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US006603055B2

(12) United States Patent

(10) Patent N0.:


(45) Date of Patent:

Mitchell et al.

(54)

POLY (VINYLAMINE) - BASE

(56)

Us PATENT DOCUMENTS

Inventors: Michael A. Mitchell, Lake Zurich, IL

(US); Thomas W. Beiho?'er, Arlington


Heights, IL (US); Ra?'at S. Sultana,
Algonquin, IL (US)

4,569,344 A

2/1986 Palmer

4,638,539 A
4,696,296 A
4,850,350 A

1/1987 Palmer
9/1987 Palmer
7/1989 Jackson

5,073,164 A

(73)

Assignee: BASF Aktiengesellschaft,

LudWigshafen (DE)

12/1991 Hollister et a1.

5,083,561 A

1/1992 Russo

5,125,893 A

6/1992 Dryden

5,139,018 A

Notice:

8/1992 Brodsky et a1.

Subject to any disclaimer, the term of this


patent is extended or adjusted under 35
U_S_C_ 154(k)) by 191 days_

5,269,756 A
5,279,549 A
5,309,902 A

12/1993 Dryden
1/1994 Ranford
5/1994 Kee et 211.

This patent is subject to a terminal dis-

53497950 A

9/1994 Ulrich ct a1~

C1aimer_

5,449,348 A

9/1995 Dryden

5,333,606 A

8/1994 Schneider et al.

5,641,184 A

(21)
(22)
(65)

6,072,101 A

APP1~N~109/746177

Filed:

(58)

6/2000

Beihoffer et a1. ......... .. 604/372

6,222,091 B1 *

4/2001

Beihoffer et a1. ......... .. 604/368

* cited by examiner

Prior Publication Data

Primary ExaminerWeilun Lo
Assistant ExaminerMichael G. Bogart
(74) Attorney, Agent, or FirmMarshall, Gerstein & Borun

Related US. Application Data

(51)
(52)

6/1997 Mortensen
*

Dec. 22, 2000

US 2001/0007064 A1 Jul. 5, 2001

(63)

*Aug. 5, 2003

References Cited

SUPERABSORBENT GELS AND METHOD


OF MANUFACTURING THE SAME

(75)

US 6,603,055 B2

Continuation-in-part of application No. 09/179,554, ?led on


Oct. 28, 1998, now Pat. No. 6,194,631, which is a continu

ation-in-part of application No. 08/974,119, ?led on Nov.


19, 1997, HOW Pat- N0~ 5,981,689
Int. Cl.7 ........................... .. A61F 13/15; C08L 8/00

(57)

ABSTRACT

US. Cl. ..................... .. 604/372; 603/368; 525/191;

Bi-component superabsorbent materials are disclosed. The


Superabsorbent materials comprise a mixture of about 20%
0 about 40% by Weight> POlF/(VinYlamine) Polymer or Other

525/206; 525/218; 525/221

basic resin and about 60% to about 80%, by Weight of an

Field of Search ............................... .. 504/364, 367,

acidic water'absorbing polymer like polyacryhc acid

504/368, 372, 375; 525/191, 206, 218,


221; 428/327, 402, 407

33 Claims, 8 Drawing Sheets

70

1O

20

30

4O

50

6O

70

80

90

100

110

U.S. Patent

Aug. 5, 2003

Sheet 2 0f 8

US 6,603,055 B2

100

FIG.2

RBalteinod
20
1O

50

45

40

35

30

25a

O.20

15

.0

U.S. Patent

Aug. 5, 2003

Sheet 3 0f 8

US 6,603,055 B2

50:r+ 50;wI I

omow

on

5owom 032wm-

on

low

low

low

|ON

U.S. Patent

Aug. 5, 2003

Sheet 4 0f 8

US 6,603,055 B2

100

+lhourAUL h4ourIAUL
FIG.4

RBalteinod

50

45

40

35

U.S. Patent

Aug. 5,2003

Sheet 5 0f 8

US 6,603,055 B2

100
90

h+ourA1UL h+our4AUL
RBalteinod

FIG.5

70

60

50

40

30

20

10

U.S. Patent

Aug. 5,2003

Sheet 6 6f 8

US 6,603,055 B2

100

1+h0urAUL h4ouIrA-UL
FIG.6

RBalteinod

45

40

35

HIV !sd L'O

10

U.S. Patent

Aug. 5, 2003

Sheet 7 0f 8

US 6,603,055 B2

#T3Q5I2 4w3i,1l50:
2O28onON2Eom

.mzlM

om

h
_
P
_
_

low

low

low

low.

low

32 m

U.S. Patent

Aug. 5,2003

Sheet 8 0f 8

US 6,603,055 B2

100

14h0ur-AUL 4ho+urAUL
60

RBalteinod

F8IG.
3O
20
10

45

40

US 6,603,055 B2
1

POLY (VINYLAMINE) - BASE

psi. In contrast, the same sodium polyacrylate is capable of


absorbing only 43.5 g, 29.7 g, and 24.8 g of 0.9% aqueous
NaCl at 0 psi, 0.28 psi, and 0.7 psi, respectively. The
absorption capacity of SAPs for body ?uids, like urine or
menses, therefore, is dramatically loWer than for deioniZed
Water because such ?uids contain electrolytes. This dramatic
decrease in absorption is termed salt poisoning.
The salt poisoning effect has been explained as folloWs.
Water-absorption and Water-retention characteristics of

SUPERABSORBENT GELS AND METHOD


OF MANUFACTURING THE SAME
CROSS-REFERENCE TO RELATED
APPLICATIONS

This is a continuation-in-part application of US. appli


cation Ser. No. 09/179,554, ?led Oct. 28, 1998, now US.
Pat. No. 6,194,631, Which is a continuation-in-part applica
tion of US. application Ser. No. 08/974,119, ?led Nov. 19,
1997, now US. Pat. No. 5,981,689.

10

SAPs are attributed to the presence of ioniZable functional

groups in the polymer structure. The ioniZable groups typi


cally are carboxyl groups, a high proportion of Which are in

the salt form When the polymer is dry, and Which undergo

FIELD OF THE INVENTION

dissociation and salvation upon contact With Water. In the

The present invention relates to superabsorbent gels con

15

taining a poly(vinylamine), or a salt thereof, and to an

improved method of manufacturing a poly(vinylamine). The


superabsorbent gels comprise a basic superabsorbent
polymer, and preferably a poly(vinylamine), in an amount of

about 20% to about 40% by Weight of superabsorbent


polymers, admixed With an acidic superabsorbent polymer,

20

solubiliZation of the polymer.

(vinylamine).

It is theoriZed that the presence of a signi?cant concen


25

Water-absorbing resins are Widely used in sanitary goods,

hygienic goods, Wiping cloths, Water-retaining agents, dehy


drating agents, sludge coagulants, disposable toWels and
bath mats, disposable door mats, thickening agents, dispos

graft polymers, carboxymethylcellulose, crosslinked


polyacrylates, sulfonated polystyrenes, hydrolyZed
polyacrylamides, polyvinyl alcohols, polyethylene oxides,
polyvinylpyrrolidines, and polyacrylonitriles.
Such Water-absorbing resins are termed superabsorbent
polymers, or SAPs, and typically are lightly crosslinked
hydrophilic polymers. SAPs are generally discussed in

and outside of the gel. The dissolved ions, therefore, effec


tively convert an ionic gel into a nonionic gel, and sWelling
properties are lost.

The most commonly used SAP for absorbing electrolyte


35

containing liquids, like urine, is neutraliZed polyacrylic acid,


i.e., containing at least 50%, and up to 100%, neutraliZed

carboxyl groups. NeutraliZed polyacrylic acid, hoWever, is

40

susceptible to salt poisoning. Therefore, to provide an SAP


that is less susceptible to salt poisoning, either an SAP
different from neutraliZed polyacrylic acid must be
developed, or the neutraliZed polyacrylic acid must be
modi?ed or treated to at least partially overcome the salt

poisoning effect.

Goldman et al. US. Pat. No. 5,669,894. SAPs can differ in

their chemical identity, but all SAPs are capable of absorb


ing and retaining amounts of aqueous ?uids equivalent to

tration of electrolytes interferes With dissociation of the


ioniZable functional groups, and leads to the salt poison
ing effect. Dissolved ions, such as sodium and chloride
ions, therefore, have tWo effects on SAP gels. The ions
screen the polymer charges and the ions eliminate the
osmotic imbalance due to the presence of counter ions inside

able 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, such as hydrolysis products of starch acrylonitrile

sion of the polymer structure, Which, in turn, permits further


absorption of Water molecules. Polymer expansion,
hoWever, is limited by the crosslinks in the polymer
structure, Which are present in a suf?cient number to prevent

like a polyacrylic acid, or comprise a salt of a poly


BACKGROUND OF THE INVENTION

dissociated state, the polymer chain contains a plurality of


functional groups having the same electric charge and, thus,
repel one another. This electronic repulsion leads to expan

Prior investigators have attempted to counteract the salt


45

many times their oWn Weight, even under moderate pressure.


