WO2011075734A2

WO2011075734A2 - Manufacture of antimicrobial nylon, poly(meth)acrylates, and poly(meth)acrylamides

Info

Publication number: WO2011075734A2
Application number: PCT/US2010/061355
Authority: WO
Inventors: Robert Engel
Original assignee: Research Foundation Of The City University Of New York
Priority date: 2009-12-18
Filing date: 2010-12-20
Publication date: 2011-06-23
Also published as: WO2011075734A3

Abstract

An antimicrobial nylon polymer, antimicrobial polymethacrylate, and antimicrobial polymethacrylamide are claimed along with methods of making the antimicrobial polymers.

Description

MANUFACTURE OF ANTIMICROBIAL NYLON, POLY(METH)ACRYLATES,

AND POL Y(METH)ACRYL AMIDE S

CROSS-REFERENCE TO RELATED APPLICATION

This application asserts priority to U.S. Provisional Application Serial No.

61/288,066, filed on December 18, 2009, the contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

Current fears of antibiotic-resistant bacteria and other microbes as well as of bioterrorism have increased the importance of developing new ways to protect people from microbial infection. It is, for example, important to develop new materials for making clothing that can be more safely worn in contaminated environments. Such materials would be useful, for example, in hospitals and during military and civilian operations where bacterial contamination has occurred, or is expected.

In developing new antimicrobial compositions, it is important to discourage further antibiotic resistance. Ideally, therefore, novel antimicrobial compositions will function through non-specific, non-metabolic mechanisms.

For example, polycationic (quaternary ammonium) strings were developed in the laboratory of Robert Engel. See Fabian et al, Syn. Lett., 1007 (1997); Strekas et al, Arch. Biochem. and Biophys. 364, 129-131 (1999). These strings are reported to have antibacterial activity. See Cohen et al., Heteroat. Chem. 11, 546-555 (2000).

Methods of coating antimicrobial agents on surfaces are known. However, the coating may wash or wear-off, causing the surface to be unprotected from microbes. There is a need for improved new solid antimicrobial compositions and products that are more stable than those already known. Ideally, the compositions and products do not lead to bacterial resistance, and are permanent over time. Through the prior efforts of Robert Engel et al. procedures have been developed for the generation of a variety of fabric materials that are permanently antimicrobial. For example, U.S. Patents 7,241,453 and 7,285,286 and U.S. Patent Publication No. 2009- 0233935 to Engel, et al. are directed to covalent attachment of polycationic (quaternary ammonium) strings to fabric surfaces (natural or synthetic) in order to render them antimicrobial; whereas U.S. Patent Publication No. 2008-0300252 to Engel, et al teaches embedding of polycationic lipids (quaternary ammonium) into a polymeric material at elevated temperatures for the same purpose. These earlier disclosed procedures involve the incorporation into the fabric material, either by covalent attachment or by embedding, polycationic lipids that kill bacteria or fungi through lipophilic invasion of the cell wall followed by electrostatic disruption of that cell wall causing the cell to lose its containment integrity.

These procedures, however, have limitations. For example, covalent attachment can only occur if the fabric material has appropriate functional groups. Similarly, the embedding procedure requires a fabric material that is solid at room temperature and molten at elevated temperatures.

However, these earlier procedures encounter a difficult situation when it comes to nylon. When used in association with cotton or polyester, it is possible to attain antimicrobial characteristics using the portion of the fabric that is cotton, wool, or polyester (by covalent attachment or embedding), as long as that portion is present in sufficient proportion. In contrast, when using only nylon in a fabric, or nylon with only a small component of other fibers, incorporation of antimicrobial characteristics becomes extremely difficult.

The fundamental difficulties with nylon itself are twofold: 1) nylon, unlike other fabricated fibers such as polyester, has a relatively high melting temperature that does not allow facile embedding of the (poly)cationic lipids within its structure, and 2) nylon does not have pendant reactive functionalities that would allow facile covalent attachment of the antimicrobial (poly)cationic lipids. Beyond the application to nylon, a related situation exists with poly(meth)acrylate or poly(meth)acrylamide fibers and fabrics. While poly(meth)acrylates or

poly(meth)acrylamides are capable of having antimicrobial agents embedded within them, it would be better if antimicrobial agents could be incorporated into the

poly(meth)acrylate or poly(meth)acrylamide chains themselves using a covalent mode of attachment.

Accordingly, there is a need for new and more effective methods for rendering nylon or other non-hydroxyl-containing fibers (such as poly(meth)acrylate or

poly(meth)acrylamide fabrics) and surfaces antimicrobial.

