(12) United States Patent
US007504551B2
(12) United States Patent
(10) Patent N0.:
Herfert et a]. (54)
US 7,504,551 B2
(45) Date of Patent:
COLOR-STABLE SUPERABSORBENT
(52)
POLYMER COMPOSITION
*Mar. 17, 2009
US. Cl. ..................... .. 604/372; 604/358; 526/220;
526/222; 526/915; 524/815; 524/827; 524/831;
524/832; 522/42; 522/84; 522/152; 522/153; (75) Inventors: Norbert Herfert, Charlotte, NC (US); Michael M- Azfwl, Charlotte, NC (Us);
522/ 154; 428/402 (58)
Field of Classi?cation Search ................. .. 522/42,
Peter W- Cameo, West PO11“, MS (Us); Guy Thomas W99drum, Suff01k,VA
522/84, 152, 153, 154; 524/815, 831, 827, 524/832; 604/358, 372; 526/915, 220, 222;
(US); Michael A. Mitchell, WaxhaW, NC
(Us); Ma-Ikay Kikama Miatudila, Monroe, NC (U S)
428/402
See application ?le for complete search history. (56)
References Cited
(73) Assignee: BASF Aktiengesellschaft, Ludwigshafen (DE)
US. PATENT DOCUMENTS 5,408,019 A
(*)
Notice:
Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U_S_C_ 154(b) by 564 days_
This patent is subject to a terminal disClalmer-
(21)
APP1- NO-I
10/547,353
(22)
PCT Flled:
Mar. 19, 2004
(86)
PCT No.:
PCT/EP2004/002874
(87)
Aug. 29, 2005
(65)
Prior Publication Data US 2006/0089611 A1
(51)
3/1992 11/1988
0 942 014
9/1999
W0
WO 00/55245
9/2000
W0
WO 01/25289
4/2001
W0
WO 01/55228
8/2001
LLp
PCT Pub. No.: WO2004/084962 PCT Pub. Date: Oct. 7, 2004
(60)
EP
41 23 889 0 290 814
Primary ExamineriFred M Teskin (74) Attorney, Agent, or FirmiMarshall, Gerstein & Borun
§ 371 (9X1),
(2), (4) Date:
2/1997 Goldman et a1. 9/1997 Goldman et a1. 6/2002 Brown et al.
FOREIGN PATENT DOCUMENTS DE EP
_
4/1995 Mertens et a1.
5,599,335 A 5,669,894 A 2002/0068791 A1
Apr. 27, 2006
(57)
ABSTRACT
A color-stable superabsorbent polymer having long-term color stability, and methods of manufacturing the polymer, are disclosed. The superabsorbent polymer is prepared using
26 2003
a sul?nic acid derivative, like 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture thereof, as the reducing agent in a polymerization initiator system for the preparation of a superabsorbent polymer from monomers. The resulting
’ ' Int CL
superabsorbent polymer resists color degradation during periods of extended storage, even at an elevated temperature
Related U-s- Application Data Provisional application NO 60M528 41’ ?led on Mar‘
A61F 13/49 C08F 2/48 C08F 4/40
(2006.01) (2006.01) (2006.01)
and humidity 31 Claims, N0 Drawings
US 7,504,551 B2 1
2
COLOR-STABLE SUPERABSORBENT POLYMER COMPOSITION
Europe, the rate at Which an SAP undergoes color degradation is su?iciently sloW such that the SAP, or article containing the SAP, typically is consumed before a color change is observ
CROSS-REFERENCE TO RELATED APPLICATION
able to the naked eye.
HoWever, in tropical and subtropical climates, such as in South America and Southeast Asia, SAP color degradation is suf?ciently rapid such that a color change often occurs before
This is the US. national phase application of International
Application No. PCT/EP2004/002874, ?led Mar. 19, 2004, Which claims the bene?t of US. provisional patent applica tion Ser. No. 60/457,841, ?led Mar. 26, 2003.
the SAP, or article containing the SAP, is consumed. In areas like Southeast Asia, an SAP can change color from White to honey broWn in about 4 to 6 Weeks. This problem is exacer
FIELD OF THE INVENTION
bated because the SAPs may be produced far from the tropical
The present invention relates to superabsorbent polymers (SAPS) having long-term color stability, and to methods of preparing the color-stable SAPs. More particularly, the
tion to use. Furthermore, consumption of articles containing an SAP in such climates is relatively loW, therefore further increasing the time period betWeen SAP production and use. The change in color of the SAP does not affect SAP per formance, but adversely affects consumer acceptance of
climate, thereby increasing the time span from SAP produc
present invention relates to methods of preparing a color stable SAP using a monomer mixture containing a polymer iZation initiator comprising a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture
articles containing the color-degraded SAPs. In particular, 20
thereof, and, optionally, subjecting the resulting SAP hydro gel to a loW dose of UV radiation. The color-stable SAP can
be incorporated into articles, such as bandages, diapers, sani tary napkins, and other absorbent products, Wherein the SAP retains a clean, White color during extended storage periods, even under high temperature and humidity conditions.
hoW soiled or faulty, or is of loW quality. The diaper typically is returned for a refund, and the consumer is less likely to
repurchase that brand of diaper. 25
BACKGROUND OF THE INVENTION
Water-absorbing resins are Widely used in sanitary and
mats, disposable door mats, thickening agents, disposable
even under moderate pressure. For example, SAPs can absorb one hundred times their oWn Weight, or more, of distilled
retains its crisp, White color throughout the useful life of the SAP, or an article containing the SAP, even When stored under
Would be desirable to provide an SAP having a long-term color stability and loW residual monomer content, Without 40
adversely affecting the absorbent properties of the SAP, such as absorbing a large amount of liquids quickly, having a good ?uid permeability into and through the SAP, and having a high gel strength, such that an SAP hydro gel formed from the SAP does not deform or ?oW under an applied stress or
45
pressure.
Currently, SAPs, like partially neutraliZed, lightly
50
crosslinked, polyacrylic acid, are manufactured using a per sulfate as a component of the polymerization initiator system. A persulfate is included in the initiator system as the oxidiZ ing agent of a redox initiator pair and to reduce the amount of residual acrylic acid monomer in the SAP to acceptable lev els. A persulfate also can act as a thermal initiator. HoWever,
Water. The ability to absorb aqueous ?uids under a con?ning pressure is an important requirement for an SAP used in a
hygienic article, such as a diaper. As used herein, the term “SAP particles” refers to super
the manufacturer of articles and the manufacturer of the SAP, Who must absorb the cost of the returned goods. It Would be desirable to provide an SAP that exhibits
high temperature and humidity conditions. Furthermore, it
and polyacrylonitriles. Such Water-absorbing resins are termed “superabsorbent polymers,” or SAPs, and typically are lightly crosslinked hydrophilic polymers. SAPs are discussed generally in US. Pat. Nos. 5,669,894 and 5,559,335, each incorporated herein by reference. SAPs can differ in their chemical identity, but all SAPs are capable of absorbing and retaining amounts of aqueous ?uids equivalent to many times their oWn Weight,
A color-degraded SAP, therefore, ultimately adversely affects
exceptional color stability properties, such that the SAP 35
such as hydrolysis products of starch acrylonitrile graft poly mers, carboxymethylcellulose, crosslinked polyacrylates,
sulfonated polystyrenes, hydrolyzed polyacrylamides, poly vinyl alcohols, polyethylene oxides, polyvinylpyrrolidones,
Problems also arise at the manufacturing level because manufacturers of diapers and other articles containing an SAP refuse to incorporate a discolored SAP into their prod ucts, and return the discolored SAP to the SAP manufacturer.
30
hygienic goods, Wiping cloths, Water-retaining agents, dehy drating agents, sludge coagulants, disposable toWels and bath litter mats for pets, condensation-preventing agents, and release control agents for various chemicals. Water-absorbing resins are available in a variety of chemical forms, including substituted and unsubstituted natural and synthetic polymers,
consumers observing a color-degraded SAP in a diaper form an opinion that the diaper contains a contaminant, is some
the persulfate further interacts With the MEHQ inhibitor present in acrylic acid monomer and imparts a loW initial 55
color to the SAP. This loW initial SAP color progresses to a severe SAP discoloration over time, and especially under
absorbent polymer particles in the dry state, more speci? cally, particles containing from no Water up to about 10%, by
high temperature and humidity conditions.