For example, SAPs can absorb one hundred times their oWn

poisoning effect and thereby improve the performance of


SAPs With respect to absorbing electrolyte-containing
liquids, such as menses and urine. For example, Tanaka et al.
US. Pat. No. 5,274,018 discloses an SAP composition

Weight, or more, of distilled Water. The ability to absorb


aqueous ?uids under a con?ning pressure is an important
requirement for an SAP used in a hygienic article, like a

comprising a sWellable hydrophilic polymer, like poly

diaper.

acrylic acid, and an amount of an ioniZable surfactant


suf?cient to form at least a monolayer of surfactant on the

The dramatic sWelling and absorbent properties of SAPs


are attributed to (a) electrostatic repulsion betWeen the

polymer. In another embodiment, a cationic gel, like a gel


containing quaterniZed ammonium groups and in the

hydroxide (i.e., OH) form, is used With an anionic gel (i.e.,

charges along the polymer chains, and (b) osmotic pressure


of the counter ions. It is knoWn, hoWever, that these absorp
tion properties are drastically reduced in solutions contain
ing electrolytes, such as saline, urine, and blood. The poly

55

Wong US. Pat. No. 4,818,598 discloses admixing a


?brous anion exchange material, like DEAE cellulose, and
a hydrogel, like a polyacrylate, to improve absorption prop

mers do not function as effective SAPs in the presence of

such physiologic ?uids.


The decreased absorbency of electrolyte-containing liq
uids is illustrated by the absorption properties of a typical,
commercially available SAP, i.e., sodium polyacrylate, in
deioniZed Water and in 0.9% by Weight sodium chloride
(NaCl) solution. The sodium polyacrylate can absorb 146.2
grams (g) of deioniZed Water per gram of SAP (g/g) at 0 psi,
103.8 g of deioniZed Water per gram of polymer at 0.28 psi,
and 34.3 g of deioniZed Water per gram of polymer of 0.7

a polyacrylic acid) to remove electrolytes from the solution

by ion exchange.

60

erties. WO 96/17681 discloses admixing an anionic SAP,


like polyacrylic acid, With a polysaccharide-based cationic
SAP to overcome the salt poisoning effect. Similarly, WO
96/15163 discloses admixing a cationic SAP having at least
20% of the functional groups in a basic (i.e., OH) form With

65

a cationic exchanges resin, i.e., a nonsWelling ion exchange


resin, having at least 50% of the functional groups in the acid
form. WO 96/15180 discloses an absorbent material com

US 6,603,055 B2
3

prising an anionic SAP, e.g., a polyacrylic acid and an anion

resins, yet performs as Well as an SAP material containing

exchange resin, i.e., a nonsWelling ion exchange resin.

a signi?cantly higher Weight percent of basic resin. Apresent

These references disclose combinations that attempt to


overcome the salt poisoning effect. It Would be desirable,
hoWever, to provide an SAP that exhibits exceptional absor

SAP material, therefore, provides economies by utiliZing


less of an expensive basic resin, While exhibiting excellent

absorption and retention properties.

bency and retention, like a sodium polyacrylate, and,

Yet another important feature of the present invention is

therefore, can be used alone as an SAP. It also Would be


desirable to admix such an SAP With polyacrylic acid, or

to provide an SAP material containing about 60% to about

another acid-containing SAP, to overcome the salt poisoning


effect.

10

and basic resin.


An example of a Weak acidic resin is polyacrylic acid

SUMMARY OF THE INVENTION

The present invention is directed to poly(vinylamine)

based superabsorbent gels. Apoly(vinylamine) polymer can


be used in conjunction With an acidic Water-absorbing resin,
like polyacrylic acid, to help overcome the salt poisoning
effect, or a salt of a poly(vinylamine) polymer can be used
alone as an SAP. The poly(vinylamine) polymer also can be
used, alone, as an SAP to absorb and retain acidic media.
More particularly, the poly(vinylamine) used as an SAP, or
as a component of an SAP, is lightly crosslinked and, in

15

20

?uids.
25

(vinylamine) comprising vinylamine monomer units, and

(N-vinylamide) precursor of the poly(vinylamine), and,


therefore, eliminates the stringent puri?cation procedures, or
reduces the long polymeriZation reaction times, previously
time and production costs.
Another aspect of the present invention is to provide an

BRIEF DESCRIPTION OF THE DRAWINGS


30

FIG. 1 contains plots of Wt % poly(vinylamine) in a

superabsorbent material vs. AUL (0.28 psi) and (0.7 psi),


and vs. AUNL, in g/g, after 3 hours;
35

FIGS. 2, 4, 6, and 8 contain plots of Wt % poly


(vinylamine) in a superabsorbent material vs. AUL (0.7 psi),
in g/g, after 1 hour and 4 hours, Wherein the poly

(vinylamine) and poly(acrylic acid) contain different


amounts of internal crosslinker; and

SAP having absorbency and retention properties comparable


to a conventional SAP, like sodium polyacrylate. Apresent
SAP is produced by neutraliZing a poly(vinylamine) With a
sufficient amount of acid, like hydrochloric acid, such that at
least about 10%, i.e., about 10% to 100%, of the amine
functional groups are neutraliZed. The resulting poly
(vinylamine) salt is an excellent SAP for absorbing aqueous
media.
In accordance With another important aspect of the

These and other aspects and advantages of the present


invention Will become apparent from the folloWing detailed

description of the preferred embodiments.

used to overcome the problem of residual monomer content.

Consequently, the present improved process reduces process

having a core comprising an SAP material of the present


invention. Other articles that can contain an SAP material of

the present invention include adult incontinence products,


and devices for absorbing saline and other ion-containing

Which can be crosslinked using a suitable polyfunctional

vinyl monomer. The present method substantially reduces


the amount of residual N-vinylamide monomer in the poly

resins are a poly(vinylamine), a poly(allylamine), and a

Still another aspect of the present invention is to provide


articles of manufacture, like diapers and catamenial devices,

absorption properties.
provide an improved method of manufacturing a poly

having 0% to 25% neutraliZed carboxylic acid groups (i.e.,


DN=0 to DN=25). Examples of Weak basic Water-absorbing

polyethylenimine.

preferred embodiments, is surface treated to improve


Accordingly, one aspect of the present invention is to

80%, by Weight, of a Weak acidic Water-absorbing resin and


about 20% to about 40%, by Weight, of a Weak basic
Water-absorbing resin, based on the total Weight of the acidic

FIGS. 3, 5, and 7 contain plots of Wt % poly(vinylamine)


40

in a superabsorbent material vs. AUNL, in 1 g/g, after 1 hour

and 4 hours, Wherein the poly(vinylamine) and poly(acrylic


acid) contain different amounts of internal crosslinker.

45

DETAILED DESCRIPTION OF THE


PREFERRED EMBODIMENTS

The present invention is directed to: (a) an improved

present invention, a lightly crosslinked poly(vinylamine),

method of manufacturing poly(vinylamine), (b) poly

alone and unneutraliZed, can be used to absorb and retain


acidic aqueous media. The acidic aqueous media converts

(vinylamine) and poly(vinylamine) salts and their use as


SAPs, and (c) an improved SAP material comprising an
admixture of an acidic Water-absorbing resin and about 20%
to about 40%, by Weight, based on the total Weight of the

the loW-absorbing poly(vinylamine) to a highly absorbing


poly(vinylamine) salt, i.e., converts the polymer to an SAP,
during absorption. A poly(vinylamine), therefore, is an
excellent resin for cleaning acid spills and the remediation of

basic and acidic resin, of a poly(vinylamine) or other basic

Water-absorbing resin.
(a) An Improved Method of Manufacturing Poly

acidic species.
Yet another aspect of the present invention is to provide

55

an improved SAP that overcomes the salt poisoning effect of

(Vinylamine)
Poly(vinylamine), and salts derived therefrom, are knoWn

electrolytes. In particular, the improved SAP material con

polymers. For example, the folloWing patents disclose the

tains a mixture of an acidic sWellable resin, like polyacrylic

synthesis or manufacture of poly(vinylamine): US. Pat. No.


4,798,871; US. Pat. No. 4,843,118; and US. Pat. No.
4,804,793. In addition, US. Pat. No. 4,018,826 discloses a

acid, and about 20% to about 40%, by Weight, of a poly


(vinylamine), based on the total Weight of the acidic resin
and the poly(vinylamine).

60

process for preparing poly(vinylamine) and salts thereof.

Another aspect of the present invention is to provide an

Ford et al. US. Pat. No. 5,491,199 discloses the preparation

improved SAP material having improved absorption and

of formate-free poly(vinylamine) by heating the polymer in

retention properties compared to a conventional SAP, such


as sodium polyacrylate. The present SAP material contains
a loW Weight percentage of basic resin, e.g., about 20% to
about 40% based on the total Weight of acidic and basic

the presence of transition metal catalyst.


65

The above patents generally disclose polymers of


N-vinylformamide that subsequently are hydrolyZed. Upon
hydrolysis, the poly(N-vinylformamide) is converted into a

US 6,603,055 B2
5

poly(vinylamine). Hydrolysis can be performed under acid

In accordance With an important feature of the present


invention, a scavenging agent is added to a poly(N
vinylamide), prior to hydrolysis, in an amount of about 0.1%

or basic conditions. The cationic charge on the resulting

vinylamine, i.e., the charge density, is related to the pH of

to about 3%, and preferably about 0.1% to about 2%, by


Weight, based on the Weight of N-vinylamide monomer used
in the polymeriZation. To achieve the full advantage of the
present invention, the scavenging agent is added in an
amount of about 0.1% to about 1%, by Weight, based on the
Weight of N-vinylamide monomer.

the medium. At a loW pH, the poly(vinylamine) is proto


nated and has a high cationic charge density. Conversely, at
a high pH, the poly(vinylamine) is not protonated, and the
polymer has a substantially reduced cationic charge density,
if any.
In general, an uncrosslinked poly(vinylamine) is a Water

soluble polymer that has many practical applications, such

10

The scavenging agent can be any compound capable of

exchange resins. Poly(vinylamine) is rendered Water


insoluble by a crosslinking the polymer. Although

reacting With N-vinylamides, like N-vinylformamide, and


other aldehydic impurities, like formaldehyde or
acetaldehyde, under hydrolysis conditions, i.e., a tempera

polyvinylamines, and salts thereof, are Well knoWn, it has


not heretofore been suggested that such polymers can be

15 hours in the presence of an acid or a base. Typically, a

as in Water treatment, personal care products, and ion

ture of about 25 C. to about 80 C. for about 4 to about 24

scavenging agent is capable of reacting With an aldehyde in

used as an SAP.

