerizable arm comprising a
vinyl group and derived from one or more ethylenically unsaturated
monomers. The mono- or polyvalent cation is at least one cation
selected from the group consisting of: Na.sup.+, K.sup.+,
NH.sub.4.sup.+, organic ammonium ions, Ca.sup.2+ and Mg.sup.2+.
[0010] In some embodiments, the one or more ethylenically
unsaturated monomers comprise a polymerizable vinyl monomer.
[0011] In some embodiments, the polymerizable arm may be derived
from a divinylbenzene mono epoxide (DVBMO) monomer and have the
following structure:
##STR00002##
[0012] Wherein R.sup.3 is a polymerizable ethylenically unsaturated
group located at the ortho-, para-, or meta- substituted position
of the benzene ring. For example, R.sup.3 may be
--CH.dbd.CH.sub.2.
[0013] In some embodiments, the polymerizable arm may be derived
from an allyl glycidyl ether monomer and have the following
structure:
##STR00003##
[0014] In some embodiments, the polymerizable arm may be derived
from a glycidyl (meth)acrylate monomer and have the following
structure:
##STR00004##
wherein R.sup.3 is hydrogen or --CH.sub.3.
[0015] The present invention also provides a process for preparing
the above-described ethylenically unsaturated aminocarboxylate
monomer, comprising reacting ethylenediamine triacetic acid or its
salt with an ethylenically unsaturated monomer. In some
embodiments, the ethylenically unsaturated monomer may comprise a
polymerizable vinyl monomer which may be selected from the group
consisting of: DVBMO, allyl glycidyl ether, glycidyl
(meth)acrylate, and mixtures thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0016] All percentages stated herein are weight percentages (wt %),
unless otherwise indicated.
[0017] Temperatures are in degrees Celsius (.degree. C.), and
ambient temperature means between 20 and 25.degree. C., unless
specified otherwise.
[0018] Weight percentages of monomers are based on the total weight
of monomers in the polymerization mixture from which the subject
polymer is produced.
[0019] "Polymerizable" as used to described a monomer or other
molecule means that the monomer or other molecule has at least one
carbon-carbon double bond and, therefore, is capable of forming
additional covalent bonds with other monomers or molecules of its
kind, other polymerizable monomers or molecules, or polymers having
polymerizable pendant groups, under normal polymerization
conditions, and become incorporated in to the product polymer.
[0020] As used herein, the term "(meth)acrylic" includes acrylic
acid and methacrylic acid.
[0021] As used herein, the term "(meth)acrylates" includes esters
of acrylic acid and esters of methacrylic acid.
[0022] The present invention relates to new monomer compositions
which are polymerizable monomers having chelating functionality and
are referred to hereinafter as "ethylenically unsaturated
aminocarboxylate monomers." The ethylenically unsaturated
aminocarboxylate monomers of the present invention have the
following general Structure I:
##STR00005##
wherein X.sup.1, X.sup.2 and X.sup.3 are each, independently,
hydrogen or a mono- or polyvalent cation and the total charge on
the monomer is zero; and one, and only one, of R.sup.1 and R.sup.2
is an --OH group, and the other is a polymerizable arm comprising a
vinyl group and having one of the following structures:
##STR00006##
wherein R.sup.3 of Structure A is a polymerizable ethylenically
unsaturated group located at the ortho-, para-, or meta-
substituted position of the benzene ring. For example, R.sup.3 may
be --CH.dbd.CH.sub.2. Hereinafter, abbreviations for the possible
structures of DVBMO in the ortho, para, and meta positions are
o-DVBMO, p-DVBMO, and m-DVBMO. Note that "(o-, p-, m-)DVBMO" means
one or more of the o-DVBMO, p-DVBMO, and m-DVBMO.
[0023] Wherein R.sup.3 of Structure C is hydrogen or
--CH.sub.3.
[0024] In some embodiments, for example, X.sup.1, X.sup.2 and
X.sup.3 of Structure I may each, independently, be at least one
cation selected from the group consisting of: Na.sup.+, K.sup.+,
NH.sub.4.sup.+, organic ammonium ions, Ca.sup.2+ and Mg.sup.2+.
[0025] Each of Structures A, B and C are derived from one or more
polymerizable vinyl monomers. Structure A may, for example, be
derived from a DVBMO monomer, such as o-DVBMO, p-DVBMO, and
m-DVBMO, or mixtures thereof. DVBMO has the general structure shown
below:
##STR00007##
wherein R.sup.3 is a polymerizable vinyl (--HC.dbd.CH.sub.2) group
located at the ortho-, para-, or meta-substituted position of the
benzene ring.
[0026] Structure B may, for example, be derived from an allyl
glycidyl ether (AGE) monomer of the following structure:
##STR00008##
[0027] Structure C may, for example, be derived from a glycidyl
(meth)acrylate (GA or GMA) monomer of the following structure:
##STR00009##
wherein R.sup.3 is hydrogen or --CH.sub.3.
[0028] The ethylenediamine triacetic acid (ED3A) may, for example,
be prepared according to the following reaction equation:
##STR00010##
[0029] The foregoing reaction may be accomplished by reacting
ethylene diamine in water, in the presence of sodium hydroxide,
with chloroacetic acid at reaction temperatures of 50-70.degree.C.
and a pH of 9-10. The total amount of chloroacetic acid to be
reacted is added to the ethylene diamine-in-water gradually and
continuously over time, such as, over about an hour. The pH of the
reaction mixture is maintained at 9-10 by addition of aqueous
sodium hydroxide. More specifically, the foregoing reaction will
produce a mixed product containing ethylenediamine diacetic acid
(ED2A), ethylenediamine triacetic acid (ED3A), and ethylenediamine
tetra-acetic acid (EDTA) having the following structures, in
approximately the molar proportions indicated:
##STR00011##
[0030] When EDA is reacted with chloroacetic acid at a molar ratio
of EDA:chloroacteic acid of 1:2, the product mixture will contain a
mixture having molar proportions closer to the following:
##STR00012##
[0031] It will be noted that the foregoing mixture contains
significantly less of the EDTA compound and more of the preferred
ED3A and ED2A compounds. As understood by persons of ordinary skill
in the relevant art, the EDA-chlororoacteic acid reaction may be
further optimized between stoichiometries of 1:2 and 1:3 to
maximize the proportion of ED3A contained in the product
mixture.