Weight, Water. The terms “SAP gel,” “SAP hydrogel,” or “hydrogel” refer to a superabsorbent polymer containing at
lem of SAP discoloration attributed to the presence of a
least about 10%, by Weight, Water, and typically, particles that have absorbed at least their Weight in Water, and more typi cally several times their Weight in Water. SAPs have a tendency to degrade in color after long periods of storage. The tendency of an SAP to undergo a color tran sition from a clean, crisp, White color to a honey broWn color
accelerates as storage time, temperature, and humidity increase. In temperate climates, such as the United States and
The present invention is directed to overcoming the prob 60
color-producing oxidiZing agent, like a persulfate, in the preparation of an SAP. As discussed in detail hereafter, the present invention overcomes the SAP discoloration problem
(a) by utiliZing a polymeriZation initiator system comprising a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic 65
acid, optionally 2-hydroxy-2-sulfonatoacetic acid, salts thereof, or a mixture thereof, (b) by essentially omitting a color-producing oxidiZing agent from the monomer mixture,
US 7,504,551 B2 3
4
and, (c) optionally, by subjecting the SAP hydrogel resulting
White color over an extended time, even under high tempera
from the polymerization to a loW dose of ultraviolet (UV) radiation.
ture and humidity storage conditions. Another aspect of the present invention is to provide a method of manufacturing a color-stable SAP including the
2-Hydroxy-2-sul?natoacetic acid disodium salt and 2-hy droxy-2-sulfonatoacetic acid disodium salt have been used as a reducing agent in a redox initiator in emulsion polymeriza
steps of polymerizing a monomer mixture comprising a
sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture thereof, that provides an SAP,
tions. US. Pat. No. 5,408,019 discloses using formamidine sulfonic acid as the reducing agent in a redox initiator system. Ultraviolet radiation previously has been used in the prepa ration of SAPs. For example, UV radiation has been used in
for example, a polymerized 0t,[3-unsaturated carboxylic acid,
conjunction With a photoinitiator to initiate polymerization of
to form an SAP hydrogel, optionally subjecting the SAP hydrogel to UV radiation for about 3 to about 1 5 minutes from
monomers and provide an SAP hydrogel, as disclosed in EP 0 290 814 B1. DE 41 23 889 A1 discloses UV irradiation ofa
UV radiation dose, comminuting the SAP hydrogel to form
Water-ab sorbing resin prepared from a Water- soluble polymer and a polysaccharide and/or crosslinking agent, in the pres
SAP hydrogel particles, then drying the SAP hydrogel par ticles to provide color-stable SAP particles. The SAP hydro gel optionally is subjected to a loW dose of UV radiation, i.e.,
a distance of about 2 to about 30 centimeters, or an equivalent
ence of a radical scavenger, to provide a Water-absorbing
0 to about 2000 milliWatts (mW) of UV radiation per square
resin having a loW otmount of Water-soluble components (27 Wt %) and a loW amount of residual monomer (2500 ppm). The UV radiation is applied during drying or crushing of the
Water-absorbing resin.
centimeter (cm2) of SAP hydrogel. In another embodiment, 20
PCT publication WO 01/ 55228 discloses subjecting a Water-soluble or Water-sWellable polymer to UV radiation to reduce residual monomer content. An ultraviolet initiator is used in an amount of up to 10,000 ppm, by Weight of mono
mers, preferably up to 5000 ppm, more preferably 50 to 3,000 ppm, and still more preferably 500 to 2,000 ppm. UV radia tion typically is conducted for about 20 minutes. PCT publication WO 01/ 25289 discloses subjecting an
25
R3
acrylic polymer to UV radiation after, or simultaneously With,
comminuting a gelled polymer to gelled polymer particles.
30
In particular, the comminuted gel particles can be irradi ated during a drying step in a ?uid bed dryer.
Wherein M is hydrogen, an ammonium ion, or a monovalent or a divalent metal ion of groups Ia, 11a, 11b, IVa, and VIIIb of
the Periodic Table of the Elements;
SUMMARY OF THE INVENTION 35
The present invention is directed to a superabsorbent poly mer (SAP) having long-term color stability, and to methods of manufacturing a color-stable SAP composition. More par ticularly, the present invention is directed to a method of
preparing a color-stable SAP, Without adversely affecting the ?uid absorption and retention properties of the SAP particles,
40
ally having 1-3 substituents independently selected from the group consisting of Cl-C6alkyl, OH, O4Cl-C6alkyl, halogen, and CF3; and R3 is COOM, SO3M, COR4, CONR4R5 , or COOR4, Wherein M, R4, and R5 are as de?ned above, or, if R2 is unsubstituted or substituted aryl, R3 is H;
(a) by utilizing a polymerization initiator system comprising
acid, optionally 2-hydroxy-2-sulfonatoacetic acid, salts 45
and the salts thereof. In preferred embodiments, the monomer mixture com
prises (a) an 0t,[3-unsaturated carboxylic acid, (b) a crosslink ing agent, (b) a polymerization initiator system comprising
hydrogel resulting from the polymerization to a loW dose of UV radiation. A color-stable SAP prepared by the present method retains a crisp, clean White color over an extended
R1 is OH or NR4R5, Wherein R4 and R5 , independently, are H or Cl-C6alkyl;
R2 is H or an alkyl, alkenyl, cycloalkyl, or aryl group, option
a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic
thereof, or mixtures thereof, (b) by essentially omitting a coloring-forming oxidizing agent, like a persulfate, from the monomer mixture, and, optionally, (c) by subjecting the SAP
the SAP hydrogel is comminuted to form SAP hydrogel par ticles before being subjected to UV radiation. A sul?nic acid derivative useful in the present invention has a general structural formula:
50
2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture
storage period at a high temperature and humidity, i.e., at least 30 days When stored at 60° C. and 90% relative humidity. One aspect of the present invention, therefore, is to provide
thereof, that is essentially free of a persulfate and other color
a method of manufacturing a color-stable SAP, including the
ated carboxylic acid and crosslinking agent, and (e) Water. After drying, the color-stable SAP particles optionally are
steps of (a) polymerizing a monomer mixture comprising (i)
producing oxidizing agents, (d) an optional photoinitiator in an amount of 0 to about 1000 ppm by Weight of 0t,[3-unsatur 55
a monomer that provides an SAP, like an 0t,[3-unsaturated
surface treated to provide surface crosslinks on the color
carboxylic acid, such as acrylic acid, either neutralized, unneutralized, or partially neutralized, (ii) a crosslinking
stable SAP particles. Yet another aspect of the present invention is to incorporate
agent, (iii) an initiator system comprising a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture thereof, and that is essentially free of
60
hygiene product, an adult incontinence product, general pur pose Wipes and cloths, and similar absorbent products. The
color-producing oxidizing agent, e.g., a persulfate, and (ivy an optional photoinitiator, to form an SAP hydrogel, (b) optionally subjecting the SAP hydrogel to a loW dose of UV
radiation, and (c) comminuting and drying the SAP hydro gel to provide a color-stable SAP. The resulting color-stable SAP has a loW residual monomer content and maintains a crisp
the color-stable SAP particles into articles used to absorb liquids, for example, a diaper, a catamenial device, a feminine
articles resist color degradation over the expected life of the 65
article, even in high temperature and humidity climates. The above and other aspects and advantages of the present invention Will become apparent from the folloWing detailed
US 7,504,551 B2 5
6
description of the preferred embodiments of the invention, taken in conjunction With the examples and the claims.
crosslinking agent, (iii) a polymerization initiator comprising
DETAILED DESCRIPTION OF THE INVENTION
a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture thereof, that is essentially free of a color-forming oxidizing agent, like a persulfate, (iv) an
The present invention is directed to SAPs having a long term color stability, and to methods of preparing the color
optional photoinitiator, and (v) Water, to form an SAP hydro gel, (b) optionally subjecting the SAP hydrogel to a loW dose of UV radiation, (c) comminuting the SAP hydrogel to form
stable SAPs. The color-stable SAPs shoW a minor color
SAP hydrogel particles, (d) then drying the resulting SAP hydrogel particles, and (e) optionally surface treating the
change, to the naked eye, after storage for 30 days at 60° C. and 90% relative humidity. The present SAPs are prepared
color-stable SAP particles.
from a monomer mixture containing a polymerization initia
The present color-stable SAPs are based on polymerized
tor comprising a sul?nic acid derivative, such as 2-hydroxy 2-sul?natoacetic acid, a salt thereof, or a mixture thereof, that is essentially free of a color-forming oxidizing agent, like a
vinyl monomers, particularly 0t,[3-unsaturated carboxylic acids, that, after polymerization, have the ability to absorb several times their Weight of a liquid When crosslinked. The remainder of the speci?cation is directed to a color-stable
persulfate. The SAP hydrogel resulting from polymerizing the monomer mixture optionally is subj ected to a loW dose of
SAP based on acrylic acid, hoWever, other vinyl monomers,
UV radiation. The present polymerization initiator, and optional UV radiation, impart color stability to the SAP and
like (meth)acrylonitrile or a (meth)acrylamide, or an ethyl enic monomer having an amine substituent or a precursor to
reduce the amount of residual monomer in the SAP.
Suitable processes for preparing the present color-stable SAP particles include solution polymerization, also termed gel polymerization, for example, as disclosed in US. Pat. Nos. 4,076,663; 4,286,082; 4,654,039; and 5,145,906, each incorporated herein by reference. Another process is inverse
20
suspension polymerization disclosed, for example, in US.