Typically, a poly(vinylamine) polymer is produced by

about 1 minute to about 10 minutes at a temperature of about


20 C. to about 80 C.

hydrolysis of poly(N-vinylformamide), under either acid or


basic conditions. Poly(vinylamine) also can be produced

from other poly(N-vinylamides), like poly(N

Examples of scavenging agents include, but are not lim

vinylacetamide), poly(N-vinylpropionamide), and poly(N

ited to: (a) oxidiZing agents, like potassium permanganate,


ammonia silver salts (Tollens Reagent), potassium

vinylsuccinamide). It is desirable that hydrolysis of the

dichromate, and hydrogen peroxide; (b) reducing agents,

poly(vinylamide) is substantially to essentially complete,

like catalytic hydrogenation, lithium aluminum hydride,


sodium borohydride, diborane, aluminum hydride, LiAlH(O

i.e., about 10% to 100% complete, and preferably about 30%


to 100% complete. To achieve the full advantage of the
present invention, at least about 50%, and more preferably

20

25

at least about 90%, of the amide groups are hydrolyZed to an


amine functionality. The amine-functional polymer can con

tain other copolymeriZable units, i.e., other monoethyleni


cally unsaturated monomers, as long as the polymer is

30

substantially, i.e., at least 10%, and preferably at least 25%,


vinylamine units. To achieve the full advantage of the
present invention, the polymer contains at least 50%, and
more preferably at least 75%, vinylamine units.

t-Bu)3 (lithium aluminum tri-t-butoxy hydride), LiAlH


(OCH3)3 (lithium aluminum trimethoxy hydride), Zinc
(mercury) and concentrated hydrochloric acid, and hydra
Zine and a base; (c) Grignard reagents, like aryl and alkyl
magnesium halides; (d) sodium or potassium cyanide With
sodium bisul?te; (e) sodium bisul?te; and
ammonia
derivatives, like hydroxylamine, hydraZine, substituted
hydraZines, e.g., phenyl hydraZine, and semicarbaZine. A
reducing agent is a preferred scavenging agent, and sodium
borohydride is a most preferred scavenging agent. Such

If residual monomer or other impurities are present in the 35 scavenging agents have the advantages of being
inexpensive, greatly reducing the reaction time to form a
poly(vinylamide), hydrolysis conditions can lead to a

crosslinking, Which increases the molecular Weight of the

poly(N-vinylamide), and eliminating the need to purify the

poly(vinylamine) and can result in undesirable and unpre


dictable gel formation. Therefore, current methods of syn

poly(N-vinylamide).

thesiZing poly(vinylamine) require either a rigorous puri?

40

cation of the poly(N-vinylformamide), or an extremely long


reaction time and a relatively high reaction temperature to
ensure that all the residual poly(N-vinylformamide) mono

mer is consumed during the polymeriZation.

The production of poly(vinylamine) Would be facilitated,

45

and production costs decreased, by an improved method of


removing residual N-vinylamide monomers from the poly
(N-vinylamide). Therefore, in accordance With an important
feature of the present invention, an improved method of

manufacturing poly(vinylamine) is disclosed.

To achieve the full advantage of the present invention, the


scavenging agent is an aqueous solution containing sodium
borohydride, e.g., about 10% to about 15% by Weight, and
sodium hydroxide. The sodium borohydride acts quickly, is
highly effective, and is inexpensive. As an added advantage,
the sodium hydroxide is useful in a subsequent basic

hydrolysis of the poly(N-vinylamide). Prior to hydrolyZing


the poly(N-vinylamide), the poly(N-vinylamide) and scav
enging agent are held at about 25 C. to about 80 C. for
about 1 minute to about 10 minutes to eliminate essentially
all, i.e., about 95% to 100%, of the residual monomers and

50

impurities.

As set forth above, polymeriZation of N-vinylformamide,

After using a scavenging agent to remove residual mono

folloWed by hydrolysis, is the most common method of

mers and other impurities, the poly(N-vinylamide) is hydro

producing poly(vinylamine). The polymeriZation can be

lyZed. The amount of acid or base used to hydrolyZe the


poly(N-vinylamide) in solution can vary Widely, and is

performed in the presence or absence of a crosslinker, i.e., a

polyfunctional organic compound. HoWever, residual

55

generally added in a molar ratio of acid or base to

N-vinylformamide monomer, or other monomer impurities,

N-vinylamide monomer content of the initially formed poly

like aldehydes, can cause crosslinking and undesired gel


formation during hydrolysis. In accordance With an impor
tant feature of the present invention, it has been found that
the problem of residual monomer content, and the presence

mer of about 0.05:1 to about 3:1, preferably of about 0.3:1


to about 1:1. To achieve the full advantage of the present
invention, the molar ratio of acid or base to N-vinylamide
60

monomer is about 0.7:1 to about 1:1.

of other impurities, can be overcome by the use of suitable


scavenging agents to remove the residual monomer and

Generally, hydrolysis is achieved With a suitable acid,


such as an inorganic acid, for example, hydrochloric acid,

other impurities from the poly(N-vinylamide). The use of

hydrobromic acid, hydro?uoric acid, sulfuric acid, nitric

scavenging agents has the advantage of greatly reducing the


process time, and costs, currently invested to insure that all

acid, phosphoric acid, and the like. In addition, suitable


65

bases, such as an inorganic base, for example, sodium

the N-vinylamide monomer and other impurities are con

hydroxide, ammonia, ammonium hydroxide, potassium

sumed prior to hydrolysis.

hydroxide, and the like, can also be used. Hydrolysis is

US 6,603,055 B2
7

conducted at a temperature of about 25 C. to about 100 C.


for about 4 to about 24 hours.

The remainder of the initiator solution Was added to the


monomer solution over a one-hour time period, While the
resulting reaction mixture Was heated to 45 C. The reaction
mixture Was held at 45 C. for 2.5 hours, then heated to 55

The degree of hydrolysis is controlled by the amount of


acid or base, the reaction temperature, and/or the reaction
time. In general, greater amounts of acid or base, higher
reaction temperatures, and longer reaction times result in

C. and held for an additional 2.5 hours, and ?nally heated to


65 C. and held for an additional one hour. Next, 20 g of

higher degrees of hydrolysis.

12% sodium borohydride in a 41% aqueous sodium hydrox

The present method, therefore, is an improved method of


manufacturing either crosslinked or uncrosslinked poly

(vinylamine). The folloWing examples illustrate the

ide solution Was added to the reaction mixture, folloWed


10

improved method in the manufacture of uncrosslinked poly

but then returned to colorless. The hydrolysis step Was


continued at 70 C. for an additional 8 hours. The resulting

(vinylamine).

poly(vinylamine) solution can then be puri?ed, if desired, by

EXAMPLE 1

N-vinylformamide (400 g, 5.6 mole) Was dissolved in

15

ultra?ltration as set forth in Example 1. In the absence of a

sodium borohydride scavenger, the reaction requires an


additional several hours to react all the N-vinylformamide

3,000 g of deioniZed Water, then the resulting monomer


solution Was sparged With argon for one hour. In a separate

monomers and other impurities, as set forth in Example 1.

vessel, 5 g of 2,2-aZobis(2-amidinopropane)hydrochloride
initiator (i.e., V-50 initiator available from Wako Pure
Chemical Industries, Inc., Osaka, Japan) Was dissolved in 70
g of deioniZed Water, then the resulting initiator solution Was
sparged With argon for one-half hour. A 7 g portion of the

immediately by 480 g of a 50% aqueous sodium hydroxide


solution. The reaction mixture quickly turned pink in color

EXAMPLE 3

20

Freshly distilled N-vinylformamide (250 g, 3.5 mole) and

2.8 g of 15% V-50 initiator Were dissolved


initiator solution Was added to the monomer solution, and
deioniZed Water, then the resulting reaction
the remainder of the initiator solution Was added to the
monomer solution over an hour period While heating the 25 sparged With argon for 15 minutes. Next,
solution Was poured into a glass pan and
resulting reaction mixture to about 45 C. The reaction

mW/cm2 of UV light for 25 minutes. The polymeriZation


Was exothermic, eventually reaching about 100 C. The

temperature Was maintained at about 45 C. for about 4


hours. The reaction mixture then Was heated to 55 C. and

resulting concentrated poly(N-vinylformamide) solution

held for tWo hours. Finally, 20 g of a 15% by Weight aqueous


V-50 solution Was added to the reaction mixture, and the
polymeriZation reaction Was held at 65 C. for 12 hours to

30 Was very viscous.

The concentrated poly(N-vinylformamide) solution (312

provide poly(N-vinylformamide).
The aqueous poly(N-vinylformamide) solution then Was
heated to about 70 C., While 20 g of a 12% by Weight

sodium borohydride solution (in 41% aqueous sodium

g) then Was diluted With 2 liters of deioniZed Water, and the


diluted polymer solution Was heated to 70 C. Six (6) g of
35

hydroxide) Was added to the polymer solution. After the


scavenger solution Was added, 480 g of 50% aqueous
sodium hydroxide Was added to the polymer solution, and
the resulting solution Was stirred for about 8 hours at about

70 C. to hydrolyZe the poly(N-vinylformamide).


If desired, the resulting poly(vinylamine) solution then
can be puri?ed by ultra?ltration. In this optional puri?cation,

40

With a 100,000 molecular Weight cut-off tangential ?oW

The present improved method of manufacturing a poly


50

crosslinked poly(vinylamine). As described above, SAPs are


crosslinked to a suf?cient extent such that the polymer is
Water insoluble. Crosslinking serves to render the poly

(vinylamine) polymers substantially Water insoluble, and, in

aqueous solution of poly(N-vinylformamide) gelled. Gelling

part, serves to determine the absorptive capacity of the

Was attributed to impurities present in the N-vinylformamide


55

The folloWing example illustrates the ability of a


scavenger, like sodium borohydride, to reduce the reaction
time in the synthesis of a poly(vinylamine).

polymers. For use in absorption applications, the poly


(vinylamine) is lightly crosslinked, i.e., has a crosslinking
density of less than about 20%, and preferably less than
about 10%, and most preferably about 0.01% to about 7%.