SUMMARY OF THE INVENTION

In a first aspect, the invention relates to an antimicrobial nylon polymer comprising: first monomeric amide units having the formula:

-HN-(CH₂)_nl-NH-(0)C-(CH₂)_n2-C(0)- and second monomeric amide units having the formula:

O H H II H II

N— (CH₂)n4 N— C— C— C

(CH₂)_n3

I

x

I

R wherein the ratio of first monomeric amide units and second monomeric amide units in the polymer is sufficiently low to cause the polymer to be resistant to antimicrobial infestation; wherein the ratio of first monomeric amide units and second monomeric amide units in the polymer is sufficiently high to cause the polymer to be capable of being formed into useful nylon fibers; and wherein: nl represents a minimum of 5 and a maximum of 12; n2 represents a minimum of 5 and a maximum of 12; n3 represents a minimum of 2 and a maximum of 24; n4 represents a minimum of 5 and a maximum of 12; R represents an unbranched, saturated or unsaturated hydrocarbyl chain having a minimum of 10 carbon atoms in the chain and a maximum of 24 carbon atoms in the chain and wherein each carbon atom in the chain independently is optionally replaced by a heteroatom selected from the group consisting of -O- or -NH₂-, with the proviso that each heteroatom is separated from each other heteroatom by at least two carbon atoms;

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

W represents an anion; m2 represents the valence of the anion; and ml x m2 = -2.

In an embodiment of the first aspect, the polymer is in the form of a fiber.

In another embodiment of the first aspect, nl represents 6 and n2 represents 6, nl represents 6 and n2 represents 12, nl represents 5 and n2 represents 10, nl represents 6 and n2 represents 11, or nl represents 10 and n2 represents 12.

In another embodiment of the first aspect, the molar ratio of first monomeric amide units and second monomeric amide units is a minimum of 5 : 1 and a maximum of 100: 1.

In another embodiment of the first aspect, the number-average molecular weight of the nylon polymer ranges from about 14,000 to about 20,000.

In another embodiment of the first aspect, n3 represents 2-6.

In another embodiment of the first aspect, W represents chloride, bromide, nitrate, sulfate, formate, acetate, or benzoate. In a second aspect, the invention relates to a method for producing any of the antimicrobial nylon polymers described above. The method comprising reacting:

(a) a diamine having the formula H₂N-(CH₂)_ni-NH₂; with

(b) a first dicarboxylic acid having the formula HO(0)C-(CH₂)_n2-C(0)OH or a derivative thereof having two activated carboxylate groups; and

(c) a second dicarboxylic acid having the formula

O O

H

HO— C— C— C— OH

(CH₂)_n3

I

x

R or a derivative thereof having two activated carboxylate groups; under conditions that form nylon polymers comprising first monomeric amide units having the formula:

^{0 0}

H H II H II

N— (CH2)n4 — C— C— C

(CH₂)_n3

I

x

R wherein the ratio of first monomeric amide units and second monomeric amide units in the polymer is sufficiently low to cause the polymer to be resistant to antimicrobial infestation; wherein the ratio of first monomeric amide units and second monomeric amide units in the polymer is sufficiently high to cause the polymer to be capable of being formed into a useful nylon fibers; and wherein: nl represents a minimum of 5 and a maximum of 12; n2 represents a minimum of 5 and a maximum of 12; n3 represents a minimum of 2 and a maximum of 24; n4 represents a minimum of 5 and a maximum of 12;

R represents an unbranched, saturated or unsaturated hydrocarbyl chain having a minimum of 10 carbon atoms in the chain and a maximum of 24 carbon atoms in the chain and wherein each carbon atom in the chain independently is optionally replaced by a heteroatom selected from the group consisting of -O- or -NH₂-, with the proviso that each heteroatom is separated from each other heteroatom by at least two carbon atoms; and

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

W represents an anion; m2 represents the valence of the anion; and ml x m2 = -2. further comprising forming a fiber from the polymer.

In an embodiment of the second aspect, the invention further comprises forming a fiber from the polymer. In a third aspect, the invention relates to an antimicrobial (meth)acrylate or (meth)acrylamide polymer comprising:

(a) first (meth)acrylate or (meth)acrylamide monomer unit

(b) second (meth) acrylate or (meth) acrylamide monomer unit

wherein:

R and R independently represent -H or -CH₃;

Y¹ and Y² independently represent -O- or -N-;

R¹¹ and R¹² independently represent -H, -CH₃, -CH₂CH ,

-CH₂CH₂OH, or -(CH₂CH₂0)_ni₄CH₂CH₂OH;

R represents -(CH₂)_ni2-X-R ;

