CA2296891A1 - Modified condensation polymers containing azetidinium groups in conjunction with amphiphilic hydrocarbon moieties - Google Patents

Abstract

Modified condensation polymers containing azetidinium groups, such as polyamide epichlorohydrin (PAE) resins, can be 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 controlled decay rate after wetting;
and (g) Yankee dryer additives that provide surface protection and adhesion with controlled release properties.

Description

' 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.

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 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 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.

~(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.

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 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 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 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, 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 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;

K-C 14632 ' ' n > 1;
Z = H or other counterion~.
Structure commonly shared by sulfuric acid derivatives:

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:

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 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 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.

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:

2s HOOCCHZNHCHZCOOH

NHZCHZCHZNHCHZCHZOH

NHZCHZCHZNHCHZCHZNHCHZCHZNH
so NHZ(CHZ)xNH(CHZ)yNH2 HN(CHZCHZCN)Z
An example of the reaction of Figure 4 is illustrated below in Figure 5.

- 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:

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 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 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 Fi ure K-C 14632 ' 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 K-C 14632 ' 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.

Claims (27)

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 having 4 or more carbon atoms and having amphiphilic functionality; 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.

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- and mixtures thereof.

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 the amphiphilic portion of the polymer backbone is a polyalkylene oxide moiety of structure:
where:
R1, R2 = independently H or CH3;
Z1, Z2 = bridging radicals which serve to incorporate the polyalkylene oxide moiety into the polymer backbone;
a, b, c ~ 0;
a + b + c ~ 1; and X = 2 to 6.

5. The polymer of claim 1 wherein the amphiphilic portion of the polymer backbone is incorporated into the polymer via a polyalkylene oxide of structure:
where:
R1, R2 = independently H or CH3;
R3, R4 = independently OH, NH2, -OCH2COOH or -OCH2COOCH3;
a, b, c ~ 0;
a + b + c ~ 1; and x = 2 to 6.

6. The polymer of claim 1 wherein the functional group capable of forming intramolecular or intermolecular covalent bonds is chosen from the group consisting of azetidinium, epoxy, silanol or mixtures of said groups.

7. The polymer of claim 1 having the following structure:
where:

R1, R2 are independently H or CH3;
x, y = 1 to 6;
a, b, c ~ 0;
a + b + c ~ 1;
w = 1 - 2,000;

Z1 = NH, or mixtures thereof;
R3 = C1-4 alkyl; and R4 = H or C1-4 alkyl.

8. The polymer of claim 1 having the following structure:
where:
R1, R2 are independently H or CH3;
x, y = 1 to 6;
a, b, c ~ 0;
a + b + c ~ 1;
w = 1 - 2,000;

Z1 = NH, or mixtures thereof;
R3 = C1-4 alkyl; and R4 = H or C1-4 alkyl.

9. The polymer of claim 1 having the following structure:
where:
R1, R2 are independently H or CH3;
x, y = 1 to 6;
z = 1 to 22;
a, b, c ~ 0;
a + b + c ~ 1;
p,q ~ 1;
w = 1 - 2,000;

Z1 = NH, or mixtures thereof;
R3 = C1-4 alkyl; and R4 = H or C1-4 alkyl.

10. 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 having 4 or more carbon atoms and having amphiphilic functionality; 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.

11. The paper sheet of claim 10 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- and mixtures thereof.

12. The paper sheet of claim 10 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

13. The paper sheet of claim 10 wherein the amphiphilic portion of the polymer backbone is a polyalkylene oxide moiety of structure:
where:
R1, R2 = independently H or CH3;
Z1, Z2 = bridging radicals which serve to incorporate the polyalkylene oxide moiety into the polymer backbone;

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

14. The paper sheet of claim 10 wherein the amphiphilic portion of the polymer backbone is incorporated into the polymer via a polyalkylene oxide of structure:
where:
R1, R2 = independently H or CH3;
R3, R4 = independently OH, NH2, -OCH2COOH or -OCH2COOCH3;
a, b, c ~ 0;
a + b + c ~ 1; and x = 2 to 6.

15. The paper sheet of claim 10 wherein the functional group capable of forming intramolecular or intermolecular covalent bonds is chosen from the group consisting of azetidinium, epoxy, silanol or mixtures of said groups.

16. The paper sheet of claim 10 wherein the polymer has the following structure:
where:
R1, R2 are independently H or CH3;
x, y = 1 to 6;
a, b, c ~ 0;
a + b + c ~ 1;
w = 1 - 2,000;

Z1 = NH, or mixtures thereof;
R3 = C1-4 alkyl; and R4 = H or C1-4 alkyl.

17. The paper sheet of claim 10 wherein the polymer has the following structure:
where:
R1, R2 are independently H or CH3;
x, y = 1 to 6;
a, b, c ~ 0;
a + b + c ~ 1;
w = 1 - 2,000;

Z1 = NH, or mixtures thereof;
R3 = C1-4 alkyl; and R4 = H or C1-4 alkyl.

18. The paper sheet of claim 10 wherein the polymer has the following structure:
27~

where:

R1, R2 are independently H or CH3;
x, y = 1 to 6;
z = 1 to 22;
a, b, c ~ 0;
a + b + c ~ 1;
p, q ~ 1;
w = 1 -2,000;
Z1 = NH, or mixtures thereof;
R3 = C1-4 alkyl; and R4 = H or C1-4 alkyl.

19. 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 fibers in the aqueous suspension or to the web upon drying, 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 having 4 or more carbon atoms and having amphiphilic functionality; 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.

20. The method of claim 19 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- and mixtures thereof.

21. The method of claim 19 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

22. The method of claim 19 wherein the amphiphilic portion of the polymer backbone is a polyalkylene oxide moiety of structure:
where:
R1, R2 = independently H or CH3;
Z1, Z2 = bridging radicals which serve to incorporate the polyalkylene oxide moiety into the polymer backbone;
a, b,c ~ 0;
a+b+c ~ 1; and X = 2 to 6.

23. The method of claim 19 wherein the amphiphilic portion of the polymer backbone is incorporated into the polymer via a polyalkylene oxide of structure:
where:
R1, R2 = independently H or CH3;
R3, R4 = independently OH, NH2, -OCH2COOH or -OCH2COOCH3;
a, b,c ~ 0;
a+b+c ~ 1; and x = 2 to 6.

24. The method of claim 19 wherein the functional group capable of forming intramolecular or intermolecular covalent bonds is chosen from the group consisting of azetidinium, epoxy, silanol or mixtures of said groups.

25. The method of claim 19 wherein the polymer has the following structure:
where:
R1, R2 are independently H or CH3;
x, y = 1 to 6;
a, b, c ~ 0;
a+b+c ~ 1;
w = 1 - 2,000;
Z1 = NH, or mixtures thereof;
R3= C1-4 alkyl; and R4 = H or C1-4 alkyl.

26. The method of claim 19 wherein the polymer has the following structure:
where:
R1, R2 are independently H or CH3;
x, y = 1 to 6;
a, b, c ~ 0;
a+b+c ~ 1;
w = 1 - 2,000;
Z1 = NH, , or mixtures thereof;
R3 = C1-4 alkyl; and R4 = H or C1-4 alkyl.
or mixtures thereof;

27. The method of claim 19 wherein the polymer has the following structure:
where:
R1, R2 are independently H or CH3;
x, y = 1 to 6;
z = 1 to 22;

a, b, c ~ 0;
a+b+c ~ 1;
p,q ~ 1;
w = 1 - 2,000;
Z1 = NH, , or mixtures thereof;
R3= C-4 alkyl; and R4 = H or C1-4 alkyl.