When used, a crosslinking agent most preferably is


60

A ?ve liter ?ask Was charged With 400 g of


N-vinylformamide monomer and 2,970 g of deioniZed
Water, and the resulting monomer solution Was sparged With

included 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. Apoly(vinylamine) can be crosslinked

by tWo different pathWays. One pathWay utiliZes ole?nically

argon for one hour. Separately, an initiator solution Was

initiator solution (7 g) Was added to the monomer solution.

(vinylamine) is derived from, for example, poly(N

vinylacetamide), poly(N-vinylpropionamide), poly(N


(vinylamine) can also be used in the manufacture of a

Example 1 Was repeated, but the scavenger step using


sodium borohydride Was omitted. During hydrolysis, the

prepared by dissolving 5 g of V-50 in 67 g of deioniZed


Water, and sparging With argon for 0.5 hours. Aportion of the

for 8 hours to hydrolyZe the poly(N-vinylformamide), then


cooled and puri?ed as in Example 1.

vinylsuccinamide), and similar N-vinylcarboxamides.

ultra?ltration module. The diluted polymer solution Was


Washed With 25 liters of deioniZed Water, and then concen
trated to 2,500 ml to give a 4 Wt % solution of sodium

EXAMPLE 2

aqueous sodium hydroxide) Was added dropWise to the


heated polymer solution over a ?ve-minute time period,
folloWed by the addition of 143 g of 50% aqueous sodium
hydroxide. The resulting solution Was maintained at 70 C.

The present improved method of manufacturing poly

deioniZed Water. The diluted solution then Was ultra?ltered 45

monomer that Were not removed in a scavenging step.

a sodium borohydride solution (15% by Weight of 41%

(vinylamine) also can be used in processes Wherein poly

the poly(vinylamine) solution Was diluted With 3 liters of

formate-free poly(vinylamine).

in 400 g of
solution Was
the reaction
cured at 15

65

unsaturated crosslinking monomers that copolymeriZe With


the N-vinylamide, and, therefore, form a part of the poly
meric backbone. The crosslinked poly(N-vinylamide) then

is hydrolyZed to provide crosslinked polyvinylamine.

US 6,603,055 B2
9

10

Examples of crosslinking polyvinyl monomers include,

EXAMPLE 4

but are not limited to, polyacrylic (or polymethacrylic) acid

A monomer mixture containing N-vinylformamide (250

esters represented by the following formula (I); and

grams), deioniZed Water (250 grams), methylenebisacryla

bisacrylamides, represented by the following formula (II).

mide (1.09 grams), and V-50 initiator (0.42 grams) Was


placed in a shalloW dish, then polymeriZed under an ultra
violet lamp as set forth in Example 3 until the mixture

(1)
CH2: CH

polymeriZed into a rubbery gel. The concentrated poly(N


vinylformamide) then Was treated With a sodium
10

Wherein X is ethylene, propylene, trimethylene, hexa

methylene, 2-hydroxypropylene, (CH2CH2O)n


CHZCHZ, or
15

CH3

CH3

borohydride/sodium hydroxide solution, as set forth in

Example 1, to yield a lightly crosslinked poly(vinylamine).


Sodium formate present in the crosslinked poly(vinylamine)
can be removed by Washing the resin With acetone/Water
mixtures, or by other suitable methods knoWn to persons
skilled in the art.
Poly(vinylamine) also can be crosslinked in solution by

suspending or dissolving uncrosslinked poly(vinylamine) in


an aqueous medium, then adding a di- or poly-functional

compound capable of crosslinking the poly(vinylamine) by


n and m are each an integer 5 to 40, and k is 1 or 2;

20

reaction With the amino groups of the polymer. Such

crosslinking agents include, for example, multifunctional

aldehydes (e.g., glutaraldehyde), multifunctional acrylates


(e.g., butanediol diacrylate, TMPTA), halohydrins (e.g.,
epichlorohydrin), dihalides (e.g., dibromopropane), disul

(II)
25

fonate esters (e.g., WS(O2)O(CH2)nOF(O)2W, Wherein


n is one to 10, and W is methyl or tosyl), multifunctional

epoxies (e.g., ethylene glycol diglycidyl ether), multifunc

Wherein 1 is 2 or 3.

The compounds of formula (I) are prepared by reacting


polyols, such as ethylene glycol, propylene glycol,
trimethylolprop ane, 1 ,6-hexanediol, glycerin,
pentaerythritol, polyethylene glycol, or polypropylene

tional esters (e.g., dimethyl adipate), multifunctional acid


30

succinic anhydride), organic titanates (e.g., TYZOR AA


from DuPont), melamine resins (e.g., CYMEL 301, CYMEL

glycol, With acrylic acid or methacrylic acid. The com

303, CY MEL 370, and CYMEL 373 from Cytec Industries,

pounds of formula (II) are obtained by reacting polyalkylene

Wayne, N.J.), hydroxymethyl ureas (e.g., N,N

polyamines, such as diethylenetriamine and

triethylenetetramine, With acrylic acid.

35

Speci?c crosslinking monomers include, but are not lim

al. US. Pat. No. 5,085,787, incorporated herein by

dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene


glycol dimethacrylate, diethylene glycol diacrylate, diethyl
40

diacrylate, ethoxylated bisphenolAdimethacrylate, ethylene


glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6

and possess suf?cient reactivity With poly(vinylamine) such

crosslinking agent is ethylene glycol diglycidyl ether

dimethacrylate, polyethylene glycol diacrylate, polyethyl


45

triethylene glycol dimethacrylate, tripropylene glycol


diacrylate, tetraethylene glycol diacrylate, tetraethylene gly
col dimethacrylate, dipentaerythritol pentaacrylate, pen

taerythritol tetraacrylate, pentaerythritol triacylate, trim


ethylolpropane triacrylate, trimethylolpropane
trimethacrylate, tris(2-hydroxyethyl)isocyanurate
triacrylate, tris(2-hydroxyethyl)isocyanurate
55

adipate, diallyl succinate, a divinyl ether of ethylene glycol,

vinylamide). Especially preferred crosslinking agents are

N,N-methylenebisacrylamide,
N,N
methylenebismethacrylamide, ethylene glycol
dimethacrylate, and trimethylolpropane triacrylate.
The folloWing example illustrates a cross-linked poly
(vinylamine) prepared in accordance With the present inven
tion.

To 2 liters of a 3% by Weight aqueous poly(vinylamine)


solution Was added 0.18 g of ethyleneglycol diglycidyl ether
(EGDGE). The resulting mixture Was stirred to dissolve the
EGDGE, then the mixture Was heated to about 60 C. and
held for one hour to gel. The gel Was heated to about 80 C.
and held until about 90% of the Water Was removed. The
resulting gel then Was extruded and dried to a constant

cyclopentadiene diacrylate, tetraallyl ammonium halides or


mixtures thereof. Compounds like divinylbenZene and divi
nyl ether also can be used to crosslink the poly(N

(EGDGE), a Water-soluble diglycidyl ether.


The folloWing example illustrates light crosslinking of a
sodium formate-free poly(vinylamine) of the present inven
tion using a polyfunctional crosslinking agent that reacts
With the amino groups of the polymer.
EXAMPLE 5

trimethacrylate, divinyl esters of a polycarboxylic acid,


diallyl esters of a polycarboxylic acid, triallyl terephthalate,

diallyl
maleate,
diallyl
fumarate,
hexamethylenebismaleimide, trivinyl trimellitate, divinyl

reference, and in EP 450 923.


In general, the crosslinking agent should be Water soluble
that crosslinking occurs in a controlled fashion, preferably at
a temperature of about 25 C. to about 150 C. Apreferred

hexane diol dimethacrylate, neopentyl glycol

ene glycol dimethacrylate, triethylene glycol diacrylate,

dihydroxymethyl-4,5-dihydroxyethyleneurea), and multi

functional isocyanates (e.g., toluene diisocyanate).


Crosslinking agents also are disclosed in Pinschmidt, Jr. et

ited to, 1,4-butanediol diacrylate, 1,4-butanediol


ene glycol dimethacrylate, ethoxylated bisphenol A

halides (e.g., oxalyl chloride), multifunctional carboxylic


acids (e.g., succinic acid), carboxylic acid anhydrides (e.g.,

60

Weight at 80 C. The dried, lightly crosslinked poly


(vinylamine) then Was cryogenically milled to form a granu
lar material capable of absorbing Water or acid solutions.

The gel exhibited the folloWing absorption characteristics in


0.1 M hydrochloric acid (HCl):

AUNL1)=59.3 g/g

AULZ) (0.28 psi)=37.8 g/g

US 6,603,055 B2
11

12

1 Absorption under no load; and


2 Absorption under load.

that crosslinking occurs in a controlled fashion at a tem

perature of about 25 C. to about 150 C.

Nonlimiting examples of suitable surface crosslinking

Absorption under load (AUL) is a measure of the ability

agents include:
(a) dihalides and disulfonate esters, for example, com
pounds of the formula

of an SAP to absorb ?uid under an applied pressure. The

AUL Was determined by the following method, as disclosed

in US. Pat. No. 5,149,335, incorporated herein by reference.