R represents H or -(CH₂)_ni₃-X-R ;

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

W represents an anion; m2 represents the valence of the anion; and ml x m2 = -2 R¹⁶ and R¹⁷ independently represent an unbranched, saturated or unsaturated hydrocarbyl chain having a minimum of 10 carbon atoms in the chain and a maximum of 24 carbon atoms in the chain and wherein each carbon atom in the chain independently is optionally replaced by a heteroatom selected from the group consisting of -O- or -NH₂-, with the proviso that each heteroatom is separated from each other heteroatom by at least two carbon atoms; nlO represents 0 when Y¹ represents O; nlO represents 1 when Y¹ represents N; nl 1 represents 0 when Y² represents O; nl 1 represents 1 when Y² represents N; nl2 and nl3 independently represent 2-24; and nl4 represents 1-10.

In an embodiment of the third aspect, the invention relates to an antimicrobial polymer in the form of a fiber. In another embodiment of the third aspect, the invention relates to an antimicrobial polymer, wherein the molar ratio of the first (meth)acrylate or (meth)acrylamide monomer unit and the second (meth)acrylate or (meth)acrylamide monomer unit is a minimum of 5 : 1 and a maximum of 100 : 1.

In another embodiment of the third aspect, the invention relates to an antimicrobial polymer wherein R¹⁰ and R¹³ represent -H.

In another embodiment of the third aspect, the invention relates to an antimicrobial polymer wherein R¹⁰ and R¹³ represent -CH₃.

In another embodiment of the third aspect, the invention relates to an antimicrobial polymer wherein Y¹ and Y² represent -O- and nlO and ni l represent 0.

In another embodiment of the third aspect, the invention relates to an antimicrobial polymer, wherein nl2 and nl3 independently represent 2-

6.

In a fourth aspect, the invention relates to a method for producing any of the antimicrobial (meth)acrylate or (meth)acrylamide polymers described above. The method comprising reacting:

(a) first (meth)acrylate or (meth)acrylamide monomer

(b) second (meth)acrylate or (meth)acrylamide monomer

under conditions that form a polymer comprising:

(a) first (meth)acrylate or (meth)acrylamide monomer unit

(b) second (meth) acrylate or (meth) acrylamide monomer unit

wherein the ratio of the first (meth)acrylate or (meth)acrylamide monomer unit and the second (meth)acrylate or (meth)acrylamide monomer unit in the polymer is sufficiently low to cause the polymer to be resistant to antimicrobial infestation; wherein the ratio of the first (meth)acrylate or (meth)acrylamide monomer unit and the second (meth)acrylate or (meth)acrylamide monomer unit in the polymer is sufficiently high to cause the polymer to be capable of being formed into a useful (meth)acrylic or (meth)acrylamide polymer fiber;and wherein:

R¹⁰ and R¹³ independently represent -H or -CH₃; Y¹ and Y² independently represent -O- or -N-;

R¹¹ and R¹² independently represent -H, -CH₃, -CH₂CH₃,

-CH₂CH₂OH, or -(CH₂CH₂0)_ni₄CH₂CH₂OH; R¹⁴ represents -(CH₂)_ni₂-X-R¹⁶; R¹⁵ represents H or -(CH₂)_ni₃-X-R¹⁷;

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

In an embodiment of the fourth aspect, the invention further comprises forming a fiber from the polymer.

DETAILED DESCRIPTION

The invention relates to nylon polymers, poly(meth)acrylate, and

poly(meth)acrylamide. The polymers have chains of repeating monomeric amide units in the case of the nylon polymers or monomeric substituted ethylene units in the case of (meth)acrylate and (meth)acrylamide polymers. The ends of the chain are capped with atoms or groups that depend of how the polymerization reaction is initiated and terminated. One or both of the ends may, for example, be capped with hydrogen atoms. In the case of (meth)acrylate and (meth)acrylamide polymers, the ends are usually capped with the radicals that initiated and terminated the polymerization of the (meth)acrylate and (meth)acrylamide monomers, respectively.

In one aspect, the invention relates to an antimicrobial nylon polymer. The antimicrobial nylon polymer comprises: first monomeric amide units having the formula:

H H II H II

N— (CH₂)n4 N— C— C— C

(CH₂)_n3

I

x

I

R

The ratio of first monomeric amide units and second monomeric amide units in the polymer is sufficiently low to cause the polymer to be resistant to antimicrobial infestation. At the same time, the ratio of first monomeric amide units and second monomeric amide units in the polymer is sufficiently high to cause the polymer to be capable of being formed into a useful nylon fibers. For example, the minimum molar ratio of first monomeric amide units and second monomeric amide units may be 5 : 1 , 10 : 1 , or 15 : 1. The maximum molar ratio of first monomeric amide units and second monomeric amide units may, for example, be 75:1, 90: 1, or 100:1.

