CA2296826A1 - Modified condensation polymers containing azetidinium groups in conjunction with aliphatic hydrocarbon moieties suitable for papermaking - Google Patents

Modified condensation polymers containing azetidinium groups in conjunction with aliphatic hydrocarbon moieties suitable for papermaking

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Publication number
CA2296826A1
CA2296826A1 CA 2296826 CA2296826A CA2296826A1 CA 2296826 A1 CA2296826 A1 CA 2296826A1 CA 2296826 CA2296826 CA 2296826 CA 2296826 A CA2296826 A CA 2296826A CA 2296826 A1 CA2296826 A1 CA 2296826A1
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Prior art keywords
r3
substituted
r1
polymer
r2
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Abandoned
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CA 2296826
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French (fr)
Inventor
Thomas Gerard Shannon
Daniel Arthur Clarahan
Mike Thomas Goulet
Wen Zyo Schroeder
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Kimberly-Clark Worldwide Inc
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Kimberly-Clark Worldwide Inc
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Abstract

Polyamide epichlorohydrin (PAE) resins can be combined with modified aliphatic hydrocarbons in a single condensation polymer molecule to provide several potential benefits, depending upon the specific combination employed, including: (a) wet strength resins that soften; (b) softeners that do not reduce dry or wet tensile strength; (c) wet strength with improved wet/dry tensile ratio; (d) softeners/debonders with reduced linting and sloughing; (e) wet strength aids with controlled absorbency rate; and (f) Yankee dryer additives that provide surface protection and adhesion with controlled release properties.

Description

Modified Condensation Polymers Containing Azetidinium Groups in Conjunction with Aliahatic Hydrocarbon Moieties Suitable for Papermakina 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, 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 functionality 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 Zo 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 more different molecules. More specifically, polyamide epichlorohydrin (PAE) resins can be combined with modified aliphatic hydrocarbons in a single molecule to is provide several potential benefits, depending upon the specific combination employed, including: (a) wet strength resins that soften; (b) softeners that do not reduce dry or wet tensile strength; (c) wet strength with improved wet/dry tensile ratio; (d) softeners/debonders with reduced tinting and sloughing; (e) wet strength aids with controlled absorbency rate; and (f) Yankee dryer additives that provide surface protection so and adhesion with controlled release properties.
Hence in one aspect, the invention resides in a condensation polymer having the following structure:

-Z~ _ R~ _ Z2 _ R2 _ Zs _ Rs _ Za_ where Z,, Z2, Z3, Z4 = bridging radicals, which can be the same or different, which serve to s 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; and RZ = a hydrocarbon radical of the form:
~4 Zs~s-~o where:
R4, RS are linear or branched, substituted or non-substituted, saturated or unsaturated aliphatic hydrocarbons; and QH
C'H
H2 \CHZ RB ~- ~~ Re +
-N-R'CH-CH -N-R'Si OH
Z5= NH, ~+~ , ~ 2, ~ ~ ~, or mixtures thereof;
~s where Re and R' = H or C,~ alkyl; and wherein at least one of R,, RZ or R3 is or contains an aliphatic hydrocarbon, linear or branched, substituted or unsubstituted, of CB or higher chain length and wherein R, and R3 can be the same or different.
zo 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:
-Z~ _ R~ _ Z2 _ R2 _ Zs _ Rs _ Za_ where 25 Z,, ZZ, Z3, Z4 = bridging radicals, which can be the same or different, which serve to 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; and RZ = a hydrocarbon radical of the form:
30 -"R4-Z5~5 where:

R', R5 are linear or branched, substituted or non-substituted, saturated or unsaturated aliphatic hydrocarbons; and QH
CIH
HpC \CHZ RB ~- /O~ Re +
\N~ -N-R'CH-CHZ -N-R'Si(OHy~
Z5= NH, ~+~ , ~ , ~ , or mixtures thereof;
where Re and R' = H or C,~ alkyl; and wherein at least one of R,,Rz or R3 is or contains an aliphatic hydrocarbon, linear or branched, substituted or unsubstituted, of C8 or higher chain length and wherein R, and R3 can be the same or different.
In another aspect, the invention resides in a method of making a paper sheet such 1o 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 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, Z' = bridging radicals, which can be the same or different, which serve to incorporate the R,, RZ, and R3 groups into the polymer;
Zo R,,R3 = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon; and RZ = a hydrocarbon radical of the form:
~4 Z5~5-where:
z5 R', R5 are linear or branched, substituted or non-substituted, saturated or unsaturated aliphatic hydrocarbons; and QH
CIH
HZ \CHZ Re ~- ~~ Re +
~N/ -N-RICH-CH -N-R'Si(OH~
Z5= NH, ~+~ , I 2, I , or mixtures thereof;
where Re and R' = H or C,~ alkyl; and wherein at least one of R,,Rz or R3 is or contains an aliphatic hydrocarbon, linear or branched, substituted or unsubstituted, of CB or higher chain length and wherein R, and R3 can be the same or different.
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.
~o Detailed Description of the Invention In order to further describe the invention, examples of the synthesis of some of the various chemical species are described below.
Pol~amide Epichloroh~,rdrin 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 during the curing reaction, covalent bonds are formed between polymers and fibers and 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 Zo 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 Yankee surface while at the same time promoting adhesion of the sheet to the dryer surface.
A multistep synthesis is used to prepare these resins. For the primary commercial is 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 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 so example of a polyamidoamine synthesis is shown in Figure 1.

H
~N~ ~
HZN NHz RO~(CH2)~OR R - H, Me DETA Adipic Acid H
H~N~H~(CHz)a Figure 1 In the second stage of the synthesis, the secondary amine groups are alkylated for example by reaction with epichlorohydrin to produce tertiary aminochlorhydrin groups.
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 1o 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 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.
H ~ yR~
~(CH2)a~~N~N~(CHp)~
CIHyC-CH~~H E~ichlorhvdrin H2G~OHCHyG H
R H2~H~H2 (CH2~~~ ~N (CH2)e (CH2)a~~ ~
(CH2 a 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 group in one molecule with an unreacted secondary amine group in another molecule to produce a cross-link between the two molecules. In the second reaction at least two azetidinium groups on a single resin molecule react with carboxyl groups on two different fibers to produce an interfiber ~o 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 ~s insoluble materials by action of heat alone.
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 Zo refining; chlorine residuals; pH; stock temperature; and anionic contaminants.
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 zs 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 so presumed due to the polymer molecules having a shorter distance to travel before colliding with a fiber surface.
The 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 that can react with the resins and neutralize them.
35 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
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 are available for the cationic groups on the resin. Also the secondary amine groups are ~o 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.
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.
The reaction between PAE and anionic materials can be beneficial in enhancing 2o resin retention by fibers. This is illustrated by the use of anionic carboxymethyl cellulose 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.
25 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. Commercially available PAE
resins are primarily formed from adipic acid and diethylenetriamine (DETA}.
However, ao condensation polymerization reactions necessary for preparation of the PAE
resins are not limited to reactions between diamines and diacid derivatives (esters or free acids).
Suitable condensation polymers include, without limitation, esters, carbonates, urethanes, imides, ureas and others.

Modified Aliphatic Hydrocarbons Modified aliphatic hydrocarbons are utilized, in conjunction with cationic moieties, as softeners, debonders, lubricants and sizing agents. Modified aliphatic hydrocarbons are also utilized as components of Yankee dryer adhesive spray packages to provide s controlled release of the sheet from the Yankee dryer surface. Modified aliphatic hydrocarbons encompasses a broad group of organic compounds, including in general alkanes, alkenes, alkynes and cyclic aliphatic classifications. For purposes herein, the modified aliphatic hydrocarbons can be linear or branched, saturated or unsaturated, substituted or non-substituted, with a chain length of 8 or more carbon atoms.
~o Modified Condensation Polymers Condensation polymerization reactions necessary for preparation of the PAE
resins are not limited to reactions between diamines and diacid derivatives (esters or free acids). Without limitation, suitable condensation polymers include esters, carbonates, ~s urethanes, imides, ureas and others. A variety of methods and reagents can be employed to obtain suitable condensation polymers. In general suitable condensation polymers for purposes of this invention are of the type shown in Figure 3 below.
-Z~_R~_Z2_R2_Z3_R3_~_ Figure 3 where Z,, Zz, Z3, Z4 = bridging radicals including -OOC- , - COO -, -NHCO-, -OCNH-, -O-, -S-, CONHCO, -NCOO, -OS020-, OCOO, -OOC-Ar-O-, or any other suitable is bridging radical. Z,, Zz, Z3, Z, may be the same or different. The purpose of the Z,, ZZ, Z3, Z, 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.
R,,R3 = any linear or branched, saturated or unsaturated, substituted or non-so substituted aliphatic hydrocarbon.
RZ = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon containing at least one secondary amine group.
R,, RZ or R3 must be chosen such that at least one of R,,RZ or R3 is or contains a Cg or 35 higher chain length. R,, R3 may be the same or different.