An SAP (0.160 g:0.001 g) is carefully scattered onto a
140-micron, Water-permeable mesh attached to the base of a
holloW plexiglass cylinder With an internal diameter of 25
mm. The sample is covered With a 100 g cover plate and the

10

Wherein p is a number from 2 to 12, and Z, independently,

is halo (preferably bromo), tosylate, mesylate, or other alkyl

cylinder assembly Weighed. This gives an applied pressure


of 20 g/cm2 (0.28 psi). Alternatively, the sample can be

or aryl sulfonate esters;

(b) multifunctional aZiridines;


(c) multifunctional aldehydes, for example,

covered With a 250 g cover plate to give an applied pressure

of 51 g/cm2 (0.7 psi). The screened base of the cylinder is


placed in a 100 mm petri dish containing 25 milliliters of a

glutaraldehyde, trioxane, paraformaldehyde,

test solution (usually 0.9% saline), and the polymer is


alloWed to absorb for 1 hour (or 3 hours). By reWeighing the
cylinder assembly, the AUL (at a given pressure) is calcu

terephthaldehyde, malonaldehyde, and glyoxal, and


acetals and bisul?tes thereof;

(d) halohydrins, like epichlorohydrin;

lated by dividing the Weight of liquid absorbed by the dry


Weight of polymer before liquid contact. As discussed
hereafter, the poly(vinylamine) particles also can be surface
treated With a crosslinking agent, like ethyleneglycol digly
cidyl ether, to give an absorbent having improved perfor

20

25

(vinylamine) enhances the ability of the polymer to absorb


and retain aqueous media under load.

30

(g) organic titanates, like TYZOR AA, available from E.


I. DuPont de Nemours, Wilmington, Del.;
(h) melamine resins, like the CYMEL resins available

(vinylamine) particles With an isopropyl alcohol solution of


a surface crosslinking agent to Wet predominantly only the
outer surfaces of the poly(vinylamine) particles. Surface
35

preferably by heating at least the Wetted surfaces of the

poly(vinylamine) particles.

from Cytec Industries, Wayne, N.J.;


(i) hydroxymethyl ureas, like N,N-dihydroxymethyl-4,5
dihydroxyethylene urea; and

Typically, the poly(vinylamine) particles are surface

multifunctional isocyanates, like toluene diisocyanate,

treated With an alcoholic solution of a surface crosslinking

agent. The particles can be in the form of granules, a foam,

(f) multifunctional carboxylic acids and esters, acid


chlorides, and anhydrides derived therefrom, for
example, di- and poly-carboxylic acids containing tWo
to tWelve carbon atoms, and the methyl and ethyl
esters, acid chlorides, and anhydrides derived
therefrom, like oxalic acid, adipic acid, succinic acid,
dodecanoic acid, malonic acid, and glutaric acid, and
esters, anhydrides, and acid chlorides derived there

from;

Surface crosslinking is achieved by spraying poly

crosslinking and drying of the polymer then is performed,

ylene glycol diglycidyl ether, bisphenol A diglycidyl


ether, and bisphenol F diglycidyl ether;

mance under external pressure.

In a preferred embodiment, a lightly crosslinked poly


(vinylamine) is subjected to a process step Wherein the
surface of the poly(N-vinylamine) is further crosslinked. It
has been found that surface crosslinking of a poly

(e) multifunctional epoxy compounds, for example, eth

40

beads, ?akes, ?bers, or poWders, for example. The solution


contains about 0.01% to about 4%, by Weight, surface
crosslinking agent, and preferably about 0.4% to about 2%,
by Weight, surface crosslinking agent in a suitable solvent.

isophorone diisocyanate, xylene diisocyanate, and hex

amethylene diisocyanate.
A preferred surface crosslinking agent is ethylene glycol
diglycidyl ether (EGDGE), Which is a Water-soluble digly
cidyl ether Which crosslinks poly(vinylamine) at a tempera

The solution can be applied as a ?ne spray onto the surface 45

of freely tumbling poly(vinylamine) particles at a ratio of


about 11001 to about 1105 parts by Weight poly(vinylamine)
to solution of surface crosslinking agent. The surface

ture of about 25 C. to about 150 C.

The folloWing Example 6 illustrates surface treatment and

crosslinking of a lightly crosslinked poly(vinylamine).


EXAMPLE 6

crosslinker is present in an amount of 0% to about 1%, by

DivinylbenZene crosslinker (1.085 g, 55% active, by

Weight of the poly(vinylamine), and preferably 0% to about


0.5% by Weight. To achieve the full advantage of the present

Weight, in styrene/ethylstyrene), aqueous V-50 initiator

invention, the surface crosslinker is present in an amount of

(2.541 g, 15%), and N-vinylformamide (245 g, 3.45 moles)

about 0.001% to about 0.1% by Weight.


The crosslinking reaction and drying of the surface

Were mixed in 350 g of deioniZed Water. The resulting


solution Was sparged With argon for 15 minutes, and then

treated poly(vinylamine) particles are achieved by heating

55

crosslinking agent to achieve surface crosslinking of the


poly(vinylamine) particle, and any other method of drying

polymeriZed under UV light (15 mW/cm2) for one hour. The


resulting gel Was extruded, dried at 100 C., and milled to

the surface-treated polymer at a suitable temperature, e.g.,


about 25 C. to about 150 C., and preferably about 105 C.
to about 120 C. HoWever, any other method of reacting the

produce particles of lightly crosslinked poly(vinylamine).


Aportion of the poly(N-vinylformamide) particles (82 g)
60

Was hydrolyZed by dispersing the particles in a solution


containing 168 g cyclohexane, 112 g 1-butanol, and 46 g of

the poly(vinylamine) particles, such as microWave energy,

poWdered sodium hydroxide. The resulting suspension then

or the like, can be used.

Was heated at about 70 C. for about 6 hours. Next, 150 g of


deioniZed Water Was added to the suspension, and the

Suitable surface crosslinking agents include the di- or

poly-functional molecules capable of reacting With amino


groups and crosslinking poly(vinylamine). Preferably, the
surface crosslinking agent is alcohol or Water soluble and
possesses suf?cient reactivity With a poly(vinylamine) such

65

organic solvents Were decanted. Acetone (230 g) then Was


added to collapse the gel and remove the sodium formate
by-product. The Water/acetone Wash Was repeated three
more times, and the gel Was dried then remilled. The

US 6,603,055 B2
14

13

In particular, poly(vinylamine) samples, as prepared in

resulting poly(vinylamine) gel then Was surface treated With


ethylene glycol diglycidyl ether at various levels, and dried

Example 5, Were converted to the hydrochloride salt using


different amounts of 1N hydrochloric acid (HCl). The result
ing gels of poly(vinylamine) salt then Were dried and
evaluated for an ability to absorb a 0.9% by Weight aqueous

at 145 C. to provide a surface crosslink.


The poly(vinylamine) then Was tested for an ability to

absorb and retain 0.1 M hydrochloric acid.

NaCl solution. The results are summarized in Table 2.

TABLE 1
TABLE 2
Surface crosslink

AUNLl) and AUL2) (0.1M HCl)

Level (ppm)3)

No Load

0.28 psi

0.7 psi

0
100
500
1000
2000

51
47
47
46
41

23
27
27
28
26

9.9
19
19
20
20

10

Mole % HCL4)

AUNLl)

AUL2)
(0.28 psi)

AUL2
(0.7 psi)

15

0
30
50
70
100

18.7
31.6
39.8
43.0
28.5

13.7
21.5
25.6
23.4
9.1

12.6
15.9
20.1
13.5
9.5

3)ppmnparts per million of surface crosslinker.

The absorption data shoWs that surface crosslinking sub


stantially improves the absorption under load of a poly
(vinylamine), especially at a load of 0.7 psi.

4)mole % HCl added to the poly(vinylamine) based on the moles of


N-vinylformamide monomer used to prepare the poly(vinylamine).

The absorbency results summariZed in Table 2 shoW that


20

under no load, When the poly(vinylamine) is converted to a

(b) Poly(Vinylamine)-Based SAPs

hydrochloride salt, especially in the range of about 30 to

Poly(vinylamine) typically does not function as an SAP in


its neutral form because there is no ionic charge on the

about 70 mole % conversion to the salt. In accordance With


an important feature of the present invention, a polyl
(vinylamine) exhibits the properties of an SAP When con

polymer. The driving force for Water absorption and reten


tion therefore is lacking. HoWever, When converted to a salt,
or used in conjunction With an acidic Water-absorbing resin,
like a polyacrylic acid, a poly(vinylamine) then behaves

verted to a salt in an amount of about 10 to about 100, and

preferably about 20 to about 90, mole percent. To achieve

the full advantage of the present invention, the poly

likes an SAP. It should be understood that a poly

(vinylamine) is converted to a salt in an amount of about 25

(vinylamine) produced either by the above-described


improved method, or by a prior, conventional method, can
be used in a poly(vinylamine)-based SAP.

