Polymers containing phosphono-phosphate groups and anionic groups

文档序号：1342671 发布日期：2020-07-17 浏览：31次中文

阅读说明：本技术 含膦酰基-磷酸根基团和阴离子基团的聚合物 (Polymers containing phosphono-phosphate groups and anionic groups ) 是由赖安·迈克尔·威斯特斯科特·勒罗伊·克朗于 2018-12-11 设计创作，主要内容包括：本发明公开了含有膦酰基-磷酸根基团和阴离子基团的新型聚合物组合物,所述聚合物组合物具有对于二价阳离子和具有二价阳离子的表面的靶向用途。这些化合物可用于向表面诸如钙羟基磷灰石递送阴离子特征。(Novel polymer compositions containing phosphono-phosphate groups and anionic groups are disclosed, which have targeted utility for divalent cations and surfaces having divalent cations. These compounds are useful for delivering anionic character to surfaces such as calcium hydroxyapatite.)

1. A polymer comprising a phosphono-phosphate group and an anionic group, wherein the phosphono-phosphate group has the structure of formula 1:

wherein:

is a site of attachment to a carbon atom in a main, pendant, or side chain of the polymer;

R₁selected from the group consisting of-H, alkyl, alkanediylalkoxy, metal salts having Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cations, amine cation salts, and structures of formula 2:

wherein:

theta is the attachment site to formula 1,

R₄and R₅Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts;

R₂selected from the group consisting of-H, alkyl, alkanediylalkoxy, metal salts having Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cations, amine cation salts, and structures of formula 3:

wherein:

theta is the attachment site to formula 1,

R₆and R₇Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts; and is

n is an integer from 1 to 22; and is

R₃Selected from the group consisting of-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts,

wherein the anionic groups are covalently bonded to the backbone, pendant or side chain of the polymer and are selected from the following chemical groups: phosphate, phosphonate, phosphinate, sulfate, sulfonate, sulfinate, thiol, carboxylate, hydroxylamino, amine oxide, and hydroxamate.

2. The polymer of claim 1, wherein the polymer is formed using monomers, and at least one monomer used to form the polymer comprises the phosphono-phosphate group.

3. The polymer of claim 1, wherein the polymer is formed using monomers and at least one monomer used to form the polymer comprises the anionic group.

4. The polymer of claim 1, wherein the polymer is formed using monomers, and at least one monomer used to form the polymer comprises the anionic group, and at least one monomer used to form the polymer comprises the phosphono-phosphate group.

5. The polymer of any one of the preceding claims, wherein the phosphono-phosphate groups are added during post-polymerization modification.

6. The polymer of claim 2, wherein the at least one monomer has the structure of formula 4

Wherein:

β is the site of attachment to the phosphono-phosphate group of formula 1;

R₈is selected from-H and-CH₃；

L₁A structure selected from the group consisting of a bond, an aryldiyl, and formula 5:

wherein:

α is the attachment site to the alkenyl group in formula 4;

β is the site of attachment to the phosphono-phosphate group of formula 1;

x is selected from the group consisting of structures in formulas 6 to 12;

wherein:

R₉selected from-H, alkyl_(C1-8)Phosphonoalkyl and phosphono (phospho) alkyl; and is

Y is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl.

7. The polymer of claim 6, wherein L₁Is a covalent bond.

8. The polymer of claim 6, wherein L₁Has the structure of formula 5.

9. The polymer of claim 8, wherein the structure of X is selected from the group consisting of formula 6, formula 9, and formula 11.

10. The polymer of any of the preceding claims, wherein the anionic group is selected from the group consisting of phosphate, phosphonate, sulfate, sulfonate, and carboxylate.

11. The polymer of claim 3, wherein the at least one monomer further comprises an alkenyl group having the structure shown in formula 13,

wherein:

R₁₀is selected from H or CH₃And is andL₂is a linking group to the anionic group.

12. The polymer of claim 3, wherein the at least one monomer has the structure shown in formula 14,

wherein:

R₁₁selected from H and alkyl;

is a site of attachment to the anionic group;

L₃a structure selected from the group consisting of a bond, an aryldiyl, and formula 15;

wherein:

γ is the attachment site to the alkenyl group;

is a site of attachment to the anionic group;

w is selected from structures in formulas 16-22:

wherein:

R₁₂selected from-H and alkyl_(C1-8)(ii) a And is

V is selected from alkanediyl, alkoxydiyl, alkylaminodiyl or alkenediyl.

13. The polymer of claim 3, wherein the at least one monomer is selected from the group consisting of vinyl phosphonate, vinyl sulfonate, acrylate, methyl vinyl phosphonate, methyl vinyl sulfonate, methacrylate, styrene phosphonate, styrene sulfonate, vinyl benzene phosphonate, vinyl benzene sulfonate, 2-acrylamido-2-methylpropane sulfonate (AMPS), and 2-sulfopropyl acrylate (SPA).