25
exhibit improved color stability regardless of the identity of
Pat. Nos. 4,340,706; 4,497,930; 4,666,975; 4,507,438; and 4,683,274, each incorporated herein by reference. The present disclosure is directed primarily to gel polymer
Accordingly, neither the chemical makeup of the color color-stable SAPs, therefore, can be prepared by any SAP 30
polymerization. In gel polymerization, SAPs are prepared from an aqueous 35
aqueous monomer mixture also contains polymerization ini fate. A persulfate has been considered an important or essen
tial polymerization initiator ingredient in order to reduce the 40
herein by reference. An extensive list of suitable SAP-form ing monomers can be found in US. Pat. Nos. 4,076,663 and
chain. Polymers containing these acid moieties are synthe sized either from monomers previously substituted With one or more of these acidic functional groups or by incorporating
acceptable levels. In the typical manufacture of an SAP, the SAP is neutral ized at least about 25 mole percent, more preferably at least about 50 mole percent, and usually about 70 to about 80 mole percent, to achieve optimum absorbency. Neutralization can
acidic Water-absorbing resin (i.e., an anionic SAP), a basic Water-absorbing resin (i.e., a cationic SAP), or a multicom ponent SAP particle as disclosed in US. Pat. Nos. 6,072,101;
5,149,750, each incorporated herein by reference. Generally, acidic SAPs have carboxylate, sulfonate, sul fate, and/or phosphate groups incorporated along the polymer
tiators, typically including a persulfate, like sodium persul residual acrylic acid monomer content in SAP particles to
polymerization process knoWn in the art and can comprise an
6,159,591; 6,222,091; and 6,329,062, each incorporated
mixture of monomers and one or more crosslinking agents to
provide a Water-ab sorbent, but Water-insoluble, polymer. The
the monomers used to prepare the SAP, and particularly SAPs based on an 0t,[3-unsaturated carboxylic acid or anhydride.
stable SAP, nor its method of manufacture, is limited. The
ization for illustrative purposes. HoWever, the invention can
be practiced using all SAP manufacturing processes, includ ing modi?ed bulk polymerization and inverse suspension
an amine substituent, e. g., N-vinyl acetamide, and other 0t,[3 unsaturated carboxylic acids and anhydrides, also canbe used in the manufacture of color-stable SAPs of the present inven tion. The color-stable SAPs prepared by the present methods
ization, or the polymer can be neutralized after the polymer
the acidic functional group into the polymer after synthesis. To incorporate carboxyl groups into a polymer, any of a number of ethylenically unsaturated carboxylic acids can be homopolymerized or copolymerized. Carboxyl groups also can be incorporated into the polymer chain indirectly by
ization reaction is substantially complete. After polymeriza
hydrolyzing a homopolymer or copolymer of monomers such
45
be achieved by neutralizing the monomers before polymer tion and internal crosslinking of the monomers, folloWed by partial neutralization, e.g., about 50 to about 100 mole per cent neutralization, preferably about 70 to about 80 mole
as acrylamide, acrylonitrile, methacrylamide, and alkyl acry 50
lates or methacrylates. An acidic SAP canbe either a strong or a Weak acidic Water-absorbing resin, and can be a homopoly
percent neutralization, the polymer is comminuted, e.g.,
mer or a copolymer.
shredded or chopped, for more ef?cient drying, then dried and
The acidic SAP typically is a neutralized, lightly crosslinked acrylic-type resin, such as neutralized, lightly crosslinked polyacrylic acid. The lightly crosslinked acidic SAP typically is prepared by polymerizing an acidic mono
milled to a desired particle size. The polymer preferably then is surface treated. In embodiments Wherein surface treatment
55
is employed, a surface crosslinking agent typically is applied to the dried. SAP particles. Generally, after application of the
mer containing an acyl moiety, e. g., acrylic acid, or a moiety
surface crosslinking agent, the SAP particles then are sub jected to conditions Wherein the surface crosslinking agent reacts With a portion of the SAP to crosslink the surfaces of
60
the SAP particles.
capable of providing an acid group, i.e., acrylonitrile, in the presence of a crosslinking agent, i.e., a polyfunctional organic compound. The acidic resin can contain other copolymeriz able units, i.e., other monoethylenically unsaturated comono mers, Well knoWn in the art, as long as the polymer is sub
In one embodiment of the present invention, a color-stable
SAP is prepared by a method comprising the steps of (a)
stantially, i.e., at least 10%, and preferably at least 25%,
solution polymerizing a monomer mixture comprising (i) a monomer capable of providing an SAP polymer, like an 0t,[3
acidic monomer units. To achieve the full advantage of the present invention, the acidic SAP contains at least 50%, and more preferably, at least 75%, and up to 100%, acidic mono
unsaturated carboxylic acid, such as acrylic acid, either neu tralized, unneutralized, or partially neutralized, (ii) a
65
mer units. The acidic resin can be unneutralized or neutral
US 7,504,551 B2 8
7 iZed, preferably neutralized at least 50 mole %, and most preferably at least 70 mole %, With a base prior to drying. Ethylenically unsaturated carboxylic acid monomers, and
The basic SAP, either strongly or Weakly basic, therefore, can be any resin that acts as an SAP in its charged form. The basic SAP typically is a lightly crosslinked resin, such as a
lightly crosslinked polyethylenimine, a poly(allylamine), a poly(allylguanidine), a poly(dimethyldiallylammonium hydroxide), a quaterniZed polystyrene derivative, a guani
anhydrides, amides, esters, and salts thereof, useful in the acidic SAP include, but are not limited to, acrylic acid, meth
acrylic acid, ethacrylic acid, ot-chloroacrylic acid, ot-cy anoacrylic acid, [3-methylacrylic acid (crotonic acid), ot-phe nylacrylic acid, [3-acryloxypropionic acid, sorbic acid, ot-chlorosorbic acid, angelic acid, cinnamic acid, p-chloro
dine-modi?ed polystyrene, a poly(vinylguanidine), or a poly
(dialkylaminoalkyl (meth)acrylamide) prepared by polymer iZing and lightly crosslinking a monomer having the structure
cinnamic acid, [3-stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic
acid, fumaric acid, tricarboxyethylene, 2-methyl-2-butene dicarboxylic acid, maleamic acid, N-phenyl maleamide,
H
Rs C=C
maleamide, maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride,
R7
\
methyl itaconic anhydride, ethyl maleic anhydride, diethyl maleate, methyl maleate, and maleic anhydride. Sulfonate-containing acidic SAPs can be prepared from monomers containing functional groups hydrolyZable to the sulfonic acid form, for example, alkenyl sulfonic acid com
R9
C—NH—(Y)—N 0
R10
or its ester analog 20
pounds and sulfoalkyl acrylate compounds. Ethylenically unsaturated sulfonic acid monomers include, but are not lim
H
Rs
ited to, aliphatic or aromatic vinyl sulfonic acids, such as
\
vinylsulfonic acid, allylsulfonic acid, vinyltoluene sulfonic acid, styrenesulfonic acid, acrylic and methacrylic sulfonic
R/
/
C=C
7
25
acids, such as sulfoethyl acrylate, sulfoethyl methacrylate,
sulfopropyl acrylate, 2-vinyl-4-ethylbenZenesulfonic acid,
R9
c 0 —
u
—
(Y)
—
N/
\R
,
10
2-allylbenZenesulfonic acid, 1-phenylethylene sulfonic acid,
sulfopropyl methacrylate, 2-hydroxy-3 -methacryloxypropyl sulfonic acid, and 2-acrylamide-2-methylpropane sulfonic
30
acid.
straight chain or branched organic radical having 1 to 8 car
Sulfate-containing acidic SAPs are prepared by reacting
bon atoms, R9 is hydrogen, and R10 is hydrogen or an alkyl
homopolymers or copolymers containing hydroxyl groups or
radical having 1 to 4 carbon atoms. Preferred basic SAPs include a poly(vinylamine), polyeth
residual ethylenic unsaturation With sulfuric acid or sulfur
trioxide. Examples of such sulfated polymers include sulfated
35
polyvinyl alcohol, sulfated hydroxyethyl acrylate, and sul
mixtures thereof. Basic SAPs are disclosed in US. Pat. No.
acidic SAPs are prepared by homopolymeriZing or copoly meriZing ethylenically unsaturated monomers containing a
6,159,591, incorporated herein by reference. The lightly 40
phate. The acidic SAP, either strongly or Weakly acidic, can be any resin that acts as an SAP in its neutralized form. Examples
of acidic resins include, but are not limited to, polyacrylic
acid, hydrolyZed starch-acrylonitrile graft copolymers, starch-acrylic acid graft copolymers, saponi?ed vinyl
45
acetate-acrylic ester copolymers, hydrolyZed acrylonitrile
copolymers, hydrolyZed acrylamide copolymers, ethylene maleic anhydride copolymers, isobutylene-maleic anhydride copolymers, poly(vinylsulfonic acid), poly(vinylphosphonic acid), poly(vinylphosphoric acid), poly(vinylsulfuric acid), sulfonated polystyrene, poly(aspartic acid), poly(lactic acid),
ylenimine, poly(vinylguanadine), poly(methylaminoethyl acrylamide), poly(methylaminopropyl methacrylamide), or
fated hydroxypropyl methacrylate. Phosphate-containing phosphoric acid moiety, such as methacryloxy ethyl phos
Wherein R7 and R8, independently, are selected from the group consisting of hydrogen and methyl, Y is a divalent
crosslinked basic SAP can contain other copolymeriZable units and is crosslinked using a polyfunctional organic com pound, as set forth above With respect to the acidic SAP. CopolymeriZable monomers for introduction into an acidic SAP or a basic SAP include, but are not limited to, ethylene,
propylene, isobutylene, Cl_4 alkyl acrylates and methacry lates, vinyl acetate, methyl vinyl ether, and styrenic com pounds having the formula:
50
and mixtures thereof. The preferred acidic resins are the poly
acrylic acids. The acidic SAP contains 0 to 100 percent neutraliZed pen
55
dant carboxylate groups (i.e., DNIO to DNIlOO). Neutraliza tion of carboxylic acid groups is accomplished using a strong organic or inorganic base, such as sodium hydroxide, potas
Wherein R represents hydrogen or a C1_6 alkyl group, and Wherein the phenyl ring optionally is substituted With one to
sium hydroxide, ammonia, ammonium hydroxide, or an
organic amine. Analogous to the acidic SAP, a color-stable basic SAP can be manufactured by the present method. The basic SAP can be a strong or Weak basic Water-absorbing resin. The strong basic resins typically are present in the hydroxide (OH) or bicarbonate (HCO3) form. The basic SAP can be a single
60
four C1_4 alkyl or hydroxy groups. Suitable C1_4 alkyl acrylates include, but are not limited to,
methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, and the like, and mixtures thereof. Suitable C 1_ 4 alkyl methacrylates include, but are not limited
to, methyl methacrylate, ethyl methacrylate, isopropyl meth 65
acrylate, n-propylmethylmethacrylate, n-butyl methacrylate,
resin or a mixture of resins. The basic SAP can be a
and the like, and mixtures thereof or With C 1_ 4 alkyl acrylates.
homopolymer or a copolymer.