In addition said polymer shall have a portion of its secondary amine groups reacted in such a manner as to render the polymer substantive to cellulose through one or more of the following mechanisms:
1.) Intermolecular covalent bonding with cellulose;
s 2.) Intramolecular covalent bonding within the polymer molecule itself;
3.) Cationic charge development.
Preferred functional groups for covalent bonding include azetidinium, epoxy, silanol and mixtures of said groups.
Three methods for achieving the condensation polymers of this invention include:
io (1 ) direct incorporation; (2) reaction of polymer functional groups; and (3) block copolymer grafting. Each method is separately described below.
Direct Incorporation:
Condensation polymers in accordance with this invention can be prepared via the ~s general reaction shown in Figure 4 . This results in direct incorporation of the aliphatic groups into the backbone in a random block pattern.
Z5-R,-Ze + ZyRz-Zs -I- Zs-R3-Zoo Zo Fi m 4 where Z5, Zs, 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,,R3 = any linear or branched, saturated or unsaturated, substituted or non-zs substituted aliphatic hydrocarbon.
RZ = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon containing at least one secondary amine group.
R,, RZ or R3 must be chosen such that at least one of R,,RZ or R3 is or contains a C8 or so higher chain length. R,, R3 may be the same or different.
Suitable Rz monomers include, but are not limited to, the following:

NHzCH2CHZNHCH2CH2NH2 HOOCCHzNHCHzCOOH

NHZCHzCH2NHCHZCHZOH
s HOOCCHZCHZNHCHZCHZCOOH
NHZCHZCHZNHCHZCH2NHCHZCHzNH
NHZ(CHZ)XNH(CH2)yNH2 HN(CH2CHZCN)2 where x= 1 to 22 and y= 1 to 22.
~o Specific examples of for synthesizing the modified condensation polymers of this invention are illustrated in Figures 5 and 6 below:
H O
+ ~N~ + m O
n H (CH2)~o OH p H2N NH2 H (CH2)4 OH
1.12 dodecanoic diacid DETA Adig'ic acid ~(C~)~o~~N~N~ CH
( 2)a CIH2C-CH\ ~H Epichlorhvdrin o HQ
/CI ~
H2C\N CH2 (CH2)~o~~ ~N~(CH2~
Fi_ aura 5 where n>_1 p>_1 m >_ 0.
Note that only a portion of secondary amine groups need to be reacted with epichlorhydrin. Typically 10 - 50 mole % of the secondary amine groups will be reacted upon in such a manner.
~o H
N\~
H N- CH -NH + P HO~ _ OH + ilt 2 ( z)~s 2 HO-(CHz)4-OH
1.16 hexadecyldiamine Iminodiacetic Acid Butane diol H
NOCHz)~6'N ~N~~(CH2)4 ~
CIH2C-CH-,CH Enichlorhvdrin HO
CH
H2 ~ ~Hz N-(CHZ)~s-N ~N~O (CHz)a ~
Figure 6 where ~s n >_ 1 p>_1 m >_ 0.