In the monomer units, nl, n2 and n4 independently represent a minimum of 5 and a maximum of 12. n3 represents a minimum of 12 and a maximum of 24. All numbers included within each limitation are contemplated. Preferably, nl represents 6 and n2 represents 6, nl represents 6 and n2 represents 12, nl represents 5 and n2 represents 10, nl represents 6 and n2 represents 11, or nl represents 10 and n2 represents 12.

R represents an unbranched, saturated or unsaturated hydrocarbyl chain having a minimum of 10 carbon atoms and a maximum of 24 carbon atoms in the chain. The unbranched hydrocarbyl chain may, for example, be an alkylene or alkenylene chain having a minimum of 10 carbon atoms in the chain. The maximum number of carbon atoms in the chain is 24, preferably 18, and more preferably 16. The carbon atoms of a chain can all be saturated, or can all be unsaturated. Alternatively, the chain can comprise a mixture of saturated and unsaturated carbon atoms. The unsaturated hydrocarbyl chains contain one or more double bonds. In addition, the interior carbon atoms in the hydrocarbyl chain may optionally be replaced by at least one heteroatom selected from the group consisting of -O- or -NH₂-; and wherein each heteroatom is separated from each other heteroatom by at least two carbon atoms. The interior carbon atoms are the carbon atoms other than those at the beginning and the end of the hydrocarbyl chain.

Some examples of saturated straight hydrocarbyl chains include alpha-omega n- dodecylene, n-hexadecylene, and n-octadecylene chains. Some examples of suitable, unsaturated straight hydrocarbyl chains include alpha-omega dec-3-enylene, heptadec- 1,3-dienylene, dodec-2-enylene, oleylene, linoleylene, and linolenylene chains. Examples of hydrocarbyl chains containing one or more heteroatom include CH₃-

(CH₂)₄-0-(CH₂)₂-NH₂-(CH₂)₅-; CH₃-NH₂-(CH₂)₃-0-(CH₂)₄-0-(CH₂)₂-NH₂-(CH₂)₅-0- CH₂-; or CH₃-(CH₂)₅-NH₂-(CH₂)₉.

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

In the formula for X, W represents an anion, m2 represents the valence of the anion; and ml is any number such that mi x m2 = -2. The negatively charged anion W serves to balance the double positive charge of l,4-diazoniabicyclo[2.2.2]octane, and may be any anion that is not harmful to humans that contact fabrics made from the nylon polymers of the invention. Some suitable anions include, for example, chloride, bromide, nitrate, sulfate, formate, acetate, or benzoate.

The molecular weight of the nylon of the invention is any molecular weight that is suitable for fiber production. For example, a suitable number-average molecular weight of nylon polymer ranges from about 14,000 to about 20,000. Reaction conditions suitable for making nylon having suitable ranges of molecular weights are well known in the art.

In a second aspect, the invention also relates to a method for producing any of the antimicrobial nylon polymers described above. The method comprises reacting components (a), (b), and (c) defined as follows:

(a) a diamine having the formula Η₂Ν-( Η₂)ηΐ-ΝΗ₂;

(c) a second dicarboxylic acid having the formula

or a derivative thereof having two activated carboxylate groups.

The reaction is carried out under conditions that form a nylon polymer comprising the first and second monomeric amide units described above. The conditions are such that the molar ratio of first monomeric amide units and second monomeric amide units is sufficiently low to cause the polymer to be resistant to antimicrobial infestation. At the same time, the molar ratio of first monomeric amide units and second monomeric amide units is sufficiently high to cause the polymer to be capable of being formed into a useful nylon polymer.

A person having ordinary skill is able to determine appropriate conditions that lead to suitable ranges of molar ratios of first monomeric amide units and second monomeric amide units. For example, the minimum molar ratio of first monomeric amide units and second monomeric amide units may be 5: 1, 10: 1, or 15: 1. The maximum molar ratio of first monomeric amide units and second monomeric amide units may, for example, be 75: 1, 90: 1, or 100: 1.

Nylon may be processed into nylon fibers by methods known in the art. For example, U.S. Patent No. 2,130,523 discloses linear polyamides suitable for spinning into strong pliable fibers. U.S. Patent 2,130,947 discloses diamine dicarboxylic acid salts. U.S. Patent 2,130,948 discloses synthetic fibers.