30

(i) Salts of Poly(Vinylamine)


As previously discussed, sodium poly(acrylate) is con
sidered the best SAP, and, therefore, is the most Widely used
SAP in commercial applications. Sodium poly(acrylate) has
polyelectrolytic properties that are responsible for its supe
rior performance in absorbent applications. These properties
include a high charge density, and charge relatively close to
the polymer backbone.
Poly(vinylamine) is a neutral polymer, and, accordingly,

to about 75 mole %, based on the Weight of N-vinylamide


monomer used to prepare the poly(vinylamine).
In another test, a lightly crosslinked poly(vinylamine), as

prepared in Example 6, Was surface treated With various


35

levels of ethylene glycol diglycidyl ether (EGDGE) in


isopropyl alcohol, folloWed by drying and curing at 80 C.
The surface crosslinked granules of lightly crosslinked poly
vinylamine then Were partially neutraliZed (i.e., 50 mole %)
With 1N HCl. The surface crosslinked polyvinylamine salt,
then Was tested for an ability to absorb and retain a 0.9%
aqueous NaCl solution. The results are summariZed in Table

3, and shoW that a neutraliZed and surface crosslinked

does not possess the polyelectrolytic properties necessary to


provide an SAP. HoWever, poly(vinylamine) salts have
polyelectrolytic properties sufficient to provide an SAP. The
poly(vinylamine) used to provide an SAP is a lightly

crosslinked poly(vinylamine), and preferably is surface

absorbency increases dramatically, both under load and

poly(vinylamine) shoWs an improvement in AUL.


TABLE 3
45

crosslinked, as set forth above.

Surface crosslink

Level of EGDGE

Such lightly crosslinked, and optionally surface


crosslinked, poly(vinylamine) polymers are converted into
salts by methods knoWn in the art. For example, the prepa

ration of poly(vinylamine HCl) by the addition of hydro


chloric acid to a poly(vinylamine) is set forth in Pinschmidt,
Jr. et al. US. Pat. No. 5,085,787, and in Gless, Jr. et al. US.

AUL2)

AUL2)

(ppm)4)

AUNLl)

(0.28 psi)

(0.7 psi)

0
100
500
1000
2000

35.8
35.3
31.5
31.3
28.8

16.6
18.9
16.3
17.8
18.0

9.3
11.3
11.2
11.5
11.9

Pat. No. 4,018,826, or by hydrolysis of a poly(N

vinylamide) With hydrochloric acid.


Apoly(vinylamine) salt useful as an SAP, hoWever, is not
limited to the hydrochloride salt. Poly(vinylamine) can be
reacted With a variety of acids to provide a poly(vinylamine)
salt useful as an SAP, but the preferred acids are mineral

acids. To achieve the full advantage of the present invention,


the poly(vinylamine) salt is a hydrochloride salt.
To demonstrate the ability of a poly(vinylamine) salt to
act as an SAP, the lightly crosslinked poly(vinylamine) of
Example 5 Was converted to the hydrochloride salt by
methods Well knoWn in the art. The poly(vinylamine) salt
Was tested for its ability to absorb and retain deioniZed Water

and electrolyte-containing aqueous media (i.e., 0.9% by


Weight aqueous sodium chloride).

(ii) Poly(Vinylamine) in SAPs


55

As illustrated above, poly(vinylamine), in its free base


form, does not function as an SAP for neutral-to-basic

aqueous media. Similarly, polyacrylic acid, in its free acid


form, does not function as an SAP for neutral-to-acidic

aqueous media. In each case, the polymer has a loW charge

density, and, accordingly, a major driving force for absorp


tion and retention, i.e., electrostatic repulsion, is missing. In
contrast, partially neutraliZed polyacrylic acid has a suffi
cient charge density, and is currently used as an SAP by
itself. Similarly, as disclosed above, poly(vinylamine) salts
have a high charge density and are excellent SAPs.
HoWever, a poly(vinylamine), in its free base form, can
act as an absorbent for acidic aqueous media, i.e., media

US 6,603,055 B2
15

16
The poly(vinylamine) is a basic resin, particles of Which

having a pH less than 7, as illustrated in Examples 5 and 6,


wherein one gram of poly(vinylamine) absorbed 59.3 g and
51 g of 0.1 M hydrochloric acid under no load, respectively.
The acidic media protonates the amino groups of the poly

can be any resin that acts as an SAP in its neutraliZed form.

(vinylamine), thereby providing sufficient charge density for

The acidic resin typically contains a plurality of carboxylic

are admixed With particles of an acidic resin, and as stated


above, other basic resins also can be used. The acidic resin

the protonated poly(vinylamine) to perform as an SAP.

acid, sulfonic acid, phosphonic acid, phosphoric acid, or

Accordingly, poly(vinylamine), by itself, can be used to

sulfuric acid moieties, or a mixture thereof.

An acidic resin present in an SAP material of the present

absorb acidic aqueous media, for example, to absorb an acid

spill.
It also has been found that poly(vinylamine) polymers, in
their free base form, are useful components in superabsor
bent materials further containing an acidic Water-absorbing
resin. For example, a superabsorbent material of the present

invention can be either a strong or a Weak acidic Water


10

absorbing resin. The acidic Water-absorbing resin can be a


single resin, or a mixture of resins. The acidic resin can be
a homopolymer or a copolymer. The identity of the acidic
resin is not limited as long as the resin is capable of sWelling

invention is an admixture of a poly(vinylamine) and an

and absorbing at least ten times its Weight in Water, When in

acidic Water-absorbing resin, like polyacrylic acid. The

a neutraliZed form. The acidic resin is present in its acidic


form, i.e., about 75% to 100% of the acidic moieties are

superabsorbent material contains a poly(vinylamine), or


other basic Water-absorbing resin, in an amount of about

15

present in the free acid form. As illustrated hereafter,


although the free acid form of a acidic Water-absorbing resin

20% to about 40%, by Weight, based on the total Weight of

poly(vinylamine) and acidic Water-absorbing resin. The


present superabsorbent materials are particularly useful With
respect to absorbing and retaining aqueous media containing

is generally a poor Water absorbent, the combination of an


acidic resin and a basic resin in a present SAP material
20

electrolytes.
Currently, superabsorbent materials containing tWo
absorbing components, i.e., bi-component SAP materials,
are being investigated as an improved class of SAPs.
Typically, one component is a Water-absorbing resin, and the
second component acts in an ion exchange capacity to

25

cally is prepared by polymeriZing an acidic monomer con


taining an acyl moiety, e. g., acrylic acid, or a moiety capable
of providing an acid group, i.e., acrylonitrile, in the presence

of a crosslinker, i.e., a polyfunctional organic compound.

remove electrolytes from an aqueous media.


In contrast, the present invention is directed to a

bi-component SAP material comprising tWo uncharged,


slightly crosslinked polymers, each of Which is capable of
sWelling and absorbing aqueous media. When contacted
With Water, the tWo uncharged polymers neutraliZe each

provides excellent Water absorption and retention properties.


The acidic Water-absorbing resin typically is a lightly
crosslinked acrylic-type resin, such as lightly crosslinked
polyacrylic acid. The lightly crosslinked acidic resin typi

30

other to form a superabsorbent material. Neither polymer in


its uncharged form behaves as an SAP by itself When

The acidic resin can contain other copolymeriZable units,


i.e., other monoethylenically unsaturated comonomers, Well
knoWn in the art, as long as the polymer is substantially, i.e.,
at least 10%, and preferably at least 25%, acidic monomer
units. To achieve the full advantage of the present invention,
the acidic resin contains at least 50%, and more preferably,
at least 75%, and up to 100%, acidic monomer units. The

and one basic, Which are capable of acting as an absorbent

other copolymeriZable units can, for example, help improve


the hydrophilicity of the polymer.
Ethylenically unsaturated carboxylic acid and carboxylic

material in their polyelectrolyte form. While polyacrylic

acid anhydride monomers useful in the acidic Water

contacted With Water. The present bi-component superab

35

sorbent material, therefore, contains tWo resins, one acidic


acid is an excellent choice for the acidic resin, until the
present invention, there has not been an adequate basic resin.
In accordance With an important feature of the present
invention, a poly(vinylamine), or other basic Water

absorbing resin include, but are not limited to, acrylic acid,
40

absorbing resin, is present in the bi-component superabsor

ot-chlorosorbic acid, angelic acid, cinnamic acid,


p-chlorocinnamic acid, [3-stearylacrylic acid, itaconic acid,

bent material in a loW Weight percent. The excellent absorp

tion and retention properties exhibited by the present

methacrylic acid, ethacrylic acid, ot-chloroacrylic acid,


ot-cyanoacrylic acid, [3-methylacrylic acid (crotonic acid),
ot-phenylacrylic acid, [3-acryloxypropionic acid, sorbic acid,

because the amount of poly(vinylamine), or other basic

citraconic acid, mesaconic acid, glutaconic acid, aconitic


acid, maleic acid, furmaric acid, tricarboxyethylene, and
maleic anhydride.

Water-absorbing resin, is insufficient to neutraliZe the greater


amount of acidic resin present in the bi-component super

Ethylenically unsaturated sulfonic acid monomers


include, but are not limited to, aliphatic or aromatic vinyl

absorbent material.
Therefore, in accordance With an important feature of the
present invention, a poly(vinylamine) is used as the basic
resin for a bi-component SAP material. Other basic resins

sulfonic acids, such as vinylsulfonic acid, allyl sulfonic acid,


vinyl toluene sulfonic acid, styrene sulfonic acid, acrylic and
methacrylic sulfonic acids, such as sulfoethyl acrylate, sul

45

bi-component superabsorbent material is unexpected

foethyl methacrylate, sulfopropyl acrylate, sulfopropyl


methacrylate, 2-hydroxy-3-methacryloxypropyl sulfonic

useful in a bi-component SAP material in an amount of

about 20% to about 40%, by Weight of basic resin and acidic


resin include, but are not limited to, poly(allylamine), poly

55

As set forth above, polymeriZation of acidic monomers,


and copolymeriZable monomers, if present, most commonly

(diallylamine), and poly(aZetidine). The preferred basic


resin is poly(vinylamine).
The poly(vinylamine) is lightly crosslinked, and the poly
(vinylamine) particles preferably are surface crosslinked to

is performed by free radical processes in the presence of a

polyfunctional organic compound. The acidic resins are


60

improve absorbency characteristics. The poly(vinylamine),


SAP in the presence of Water, and especially brackish Water.