Suitable styrenic compounds include, but are not limited to,
US 7,504,551 B2 9
10
styrene, ot-methylstyrene, p-methylstyrene, t-butyl styrene,
p and r each are an integer 5 to 40, and k is 1 or 2;
and the like, and mixtures thereof or With C 1_ 4 alkyl acrylates and/ or methacrylates.
(H)
As previously stated, the present invention is not limited to SAPs based on acrylic acid, but preferably extends to SAPs
CH2=CH
Hc=cH2
prepared for 0t,[3-unsaturated carboxylic acids including, but not limited to, methacrylic acid, ethacrylic acid, ot-chloro
acrylic acid, ot-cyanoacrylic acid, [3-methylacrylic acid (cro tonic acid), ot-phenylacrylic acid, [3-acryloxypropionic acid,
wherein 1 is 2 or 3.
sorbic acid, ot-chlorosorbic acid, angelic acid, cinnamic acid,
Speci?c crosslinking monomers include, but are not lim
p-chlorocinnamic acid, [3-stearylacrylic acid, itaconic acid,
ited to, 1,4-butanediol diacrylate, 1,4-butanediol dimethacry
late, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene gly
citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene, and maleic anhydride. Acrylic acid, i.e., CH2:CHCO2H, is the most preferred 0t,[3-unsaturated carboxylic acid. Especially preferred SAPs prepared by the present method are the alkali metal acrylate-type SAPs obtained, for example, by copolymerizing 100 parts of a monomer mixture
comprising about 1 to about 50 mole percent acrylic acid,
20
about 50 to about 99 mole percent of an alkali metal acrylate, and about 0.1 to about 5 percent by Weight of an internal crosslinking agent, in an aqueous solution containing at least about 15% and up to about 60%, and preferably about 20% to
about 50%, by Weight, of monomers. This is a preneutralized monomer mixture. In another preferred embodiment, the alkali metal acrylate-type SAPs are obtained by ?rst solution
25
methacrylate, divinyl esters of a polycarboxylic acid, diallyl esters or a polycarboxylic acid, triallyl terephthalate, diallyl
polymerizing acrylic acid, then neutralizing the SAP hydro gel With an alkali metal base, i.e., a postneutralization poly merization. As set forth above, polymerization of acidic or basic mono mers, and optional copolymerizable monomers, most com
30
as divinylbenzene and divinyl ether also can be used as
crosslinking agents. Especially preferred crosslinking agents
SAPs are cross-linked to a su?icient extent such that the SAP 35
is Water insoluble. Crosslinking renders the SAPs substan tially Water insoluble, and, in part, serves to determine the
are
N,N'-methylenebisacrylamide,
N,N'-methylenebis
methacrylamide, ethylene glycol dimethacrylate, and trim
ethylolpropane triacrylate. In the preparation of a color-stable SAP of the present invention, the monomers, for example, an 0t,[3-unsaturated
absorption capacity of the SAPs. For use in absorption appli cations, an acidic or basic SAP is lightly crosslinked, i.e., has 40
carboxylic acid, and especially, acrylic acid, and crosslinking agent are subj ected to a polymerization reaction in the pres
than about 10%, and most preferably about 0.01% to about 7%. A crosslinking agent most preferably is used in an amount of less than about 7 Wt %, and typically about 0.1 Wt % to about 5 Wt %, based on the total Weight of monomers.
maleate, diallyl fumarate, hexamethylenebismaleimide, trivi nyl trimellitate, divinyl adipate, diallyl succinate, a divinyl ether of ethylene glycol, cyclopentadiene diacrylate, tetraal lyl ammonium halides, or mixtures thereof. Compounds such
monly is performed by free radical processes in the presence of a polyfunctional crosslinking agent. The acidic and basic
a crosslinking density of less than about 20%, preferably less
col dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethyl ene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacry late, tripropylene glycol diacrylate, tetraethylene glycol dia crylate, tetraethylene glycol dimethacrylate, dipentaerythri tol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, tri methylolpropane trimethacrylate, tris(2-hydroxyethyl)iso cyanurate triacrylate, tris(2-hydroxyethyl)isocyanurate tri
ence of a polymerization initiator. One or more polymeriza tion initiator is added to a mixture of the monomers and 45
crosslinking agent to facilitate polymerization and formation of the SAP hydrogel. Often the initiator comprises at least one thermal initiator and at least one redox initiator. Any of the various polymer ization initiators that are knoWn foruse in preparing SAPs can be used in the present invention. HoWever, in accordance With
Examples of crosslinking polyvinyl monomers include, but are not limited to, polyacrylic (or polymethacrylic) acid
esters, represented by the folloWing formula (I), and bisacry lamides, represented by the folloWing formula (II). 50
an important feature of the present invention, the polymeriza tion initiator comprises a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture
(I) CH2=CH 55
thereof, and is essentially free of a color-forming oxidizing agent, like a persulfate, and a color-forming reducing agent, like ascorbic acid, isoascorbic acid, and sodium erythrobate. As used herein, for color-forming reducing agents, the term “essentially free” is de?ned a total concentration of color
forming reducing agents of 0 ppm up to 10 ppm, by Weight of the monomer mixture. For color-forming oxidizing agents,
Wherein X is ethylene, propylene, trimethylene, cyclohexy
lene,
hexamethylene,
2-hydroxypropylene,
i(CH2CH2O)PCH2CH2i, or CH3
60
the term “essentially free” is de?ned as less than 500 ppm,
preferably less than 300 ppm, and, and most preferably 0 ppm. In preferred embodiments, the polymerization inhibitor
is free of color-forming reducing agents and color-forming oxidizing agents, especially a persulfate.
CH3 65
Examples of useful polymerization initiators are redox initiators comprising (a) a reducing agent comprising a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic
US 7,504,551 B2 11
12
acid, a salt thereof, or a mixture thereof, and optionally,
and preferably is used as a salt, such as the disodium salt, e. g.,
2-hydroxy-2-sulfonatoacetic acid, a sul?te or bisul?te of an
alkali metal, ammonium sul?te, ammonium bisul?te, sodium metabisul?te, a sugar, an aldehyde, a primary or secondary
alcohol, and (b) an oxidizing agent, like hydrogen peroxide; an alkyl hydroperoxide, like t-butyl hydroperoxide; t-butyl
perbenZoate; t-butyl peroxy isopropyl carbonate; 1,1-di-t
butylperoxy-3,3,5-trimethylcyclohexane; benZoyl peroxide,
2-Hydroxy-2-sul?natoacetic acid is available commercially
dicumyl peroxide; caprylyl peroxide; sodium peracetate; or
in pure form as BRUGGOLITE® F137, and also as BRUG
other oxidiZing agents knoWn to persons skilled in the art. In
GOLITE® FF6, both from Briiggemann Chemical, Heilbron, Germany. BRUGGOLITE® FF6 contains, by Weight,
preferred embodiments, the reducing agent is 2-hydroxy-2 sul?natoacetic acid, and the oxidiZing agent is hydrogen per
50-60% 2-hydroxy-2-sul?natoacetic acid disodium salt, 30-35% sodium sul?te (Na2SO3), and 10-15% 2-hydroxy-2 sulfonatoacetic acid disodium salt, i.e.,
oxide. Sul?nic acid derivatives useful as the reducing agent are
disclosed in Us. Pat. No. 6,211,400, incorporated herein by reference. The sul?nic acid derivatives have a general struc tural formula:
H
20
2-Hydroxy-2-sulfonatoacetic acid also performs as a
R3
reducing agent, and can be used in combination With 2-hy 25
or a divalent metal ion of groups Ia, 11a, 11b, IVa, and VIIIb of the Periodic Table of the Elements; R1 is OH or NR4R5, Wherein R4 and R5 , independently, are H or Cl-C6alkyl; R2 is H or an alkyl, alkenyl, cycloalkyl, or aryl group, option
ally having 1-3 substituents independently selected from the group consisting of Cl-C6alkyl, OH, O4Cl-C6alkyl, halogen, and CF3; and R3 is COOM, SO3M, COR4, CONR4R5 , or COOR4, Wherein
30
natoacetic acid disodium salt, 2-hydroxy-2-sulfonatoacetic 35
acid disodium salt, or a mixture thereof, as the reducing agent,
and hydrogen peroxide as the oxidiZing agent, each used, for example, in an amount of about 2>
(12) United States Patent
(10) Patent N0.:
Herfert et a]. (54)
US 7,504,551 B2
(45) Date of Patent:
COLOR-STABLE SUPERABSORBENT
(52)
POLYMER COMPOSITION
*Mar. 17, 2009
US. Cl. ..................... .. 604/372; 604/358; 526/220;
526/222; 526/915; 524/815; 524/827; 524/831;
524/832; 522/42; 522/84; 522/152; 522/153; (75) Inventors: Norbert Herfert, Charlotte, NC (US); Michael M- Azfwl, Charlotte, NC (Us);
522/ 154; 428/402 (58)
Field of Classi?cation Search ................. .. 522/42,
Peter W- Cameo, West PO11“, MS (Us); Guy Thomas W99drum, Suff01k,VA
522/84, 152, 153, 154; 524/815, 831, 827, 524/832; 604/358, 372; 526/915, 220, 222;
(US); Michael A. Mitchell, WaxhaW, NC
(Us); Ma-Ikay Kikama Miatudila, Monroe, NC (U S)
428/402
See application ?le for complete search history. (56)
References Cited
(73) Assignee: BASF Aktiengesellschaft, Ludwigshafen (DE)
US. PATENT DOCUMENTS 5,408,019 A
(*)
Notice:
Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U_S_C_ 154(b) by 564 days_
This patent is subject to a terminal disClalmer-
(21)
APP1- NO-I
10/547,353
(22)
PCT Flled:
Mar. 19, 2004
(86)
PCT No.:
PCT/EP2004/002874
(87)
Aug. 29, 2005
(65)
Prior Publication Data US 2006/0089611 A1
(51)
3/1992 11/1988
0 942 014
9/1999
W0
WO 00/55245
9/2000
W0
WO 01/25289
4/2001
W0
WO 01/55228
8/2001
LLp
PCT Pub. No.: WO2004/084962 PCT Pub. Date: Oct. 7, 2004
(60)
EP
41 23 889 0 290 814
Primary ExamineriFred M Teskin (74) Attorney, Agent, or FirmiMarshall, Gerstein & Borun
§ 371 (9X1),
(2), (4) Date:
2/1997 Goldman et a1. 9/1997 Goldman et a1. 6/2002 Brown et al.