One such process involves two-step melt spinning, which comprises spinning and drawing. After melting, filtering, and deaerating, the molten polymer is extruded through a spinneret into a chamber where the melt solidifies into a filament form. The newly formed filaments are then drawn into useful nylon fibers. A one-step, high-speed spinning process may also be used.

Various types of nylon polymers and copolymers exist, depending, for example, on the length of the respective alkyl chains of the reactant alkyl diamines and alkyl carboxylates. Some examples of nylon polymers or copolymers include those wherein nl represents 6 and n2 represents 6 (nylon 6,6), nl represents 6 and n2 represents 12 (nylon 6,12), nl represents 5 and n2 represents 10 (nylon 5,10), nl represents 6 and n2 represents 11 (nylon 6,11), or nl represents 10 and n2 represents 12(nylon 10,12).

Activated carboxylate groups are well known in the art. Some suitable examples of activated carboxylate groups include acyl chlorides, acyl bromides, carboxylic acid esters and sulfonic acid esters. Suitable esters include, for example, methyl esters, ethyl esters, phenyl esters, nitrophenyl esters, dinitrophenyl esters, trinitrophenyl esters, benzyl esters, or N-succinimidyl esters. Suitable sulfonic acid ester groups include, for example, p-toluenesulfonic esters, benzenesulfonic esters, methanenesulfonic esters. The activated carboxylate groups are preferably acyl chlorides, acyl N-succinimidyl esters, or p- toluenesulfonic esters esters.

In a third aspect, the invention relates to antimicrobial (meth)acrylate or

(meth)acrylamide polymers.

The antimicrobial (meth)acrylate or (meth)acrylamide polymers include the following monomer units:

(a) first (meth)acrylate or (meth)acrylamide monomer unit

(b) second (meth) acrylate or (meth) acrylamide monomer unit

In the formulas above, R and R independently represent -H or -CH₃. For example, R¹⁰ may represent -H and R¹³ may represent -CH₃ or R¹⁰ and R¹³ may both represent -CH₃.

Y¹ and Y² independently represent -O- or -N-.

R¹¹ and R¹² independently represent -H, -CH₃, -CH₂CH₃, -CH₂CH₂OH, or - CH₂CH₂0)_ni₄CH₂CH₂OH. R¹⁴ represents -(CH₂)_ni₂-X-R¹⁶. R¹⁵ represents H or -

X is as described above.

R¹⁶ and R¹⁷ independently represent an unbranched, saturated or unsaturated hydrocarbyl chain having a minimum of 10 carbon atoms and a maximum of 24 carbon atoms in the chain. The unbranched hydrocarbyl chain may, for example, be an alkylene or alkenylene chain having a minimum of 10 carbon atoms in the chain. The maximum number of carbon atoms in the chain is 24, preferably 18, and more preferably 16. The carbon atoms of a chain can all be saturated, or can all be unsaturated. Alternatively, the chain can comprise a mixture of saturated and unsaturated carbon atoms. The

unsaturated hydrocarbyl chains contain one or more double bonds. In addition, the interior carbon atoms in the hydrocarbyl chain may optionally be replaced by at least one heteroatom selected from the group consisting of -O- or -NH₂-; and wherein each heteroatom is separated from each other heteroatom by at least two carbon atoms. The interior carbon atoms are the carbon atoms at the beginning or the end of the hydrocarbyl chain.

Some examples of saturated straight hydrocarbyl chains include alpha-omega n- dodecylene, n-hexadecylene, and n-octadecylene chains. Some examples of suitable, unsaturated straight hydrocarbyl chains include dec-3-enylene, heptadec-l,3-dienylene, dodec-2-enylene, oleylene, linoleylene, and linolenylene chains.

The variable nlO may be 0 or 1 depending upon Y¹. nlO represents 0 when Y¹ represents O. nlO represents 1 when Y¹ represents N. The variable ni l may be 0 or 1 depending upon Y². ni l represents 0 when Y² represents O. nl 1 represents 1 when Y² represents N. nl2 and nl3 independently represent 2-24, and preferably 2-6. nl4 represents 1-10.

The molecular weight of the antimicrobial (meth)acrylate or (meth)acrylamide polymers of the invention is any molecular weight that is suitable for fiber production. For example, suitable weight-average molecular weight of antimicrobial (meth)acrylate or (meth)acrylamide polymers range from about 1,000 to about 1,000,000, preferably about 10,000 to about 200,000, and more preferably from about 20,000 to about 100,000. Reaction conditions suitable for making antimicrobial (meth)acrylate or

(meth)acrylamide polymers having suitable ranges of molecular weights are well known in the art. See below.