Where solubility in aqueous solutions is a concern a hydrophilic monomer may s also be incorporated into the backbone to counteract any hydrophobicity introduced through addition of the aliphatic hydrocarbon moieties. An example of such monomers would be the dihydroxy and diamino alkanols and polyalkanois including ethylene glycol, and polyethylene glycols of the varying monomer repeat units of the general formula:
R3-(CHCH20)a-(CH2CH20)b-CH2 where:
R', Rz = H, CH3 R3, R4 = OH, NHZ
a,b>_0 ~s a+b>_1 A particularly preferred set of compounds is the amino functional polyethers, often referred to as Polyalkyleneoxy amines. The polyalkyleneoxy amines are well known compositions that may be prepared by the reductive amination of polyalkyleneoxy Zo 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 material, when employed is preferably in the range of from about 100 to about 5,000. Additional examples of amine containing polymers having carbon-zs 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 Chemical Corporation.
so 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 epichlorhydrin as is routinely done with cationic starches.

Reaction of Polymer Functional Groups.
The second approach to preparing azetidinium compounds containing aliphatic hydrocarbon moieties involves reaction of functional groups on the polymer with reagents containing long chain aliphatic hydrocarbon moieties in such a manner that the s hydrocarbon moieties are attached in a pendant fashion on the PAE resin.
Such reactions may take place either prior to or after reaction with epichlorohydrin. In general the reactive reagents will be of the structure of Figure 7.
Z10_R4 ,o Fi ure 7 where R° = any branched or unbranched, saturated or unsaturated, substituted or ,s unsubstituted, C8 or higher aliphatic hydrocarbon.
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, -NH2. In general Z'° should be a reagent capable of reacting either with a secondary amine or one of the Zo functional groups attached to the secondary amines capable of forming a covalent bond.
Two specific examples are shown in Figures 8 and 9. 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 the structure of Figure 7. This type of is synthesis lends itself well to incorporation of the aliphatic hydrocarbon moiety prior to the epichlorohydrin reaction.

HO
CH
O O H C~ \CH O O O
~(CHy)a~~N~N~(CHz)~ + CH3(CH2)~CH CH(CH2~CI
N~(CH2)a~
Figure 8 ~HzCHOHCH3 H
O
HyNH2CHZC-N-CHzCHzNHz '~ p HzN~N~NH2 + m HD~(CH2)~OH
DETA Adi~ic acid H O ~H2CHOHCH3~
)4 N~N~N~(CHz~NCH2CH2-fI~CH2CH2N
CH3(CHZ)~CH~CH(CHZj~CI
CH3(CHZhCH°CH(CHZj~
O HZ~HCHg ,~ ~ H ~,~ ~~ ~-p~(CHz~N~N~~(CH2~NCHyCHp ~-CHZCHzN' CIHzC-C~~H E_pichlorhvdrin CH3(CHZ)~CH CH(CH2j? \
O ~ ~HzCHCH3 Fi ure s where n>_1 p>_1 m~1.

Block Copolymer Grafting A third manner by which the aliphatic hydrocarbon moiety may be introduced is via a mono or disubstituted copolymer containing linear or branched, substituted or unsubstituted, saturated or unsaturated hydrocarbon moieties. Finished polymers will be s similar to the structure of Figure 10.
-R1 - Z2 R2 - Z3 - R3 _ Z4-n ~o Figure 10 where Z,, ZZ, Z3, Z, = bridging radicals including -OOC- , - COO -, -NHCO-, -OCNH-, -O-, -S-, CONHCO, -NCOO, -OS020-, - OCOO- , or any other suitable bridging radical. Z,, ZZ, Z3, Z4 may be the same or different. The purpose of the Z,, ~s Z2, Z3, Z4 radical is to serve as a mechanism for incorporating the R,, Rz, and R3 groups into the polymer. The Z; groups may also contain aryl functionality.
R3 = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon.
Zo RZ = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon containing at least one secondary amine group.
R, = a polymer unit consisting of linear or branched, substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon repeat units is such that the block copolymer is of length C8 or higher.
It will be appreciated that the foregoing examples, given for purposes of illustration, are not to be construed as limiting the scope of this invention, which is defined by the following claims and all equivalents thereto.

