Note: Descriptions are shown in the official language in which they were submitted.
CA 02296891 2000-O1-24
' K-C 14632 =
Modified Condensation Pol,~rmers Containing Azetidinium Groups in Conjunction
with Amlahiohilic Hydrocarbon Moieties
Background of the Invention
In the manufacture of paper products, such as facial tissue, bath tissue,
paper
towels, dinner napkins and the like, a wide variety of product properties are
imparted to
the final product through the use of chemical additives. Examples of such
additives
include softeners, debonders, wet strength agents, dry strength agents, sizing
agents,
s opacifiers and the like. In many instances, more than one chemical additive
is added to
the product at some point in the manufacturing process. Unfortunately, there
are
instances where certain chemical additives may not be compatible with each
other or may
be detrimental to the efficiency of the papermaking process, such as can be
the case with
the effect of wet end chemicals on the downstream efficiency of creping
adhesives.
~o Another limitation, which is associated with wet end chemical addition, is
the limited
availability of adequate bonding sites on the papermaking fibers to which the
chemicals
can attach themselves. Under such circumstances, more than one chemical
functionaWty
compete for the limited available bonding sites, oftentimes resulting in the
insufficient
retention of one or both chemicals on the fibers.
~s Therefore, there is a need for a means of applying more than one chemical
functionality to a paper web which mitigates the limitations created by
limited number of
bonding sites.
Summary of the Invention
2o In certain instances, two or more chemical functionalities can be combined
into a
single molecule, such that the combined molecule imparts at least two distinct
product
properties to the final paper product that heretofore have been imparted
through the use
of two or mare different molecules. More specifically, modified condensation
polymers
containing azetidinium groups,such as polyamide epichlorohydrin (PAE) resins,
can be
Zs combined with amphiphilic hydrocarbons in a single molecule to provide
several potential
benefits, depending upon the specific combination employed, including: (a) wet
strength
aids that impart softness; (b) softeners that do not reduce wet strength: (c)
wet strength
with improved wet/dry strength ratio; (d) surface feel modifiers with reduced
tinting and
sloughing; (e) wet strength aids with controlled absorbency; (f) wet strength
aids with
so controlled decay rate after wetting; and (g) Yankee dryer additives that
provide surface
protection and adhesion with controlled release properties.
CA 02296891 2000-O1-24
K-C 14632 ' '
Hence in one aspect, the invention resides in a condensation polymer having
the
following structure:
-Z1 _ R1 _ Z2 _ R2 _ Zs _ Rs _ Z4_
where
Z,, ZZ, Z3, Z4 = bridging radicals, which can be the same or different, which
serve to
incorporate the R,, R2, and R3 groups into the polymer;
R,,R3 = any linear or branched, saturated or unsaturated, substituted or non-
substituted
aliphatic hydrocarbon having 4 or more carbon atoms and having amphiphilic
functionality; and
~o RZ = any linear or branched, saturated or unsaturated, substituted or non-
substituted
aliphatic hydrocarbon containing at least one secondary amine group;
wherein at least one of R,,RZ or R3 is or contains a CB or higher chain length
and wherein
R, and R3 can be the same or different.
~s In another aspect, the invention resides in a paper sheet, such as a tissue
or towel
sheet, comprising an amount of a condensation polymer having the following
structure:
-Z1_R1_Z2_R2_Z3_R3_Z4_
Where
Z,, Z2, Z3, Z, = bridging radicals, which can be the same or different, which
serve to
2o incorporate the R,, RZ, and R3 groups into the polymer;
R,,R3 = any linear or branched, saturated or unsaturated, substituted or non-
substituted
aliphatic hydrocarbon having 4 or more carbon atoms and having amphiphilic
functionality; and
RZ = any linear or branched, saturated or unsaturated, substituted or non-
substituted
is aliphatic hydrocarbon containing at least one secondary amine group;
wherein at least one of R,,RZ or R3 is or contains a C8 or higher chain length
and wherein
R, and R3 can be the same or different.