14. The polymer of claim 4, wherein the ratio of the at least one monomer comprising the phosphono-phosphate groups to the at least one monomer comprising the anionic groups is from 99.9:0.1 to 0.1:99.9, preferably from 99:1 to 1:99, more preferably from 90:10 to 10:90, more preferably from 70:30 to 30:70, respectively.

15. A polymer comprising a phosphono-phosphate group and an anionic group, wherein the polymer has the structure:

wherein:

R₁selected from the group consisting of-H, alkyl, alkanediylalkoxy, metal salts having Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cations, amine cation salts, and structures of formula 2:

wherein:

theta is the attachment site to formula 23,

R₄and R₅Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts;

R₂selected from the group consisting of-H, alkyl, alkanediylalkoxy, metal salts having Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cations, amine cation salts, and structures of formula 3:

wherein:

theta is the attachment site to formula 23,

R₆and R₇Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts; and is

n is an integer from 1 to 22; and is

R₃Selected from the group consisting of-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts,

and the anionic groups are covalently bonded to the main, pendant or side chain of the polymer and are selected from the following chemical groups: phosphate, phosphonate, phosphinate, sulfate, sulfonate, sulfinate, thiol, carboxylate, hydroxylamino, amine oxide, and hydroxamate;

R₈is selected from-H and-CH₃；

L₁A structure selected from the group consisting of a bond, an aryldiyl, and formula 5:

wherein:

α is a point of attachment to the polymer backbone;

β is the site of attachment to the phosphono-phosphate;

x is selected from the group consisting of structures in formulas 6 to 12;

wherein:

R₉selected from-H, alkyl_(C1-8)Phosphonoalkyl and phosphono (phospho) alkyl; and is

Y is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl;

R₁₁is selected from-H and-CH₃；

Is a site of attachment to the anionic group;

L₃a structure selected from the group consisting of a bond, an aryldiyl, and formula 15;

wherein:

γ is a linkage site to the polymer backbone;

is a site of attachment to the anionic group;

w is selected from structures in formulas 16-22:

wherein:

R₁₂selected from-H and alkyl_(C1-8)(ii) a And is

V is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl;

R₁₃is a chemical group generated by initiation of a polymer;

R₁₄is a chemical group that causes chain termination;

m is an integer from 2 to 450; and is

p is an integer from 2 to 450.

16. The polymer of claim 15, wherein R₁Has the following structure:

wherein:

θ is the attachment site to formula 23; and is

R₄And R₅Independently selected from-H, having Na, K, Ca,Metal salts of Zn or Sn cations, and amine cation salts.

17. The polymer of any one of claims 15 to 16, wherein R₂Has the following structure:

wherein:

theta is the attachment site to formula 23,

R₆and R₇Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts; and is

n is an integer of 1 to 3.

18. The polymer of any one of claims 15 to 17, wherein R₈Is H.

19. The polymer of any one of claims 15 to 17, wherein R₈Is CH₃。

20. The polymer of any one of claims 15 to 19, wherein L₁Has the following structure:

wherein:

α is a point of attachment to the polymer backbone;

β is the site of attachment to the phosphono-phosphate;

x is selected from the following structures:

wherein:

R₉selected from-H, alkyl_(C1-8)Phosphonoalkyl and phosphono (phospho) alkyl; and is

Y is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl.

21. The polymer of any one of claims 15 to 20, wherein the anionic group is selected from the group consisting of phosphate, phosphonate, sulfate, sulfonate, and carboxylate.

22. The polymer of any one of claims 15 to 21, wherein R₁₁Is H.

23. The polymer of any one of claims 15 to 21, wherein R₁₁Is CH₃。

24. The polymer of any one of claims 15 to 23, wherein L₃Has the following structure:

wherein:

γ is a linkage site to the polymer backbone;

is a site of attachment to the anionic group;

w is selected from the following structures:

wherein:

R₁₂selected from-H and alkyl_(C1-8)(ii) a And is

V is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl.

25. The polymer of any one of claims 15 to 24, wherein R₁₃Knot selected from formula 24 to formula 28Structure:

wherein:

R₁₅selected from-H, Na, K and amine cation salts;

τ is the attachment site to the polymer backbone; and is

Q is the non-olefinic residue of the monomer used for polymerization.

26. The polymer of claim 25, wherein Q has the structure:

wherein κ represents the attachment site to formula 28.

27. The polymer of claim 25, wherein Q has the structure:

wherein κ represents the attachment site to formula 28.