Claims (18)

1. A condensation polymer having the following structure:
~Z1-R1-Z2-R2-Z3-R3-Z4-~~
where Z1, Z2, Z3, Z4 = bridging radicals, which can be the same or different, which serve to incorporate the R1, R2, and R3 groups into the polymer;
R1,R3 = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon; and R2 = a hydrocarbon radical of the form:
~R4~Z6~R5~
where:
R4, R5 are linear or branched, substituted or non-substituted, saturated or unsaturated aliphatic hydrocarbons; and Z5= NH, or mixtures thereof;
where R6 and R7 = H, C1-4 alkyl; and wherein at least one of R1, R2 or R3 is or contains an aliphatic hydrocarbon, linear or branched, substituted or unsubstituted, of C8 or higher chain length and wherein R1 and R3 can be the same or different.
2. The polymer of claim 1 wherein the bridging radicals are selected from the group consisting of -OOC-, -COO-, -NHCO-, -OCNH-, -O-, -S-, CONHCO, -NCOO, -OSO2O-, OCOO and -OOC-Ar-O-.
3. The polymer of claim 1 wherein R2 is incorporated into the condensation polymer through use of one of the following monomers:
NH2CH2CH2NHCH2CH2NH2, HOOCCH2NHCH2COOH, HOCH2CH2NHCH2CH2OH,~
NH2CH2CH2NHCH2CH2OH, HOOCCH2CH2NHCH2CH2COOH, NH2CH2CH2NHCH2CH2NHCH2CH2NH, NH2(CH2)x NH(CH2)y NH2, and HN(CH2CH2CN)2, where x = 1 to 22 and y = 1 to 22.
4. The polymer of claim 1 wherein at least one of R1 or R3 is incorporated into the condensation polymer via a monomer selected from the group of alkyl diamines or alkyl diacids or alkyl diacid derivatives having the following structure:
Z6~R6~Z7 where:
Z6, Z7 are independently -NH2, -COOH, or -COR9;
R8 = -OCH3, OCH2CH3, -OC1-4 alkyl, or halo;
R9 = a hydrocarbon radical containing a C8 or higher, linear or branched, substituted or non-substituted aliphatic hydrocarbon.
5. The polymer of claim 1 further comprising one or more of the following groups attached to the backbone of the polymer:
where:
R10, R11 are independently H or CH3;
Z8, Z9 = bridging radicals whose purpose is to provide incorporation into the polymer backbone, Z8, Z9 include but are not limited to -OOC-, -COO-, -NHCO-, -OCNH-, -O-, -S-, CONHCO, -NCOO, -OSO2O-, OCOO and -OOC-Ar-O-;
a, b, c ~ 0;
a + b + c ~ 1; and x = 2 to 6.
6. The polymer of claim 5 wherein the polyoxyalkylene oxide group is incorporated into the condensation polymer via a polyalkylene oxide monomer of structure:

where:
R10, R11 = independently H or CH3;
R12, R13 = independently OH, NH2, -OCH2COOH or -OCH2COOCH3;
a, b, c ~ 0;
a + b + c ~ 1; and x = 2 to 6.
7. 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 Z1, Z2, Z3, Z4 = bridging radicals, which can be the same or different, which serve to incorporate the R1, R2, and R3 groups into the polymer;
R1, R3 = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon; and R2 = a hydrocarbon radical of the form:
~R4-Z5~R5~
where:
R4, R5 are linear or branched, substituted or non-substituted, saturated or unsaturated aliphatic hydrocarbons; and Z5 = NH, or mixtures thereof;
where R6 and R7 = H, C1-4 alkyl; and wherein at least one of R1, R2 or R3 is or contains an aliphatic hydrocarbon, linear or branched, substituted or unsubstituted, of C8 or higher chain length and wherein R1 and R3 can be the same or different.
8. The paper sheet of claim 7 wherein the bridging radicals are selected from the group consisting of -OOC-, -COO-, -NHCO-, -OCNH-, -O-, -S-, CONHCO, -NCOO, -OSO2O-, OCOO and -OOC-Ar-O-.
9. The paper sheet of claim 7 wherein R2 is incorporated into the condensation polymer through use of one of the following monomers:
NH2CH2CH2NHCH2CH2NH2, HOOCCH2NHCH2COOH, HOCH2CH2NHCH2CH2OH, NH2CH2CH2NHCH2CH2OH, HOOCCH2CH2NHCH2CH2COOH, NH2CH2CH2NHCH2CH2NHCH2CH2NH, NH2(CH2)x NH(CH2)y NH2, and HN(CH2CH2CN)2, where x= 1 to 22 and y= 1 to 22.
10. The paper sheet of claim 7 wherein at least one of R1 or R3 is incorporated into the condensation polymer via a monomer selected from the group of alkyl diamines or alkyl diacids or alkyl diacid derivatives having the following structure:
Z6~R8~Z7 where:
Z6, Z7 are independently -NH2, -COOH, or -COR9;
R8 = -OCH3, OCH2CH3, -OC1-4 alkyl, or halo;
R9 = a hydrocarbon radical containing a C8 or higher, linear or branched, substituted or non-substituted aliphatic hydrocarbon.
11. The paper sheet of claim 7 further comprising one or more of the following groups attached to the backbone of the polymer:
where:

R10, R11 are independently H or CH3;
Z8, Z9 = bridging radicals whose purpose is to provide incorporation into the polymer backbone. Z8, Z9 include but are not limited to -OOC-, -COO-, -NHCO-, -OCNH-, -O-, -S-, CONHCO, -NCOO, -OSO2O-, OCOO and -OOC-Ar-O-;
a, b, c ~ 0;
a + b + c ~ 1; and x = 2 to 6.
12. The paper sheet of claim 11 wherein the polyoxyalkylene oxide group is incorporated into the condensation polymer via a polyalkylene oxide monomer of structure:
where:
R10, R11 = independently H or CH3;
R12, R13 = independently OH, NH2, -OCH2COOH or -OCH2COOCH3;
a, b, c ~ 0;
a + b + c ~ 1; and x = 2 to 6.
13. 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 sheet, wherein a condensation polymer is added to the aqueous suspension, said condensation polymer having the following structure:
~Z1-R1-Z2-R2-Z3-R3-Z4-~
where Z1, Z2, Z3, Z4 = bridging radicals, which can be the same or different, which serve to incorporate the R1, R2, and R3 groups into the polymer;

R1, R3 = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon; and R2 = a hydrocarbon radical of the form:
~R4~Z5~R5~
where:
R4, R5 are linear or branched, substituted or non-substituted, saturated or unsaturated aliphatic hydrocarbons; and Z5= NH, or mixtures thereof;
where R6 and R7 = H, C1-4 alkyl; and wherein at least one of R1, R2 or R3 is or contains an aliphatic hydrocarbon, linear or branched, substituted or unsubstituted, of C8 or higher chain length and wherein R1 and R3 can be the same or different.
14. The method of claim 13 wherein the bridging radicals are selected from the group consisting of -OOC-, -COO-, -NHCO-, -OCNH-, -O-, -S-, CONHCO, -NCOO, -OSO2O-, OCOO and -OOC-Ar-O-.
15. The method of claim 13 wherein R2 is incorporated into the condensation polymer through use of one of the following monomers:
NH2CH2CH2NHCH2CH2NH2, HOOCCH2NHCH2COOH, HOCH2CH2NHCH2CH2OH, NH2CH2CH2NHCH2CH2OH, HOOCCH2CH2NHCH2CH2COOH, NH2CH2CH2NHCH2CH2NHCH2CH2NH, NH2(CH2)x NH(CH2)y NH2, and HN(CH2CH2CN)2, where x= 1 to 22 and y= 1 to 22.
16. The method of claim 13 wherein at least one of R1 or R3 is incorporated into the condensation polymer via a monomer selected from the group of alkyl diamines or alkyl diacids or alkyl diacid derivatives having the following structure:
Z6~R8~Z7 where:
Z6, Z7 are independently -NH2, -COOH, or -COR9;
R8 = -OCH3, OCH2CH3, -OC1-4 alkyl, or halo;
R9 = a hydrocarbon radical containing a C8 or higher, linear or branched, substituted or non-substituted aliphatic hydrocarbon.
17. The method of claim 13 further comprising one or more of the following groups attached to the backbone of the polymer:
where:
R10, R11 are independently H or CH3;
Z8, Z9 = bridging radicals whose purpose is to provide incorporation into the polymer backbone, Z8, Z9 include but are not limited to -OOC-, -COO-, -NHCO-, -OCNH-, -O-, -S-, CONHCO, -NCOO, -OSO2O-, OCOO and -OOC-Ar-O-;
a, b, c ~ 0;
a + b + c ~ 1; and x = 2 to 6.
18. The method of claim 17 wherein the polyoxyalkylene oxide group is incorporated into the condensation polymer via a polyalkylene oxide monomer of structure:
where:
R10, R11 = independently H or CH3;
R12, R13 = independently OH, NH2, -OCH2COOH or -OCH2COOCH3;