3o In another aspect, the invention resides in a method of making a paper
sheet such
as a tissue or towel sheet, comprising the steps of: (a) forming an aqueous
suspension of
papermaking fibers; (b) depositing the aqueous suspension of papermaking
fibers onto a
forming fabric to form a web; and (c) dewatering and drying the web to form a
paper
2
CA 02296891 2000-O1-24
K-C 14632 '
sheet, wherein a condensation polymer is added to the aqueous suspension, said
condensation polymer having the following structure:
-Z1 _ R1 _ Z2 _ R2 _ Zs _ Rs _ Z4_
where
Z,, Z2, Z3, Z4 = bridging radicals, which can be the same or different, which
serve to
incorporate the R,, R2, and R3 groups into the polymer;
R,,R3 = any linear or branched, saturated or unsaturated, substituted or non-
substituted
aliphatic hydrocarbon having 4 or more carbon atoms and having amphiphilic
functionality; and
~o RZ = any linear or branched, saturated or unsaturated, substituted or non-
substituted
aliphatic hydrocarbon containing at least one secondary amine group;
wherein at least one of R,,RZ or R3 is or contains a C8 or higher chain length
and wherein
R, and R3 can be the same or different.
~s The amount of the condensation polymer of this invention added to the
fibers can
be from about 0.01 to about 2 weight percent, on a dry fiber basis, more
specifically from
about 0.02 to about 1.5 weight percent, and still more specifically from about
0.05 to about
1.0 weight percent. The modified condensation polymers) can be added to the
fibers at
any point in the process where the fibers are suspended in water.
Zo Methods of making paper products which can benefit from the various aspects
of
this invention are well known to those skilled in the papermaking art.
Exemplary patents
include U.S. Patent No. 5,785,813 issued July 28,1998 to Smith et al. entitled
"Method of
Treating a Papermaking Furnish For Making Soft Tissue"; U.S. Patent No.
5,772,845
issued June 30, 1998 to Farrington, Jr. et al. entitled "Soft Tissue"; U.S.
Patent No.
Zs 5,746,887 issued May 5, 1998 to Wendt et al. entitled "Method of Making
Soft Tissue
Products"; and U.S. Patent No. 5,591,306 issued January 7,1997 to Kaun
entitled
"Method For Making Soft Tissue Using Cationic Silicones", all of which are
hereby
incorporated by reference.
so Detailed Descr~tion of the Invention
Polyramide E ichloroh_yrdNn Resins
Functionalized polyamide epichlorohydrin resins are commonly used in the paper
industry as alkaline curing wet strength resins. As a result of the cross-
linking that occurs
35 during the curing reaction, covalent bonds are formed between polymers and
fibers and
3
CA 02296891 2000-O1-24
K-C 14632 ' '
between polymer molecules themselves. As a result the dry tensile will also be
improved
and the tendency for tinting and sloughing will be reduced. In addition to use
as a wet
strength resin for tissue products, PAE resins are also often employed as a
component in
Yankee dryer creping adhesives. The cross-linking feature provides protection
to the
s yankee surface while at the same time promoting adhesion of the sheet to the
dryer
surface.
A multi-step synthesis is used to prepare these resins. For the primary
commercial
method, in the first step a dibasic acid is condensed with a compound
containing two
primary amine groups to form a polyamide. The amine compound must also contain
a
1o third amine functionality, a secondary amine group. Commercially,
diethylenetriamine
(DETA) is the amine of choice with adipic acid the preferred dibasic acid. The
resultant
polyamides containing secondary amine groups are referred to as
polyamidoamines. An
example of the polyamidoamine synthesis is shown in Figure 1.
H
HZN~N~NHZ ~
RO~(CHz)~OR R - H~ Me
DETA Adipic Acid
-~ H O
~(CHz)4~~N~~(CHz~~
Figure 1
In the second stage of the synthesis, the secondary amine groups are alkylated
for
example by reaction with epichlorohydrin to produce tertiary aminochlofiydrin
groups.