In a fourth aspect, the invention also relates to a method of producing any of the antimicrobial (meth)acrylate or (meth)acrylamide polymer. The method involves reacting components (a) and (b):

(a) first (meth)acrylate or (meth)acrylamide monomer

(b) second (meth)acrylate or (meth)acrylamide monomer

The reaction takes place under conditions that form a polymer comprising the first (meth)acrylate or (meth)acrylamide monomer and the second (meth)acrylate or

(meth)acrylamide monomer. The conditions are such that the ratio of the first

(meth)acrylate or (meth)acrylamide monomer and the second (meth)acrylate or

(meth)acrylamide monomer in the polymer is sufficiently low to cause the polymer to be resistant to antimicrobial infestation. At the same time, the ratio of first monomeric amide units and second monomeric amide units in the polymer is sufficiently high to cause the polymer to be capable of being formed into a useful fibers.

A person having ordinary skill in the art will be able to determine the ratio of first (meth)acrylate or (meth)acrylamide monomer to the second (meth)acrylate or

(meth)acrylamide monomer in the polymer in order to cause the polymer to be resistant to antimicrobial infestation and to be capable of being formed into a useful

(meth)acrylate or (meth)acrylamide fibers. For example, the ratio of the first

(meth)acrylate or (meth)acrylamide monomer to the second (meth)acrylate or

(meth)acrylamide monomer is preferably a minimum of 5: 1, 10: 1, or 20:1. The maximum for the molar ratio of the first (meth)acrylate or (meth)acrylamide monomer to the second (meth)acrylate or (meth)acrylamide monomer is preferably 75: 1, 90: 1, or 100: 1.

General methods of making (meth)acrylate or (meth)acrylamide polymer for use in the present invention are well known in the art. Some suitable methods include emulsion polymerization (see, for example, Cunliffe et al., Polymer 42, 9329-9333 (2001) and dye-sensitized photopolymerization (Needles, Journal of Applied Polymer Science 12, 1557-1565 (1968)).

(Meth)acrylate or (meth)acrylamide polymers may be processed into

(meth)acrylate or (meth)acrylamide fibers by methods that are also known in the art.

Miscellaneous definitions

In this specification, groups of various parameters containing multiple members are described. Within a group of parameters, each member may be combined with any one or more of the other members to make additional sub-groups. For example, if the members of a group are a, b, c, d, and e, additional sub-groups specifically contemplated include any two, three, or four of the members, e.g., a and c; a, d, and e; b, c, d, and e; etc. In some cases, the members of a first group of parameters, e.g., a, b, c, d, and e, may be combined with the members of a second group of parameters, e.g., A, B, C, D, and E. Any member of the first group or of a sub-group thereof may be combined with any member of the second group or of a sub-group thereof to form additional groups, i.e., b with C; a and c with B, D, and E, etc. For example, in the present invention, groups of various parameters are defined

(e.g. R, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, nl, n2, n3, n4, X). Each group contains multiple members. For example, R¹¹ and R¹² represent -H, -CH₃, -CH₂CH₃, -CH₂CH₂OH, or - (CH₂CH₂0)_ni₄CH₂CH₂OH. Each member may be combined with each other member to form additional sub-groups, e.g., -H and -CH₂CH₂OH; -CH₃ and -CH₂CH₃; and -H, - CH₂CH₂OH, and -(CH₂CH₂0)_ni₄CH₂CH₂OH .

The instant invention further contemplates embodiments in which each element listed under one group may be combined with each and every element listed under any other group. For example, nl represents a minimum of 5 and a maximum of 12. n3 represents a minimum of 2 and a maximum of 24. Each element of nl (a minimum of 5 and a maximum of 12) can be combined with each and every element of n3 (a minimum of 2 and a maximum of 24). For example, in one embodiment, nl may represent 11 and n3 may represent 24. Alternatively, nl may represent 6 and n3 may represent 4, etc. Similarly, a third group is n2, in which the number is defined as a minimum of 5 and a maximum of 12. Each of the above embodiments may be combined with each and every element of n2. For example, in the embodiment wherein nl is 7 and n3 is 21, n2 may be 8 (or any other number within the parameters of n2).

With each group, it is specifically contemplated that any one or more members can be excluded. For example, if R¹¹ and R¹² are defined as -H, -CH₃, -CH₂CH₃, - CH₂CH₂OH, or -(CH₂CH₂0)_ni₄CH₂CH₂OH, it is also contemplated that R¹¹ and R¹² are defined as-CH_3, -CH₂CH₂OH, or -(CH₂CH₂0)_ni₄CH₂CH₂OH.