a, b, c ~ 0;
a + b + c ~ 1; and x = 2 to 6.

~Z1-R1-Z2-R2-Z3-R3-Z4-~
where Z1, Z2, Z3, Z4 = bridging radicals, which can be the same or different, which serve to incorporate the R1, R2, and R3 groups into the polymer;
R1, R3 = any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon; and R2 = 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 R1, R2 or R3 is or contains a C8 or higher chain length and wherein R1 and R3 can be the same or different.
CA 2296826 1999-01-25 2000-01-24 Modified condensation polymers containing azetidinium groups in conjunction with aliphatic hydrocarbon moieties suitable for papermaking Abandoned CA2296826A1 (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003037960A1 (en) * 2001-10-31 2003-05-08 Kimberly-Clark Worldwide, Inc. Modified condensation polymers containing azetidinium groups in conjunction with amphiphilic hydrocarbon moieties
US6596126B1 (en) 1999-01-25 2003-07-22 Kimberly-Clark Worldwide, Inc. Modified polysaccharides containing aliphatic hydrocarbon moieties
US6620295B2 (en) 1999-01-25 2003-09-16 Kimberly-Clark Worldwide, Inc. Modified polysaccharides containing amphiphilic hydrocarbon moieties
US6673205B2 (en) 2001-05-10 2004-01-06 Fort James Corporation Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products
US7041197B2 (en) 2003-04-15 2006-05-09 Fort James Corporation Wet strength and softness enhancement of paper products
US7670459B2 (en) 2004-12-29 2010-03-02 Kimberly-Clark Worldwide, Inc. Soft and durable tissue products containing a softening agent
US7678232B2 (en) 2000-12-22 2010-03-16 Kimberly-Clark Worldwide, Inc. Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6596126B1 (en) 1999-01-25 2003-07-22 Kimberly-Clark Worldwide, Inc. Modified polysaccharides containing aliphatic hydrocarbon moieties
US6620295B2 (en) 1999-01-25 2003-09-16 Kimberly-Clark Worldwide, Inc. Modified polysaccharides containing amphiphilic hydrocarbon moieties
US6896769B2 (en) 1999-01-25 2005-05-24 Kimberly-Clark Worldwide, Inc. Modified condensation polymers containing azetidinium groups in conjunction with amphiphilic hydrocarbon moieties
US7678232B2 (en) 2000-12-22 2010-03-16 Kimberly-Clark Worldwide, Inc. Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition
US6673205B2 (en) 2001-05-10 2004-01-06 Fort James Corporation Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products
US8067524B2 (en) 2001-05-10 2011-11-29 Georgia-Pacific Consumer Products Lp Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products
WO2003037960A1 (en) * 2001-10-31 2003-05-08 Kimberly-Clark Worldwide, Inc. Modified condensation polymers containing azetidinium groups in conjunction with amphiphilic hydrocarbon moieties
US7041197B2 (en) 2003-04-15 2006-05-09 Fort James Corporation Wet strength and softness enhancement of paper products
US7670459B2 (en) 2004-12-29 2010-03-02 Kimberly-Clark Worldwide, Inc. Soft and durable tissue products containing a softening agent

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