Zo These groups self cyclize to form 3-hydroxyazetidinium groups. These 3-
hydroxyazetidinium groups are responsible for the cationic character of the
resins as well
as providing the ability of these materials to react as wet strength resins.
The resins may
also be used as retention aids. Other reactions of the secondary amine group
to attach
functional groups capable of covalent bonding are known in the art. Most
common are
is derivatization to give epoxy or silanol functional groups. High Mw and
charge densities
can be obtained. For wet strength resins molecular weights of less than
100,000 are
generally employed. Figure 2 details the reaction with epichlorohydrin.
4
CA 02296891 2000-O1-24
K-C 14632
0 Q
~(CHy)e~~N~N~(CHy)~
CIHpC-CH\~H Enichlorhvdrin
H
GHpCHOHCHyG
g H ~H ~
~(CHp)~~~N~N~(CHZ)~ -~ ~(CHy)~~~'~,+~~N~ CH ,~--
( 211
Figure 2
Typically only a portion of the secondary amine groups are functionalized with
the
crosslinking moiety. Commonly 10 - 50% of the secondary amine groups have been
functionalized.
PAE resins undergo at least two types of reactions that contribute to wet
strength.
One reaction involves the reaction of an azetidinium or other functional group
in one
molecule with an unreacted secondary amine group in another molecule to
produce a
1o cross-link between the two molecules. In the second reaction at least two
functional
groups such as the azetidinium groups on a single resin molecule react with
carboxyl
groups on two different fibers to produce an interfiber cross-link. It is also
known to utilize
promoters such as carboxymethyl cellulose to enhance the performance of these
materials in paper products.
PAE resins are stabilized by acidification to a pH of 3.5-6.0 at the end of
the
polymerization reaction. They are generally shipped as aqueous solutions of 12
- 33%
solids. PAE resins are thermosets and they will polymerize with themselves to
water
insoluble materials by action of heat alone.
2o In papermaking systems typical addition levels are on the order of 0.25% to
0.75%. They are effective when employed across a pH range of 5 - 9 although
most
effective in the 6 - 8 pH range. Other factors which affect the performance of
PAE resins
include: fiber anionic sites; pulp consistency; contact time; resin
concentration; pulp
refining; chlorine residuals; pH; stock temperature; and anionic contaminants.
5
CA 02296891 2000-O1-24
K-C 14632 ~ '
Ionized carboxyl sites on the cellulose provide anionic adsorption sites for
the resin
molecules. The higher the carboxyl content of the cellulose the more rapidly
and more
extensively will a pulp retain a resin molecule. Wet strength resins follow
normal
Langmuir adsorption behavior with the first resin added being completely
adsorbed. As
increasing amounts of resin are added adsorption rate declines due to
saturation of the
fiber anionic sites.
Both contact time and pulp consistency impact resin retention. The adsorption
process is more rapid and goes to a higher level of completion at higher
consistency and
longer contact time. Of the two pulp consistency has the largest impact. This
effect is
~o presumed due to the polymer molecules having a shorter distance to travel
before
colliding with a fiber surface.
Best resin distribution is achieved when the resin solution is diluted at
least 10:1
with fresh water. Fresh water is preferred because white water contains many
anionic
substances which can react with the resins and neutralize them.
~s Refining enhances the performance of PAE resins but only at high resin
addition
levels. A more highly refined stock will greater surface area available for
adsorption and
therefore higher resin capacity. At low addition levels, even lightly refined
fibers have
sufficient surface area to adequately absorb all the resin.
Active chlorine will react with PAE resins to reduce their effectiveness. At
low pH
Zo resins are less effective due to inadequate ionization of the pulp carboxyl
groups and also
the secondary amine groups become protonated and can not readily participate
in cross
linking reactions with azetidinium groups.
PAE resins are effective over a pH range of 5 - 9. At pH below 5 effectiveness
is
decreased due to low ionization of cellulose carboxyl groups and hence less
anionic sites
2s are available for the cationic groups on the resin. Also the secondary
amine groups are
protonated at pH's below 5 and hence are much slower to crosslink with
azetidinium
groups.