FOREIGN PATENT DOCUMENTS DE EP
_
4/1995 Mertens et a1.
5,599,335 A 5,669,894 A 2002/0068791 A1
Apr. 27, 2006
(57)
ABSTRACT
A color-stable superabsorbent polymer having long-term color stability, and methods of manufacturing the polymer, are disclosed. The superabsorbent polymer is prepared using
26 2003
a sul?nic acid derivative, like 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture thereof, as the reducing agent in a polymerization initiator system for the preparation of a superabsorbent polymer from monomers. The resulting
’ ' Int CL
superabsorbent polymer resists color degradation during periods of extended storage, even at an elevated temperature
Related U-s- Application Data Provisional application NO 60M528 41’ ?led on Mar‘
A61F 13/49 C08F 2/48 C08F 4/40
(2006.01) (2006.01) (2006.01)
and humidity 31 Claims, N0 Drawings
US 7,504,551 B2 1
2
COLOR-STABLE SUPERABSORBENT POLYMER COMPOSITION
Europe, the rate at Which an SAP undergoes color degradation is su?iciently sloW such that the SAP, or article containing the SAP, typically is consumed before a color change is observ
CROSS-REFERENCE TO RELATED APPLICATION
able to the naked eye.
HoWever, in tropical and subtropical climates, such as in South America and Southeast Asia, SAP color degradation is suf?ciently rapid such that a color change often occurs before
This is the US. national phase application of International
Application No. PCT/EP2004/002874, ?led Mar. 19, 2004, Which claims the bene?t of US. provisional patent applica tion Ser. No. 60/457,841, ?led Mar. 26, 2003.
the SAP, or article containing the SAP, is consumed. In areas like Southeast Asia, an SAP can change color from White to honey broWn in about 4 to 6 Weeks. This problem is exacer
FIELD OF THE INVENTION
bated because the SAPs may be produced far from the tropical
The present invention relates to superabsorbent polymers (SAPS) having long-term color stability, and to methods of preparing the color-stable SAPs. More particularly, the
tion to use. Furthermore, consumption of articles containing an SAP in such climates is relatively loW, therefore further increasing the time period betWeen SAP production and use. The change in color of the SAP does not affect SAP per formance, but adversely affects consumer acceptance of
climate, thereby increasing the time span from SAP produc
present invention relates to methods of preparing a color stable SAP using a monomer mixture containing a polymer iZation initiator comprising a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture
articles containing the color-degraded SAPs. In particular, 20
thereof, and, optionally, subjecting the resulting SAP hydro gel to a loW dose of UV radiation. The color-stable SAP can
be incorporated into articles, such as bandages, diapers, sani tary napkins, and other absorbent products, Wherein the SAP retains a clean, White color during extended storage periods, even under high temperature and humidity conditions.
hoW soiled or faulty, or is of loW quality. The diaper typically is returned for a refund, and the consumer is less likely to
repurchase that brand of diaper. 25
BACKGROUND OF THE INVENTION
Water-absorbing resins are Widely used in sanitary and
mats, disposable door mats, thickening agents, disposable
even under moderate pressure. For example, SAPs can absorb one hundred times their oWn Weight, or more, of distilled
retains its crisp, White color throughout the useful life of the SAP, or an article containing the SAP, even When stored under
Would be desirable to provide an SAP having a long-term color stability and loW residual monomer content, Without 40
adversely affecting the absorbent properties of the SAP, such as absorbing a large amount of liquids quickly, having a good ?uid permeability into and through the SAP, and having a high gel strength, such that an SAP hydro gel formed from the SAP does not deform or ?oW under an applied stress or
45
pressure.
Currently, SAPs, like partially neutraliZed, lightly
50
crosslinked, polyacrylic acid, are manufactured using a per sulfate as a component of the polymerization initiator system. A persulfate is included in the initiator system as the oxidiZ ing agent of a redox initiator pair and to reduce the amount of residual acrylic acid monomer in the SAP to acceptable lev els. A persulfate also can act as a thermal initiator. HoWever,
Water. The ability to absorb aqueous ?uids under a con?ning pressure is an important requirement for an SAP used in a
hygienic article, such as a diaper. As used herein, the term “SAP particles” refers to super
the manufacturer of articles and the manufacturer of the SAP, Who must absorb the cost of the returned goods. It Would be desirable to provide an SAP that exhibits
high temperature and humidity conditions. Furthermore, it
and polyacrylonitriles. Such Water-absorbing resins are termed “superabsorbent polymers,” or SAPs, and typically are lightly crosslinked hydrophilic polymers. SAPs are discussed generally in US. Pat. Nos. 5,669,894 and 5,559,335, each incorporated herein by reference. SAPs can differ in their chemical identity, but all SAPs are capable of absorbing and retaining amounts of aqueous ?uids equivalent to many times their oWn Weight,
A color-degraded SAP, therefore, ultimately adversely affects
exceptional color stability properties, such that the SAP 35
such as hydrolysis products of starch acrylonitrile graft poly mers, carboxymethylcellulose, crosslinked polyacrylates,
sulfonated polystyrenes, hydrolyzed polyacrylamides, poly vinyl alcohols, polyethylene oxides, polyvinylpyrrolidones,
Problems also arise at the manufacturing level because manufacturers of diapers and other articles containing an SAP refuse to incorporate a discolored SAP into their prod ucts, and return the discolored SAP to the SAP manufacturer.
30
hygienic goods, Wiping cloths, Water-retaining agents, dehy drating agents, sludge coagulants, disposable toWels and bath litter mats for pets, condensation-preventing agents, and release control agents for various chemicals. Water-absorbing resins are available in a variety of chemical forms, including substituted and unsubstituted natural and synthetic polymers,
consumers observing a color-degraded SAP in a diaper form an opinion that the diaper contains a contaminant, is some
the persulfate further interacts With the MEHQ inhibitor present in acrylic acid monomer and imparts a loW initial 55
color to the SAP. This loW initial SAP color progresses to a severe SAP discoloration over time, and especially under
absorbent polymer particles in the dry state, more speci? cally, particles containing from no Water up to about 10%, by
high temperature and humidity conditions.