[0032] The present invention also provides a process for making the
ethylenically unsaturated aminocarboxylate monomers which comprises
reacting ethylenediamine triacetic acid (ED3A), or its salt, with a
polymerizable vinyl monomer selected from the group consisting of:
(o-, p-, m-)DVBMO, allyl glycidyl ether (AGE) and glycidyl
(meth)acrylate. This reaction may occur in the presence of a phase
transfer catalyst such as, without limitation,
benzyltrimethylammonium chloride, tetra-n-butylammonium bromide,
methyltrioctylammonium chloride, hexadecyltributylphosphonium
bromide, dimethyldiphenylphosphonium iodide, and
methyltriphenoxyphosphonium iodide.
[0033] The ED3A and vinyl monomer may be reacted in any suitable
ratio, as is readily determinable by persons of ordinary skill. The
process for making the ethylenically unsaturated aminocarboxylate
in accordance with the present invention may be conducted at
ambient temperatures.
[0034] For example, the particular reaction scheme for the reaction
of ED3A with GMA is as follows:
##STR00013##
[0035] The foregoing reaction produces a mixture of ED3A-GMA
monomers having the following structures:
##STR00014##
[0036] As noted above, the process for producing ED3A will
typically produce a mixture of ED3A, ED2A and EDTA. When such a
mixture is reacted with the vinyl monomer, the ED2A will also react
with the vinyl monomer. For example, when a mixture of ED3A, ED2A
and EDTA is reacted with GMA, the product will be a mixture of
ethylenically unsaturated aminocarboxylate monomers including those
shown above as well as the following structures:
##STR00015##
[0037] The ED2A-GMA products may be further reacted, with addition
chloroacetic acid, to form additional ED3A-GMA monomers in the
product mixture, according to the following reaction schemes:
##STR00016##
[0038] X.sup.4, X.sup.5 and X.sup.6 in the structures above may be
at least one cation selected from the group consisting of:
Na.sup.+, K.sup.+, NH.sub.4.sup.+, organic ammonium ions, Ca.sup.2+
and Mg.sup.2+. Thus, upon reacting the mixed product of the
EDA-chloroacetic acid reaction with GMA, a mixture of ethylenically
unsaturated aminocarboxylate monomers will result which contains
all four of the above shown structures of ED2A-GMA and ED3A-GMA. As
already mentioned, if desired, further reaction with additional
quantities of chloroacetic acid will convert the ED2A-GMA monomer
to more of the ED3A-GMA monomer.
[0039] As will be readily recognized by persons of ordinary skill
in the relevant art, other vinyl monomers, such as AGE or (o-, p-,
m-)DVBMO, may be substituted for GMA in the above-described
reactions to produce ED3A-AGE or ED3A-(o-, p-, m-)DVBMO monomers
according to the present invention. In either case, obviously,
persons of ordinary skill will expect that the product will contain
the structures shown below, as well as their isomers.
##STR00017##
[0040] The use, application and benefits of the present invention
will be clarified by the following discussion and description of
exemplary embodiments of the present invention.
EXAMPLES
Example 1
Synthesis of ED2A, ED3A
[0041] 2 g ethylene diamine were added to 30 ml DI H.sub.2O,
followed by addition of 8 g of 50% aqueous NaOH. The ethylene
diamine-NaOH solution was raised to 50.degree. C. 9.45g
chloroacetic acid were added to the heated solution over a period
of 1 hour. After addition of all the chloroacetic acid, the
temperature was raised to 70.degree. C. for 5 hours and the pH was
maintained at 9-10 by addition of 50% NaOH throughout the reaction.
The resulting product contained the following compounds in the
proportions noted: ethylenediamine diacetic acid (3.1%),
ethylenediamine tri-acetic acid (36.1%), and ethylenediamine
tetra-acetic acid (60.3%).
Example 2
Synthesis of ED3A-GMA Monomer
##STR00018##
[0043] To a 1 L round bottom flask equipped with a magnetic stirbar
and an addition funnel, 175 grams of ED3A solution (28.6% active)
was charged. The solution was placed in a water bath, and set to
stir at a minimum of 300 rpm. 0.4 g of a phase transfer catalyst
(benzyltrimethylammonium chloride) was charged to the vessel and
allowed to dissolve completely over approximately five minutes.
During this time, 18.85 g of allyl glycidyl ether (AGE) was charged
to the addition funnel. The AGE was added drop wise to the stirring
reaction mass, and when complete, allowed to stir at room
temperature until the reaction mass transitioned from two phases to
a single phase. This was determined by visual observation, in which
prior to completion, the reaction mass was hazy, and would separate
into two distinct phases upon termination of stirring. Upon
completion, the reaction mass was observed to be a transparent
yellow solution, which was stable upon termination of stirring. At
this stage the product is a yellow solution of pH 13 and active
level of 33.5 wt. % ED3A-AGE. This solution is stable to storage
under ambient conditions and can be used as such.
[0044] To convert the ED3A-AGE monomer into solid form, sulfuric
acid was added drop wise while stirring in order to adjust the pH
of the solution, halting the flow of sulfuric acid when the pH was
between 7-7.5.
* * * * *