In aqueous environments, exposure to high temperature can cause hydrolysis of
the azetidinium groups thereby reducing their effectiveness.
so Anionic trash, lignin, hemicellulose and other anionic contaminants can
react with
the cationic wet strength resins and interfere with their absorption onto the
fiber. When
high levels of interfering substances are present charge neutralizing
substances such as
alum may be employed prior to addition of the PAE resin. PAE resins may also
react with
anionic dyes to precipitate color bodies onto the fibers..
ss The reaction between PAE and anionic materials can be beneficial in
enhancing
resin retention by fibers. This is illustrated by the use of anionic
carboxymethyl cellulose
6
CA 02296891 2000-O1-24
K-C 14632 '
in conjunction with PAE resin to improve wet strength performance. In this
case it is
believed that the CMC and PAE resin form a weakly cationic complex called a
°Symplex"
that absorbs onto fiber surfaces. The CMC provides the carboxyl groups
necessary to
attract more PAE onto the fiber surface.
s As was mentioned prior polyamide based compounds formed via condensation
polymerization reaction of a diamide with a diacid serve as the foundation for
the PAE
resins. A requirement is that these resins have a secondary amine group
attached for
reaction with the epichlorohydrin or other derivatizing agent so as to form a
moiety
capable of covalently bonding with cellulose or the polymer itself.
Commercially available
~o PAE resins are primarily formed from adipic acid and diethylenetriamine
(DETA).
There is no reason that condensation polymerization reactions necessary for
preparation of the PAE resins be limited to reactions between diamines and
diacid
derivatives (esters or free acids). There should be no restrictions on polymer
type and
suitable condensation polymers would include esters, carbonates, urethanes,
imides,
is ureas and others.
Amohiohilic Hydrocarbon Moieties
Surfactants are widely used by the industry for cleaning(detergency),
solublizing,
dispersing, suspending, emulsifying, wetting and foam control. In the
papermaking
Zo industry, they are often used for deinking, dispersing and foam control.
Amphiphilic
hydrocarbon moieties are a group of surface active agents (surfacatants)
capable of
modifying the interface between phases. They have an amphiphilic molecular
structure:
containing at least one hydrophilic (polar) and at least one lipophilic (non-
polar,
hydrophobic) regions within the same molecule. When placed in a given
interface, the
is hydrophilic end leans toward the polar phase while the lipophilic end
orients itself toward
the non polar phase.
Surfactant
so Polar Phase ~ No Polar Phase
35 hydrophilic end lipophilic end
7
K-C 14632 CA 02296891 2000-oi-24
The hydrophilic end can be added to a hydrophobe synthetically to create the
amphiphilic molecular structure. The following is a schematic pathway for
making a
variety of surfactants:
Add OH
R-CHI-OH functionality
or .t~--- R-CH3
R'-CH(OH) - R" - CH3
R-CHI - (OCZH~ - OH
RCFi~OS03H RCI-17COOH R-CFi~Cl
or
Add amphoteric ftuzctioriality
RCH~S03H
RCH~N"(Rl)z-RzS03' R-CHsN~'(Ri)3Cl
Based on the charge, surfactants can be grouped as amphoteric, anionic,
cationic
s and nonionic.
First, with regard to the amphoteric surfactants, the charges on the
hydrophilic end
change with the environmental pH: positive in acidic pH, negative at high pH
and become
zwitterions at the imtermediate pH. Surfactants included in this category
include
alkylamido alkyl amines and alkyl substituted amino acids.
~o
Structure commonly shared by alkylamido alkyl amines:
RCONH-(CH2)n- i =(CH2)n-COOZ
R~
~s where
8
CA 02296891 2000-O1-24
K-C 14632 ' '
R = alkyl or aliphatic hydrocarbon, normal or branched, saturated or
unsaturated,
substituted or unsubstituted, C chain >_ 4C,
n >_ 2,
s R, = hydroxy or carboxy ended alkyl or hydroxyalkyl groups, C chain >_ 2C,
with or
without ethoxylation, propoxylation or other substitution.