The compounds of this invention are limited to those that are chemically feasible and stable. Therefore, a combination of substituents or variables in the compounds described above is permissible only if such a combination results in a stable or chemically feasible compound. A stable compound or chemically feasible compound is one in which the chemical structure is not substantially altered when kept at a temperature of 40°C or less, in the absence of moisture or other chemically reactive conditions, for at least a week. A list following the word "comprising" is inclusive or open-ended, i.e., the list may or may not include additional unrecited elements. A list following the words "consisting of is exclusive or closed ended, i.e., the list excludes any element not specified in the list.

Example I A series of polycationic lipid species suitable for conversion into components for copolymerization are synthesized using the approach shown in Scheme 1.

R - C₁₂ H₂₅ ; C₁₆ H₃₃ ; C₁₈ H₃₇ ; C₂₂ H₄₅

SOCl₂ or

TsCl/pyridine

Scheme 1

In Scheme 1, R is a hydrocarbon chain with an even number of carbon atoms and one or more anions to balance the charge of the quaternary ammonium groups. The minimum number of carbon atoms for the hydrocarbon chain is 10 and the maximum is 24.

In one preferred embodiment, R is selected from the group C12H25, C16H33,

The materials "A" are taken in varying amounts with 1,6-hexanediamine and the di-acid chloride of adipic acid for the construction of Nylon 6,6 with interspersed polycationic lipid units. Such resultant constructed materials are tested for antimicrobial activity using the standard procedures to determine the optimal construction materials and conditions. These procedures for the generation of the co-polymeric materials containing the polycationic antimicrobial units are those that have been in standard use for quite some time. See E.K. Bolton, 37, 106 (1945).

Example II

A new set of monomeric species are prepared to incorporate an antimicrobial component within the monomer that becomes bound along the polymeric chain. These are to be polycationic species that will serve as copolymers with those ordinarily used for the construction of polymethacrylate and polymethacrylamide fibers. Specifically, monomers are constructed in which the polycationic antimicrobial species is present as part of the ester linkage of an acrylate ester. See Scheme 2 below. The material "B" is taken in varying amounts with ordinary acrylate esters as a copolymer reagent, using amounts sufficient to provide an antimicrobial characteristic to the final polymer. The formation of the polymethacrylate or polymethacrylamide materials containing the antimicrobial co-polymer components is accomplished using standard methods known in the art. See M. Barkowsky, J. Fock and D. Schaefer, "Use of polyacrylate esters as dispersants," US 5,744,523, April 28, 1998.

C0₂H

(acid)

"B"

Scheme 2

Example III

The second (meth)acrylamide monomers are made by substituting 1 -amino-3 - propyl chloride for l-hydroxy-3 -propyl chloride in Scheme 2 of Example II above.

Claims

1. An antimicrobial nylon polymer comprising: first monomeric amide units having the formula:

H H II H II

N— (CH₂)n4 N— C— C— C

(CH₂)_n3

I

x

I

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

2. A nylon polymer according to claim 1, wherein the polymer is in the form of a fiber.

3. A nylon polymer according to claim 1, wherein nl represents 6 and n2 represents 6, nl represents 6 and n2 represents 12, nl represents 5 and n2 represents 10, nl represents 6 and n2 represents 11, or nl represents 10 and n2 represents 12.

4. A nylon polymer according to claim 1, wherein the molar ratio of first monomeric amide units and second monomeric amide units is a minimum of 5 : 1 and a maximum of 100: 1.

5. A nylon polymer according to claim 1, wherein the number-average molecular weight of nylon polymer ranges from about 14,000 to about 20,000.

6. A nylon polymer according to claim 1, wherein n3 represents 2-6.

7. A nylon polymer according to claim 1, wherein W represents chloride, bromide, nitrate, sulfate, formate, acetate, or benzoate.

8. A method for producing an antimicrobial nylon polymer, the method comprising reacting:

(a) a diamine having the formula H₂N-(CH₂)_ni-NH₂; with

(c) a second dicarboxylic acid having the formula

O O

H

HO— C— C— C— OH

(CH₂)_n3

I

x

^{0 0}

H H II H II

N— (CH₂)n4 N— C— C— C

(CH₂)_n3

I

x

I

R represents an unbranched, saturated or unsaturated hydrocarbyl chain having a minimum of 10 carbon atoms in the chain and a maximum of 24 carbon atoms in the chain and wherein each carbon atom in the chain independently is optionally replaced by a heteroatom selected from the group consisting of -O- or -NH₂-, with the proviso that each heteroatom is separated from each other heteroatom by at least two carbon atoms;

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

9. A method according to claim 8, further comprising forming a fiber from the polymer.

10. A method according to claim 8, wherein nl represents 6 and n2 represents 6, nl represents 6 and n2 represents 12, nl represents 5 and n2 represents 10, nl represents 6 and n2 represents 11, or nl represents 10 and n2 represents 12.