The poly(vinylamine) can be prepared by the improved


as set forth above.

crosslinked to a sufficient extent such that the polymer is

Water insoluble. Crosslinking renders the acidic resins sub


stantially Water insoluble, and, in part, serves to determine
the absorption capacity of the resins. For use in absorption
applications, an acidic resin is lightly crosslinked, i.e., has a

or other basic resin, and acidic resin mixture behaves like an

method disclosed herein, or by prior methods knoWn in the


art. Crosslinking and surface crosslinking can be performed

acid, and 2-acrylamide-2-methylpropane sulfonic acid.

65

crosslinking density of less than about 20%, preferably less


than about 10%, and most preferably about 0.01% to about
7%.

US 6,603,055 B2
17

18
The acidic resin, either strongly acidic or Weakly acidic,

Acrosslinking 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.

can be any resin that acts as an SAP in its neutraliZed form.

The acidic resins typically contain a plurality of carboxylic

Examples of crosslinking polyvinyl monomers include, but


are not limited to, polyacrylic (or polymethacrylic) acid

acid, sulfonic acid, phosphonic acid, phosphoric acid, and/or


sulfuric acid moieties. Examples of acidic resins include, but
are not limited to, polyacrylic acid, hydrolyZed starch

esters, represented by the following formula (III), and


bisacrylamides, represented by the following formula (IV),

acrylonitrile graft copolymers, starch-acrylic acid graft


copolymers, saponi?ed vinyl acetate-acrylic ester

(III)
10

CH2=CH

Wherein X is ethylene, propylene, trimethylene, cyclohexyl,

hexamethylene, 2-hydroxypropylene, (CH2CH2O)

15

tures thereof. The preferred acidic resins are the polyacrylic


acids.
The poly(vinylamine), or other basic resin, is present in its

nCHZCHZ , or

CH3

CH3

uncharged, i.e., free base, form, and the acidic resin is


20

present in its free acid form. It is envisioned that a loW


percentage, i.e., 25% or less, of the basic and acidic func

tionalities can be in their charged form, due to processing,

n and m are each an integer 5 to 40, and k is 1 or 2;

(IV)
CH2: CH

copolymers, hydrolyZed acrylonitrile copolymers, hydro


lyZed 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), and mix

25

HC: CH2,

30

Wherein 1 is 2 or 3.

The compounds of formula (III) are prepared by reacting


polyols, such as ethylene glycol, propylene glycol,
trimethylolprop ane, 1 ,6-hexanediol, glycerin,
pentaerythritol, polyethylene glycol, or polypropylene
glycol, With acrylic acid or methacrylic acid. The com

resin, and particles of an acidic resin to provide a uniform


35

particulate material.
Alternatively stated, a bi-component SAP material of the

lene polyamines, such as diethylenetriamine and

triethylenetetramine, With acrylic acid.


Speci?c crosslinking monomers include, but are not lim
40

dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene


glycol dimethacrylate, diethylene glycol diacrylate, diethyl

present invention contains a mole ratio of about 0.4:1 to


about 0.9:1 of basic resin to acidic resin, and preferably a
mole ratio of about 0.45:1 to about 0.85:1, based on the total
amount of basic resin and acidic resin in the material. To

achieve the full advantage of the present invention, the mole


ratio of basic resin to acidic resin is about 0.55:1 to about
0.75:1.

ene glycol dimethacrylate, ethoxylated bisphenol A

diacrylate, ethoxylated bisphenolAdimethacrylate, ethylene


glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6

minimiZed.
The poly(vinylamine), or other basic resin, and acidic
resin are admixed in a Weight ratio of about 20:60 to about
40:60, and preferably about 22:78 to about 35:65. To achieve
the full advantage of the present invention, the resins are
admixed in a Weight ratio of about 25:75 to about 30:70. A

present bi-component SAP material is prepared by simply


admixing particles of the poly(vinylamine), or other basic

pounds of formula (IV) are obtained by reacting polyalky

ited to, 1,4-butanediol diacrylate, 1,4-butanediol

for example. The loW percentage of charged functionalities


does not adversely affect performance of the superabsorbent
material, but the amount of charged functionalities should be

45

Analogous to the acidic resin, the basic Water-absorbing


resin in the present bi-component SAP material is not

hexane diol dimethacrylate, neopentyl glycol

limited to poly(vinylamine) and can be other strong or Weak

dimethacrylate, polyethylene glycol diacrylate, polyethyl


ene glycol dimethacrylate, triethylene glycol diacrylate,

basic Water-absorbing resins. The basic Water-absorbing

triethylene glycol dimethacrylate, tripropylene glycol


diacrylate, tetraethylene glycol diacrylate, tetraethylene gly

resin can be a single resin or a mixture of resins. The basic


resin can be a homopolymer or a copolymer. The basic resin

col dimethacrylate, dipentaerythritol pentaacrylate, pen

taerythritol tetraacrylate, pentaerythritol triacrylate, trim


ethylolpropane triacrylate, trimethylolpropane
trimethacrylate, tris (2-hydroxyethyl)isocyanurate

triacrylate, tris(2-hydroxyethyl)isocyanurate

55

trimethacrylate, divinyl esters of a polycarboxylic acid,


diallyl esters of a polycarboxylic acid, triallyl terephthalate,

(OH) or bicarbonate (HCO3) form.


The basic Water-absorbing resin typically contains amino

diallyl
maleate,
diallyl
fumarate,
hexamethylenebismaleimide, trivinyl trimellitate, divinyl
adipate, diallyl succinate, a divinyl ether of ethylene glycol,
cyclopentadiene diacrylate, tetraallyl ammonium halides, or

60

mixtures thereof. Compounds such as divinylbenZene and


divinyl ether also can be used as crosslinkers. Especially

preferred

crosslinking

agents

are

N,N

methylenebisacrylamide,
N,N
methylenebismethacrylamide, ethylene glycol
dimethacrylate, and trimethylolpropane triacrylate.

is capable of sWelling and absorbing at least 10 times its


Weight in Water, When in a charged form. The Weak basic
resin typically is present in its free base, or neutral, form,
i.e., about 75% to about 100% of the basic moieties, e.g.,
amino groups, are present in a neutral, uncharged form. The
strong basic resins typically are present in the hydroxide

65

or guanidino moieties, such as a poly(vinylamine). The basic


Water-absorbing resin can be any polymer containing a
primary amine, a secondary amine, or a hydroxy function
ality. The basic resin, for example, can be a lightly
crosslinked polyethylenimine, a poly(allylamine), a poly

(diallylamine), a copolymer of a dialkylamino acrylate and


a monomer having primary amino, secondary amino, or

hydroxy functionality, a guanidine-modi?ed polystyrene,


such as

US 6,603,055 B2
19

20
in Pinschmidt, Jr. et al. US. Pat. No. 5,085,787, incorpo
rated herein by reference, and in EP 450 923.
Conventionally, the crosslinking agent is Water or alcohol
soluble, and possesses suf?cient reactivity With the basic
resin such that crosslinking occurs in a controlled fashion,
preferably at a temperature of about 25 C. to about 150 C.

Preferred crosslinking agents are ethylene glycol diglycidyl


ether (EGDGE), a Water-soluble diglycidyl ether, and a
dibromoalkane, an alcohol-soluble compound.
10

In preferred embodiments, the acidic resin, the basic resin,


and/or the SAP material are surface treated. Surface treat

ment results in surface crosslinking of the particle. In

especially preferred embodiments, the acidic and/or basic

or a poly(vinylguanidine), i.e., poly(VG), a strong basic

Water-absorbing resin having the general structural formula

(V)

15

(v)

resins comprising the SAP material are surface treated


and/or annealed, and the blended SAP material is surface
treated. It has been found that surface treating of an acidic
resin, a basic resin, and/or an SAP material of the present
invention enhances the ability of the resins or SAP material
to absorb and retain aqueous media under a load.

ll

20

Surface crosslinking is achieved by contacting an acidic


resin, a basic resin, and/or an SAP material With a solution

of a surface crosslinking agent to Wet predominantly only


the outer surfaces of the resin particles. Surface crosslinking

R >INH,
N
5\

and drying of the resin particles then is performed, prefer

/
25

Typically, the resins and/or SAP material are surface


treated With a solution of a surface crosslinking agent. The

Wherein q is a number from 10 to about 100,000, and R5 and

R6, independently, are selected from the group consisting of


30

solution contains about 0.01% to about 4%, by Weight,


surface crosslinking agent, and preferably about 0.4% to
about 2%, by Weight, surface crosslinking agent in a suitable

35

be applied as a ?ne spray onto the surface of freely tumbling


resin particles of the SAP materials at a ratio of about 11001
to about 1105 parts by Weight resin or SAP particles to
solution of surface crosslinking agent. The surface
crosslinker is present in an amount of 0% to about 5%, by
Weight of the resin or SAP material, and preferably 0% to

40

present invention, the surface crosslinker is present in an


amount of about 0.001% to about 0.1% by Weight.

hydrogen, C1C4 alkyl, C3C6 cycloalkyl, benZyl, phenyl,


alkyl-substituted phenyl, naphthyl, and similar aliphatic and
aromatic groups. The lightly crosslinked basic Water
absorbing resin can contain other copolymeriZable units and

solvent, for example, Water or an alcohol. The solution can

is crosslinked using a polyfunctional organic compound, as


set forth above With respect to the acidic Water-absorbing
resin.