Z = H' or other cationic counterion
Structure shared commonly by alkyl substituted amino acids:
~o R - NR'2 Z
where
R = alkyl or aliphatic hydrocarbon, normal or branched, saturated or
unsaturated,
substituted or unsubstituted, C chain >_ 4C,
n >_ 2,
~s Z = H or other cationic counterion
R' = carboxylic end of the amino acid.
With regard to the avionics, the hydrophilic end of the surfactant molecule is
negatively charge. Avionics consist of five major chemical structures:
acylated amino
Zo acids/acyl peptides, carboxylic acids and salts, sulfonic acid derivatives,
sulfuric acid
derivatives and phosphoric acid derivatives.
Structure commonly shared by acylated amino acids and acyl peptides:
25 RCO - R, - COOZ
or
HOOC - R, - COOZ
where
R = alkyl or aliphatic hydrocarbon, normal or branched, saturated or
unsaturated,
substituted or unsubstituted, C chain >_ 4C,
9
CA 02296891 2000-O1-24
K-C 14632 '
R1 = alkyl substituted amino acid moiety; or -- (NH-CHX-CO)n -- NH-CHX-
where n >_ 1, X=amino acid sidechain; or alkyl -- NHCOR' where R'= aliphatic
hydrocarbon, normal or branched, saturated or unsaturated, substituted or
unsubstituted, C chain >_ 4C
s Z = H or other cationic counterion
Structure commonly shared by carboxylic acid and salts:
R - COOZ
~o
where
R = alkyl or aliphatic hydrocarbon, normal or branched, saturated or
unsaturated,
substituted or unsubstituted, with or without esterification, with or without
etherification, C chain >_ 4C.
~s Z = H or other cationic counterion
Structure commonly shared by sulfonic acid derivatives:
RCO - NR, - (CHZ)n - S03 Z
or
zo alkyl aryl - S03 Z
or
R-S03Z
or
ROOC - (CHZ)n -- CH S03 - COOZ
Zs or
[RCO - NH - (OCHZ)n - OOC - CH S03 - COO] 2Z
or
R (OCHZCHZ)n - S03Z
so where
R = alkyl or aliphatic hydrocarbon, normal or branched, saturated or
unsaturated,
substituted or unsubstituted, with or without esterification, with or without
etherification, with or without sulfonation, with or without hydroxylation, C
chain >_
4C;
35 R, = alkyl or hydroxy alkyl, C chain >_1 C;
CA 02296891 2000-O1-24
K-C 14632 ' '
n > 1;
Z = H or other counterion~.
Structure commonly shared by sulfuric acid derivatives:
R - O S03Z
where
R = aliphatic hydrocarbon, normal or branched, saturated or unsaturated,
substituted
~o or unsubstituted, with or without esterification, with or without
etherification, with or
without sulfonation, with or without hydroxylation, with or without
ethoxylation or
propoxylation, C chain >_ 4C
Z = H or other counterion.
~5 Structure commonly shared by phosphoric acid derivatives:
R - OP03Z
where
2o R = aliphatic hydrocarbon, normal or branched, saturated or unsaturated,
substituted
or unsubstituted, with or without esterification, with or without
etherification, with or
without sulfonation, with or without hydroxylation, with or without
ethoxylation or
propoxylation, C chain >_ 4C
Z = H or other counterion.
With regard to the cationics, these are surfactants with a positively charged
nitrogen atom on the hydrophobic end. The charge may be permanent and non pH
dependent (such as quternary ammonium compounds) or pH dependent (such as
cationic
amines). They include alkyl substituted ammonium salts, heterocyclic ammonium
salts,
so alkyl substituted imidazolinium salts and alkyl amines.
Structure commonly shared by this group:
N R,Z
where
11
CA 02296891 2000-O1-24
K-C 14632 ' '
R = H, alkyl, hydroxyalkyl, ethoxylated and/or propoxylation alkyl, benzyl, or
aliphatic
hydrocarbon, normal or branched, saturated or unsaturated, substituted or
unsubstituted, with or without esterification, with or without etherification,
with or
without sulfonation, with or without hydroxylation, with or without
carboxylation,
with or without ethoxylation or propoxylation, C chain >_ 4C
Z = H or other counterion.