11. A method according to claim 8, wherein the molar ratio of first monomeric amide units and second monomeric amide units is a minimum of 5: 1 and a maximum of 100: 1.

12. A method according to claim 8, wherein the activated carboxylate groups are acyl chlorides, acyl N-succinimidyl esters, or p-toluenesulfonic esters esters.

13. An antimicrobial (meth)acrylate or (meth)acrylamide polymer comprising:

(a) first (meth)acrylate or (meth)acrylamide monomer unit

(b) second (meth)acrylate or (meth) acrylamide monomer unit

wherein:

R¹⁰ and R¹³ independently represent -H or -CH₃;

Y¹ and Y² independently represent -O- or -N-;

R¹¹ and R¹² independently represent -H, -CH₃, -CH₂CH₃,

-CH₂CH₂OH, or -(CH₂CH₂0)_ni₄CH₂CH₂OH; R represents -(CH₂)„i₂-X-R ; R¹⁵ represents H or -(CH₂)„i₃-X-R¹⁷;

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

W represents an anion; m2 represents the valence of the anion; and

ml x m2 = -2

R¹⁶ and R¹⁷ independently represent an unbranched, saturated or unsaturated hydrocarbyl chain having a minimum of 10 carbon atoms in the chain and a maximum of 24 carbon atoms in the chain and wherein each carbon atom in the chain independently is optionally replaced by a heteroatom selected from the group consisting of -O- or -NH₂-, with the proviso that each heteroatom is separated from each other heteroatom by at least two carbon atoms; nlO represents 0 when Y¹ represents O; nlO represents 1 when Y¹ represents N; ni l represents 0 when Y² represents O; nl 1 represents 1 when Y² represents N; nl2 and nl3 independently represent 2-24; and nl4 represents 1-10.

14. An antimicrobial polymer according to claim 13, wherein the polymer is in the form of a fiber.

15. An antimicrobial polymer according to claim 13, wherein the molar ratio of the first (meth)acrylate or (meth)acrylamide monomer unit and the second (meth)acrylate or (meth)acrylamide monomer unit is a minimum of 5 : 1 and a maximum of 100 : 1.

16. An antimicrobial polymer according to claim 13, wherein R¹⁰ and R¹³ represent -H..

17. An antimicrobial polymer according to claim 13, wherein R¹⁰ and R¹³ represent -CH₃.

18. An antimicrobial polymer according to claim 13, wherein Y¹ and Y² represent -O- and nlO and nl 1 represent 0.

19. An antimicrobial polymer according to claim 13, wherein nl2 and nl3 independently represent 2-6.

20. A method for producing antimicrobial (meth)acrylate or (meth)acrylamide polymers, the method comprising reacting:

(a) first (meth)acrylate or (meth)acrylamide monomer

(b) second (meth)acrylate or (meth)acrylamide monomer

under conditions that form a polymer comprising:

(a) first (meth)acrylate or (meth)acrylamide monomer unit

(b) second (meth) acrylate or (meth) acrylamide monomer unit

wherein the ratio of the first (meth)acrylate or (meth)acrylamide monomer unit and the second (meth)acrylate or (meth)acrylamide monomer unit in the polymer is sufficiently low to cause the polymer to be resistant to antimicrobial infestation; wherein the ratio of the first (meth)acrylate or (meth)acrylamide monomer unit and the second (meth)acrylate or (meth)acrylamide monomer unit in the polymer is sufficiently high to cause the polymer to be capable of being formed into a useful (meth)acrylic or (meth)acrylamide polymer fiber;and wherein: R and R independently represent -H or -CH₃;

Y¹ and Y² independently represent -O- or -N-;

R¹¹ and R¹² independently represent -H, -CH₃, -CH₂CH₃,

-CH₂CH₂OH, or -(CH₂CH₂0)_ni₄CH₂CH₂OH; R¹⁴ represents -(CH₂)„i₂-X-R¹⁶; R¹⁵ represents H or -(CH₂)„i₃-X-R¹⁷;

X represents l,4-diazoniabicyclo[2.2.2]octane having the formula:

W represents an anion; m2 represents the valence of the anion; and

ml x m2 = -2.

21. A method according to claim 20, further comprising forming a fiber from the polymer.

22. A method according to claim 20, wherein the molar ratio of the first (meth)acrylate or (meth)acrylamide monomer unit and the second (meth)acrylate or (meth)acrylamide monomer unit is a minimum of 5 : 1 and a maximum of 100 : 1.