Examples of preferred basic resins include a poly


(vinylamine), a polyethylenimine, a poly(vinylguanidine), a
poly(allylamine), a poly(diallylamine), or a poly

about 0.5% by Weight. To achieve the full advantage of the

(allylguanidine). Preferred basic resins include poly

(vinylamine), polyethylenimine, and poly(vinylguanadine).


The most preferred basic resin is a poly(vinylamine), a
poly(allylamine), or a poly(dialkylamine).
A basic Water-absorbing resin used in the present
bi-component SAP material typically contains an amino or
a guanidino group. Accordingly, a Water-soluble basic resin
also can be crosslinked in solution by suspending or dis

ably by heating at least the Wetted surfaces of the resin or

multicomponent SAP particles.

The crosslinking reaction and drying of the surface

45

treated resin or SAP materials are achieved by heating the


surface-treated polymer at a suitable temperature, e. g., about
25 C. to about 150 C., and preferably about 105 C. to

solving an uncrosslinked basic resin in an aqueous or

about 120 C. HoWever, any other method of reacting the


crosslinking agent to achieve surface crosslinking of the

alcoholic medium, then adding a di- or polyfunctional

resin or SAP material, and any other method of drying the

resin or SAP material, such as microWave energy, or the such


as, can be used.
50
tion With the amino groups of the basic resin. Such

compound capable of crosslinking the basic resin by reac

With respect to the basic resin, suitable surface crosslink

crosslinking agents include, for example, multifunctional

ing agents include di- or polyfunctional molecules capable


of reacting With amino or guanidino groups and crosslinking
a basic resin. Preferably, the surface crosslinking agent is

aldehydes (e.g., glutaraldehyde), multifunctional acrylates


(e.g., butanediol diacrylate, TMPTA), halohydrins (e.g.,
epichlorohydrin), dihalides (e.g., dibromopropane), disul
fonate esters (e.g., ZA(O2)O(CH2)nOS(O)2Z, Wherein

55

alcohol or Water soluble and possesses suf?cient reactivity

n is 1 to 10, and Z is methyl or tosyl), multifunctional

With a basic resin such that crosslinking occurs in a con

epoxies (e.g., ethylene glycol diglycidyl ether), multifunc

trolled fashion at a temperature of about 25 C. to about 150


C.

tional esters (e.g., dimethyl adipate), multifunctional acid

halides (e.g., oxalyl chloride), multifunctional carboxylic


acids (e.g., succinic acid), carboxylic acid anhydrides (e.g.,

Nonlimiting examples of suitable surface crosslinking


60

succinic anhydride), organic titanates (e.g., TYZOR AA


from DuPont), melamine resins (e.g., CYMEL 301, CYMEL
303, CYMEL 370, and CYMEL 373 from Cytec Industries,

agents for basic resins include:


(a) dihalides and disulfonate esters, for example, com
pounds of the formula

Wayne, N.J.), hydroxymethyl ureas (e.g., N,N


dihydroxymethyl-4,5-dihydroxyethyleneurea), and multi
functional isocyanates (e.g., toluene diisocyanate or meth
ylene diisocyanate). Crosslinking agents also are disclosed

65

Wherein p is a number from 2 to 12, and Y, independently,

is halo (preferably bromo), tosylate, mesylate, or other alkyl


or aryl sulfonate esters;

US 6,603,055 B2
21

22

(b) multifunctional aZiridines;


(c) multifunctional aldehydes, for example,

PRIMIDTM XL-552, available from EMS-CHEMIE

AG, Dornat, SWitZerland; and


(k) other crosslinking agents for acidic Water-absorbing

glutaraldehyde, trioxane, paraformaldehyde,

resins knoWn to persons skilled in the art.

terephthaldehyde, malonaldehyde, and glyoxal, and

In addition to, or in lieu of, surface treating, the SAP


material is annealed to improve Water absorption and reten
tion properties under a load. It has been found that heating

acetals and bisul?tes thereof;

(d) halohydrins, such as epichlorohydrin;


(e) multifunctional epoxy compounds, for example, eth

a resin for a suf?cient time at a sufficient temperature

ylene glycol diglycidyl ether, bisphenol A diglycidyl


ether, and bisphenol F diglycidyl ether,
(f) multifunctional carboxylic acids and esters, acid
chlorides, and anhydrides derived therefrom, for
example, di- and polycarboxylic acids containing 2 to
12 carbon atoms, and the methyl and ethyl esters, acid
chlorides, and anhydrides derived therefrom, such as
oxalic acid, adipic acid, succinic acid, dodecanoic acid,
malonic acid, and glutaric acid, and esters, anhydrides,
and acid chlorides derived therefrom;
(g) organic titanates, such as TYZOR AA, available from
E. I. DuPont de Nemours, Wilmington, Del.;

improves the absorption properties of the resin.


10

about 200 C. improves absorption properties. Preferably,


15

20

25

diisocyanate, isophorone diisocyanate, methylene


diisocyanate, xylene diisocyanate, and hexamethylene
diisocyanate;
(k) [3-hydroxyalkylamides as disclosed in US. Pat. No.

30

PRIMIDTM XL-552, available from EMS-CHEMIE

AG, Dornat, SWitZerland; and


(1) other crosslinking agents for basic Water-absorbing
35

A preferred surface crosslinking agent is a dihaloalkane,

ethylene glycol diglycidyl ether (EGDGE), PRIMIDTM

Was admixed With lightly crosslinked polyacrylic acid


(particle siZe 210710 pm, 0% neutraliZed) in a Weight ratio
of 25% poly(vinylamine) to 75% polyacrylic acid as fol
loWs. Poly(vinylamine) and polyacrylic acid gels Were pre
pared by previously described methods at a loW crosslinking
level. The resulting gels Were extruded separately, and dried
separately at either 60 C. or 125 C. After complete drying,
the polymers Were milled and siZed to 180710 pM. The
resulting dried granules then Were hand mixed and tested.
The resulting dry blend Was annealed 125 C. to improve

performance.

XL-552, or a mixture thereof, Which crosslink a basic resin


at a temperature of about 25 C. to about 150 C. Especially

preferred surface crosslinking agents are dibromoalkanes


containing 3 to 10 carbon atoms, EGDGE, and

EXAMPLE 7

PoWdered poly(vinylamine) (particle siZe 180710 pm)

4,076,917, incorporated herein by reference, such as

resins knoWn to persons skilled in the art.

annealed at a temperature greater than the glass transition


temperature, i.e., the Tg, of at least one of the Water

absorbing resins present in the SAP material.


To illustrate a present bi-component SAP material, the
folloWing examples Were prepared and tests performed:

from Cytec Industries, Wayne, N.J.;


multifunctional isocyanates, such as toluene

annealing is performed for about 30 to about 100 minutes at


about 80 C. to about 150 C. To achieve the full advantage
of annealing, the SAP material is annealed for about 40 to
about 90 minutes at about 100 C. to about 140 C. The
annealing step can be a separate heating step, or can be

performed simultaneously With surface cross-linking of the


SAP particle. In preferred embodiments, the SAP material is

(h) melamine resins, such as the CYMEL resins available

(i) hydroxymethyl ureas, such as N,N-dihydroxymethyl


4,5-dihydroxyethylene urea;

It has been shoWn that heating an SAP material for about


20 to about 120 minutes at a temperature of about 60 C. to

The absorbency characteristics of the resulting


40

bi-component SAP Were tested. The results are set forth in


Table 4.

PRIMIDTMXL-552.

With respect to the acidic Water-absorbing resin, suitable


surface crosslinking agents are capable of reacting With acid
moieties and crosslinking the acidic resin. Preferably, the

TABLE 4
45

surface crosslinking agent is alcohol soluble or Water


soluble, and possesses suf?cient reactivity With an acidic
resin such that crosslinking occurs in a controlled fashion,
preferably at a temperature of about 25 C. to about 150 C.

Nonlimiting examples of suitable surface crosslinking


agents for acidic resins include:

(a) polyhydroxy compounds, such as glycols and glyc

erol;
(b) metal salts;
(c) quaternary ammonium compounds;

4,076,917, incorporated herein by reference, such as

in

MBA) in

No Post Treatment

PVAm2)

FAA)

SFC5) 4 hr AAP (g/g))

4
4

0.35
0.5

56
265

4 hr AAP

SFC

(0.7 psi) (g/g)

232
383

41.9
36.5

29.2
34.2

3)MBAmethylene bisacrylamide internal crosslinker;


55

4)PAApolyacrylic acid;
5)SFCSaline FloW Conductivity; and

6)AAP-Absorbency against pressure.

Absorbency against pressure

is the absorptive

capacity of superabsorbent polymer (SAP) absorbing


60

tris[3-(1-aZiridine propionate]);

[3-hydroxyalkylamides as disclosed in US. Pat. No.

Post Treatment
1 Hour at 125 c.

1)EGDGEethylene glycol diglycidyl ether internal cross-linker;

propylene carbonate;
(g) a haloepoxy, such as epichlorhydrin;
(h) a polyamine, such as ethylenediamine;
(i) a polyisocyanate, such as 2,4-toluene diisocyanate;

MOle %

2)PVAmpoly(vinylamine);

(d) a multifunctional epoxy compound;


(e) an alkylene carbonate, such as ethylene carbonate or
(f) a polyaZiridine, such as 2,2-bishydroxymethyl butanol

Mole %
EGDGEl)

against an external pressure of 0.3, 0.7, or 0.9 psi for 1 hour.


In this test, a test portion of SAP is Weighed and dispersed
on the bottom ?lter screen of a Lexan cylinder. A uniform

65

pressure is applied onto the test portion, and the cylinder


apparatus is placed on a ?lter plate in a petri dish containing
saline solution. After a suction time of 1 hour, the cylinder
apparatus is removed from the ?lter plate and Weighed to
determine the amount of ?uid absorbed.