With regard to the nonionics, the molecule has no charge. The hydrophilic end
often contains a polyether (polyoxyethylene) or one or more hydroxyl groups.
They
~o generally include alcohols, alkylphenols, esters, ethers, amine oxides,
alkylamines,
alkylamides, polyalkylene oxide block copolymers.
An especially preferred set of non-ionic amphiphilic hydrocarbons are the
linear
polyether derivatives also known as polyalkylene oxides. Technically
amphiphilic
materials, these substances often behave as humectants in paper, more
specifically
~5 tissue paper products. They will correspond to the general structure shown
in figure 3.
R3-(CHCH20)a-[(CH2~C0)b'(CH2CH)~-R4
I~ Iz
R R
Figure 3
Where:
2o R', RZ = independently H, CH3
R3, R4 = independently OH, NH2, -OCHZCOOH
a, b,c>_0
a+b+c>_1
X=2to6
Plasticization in cellulose structures has been described primarily through
use of
humectants including polyethylene oxide (PEO) and polypropylene oxide (PEO)
polymers
and copolymers as well as their lower molecular weight homologues such as
propylene
so glycol, glycerol and low Mw polyethylene glycols. Several patents describe
use of such
materials to enhance softness in tissue products. Kuenn'~Zet al. (U.S. Patents
#4,764,418 and #4,824,689) describes spraying or coating a sheet with a
carboxylic acid
12
CA 02296891 2000-O1-24
K-C 14632 ' '
derivative and a water-soluble humectant blend to create a virucidal tissue
product.
Spendel3 (U.S. Patent #4,959,125) claims the use, via a spray or coating, of a
non-
cationic surfactant to increase softness, along with another °binder"
to counteract the
decreased strength. Included in this patent are the low Mw polyethers and
glycols.
Trokhan'~5et al. (U.S. Patents #5,575,891 and #5,624,532) use a polyhydroxy
compound
and an oil just after drying on the Yankee and before creping is completed to
increase the
softness of a sheet, as well as the addition of a starch or resin to increase
strength.
The polyalkylene oxides are capable of being incorporated into condensation
polymers due to the presence of free hydroxyl groups at the terminal ends of
the polymer.
~o There are derivatives of these compounds including the diacid and diamine
derivatives
which are equally suited and may be preferred for incorporation of the
polyalkylene oxide
element into the polymer backbone. Both the diacid and diamine derivatives are
known
commercially available materials where R3, R, in figure 3 are -NHZ or -
OCHCOOH. One
especially preferred class of compounds is the amino functional polyethers,
often referred
~s to as Polyalkyleneoxy amines. The polyalkyleneoxy amines are well known
compositions
that may be prepared by the reductive amination of polyalkyleneoxy alcohols
using
hydrogen and ammonia in the presence of a catalyst. This reductive amination
of polyols
is described in U.S. Pat. Nos. 3,128,311; 3,152,998; 3,236,895; 3,347,926;
3,654,370;
4,014,933; 4,153,581 and 4,766,245. The molecular weight of the
polyalkyleneoxy amine
2o material, when employed is preferably in the range of from about 100 to
about 5,000.
Additional examples of amine containing polymers having carbon-oxygen backbone
linkages and their uses are described in U.S. Pat. Nos. 3,436,359; 3,155,728;
and
4,521,490. Examples of suitable commercially available polyalkyleneoxy amines
are
materials sold under the trade name Jeffamine~ and manufactured by Huntsman
is Chemical Corporation.
Modified Condensation Polymers Containing Amghinhllic Hydrocarbon Moieties
There are several different pathways in which the modified condensation
polymers
containing azetidinium groups and amphiphilic hydrocarbon moieties of this
invention can
so be made. These include, but are not limited to: (1 ) direct Incorporation;
(2) reaction of
polymer functional groups; and (3) block copolymer grafting.