Weight, Water. The terms “SAP gel,” “SAP hydrogel,” or “hydrogel” refer to a superabsorbent polymer containing at
lem of SAP discoloration attributed to the presence of a
least about 10%, by Weight, Water, and typically, particles that have absorbed at least their Weight in Water, and more typi cally several times their Weight in Water. SAPs have a tendency to degrade in color after long periods of storage. The tendency of an SAP to undergo a color tran sition from a clean, crisp, White color to a honey broWn color
accelerates as storage time, temperature, and humidity increase. In temperate climates, such as the United States and
The present invention is directed to overcoming the prob 60
color-producing oxidiZing agent, like a persulfate, in the preparation of an SAP. As discussed in detail hereafter, the present invention overcomes the SAP discoloration problem
(a) by utiliZing a polymeriZation initiator system comprising a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic 65
acid, optionally 2-hydroxy-2-sulfonatoacetic acid, salts thereof, or a mixture thereof, (b) by essentially omitting a color-producing oxidiZing agent from the monomer mixture,
US 7,504,551 B2 3
4
and, (c) optionally, by subjecting the SAP hydrogel resulting
White color over an extended time, even under high tempera
from the polymerization to a loW dose of ultraviolet (UV) radiation.
ture and humidity storage conditions. Another aspect of the present invention is to provide a method of manufacturing a color-stable SAP including the
2-Hydroxy-2-sul?natoacetic acid disodium salt and 2-hy droxy-2-sulfonatoacetic acid disodium salt have been used as a reducing agent in a redox initiator in emulsion polymeriza
steps of polymerizing a monomer mixture comprising a
sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture thereof, that provides an SAP,
tions. US. Pat. No. 5,408,019 discloses using formamidine sulfonic acid as the reducing agent in a redox initiator system. Ultraviolet radiation previously has been used in the prepa ration of SAPs. For example, UV radiation has been used in
for example, a polymerized 0t,[3-unsaturated carboxylic acid,
conjunction With a photoinitiator to initiate polymerization of
to form an SAP hydrogel, optionally subjecting the SAP hydrogel to UV radiation for about 3 to about 1 5 minutes from
monomers and provide an SAP hydrogel, as disclosed in EP 0 290 814 B1. DE 41 23 889 A1 discloses UV irradiation ofa
UV radiation dose, comminuting the SAP hydrogel to form
Water-ab sorbing resin prepared from a Water- soluble polymer and a polysaccharide and/or crosslinking agent, in the pres
SAP hydrogel particles, then drying the SAP hydrogel par ticles to provide color-stable SAP particles. The SAP hydro gel optionally is subjected to a loW dose of UV radiation, i.e.,
a distance of about 2 to about 30 centimeters, or an equivalent
ence of a radical scavenger, to provide a Water-absorbing
0 to about 2000 milliWatts (mW) of UV radiation per square
resin having a loW otmount of Water-soluble components (27 Wt %) and a loW amount of residual monomer (2500 ppm). The UV radiation is applied during drying or crushing of the
Water-absorbing resin.
centimeter (cm2) of SAP hydrogel. In another embodiment, 20
PCT publication WO 01/ 55228 discloses subjecting a Water-soluble or Water-sWellable polymer to UV radiation to reduce residual monomer content. An ultraviolet initiator is used in an amount of up to 10,000 ppm, by Weight of mono
mers, preferably up to 5000 ppm, more preferably 50 to 3,000 ppm, and still more preferably 500 to 2,000 ppm. UV radia tion typically is conducted for about 20 minutes. PCT publication WO 01/ 25289 discloses subjecting an
25
R3
acrylic polymer to UV radiation after, or simultaneously With,
comminuting a gelled polymer to gelled polymer particles.
30
In particular, the comminuted gel particles can be irradi ated during a drying step in a ?uid bed dryer.
Wherein M is hydrogen, an ammonium ion, or a monovalent or a divalent metal ion of groups Ia, 11a, 11b, IVa, and VIIIb of
the Periodic Table of the Elements;
SUMMARY OF THE INVENTION 35
The present invention is directed to a superabsorbent poly mer (SAP) having long-term color stability, and to methods of manufacturing a color-stable SAP composition. More par ticularly, the present invention is directed to a method of
preparing a color-stable SAP, Without adversely affecting the ?uid absorption and retention properties of the SAP particles,
40
ally having 1-3 substituents independently selected from the group consisting of Cl-C6alkyl, OH, O4Cl-C6alkyl, halogen, and CF3; and R3 is COOM, SO3M, COR4, CONR4R5 , or COOR4, Wherein M, R4, and R5 are as de?ned above, or, if R2 is unsubstituted or substituted aryl, R3 is H;
(a) by utilizing a polymerization initiator system comprising
acid, optionally 2-hydroxy-2-sulfonatoacetic acid, salts 45
and the salts thereof. In preferred embodiments, the monomer mixture com
prises (a) an 0t,[3-unsaturated carboxylic acid, (b) a crosslink ing agent, (b) a polymerization initiator system comprising
hydrogel resulting from the polymerization to a loW dose of UV radiation. A color-stable SAP prepared by the present method retains a crisp, clean White color over an extended
R1 is OH or NR4R5, Wherein R4 and R5 , independently, are H or Cl-C6alkyl;
R2 is H or an alkyl, alkenyl, cycloalkyl, or aryl group, option
a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic
thereof, or mixtures thereof, (b) by essentially omitting a coloring-forming oxidizing agent, like a persulfate, from the monomer mixture, and, optionally, (c) by subjecting the SAP
the SAP hydrogel is comminuted to form SAP hydrogel par ticles before being subjected to UV radiation. A sul?nic acid derivative useful in the present invention has a general structural formula:
50
2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture
storage period at a high temperature and humidity, i.e., at least 30 days When stored at 60° C. and 90% relative humidity. One aspect of the present invention, therefore, is to provide
thereof, that is essentially free of a persulfate and other color
a method of manufacturing a color-stable SAP, including the
ated carboxylic acid and crosslinking agent, and (e) Water. After drying, the color-stable SAP particles optionally are
steps of (a) polymerizing a monomer mixture comprising (i)
producing oxidizing agents, (d) an optional photoinitiator in an amount of 0 to about 1000 ppm by Weight of 0t,[3-unsatur 55
a monomer that provides an SAP, like an 0t,[3-unsaturated
surface treated to provide surface crosslinks on the color
carboxylic acid, such as acrylic acid, either neutralized, unneutralized, or partially neutralized, (ii) a crosslinking
stable SAP particles. Yet another aspect of the present invention is to incorporate
agent, (iii) an initiator system comprising a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture thereof, and that is essentially free of
60
hygiene product, an adult incontinence product, general pur pose Wipes and cloths, and similar absorbent products. The
color-producing oxidizing agent, e.g., a persulfate, and (ivy an optional photoinitiator, to form an SAP hydrogel, (b) optionally subjecting the SAP hydrogel to a loW dose of UV
radiation, and (c) comminuting and drying the SAP hydro gel to provide a color-stable SAP. The resulting color-stable SAP has a loW residual monomer content and maintains a crisp
the color-stable SAP particles into articles used to absorb liquids, for example, a diaper, a catamenial device, a feminine
articles resist color degradation over the expected life of the 65
article, even in high temperature and humidity climates. The above and other aspects and advantages of the present invention Will become apparent from the folloWing detailed
US 7,504,551 B2 5
6
description of the preferred embodiments of the invention, taken in conjunction With the examples and the claims.
crosslinking agent, (iii) a polymerization initiator comprising
DETAILED DESCRIPTION OF THE INVENTION
a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture thereof, that is essentially free of a color-forming oxidizing agent, like a persulfate, (iv) an
The present invention is directed to SAPs having a long term color stability, and to methods of preparing the color
optional photoinitiator, and (v) Water, to form an SAP hydro gel, (b) optionally subjecting the SAP hydrogel to a loW dose of UV radiation, (c) comminuting the SAP hydrogel to form
stable SAPs. The color-stable SAPs shoW a minor color
SAP hydrogel particles, (d) then drying the resulting SAP hydrogel particles, and (e) optionally surface treating the
change, to the naked eye, after storage for 30 days at 60° C. and 90% relative humidity. The present SAPs are prepared
color-stable SAP particles.
from a monomer mixture containing a polymerization initia
The present color-stable SAPs are based on polymerized
tor comprising a sul?nic acid derivative, such as 2-hydroxy 2-sul?natoacetic acid, a salt thereof, or a mixture thereof, that is essentially free of a color-forming oxidizing agent, like a
vinyl monomers, particularly 0t,[3-unsaturated carboxylic acids, that, after polymerization, have the ability to absorb several times their Weight of a liquid When crosslinked. The remainder of the speci?cation is directed to a color-stable
persulfate. The SAP hydrogel resulting from polymerizing the monomer mixture optionally is subj ected to a loW dose of
SAP based on acrylic acid, hoWever, other vinyl monomers,
UV radiation. The present polymerization initiator, and optional UV radiation, impart color stability to the SAP and
like (meth)acrylonitrile or a (meth)acrylamide, or an ethyl enic monomer having an amine substituent or a precursor to
reduce the amount of residual monomer in the SAP.
Suitable processes for preparing the present color-stable SAP particles include solution polymerization, also termed gel polymerization, for example, as disclosed in US. Pat. Nos. 4,076,663; 4,286,082; 4,654,039; and 5,145,906, each incorporated herein by reference. Another process is inverse
20
suspension polymerization disclosed, for example, in US.
25
exhibit improved color stability regardless of the identity of
Pat. Nos. 4,340,706; 4,497,930; 4,666,975; 4,507,438; and 4,683,274, each incorporated herein by reference. The present disclosure is directed primarily to gel polymer
Accordingly, neither the chemical makeup of the color color-stable SAPs, therefore, can be prepared by any SAP 30
polymerization. In gel polymerization, SAPs are prepared from an aqueous 35
aqueous monomer mixture also contains polymerization ini fate. A persulfate has been considered an important or essen
tial polymerization initiator ingredient in order to reduce the 40
herein by reference. An extensive list of suitable SAP-form ing monomers can be found in US. Pat. Nos. 4,076,663 and
chain. Polymers containing these acid moieties are synthe sized either from monomers previously substituted With one or more of these acidic functional groups or by incorporating
acceptable levels. In the typical manufacture of an SAP, the SAP is neutral ized at least about 25 mole percent, more preferably at least about 50 mole percent, and usually about 70 to about 80 mole percent, to achieve optimum absorbency. Neutralization can
acidic Water-absorbing resin (i.e., an anionic SAP), a basic Water-absorbing resin (i.e., a cationic SAP), or a multicom ponent SAP particle as disclosed in US. Pat. Nos. 6,072,101;
5,149,750, each incorporated herein by reference. Generally, acidic SAPs have carboxylate, sulfonate, sul fate, and/or phosphate groups incorporated along the polymer
tiators, typically including a persulfate, like sodium persul residual acrylic acid monomer content in SAP particles to
polymerization process knoWn in the art and can comprise an
6,159,591; 6,222,091; and 6,329,062, each incorporated
mixture of monomers and one or more crosslinking agents to
provide a Water-ab sorbent, but Water-insoluble, polymer. The
the monomers used to prepare the SAP, and particularly SAPs based on an 0t,[3-unsaturated carboxylic acid or anhydride.
stable SAP, nor its method of manufacture, is limited. The
ization for illustrative purposes. HoWever, the invention can
be practiced using all SAP manufacturing processes, includ ing modi?ed bulk polymerization and inverse suspension
an amine substituent, e. g., N-vinyl acetamide, and other 0t,[3 unsaturated carboxylic acids and anhydrides, also canbe used in the manufacture of color-stable SAPs of the present inven tion. The color-stable SAPs prepared by the present methods
ization, or the polymer can be neutralized after the polymer
the acidic functional group into the polymer after synthesis. To incorporate carboxyl groups into a polymer, any of a number of ethylenically unsaturated carboxylic acids can be homopolymerized or copolymerized. Carboxyl groups also can be incorporated into the polymer chain indirectly by
ization reaction is substantially complete. After polymeriza
hydrolyzing a homopolymer or copolymer of monomers such
45
be achieved by neutralizing the monomers before polymer tion and internal crosslinking of the monomers, folloWed by partial neutralization, e.g., about 50 to about 100 mole per cent neutralization, preferably about 70 to about 80 mole
as acrylamide, acrylonitrile, methacrylamide, and alkyl acry 50
lates or methacrylates. An acidic SAP canbe either a strong or a Weak acidic Water-absorbing resin, and can be a homopoly
percent neutralization, the polymer is comminuted, e.g.,
mer or a copolymer.
shredded or chopped, for more ef?cient drying, then dried and
The acidic SAP typically is a neutralized, lightly crosslinked acrylic-type resin, such as neutralized, lightly crosslinked polyacrylic acid. The lightly crosslinked acidic SAP typically is prepared by polymerizing an acidic mono
milled to a desired particle size. The polymer preferably then is surface treated. In embodiments Wherein surface treatment
55
is employed, a surface crosslinking agent typically is applied to the dried. SAP particles. Generally, after application of the
mer containing an acyl moiety, e. g., acrylic acid, or a moiety
surface crosslinking agent, the SAP particles then are sub jected to conditions Wherein the surface crosslinking agent reacts With a portion of the SAP to crosslink the surfaces of
60
the SAP particles.
capable of providing an acid group, i.e., acrylonitrile, in the presence of a crosslinking agent, i.e., a polyfunctional organic compound. The acidic resin can contain other copolymeriz able units, i.e., other monoethylenically unsaturated comono mers, Well knoWn in the art, as long as the polymer is sub
In one embodiment of the present invention, a color-stable
SAP is prepared by a method comprising the steps of (a)
stantially, i.e., at least 10%, and preferably at least 25%,
solution polymerizing a monomer mixture comprising (i) a monomer capable of providing an SAP polymer, like an 0t,[3
acidic monomer units. To achieve the full advantage of the present invention, the acidic SAP contains at least 50%, and more preferably, at least 75%, and up to 100%, acidic mono
unsaturated carboxylic acid, such as acrylic acid, either neu tralized, unneutralized, or partially neutralized, (ii) a
65
mer units. The acidic resin can be unneutralized or neutral
US 7,504,551 B2 8
7 iZed, preferably neutralized at least 50 mole %, and most preferably at least 70 mole %, With a base prior to drying. Ethylenically unsaturated carboxylic acid monomers, and
The basic SAP, either strongly or Weakly basic, therefore, can be any resin that acts as an SAP in its charged form. The basic SAP typically is a lightly crosslinked resin, such as a
lightly crosslinked polyethylenimine, a poly(allylamine), a poly(allylguanidine), a poly(dimethyldiallylammonium hydroxide), a quaterniZed polystyrene derivative, a guani
anhydrides, amides, esters, and salts thereof, useful in the acidic SAP include, but are not limited to, acrylic acid, meth
acrylic acid, ethacrylic acid, ot-chloroacrylic acid, ot-cy anoacrylic acid, [3-methylacrylic acid (crotonic acid), ot-phe nylacrylic acid, [3-acryloxypropionic acid, sorbic acid, ot-chlorosorbic acid, angelic acid, cinnamic acid, p-chloro
dine-modi?ed polystyrene, a poly(vinylguanidine), or a poly
(dialkylaminoalkyl (meth)acrylamide) prepared by polymer iZing and lightly crosslinking a monomer having the structure
cinnamic acid, [3-stearylacrylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic
acid, fumaric acid, tricarboxyethylene, 2-methyl-2-butene dicarboxylic acid, maleamic acid, N-phenyl maleamide,
H
Rs C=C
maleamide, maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride,
R7
\
methyl itaconic anhydride, ethyl maleic anhydride, diethyl maleate, methyl maleate, and maleic anhydride. Sulfonate-containing acidic SAPs can be prepared from monomers containing functional groups hydrolyZable to the sulfonic acid form, for example, alkenyl sulfonic acid com
R9
C—NH—(Y)—N 0
R10
or its ester analog 20
pounds and sulfoalkyl acrylate compounds. Ethylenically unsaturated sulfonic acid monomers include, but are not lim
H
Rs
ited to, aliphatic or aromatic vinyl sulfonic acids, such as
\
vinylsulfonic acid, allylsulfonic acid, vinyltoluene sulfonic acid, styrenesulfonic acid, acrylic and methacrylic sulfonic
R/
/
C=C
7
25
acids, such as sulfoethyl acrylate, sulfoethyl methacrylate,
sulfopropyl acrylate, 2-vinyl-4-ethylbenZenesulfonic acid,
R9
c 0 —
u
—
(Y)
—
N/
\R
,
10
2-allylbenZenesulfonic acid, 1-phenylethylene sulfonic acid,
sulfopropyl methacrylate, 2-hydroxy-3 -methacryloxypropyl sulfonic acid, and 2-acrylamide-2-methylpropane sulfonic
30
acid.
straight chain or branched organic radical having 1 to 8 car
Sulfate-containing acidic SAPs are prepared by reacting
bon atoms, R9 is hydrogen, and R10 is hydrogen or an alkyl
homopolymers or copolymers containing hydroxyl groups or
radical having 1 to 4 carbon atoms. Preferred basic SAPs include a poly(vinylamine), polyeth
residual ethylenic unsaturation With sulfuric acid or sulfur
trioxide. Examples of such sulfated polymers include sulfated
35
polyvinyl alcohol, sulfated hydroxyethyl acrylate, and sul
mixtures thereof. Basic SAPs are disclosed in US. Pat. No.
acidic SAPs are prepared by homopolymeriZing or copoly meriZing ethylenically unsaturated monomers containing a
6,159,591, incorporated herein by reference. The lightly 40
phate. The acidic SAP, either strongly or Weakly acidic, can be any resin that acts as an SAP in its neutralized form. Examples
of acidic resins include, but are not limited to, polyacrylic
acid, hydrolyZed starch-acrylonitrile graft copolymers, starch-acrylic acid graft copolymers, saponi?ed vinyl
45
acetate-acrylic ester copolymers, hydrolyZed acrylonitrile
copolymers, hydrolyZed acrylamide copolymers, ethylene maleic anhydride copolymers, isobutylene-maleic anhydride copolymers, poly(vinylsulfonic acid), poly(vinylphosphonic acid), poly(vinylphosphoric acid), poly(vinylsulfuric acid), sulfonated polystyrene, poly(aspartic acid), poly(lactic acid),
ylenimine, poly(vinylguanadine), poly(methylaminoethyl acrylamide), poly(methylaminopropyl methacrylamide), or
fated hydroxypropyl methacrylate. Phosphate-containing phosphoric acid moiety, such as methacryloxy ethyl phos
Wherein R7 and R8, independently, are selected from the group consisting of hydrogen and methyl, Y is a divalent
crosslinked basic SAP can contain other copolymeriZable units and is crosslinked using a polyfunctional organic com pound, as set forth above With respect to the acidic SAP. CopolymeriZable monomers for introduction into an acidic SAP or a basic SAP include, but are not limited to, ethylene,
propylene, isobutylene, Cl_4 alkyl acrylates and methacry lates, vinyl acetate, methyl vinyl ether, and styrenic com pounds having the formula:
50
and mixtures thereof. The preferred acidic resins are the poly
acrylic acids. The acidic SAP contains 0 to 100 percent neutraliZed pen
55
dant carboxylate groups (i.e., DNIO to DNIlOO). Neutraliza tion of carboxylic acid groups is accomplished using a strong organic or inorganic base, such as sodium hydroxide, potas
Wherein R represents hydrogen or a C1_6 alkyl group, and Wherein the phenyl ring optionally is substituted With one to
sium hydroxide, ammonia, ammonium hydroxide, or an
organic amine. Analogous to the acidic SAP, a color-stable basic SAP can be manufactured by the present method. The basic SAP can be a strong or Weak basic Water-absorbing resin. The strong basic resins typically are present in the hydroxide (OH) or bicarbonate (HCO3) form. The basic SAP can be a single
60
four C1_4 alkyl or hydroxy groups. Suitable C1_4 alkyl acrylates include, but are not limited to,
methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, and the like, and mixtures thereof. Suitable C 1_ 4 alkyl methacrylates include, but are not limited
to, methyl methacrylate, ethyl methacrylate, isopropyl meth 65
acrylate, n-propylmethylmethacrylate, n-butyl methacrylate,
resin or a mixture of resins. The basic SAP can be a
and the like, and mixtures thereof or With C 1_ 4 alkyl acrylates.
homopolymer or a copolymer.