13
CA 02296891 2000-O1-24
K-C 14632 ' '
Direct Incoraoration:
The condensation polymers of this invention can be prepared via the general
reaction shown in Figure 4 using reactants of the type illustrated by
structure (I). This
results in direct incorporation of the amphiphilic hydrocarbon groups into the
backbone in
s a random block pattern.
Z~-R2-Za + Zs-Rs-Zoo
Fi use 4
~o
where
Z5, Z~, Z,, Z8, Zs, Z,o = functional groups such that Z; must be capable of
reacting with at
least one Z~ to incorporate the RI functionality into the molecule.
R, and R3 must be chosen such that at least one of R, or R, contains
amphiphilic
~s functionality. It may be alkyl hydrocarbons with hydrophilic (such as -OH,
or
ethoxy groups) functionality, or aliphatic hydrocarbons with hydrophilic
functionality. The hydrocarbons could be linear or branched, saturated or
unsaturated, substituted or unsubstituted, with 4 or more hydrocarbons.
RZ = any linear or branched, saturated or unsaturated, substituted or non-
substituted
zo aliphatic hydrocarbon containing at least one secondary amine group.
Suitable Rz monomers would include but are not limited to the following:
NHZCHZCHZNHCHZCHZNH2
2s HOOCCHZNHCHZCOOH
HOCH2CHZNHCHZCHZOH
NHZCHZCHZNHCHZCHZOH
HOOCCHZCHZNHCH2CH2COOH
NHZCHZCHZNHCHZCHZNHCHZCHZNH
so NHZ(CHZ)xNH(CHZ)yNH2
HN(CHZCHZCN)Z
An example of the reaction of Figure 4 is illustrated below in Figure 5.
14
- K-C 14632 CA 02296891 2000-oi-24
n H
HO~H2(OCHZCHZ~OCHZ OH + P HZN~N~NHZ + ~ ~~
HO' _(CHzI4 'OH
PoN(ethvlene olvcol~is(carboxvmethvllether DETA
A i is acid
H
NH CHZ(OCHZCHZ~OCH2~~N~~(CHZ~
CIHZC-CI-H-~H Erl~huth~
HQ
CIH
HZ ~CHp
NH H2(OCH2CHZ~OCFiy~~ ~N~(CFip~
Figure 5
where
n>_1
s p>1
m>_1
Other examples are illustrated in Figures 6 and 7 below:
CA 02296891 2000-O1-24
K-C 14632 ~ '
H
Cl6i"~33-(~H2CHZhoCH + P HO _ N - OH + m Hp-(CH2)WOH
Polyoyethvlene 101 Ce tether Iminodiacetic Acid
Butane diol
X " - ~'' ~(OCHZCHZ) 10~ 16H33
CIHZGCH---OH Epichlorhvdrin
HQ
CIH
H2~~H2
O
Ct6H33-(~I"I2CH?)10~+~~~2k-~ (OCHZCH~10~16H33
Fi ur
s where
nz1
pz1
m~1
16
K-C 14632 CA 02296891 2000-oi-24
~H3 ~H3 CH3
I! Hz HCHp-(p~HCHp~a-'(OCH2CH2~-'(OCH2~H}~IHz + p HzN~~NH2 ~ ,~~
HO' _(CH2M DH
Polval_l~vleneoxv amine l7ETp
A i i i
CIHZC-CH-~H Epichlor vdrin
HQ
CIH
HzC~Hz N
~ ~3 H3
~(CHp~ ~ ~ (CH2~HN~CHy-(D~HCHz~--(OCHZCHz~-(OCIi~H~-NH--
Fi-gure 7
Where:
m,n,pz1
n+p=m
a=1
c=1
1o b = 10
Where enhanced cationicity is desired, difunctional compounds containing
tertiary
amine groups may also be employed. These tertiary amine groups are capable of
being
quatemized via reaction with epichlorohydrin as is routinely done with
cationic starches.
Reaction of Polymer Functional Groups.
The second approach to preparing azetidinium compounds containing amphiphilic
hydrocarbon moieties involves reaction of functional groups on the polymer
with reagents
containing amphiphilic hydrocarbon moieties in such a manner that the
hydrocarbon
Zo moieties are attached in a pendant fashion on the PAE resin. Such reactions
may take
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K-C 14632
place either prior to or after reaction with epichlorohydrin. In general the
reactive reagents
will be of Formula (III) Figure 6.
Z10_R4
Fi ure 6
where
R' _ any branched or unbranched, saturated or unsaturated, substituted or
unsubstituted amphiphilic chain (with or without ethoxylation).
Z,° = any endgroup capable of reacting with functional groups on the
polymer
backbone. Included in this list, but not limited to would be -COOH,,~COCI, -
COOOC-, -OCOCI, -NCO, NCS, -OH, -NHz. In general Z'° should be a
reagent capable of reacting either with a secondary amine or one of the
functional groups attached to the secondary amines capable of forming a
covalent bond.
Two specific examples are shown in Figures 9 and 10 below. Figure 9 involves
the concept of specifically incorporating a co-monomer into the polymer
backbone which
is capable of being reacted upon by a material of structure (III). This type
of synthesis
lends itself well to incorporation of the amphiphilic hydrocarbon moiety prior
to the
Zo epichlorohydrin reaction.
HO
CHI
OII O H2~ ~CHy O O O
+ CHg(CHp)2(OCH2CH2)gOCH ~CI
~(CH2)4~~ ~N~(CH2)4 [~
CH3(CH2)2(OCH
O O H2~ jCH2 O
~(CH2)4~~+~~(CH )4
2
Fi ure
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CHpCHOHCH3
HOHzCH2C- IN-CHzCH20H + p H2N~N~NHp ~' m ~O
HO~(CH2~OH
DETA Adioic acid
H3C0(CI~CH20)4CHz~CI
CIHZC-C~~H Egichlorhvdrin
H g
C H3C0(CH2CH20)4CHz/\
H2 ~ H2
~ Hz~HCH3
p~(CHz~N~ ~N~ C ~~,, CH2CHz ~ CH CH
( Hz~ 2 z
Fi ur 1
Whefe
n>_0
p>_0
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m>_0
Block Co~olvmer Graftin_a-
A third manner by which the amphiphilic hydrocarbon moiety may be introduced
is
s via a mono or disubstituted copolymer containing linear or branched,
substituted or
unsubstituted, saturated or unsaturated amphiphilic hydrocarbon moieties.
Finished
polymers will be similar to the structure of Figure 11.
.-R~ _ Z2 R2 _ Z3 _ R3 _ Z4-
n
Figure 11
where
n= 1 to 5000
Z,, Z2, Z3, Z, = bridging radicals including -OOC- , - COO -, -NHCO-, -OCNH-, -
O-, -S-,
~s CONHCO, -NCOO, -OS020-, - OCOO- , or any other suitable bridging radical.
Z,, Z2, Z3, Z4 may be the same or different. The purpose of the Z,, Z2, Z3, Z4
radical is to serve as a mechanism for incorporating the R,, R2, and R3 groups
into
the polymer. The Z, groups may also contain aryl functionality.
zo R, and R3 must be chosen such that at least one of R, or R3 is a graft or
block copolymer
containing amphiphilic functionality. It may be alky hydrocarbons with
hydrophilic
(such as -OH, or ethoxy groups) functionality, or aliphatic hydrocarbons with
hydrophilic functionality. The hydrocarbons could be linear or branched,
saturated
or unsaturated, substituted or unsubstituted, with 4 or more hydrocarbons.
25 R2 = any linear or branched, saturated or unsaturated, substituted or non-
substituted
aliphatic hydrocarbon block or graft co-polymer containing at least one
secondary
amine group.
It will be appreciated that the foregoing examples, given for purposes of
so illustration, are not to be construed as limiting the scope of this
invention, which is defined
by the following claims and all equivalents thereto.