Suitable styrenic compounds include, but are not limited to,
US 7,504,551 B2 9
10
styrene, ot-methylstyrene, p-methylstyrene, t-butyl styrene,
p and r each are an integer 5 to 40, and k is 1 or 2;
and the like, and mixtures thereof or With C 1_ 4 alkyl acrylates and/ or methacrylates.
(H)
As previously stated, the present invention is not limited to SAPs based on acrylic acid, but preferably extends to SAPs
CH2=CH
Hc=cH2
prepared for 0t,[3-unsaturated carboxylic acids including, but not limited to, methacrylic acid, ethacrylic acid, ot-chloro
acrylic acid, ot-cyanoacrylic acid, [3-methylacrylic acid (cro tonic acid), ot-phenylacrylic acid, [3-acryloxypropionic acid,
wherein 1 is 2 or 3.
sorbic acid, ot-chlorosorbic acid, angelic acid, cinnamic acid,
Speci?c crosslinking monomers include, but are not lim
p-chlorocinnamic acid, [3-stearylacrylic acid, itaconic acid,
ited to, 1,4-butanediol diacrylate, 1,4-butanediol dimethacry
late, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene gly
citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene, and maleic anhydride. Acrylic acid, i.e., CH2:CHCO2H, is the most preferred 0t,[3-unsaturated carboxylic acid. Especially preferred SAPs prepared by the present method are the alkali metal acrylate-type SAPs obtained, for example, by copolymerizing 100 parts of a monomer mixture
comprising about 1 to about 50 mole percent acrylic acid,
20
about 50 to about 99 mole percent of an alkali metal acrylate, and about 0.1 to about 5 percent by Weight of an internal crosslinking agent, in an aqueous solution containing at least about 15% and up to about 60%, and preferably about 20% to
about 50%, by Weight, of monomers. This is a preneutralized monomer mixture. In another preferred embodiment, the alkali metal acrylate-type SAPs are obtained by ?rst solution
25
methacrylate, divinyl esters of a polycarboxylic acid, diallyl esters or a polycarboxylic acid, triallyl terephthalate, diallyl
polymerizing acrylic acid, then neutralizing the SAP hydro gel With an alkali metal base, i.e., a postneutralization poly merization. As set forth above, polymerization of acidic or basic mono mers, and optional copolymerizable monomers, most com
30
as divinylbenzene and divinyl ether also can be used as
crosslinking agents. Especially preferred crosslinking agents
SAPs are cross-linked to a su?icient extent such that the SAP 35
is Water insoluble. Crosslinking renders the SAPs substan tially Water insoluble, and, in part, serves to determine the
are
N,N'-methylenebisacrylamide,
N,N'-methylenebis
methacrylamide, ethylene glycol dimethacrylate, and trim
ethylolpropane triacrylate. In the preparation of a color-stable SAP of the present invention, the monomers, for example, an 0t,[3-unsaturated
absorption capacity of the SAPs. For use in absorption appli cations, an acidic or basic SAP is lightly crosslinked, i.e., has 40
carboxylic acid, and especially, acrylic acid, and crosslinking agent are subj ected to a polymerization reaction in the pres
than about 10%, and most preferably about 0.01% to about 7%. A crosslinking agent most preferably is used in an amount of less than about 7 Wt %, and typically about 0.1 Wt % to about 5 Wt %, based on the total Weight of monomers.
maleate, diallyl fumarate, hexamethylenebismaleimide, trivi nyl trimellitate, divinyl adipate, diallyl succinate, a divinyl ether of ethylene glycol, cyclopentadiene diacrylate, tetraal lyl ammonium halides, or mixtures thereof. Compounds such
monly is performed by free radical processes in the presence of a polyfunctional crosslinking agent. The acidic and basic
a crosslinking density of less than about 20%, preferably less
col dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethyl ene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacry late, tripropylene glycol diacrylate, tetraethylene glycol dia crylate, tetraethylene glycol dimethacrylate, dipentaerythri tol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, tri methylolpropane trimethacrylate, tris(2-hydroxyethyl)iso cyanurate triacrylate, tris(2-hydroxyethyl)isocyanurate tri
ence of a polymerization initiator. One or more polymeriza tion initiator is added to a mixture of the monomers and 45
crosslinking agent to facilitate polymerization and formation of the SAP hydrogel. Often the initiator comprises at least one thermal initiator and at least one redox initiator. Any of the various polymer ization initiators that are knoWn foruse in preparing SAPs can be used in the present invention. HoWever, in accordance With
Examples of crosslinking polyvinyl monomers include, but are not limited to, polyacrylic (or polymethacrylic) acid
esters, represented by the folloWing formula (I), and bisacry lamides, represented by the folloWing formula (II). 50
an important feature of the present invention, the polymeriza tion initiator comprises a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic acid, a salt thereof, or a mixture
(I) CH2=CH 55
thereof, and is essentially free of a color-forming oxidizing agent, like a persulfate, and a color-forming reducing agent, like ascorbic acid, isoascorbic acid, and sodium erythrobate. As used herein, for color-forming reducing agents, the term “essentially free” is de?ned a total concentration of color
forming reducing agents of 0 ppm up to 10 ppm, by Weight of the monomer mixture. For color-forming oxidizing agents,
Wherein X is ethylene, propylene, trimethylene, cyclohexy
lene,
hexamethylene,
2-hydroxypropylene,
i(CH2CH2O)PCH2CH2i, or CH3
60
the term “essentially free” is de?ned as less than 500 ppm,
preferably less than 300 ppm, and, and most preferably 0 ppm. In preferred embodiments, the polymerization inhibitor
is free of color-forming reducing agents and color-forming oxidizing agents, especially a persulfate.
CH3 65
Examples of useful polymerization initiators are redox initiators comprising (a) a reducing agent comprising a sul?nic acid derivative, such as 2-hydroxy-2-sul?natoacetic
US 7,504,551 B2 11
12
acid, a salt thereof, or a mixture thereof, and optionally,
and preferably is used as a salt, such as the disodium salt, e. g.,
2-hydroxy-2-sulfonatoacetic acid, a sul?te or bisul?te of an
alkali metal, ammonium sul?te, ammonium bisul?te, sodium metabisul?te, a sugar, an aldehyde, a primary or secondary
alcohol, and (b) an oxidizing agent, like hydrogen peroxide; an alkyl hydroperoxide, like t-butyl hydroperoxide; t-butyl
perbenZoate; t-butyl peroxy isopropyl carbonate; 1,1-di-t
butylperoxy-3,3,5-trimethylcyclohexane; benZoyl peroxide,
2-Hydroxy-2-sul?natoacetic acid is available commercially
dicumyl peroxide; caprylyl peroxide; sodium peracetate; or
in pure form as BRUGGOLITE® F137, and also as BRUG
other oxidiZing agents knoWn to persons skilled in the art. In
GOLITE® FF6, both from Briiggemann Chemical, Heilbron, Germany. BRUGGOLITE® FF6 contains, by Weight,
preferred embodiments, the reducing agent is 2-hydroxy-2 sul?natoacetic acid, and the oxidiZing agent is hydrogen per
50-60% 2-hydroxy-2-sul?natoacetic acid disodium salt, 30-35% sodium sul?te (Na2SO3), and 10-15% 2-hydroxy-2 sulfonatoacetic acid disodium salt, i.e.,
oxide. Sul?nic acid derivatives useful as the reducing agent are
disclosed in Us. Pat. No. 6,211,400, incorporated herein by reference. The sul?nic acid derivatives have a general struc tural formula:
H
20
2-Hydroxy-2-sulfonatoacetic acid also performs as a
R3
reducing agent, and can be used in combination With 2-hy 25
or a divalent metal ion of groups Ia, 11a, 11b, IVa, and VIIIb of the Periodic Table of the Elements; R1 is OH or NR4R5, Wherein R4 and R5 , independently, are H or Cl-C6alkyl; R2 is H or an alkyl, alkenyl, cycloalkyl, or aryl group, option
ally having 1-3 substituents independently selected from the group consisting of Cl-C6alkyl, OH, O4Cl-C6alkyl, halogen, and CF3; and R3 is COOM, SO3M, COR4, CONR4R5 , or COOR4, Wherein
30
natoacetic acid disodium salt, 2-hydroxy-2-sulfonatoacetic 35
acid disodium salt, or a mixture thereof, as the reducing agent,
and hydrogen peroxide as the oxidiZing agent, each used, for example, in an amount of about 2>