28. The polymer of claim 25, wherein Q is selected from phosphono-phosphate, sulfonate, and phosphonate.

29. The polymer of any one of claims 15 to 28, wherein R₁₄is-H.

30. The polymer of any one of claims 15 to 28, wherein R₁₄To another polymer having a head-to-head connectionAnd (3) a chain.

31. The polymer of claim 15, wherein:

R₁、R₂and R₃Independently selected from the group consisting of H, Na salts, K salts, and amine cation salts;

R₈is H;

L₁is a covalent bond;

L₃is a covalent bond;

the anionic group is a sulfonate group;

R₁₃has the following structure:

wherein:

τ is the attachment site to the polymer backbone; and is

Q is selected from the structures of formula 29 to formula 30:

wherein κ represents the attachment site to formula 28; and is

R₁₄Is H.

Technical Field

The present invention relates to novel polymers containing phosphono-phosphate groups and anionic groups. The invention also relates to compositions comprising the novel polymers.

Background

Chemical structures that interact with multivalent cations in solution and with surfaces comprising multivalent cations may be used for the treatment of these systems. For example, polyphosphates and pyrophosphates have been used as builders in laundry and dish washing formulations to control calcium, and in drilling muds to prevent precipitation. They have also been used in the oral care industry to help control tartar and reduce the thickness of the pellicle film on teeth to achieve a smooth feel to the teeth. Similarly, bisphosphonates and hydroxy-bisphosphonates are active components in osteoporosis drugs due to their strong interaction with the calcium hydroxyapatite surface, and also act as crystal growth inhibitors in dishwashing liquids and boiler systems. Each of these examples has inherent limitations. Polyphosphates tend to degrade in aqueous solutions over time at all pH's, eventually leading to an increase in orthophosphate in solution. Polyphosphates are also quite anionic in nature and insoluble in non-polar organic systems. However, polyphosphates are generally safe to eat and can be used in different food products. In contrast, bisphosphonates and hydroxy-bisphosphonates are stable in water for long periods of time and can be made to dissolve completely in organic systems depending on the nature of the organic group attached to the bisphosphonate carbon. Bisphosphonates, however, are active on bone surfaces and, due to their potent pharmacological effects, cannot be used in food or other systems that may be accidentally ingested. Polymers comprising bisphosphonates with insufficient molecular weight to pass through the intestinal wall will likely not be osteoactive, however any low molecular weight residual monomer or oligomer that can pass through the intestinal wall renders such polymers prohibitive in a potentially ingestible environment. In addition, because bisphosphonates do not readily decompose, their activity can persist in the environment after use.

Thus, there remains a need for phosphate compositions that are not readily degradable and are safe for human consumption.

Disclosure of Invention

It has been surprisingly found that phosphono-phosphate chemical groups improve the focus on polyphosphates and bisphosphonates, while finding utility in similar systems. In particular, polymers containing phosphono-phosphate groups, whether modified by incorporation of monomers containing phosphono-phosphate groups or by post-polymerization to add phosphono-phosphate groups as well as anionic groups, can be used in many applications where polyphosphate and bisphosphonate containing structures are used. Such applications typically include those in which the binding interaction involves multivalent cations in solution and on divalent cation-containing surfaces. Polymers containing phosphono-phosphate and anions are also useful in applications where the use of polyphosphates and bisphosphonates is limited. The phosphono-phosphate group is conditionally stable and will only release phosphate under acidic or catalytic conditions. Thus, the phosphono-phosphate groups are more stable than polyphosphates, but less stable than bisphosphonates. This enables the formulation of systems where the anion containing polymer provides a beneficial effect and where food harmlessness and water stability are essential requirements.

In certain embodiments, the present invention relates to compositions comprising novel polymers comprising a phosphono-phosphate group and an anionic group, wherein the phosphono-phosphate group has the structure of formula 1:

wherein:

is a site of attachment to a carbon atom in a main, pendant, or side chain of the polymer;

R₁a metal salt selected from the group consisting of-H, alkyl, alkanediylalkoxy, a metal salt having a Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cation, an amine cation salt, and a structure of formula 2:

wherein:

theta is the attachment site to formula 1,

R₄and R₅Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts;

R₂a metal salt selected from-H, alkyl, alkanediylalkoxy, a metal salt having a Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cation, an amine cation salt, and a structure of formula 3:

wherein:

theta is the attachment site to formula 1,

R₆and R₇Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts; and is

n is an integer from 1 to 22; and is

R₃Selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts;

In certain embodiments, at least one monomer used to form the polymer comprises a phosphono-phosphate group. In another embodiment, at least one monomer used to form the polymer comprises an anionic group. In another embodiment, at least one monomer used to form the polymer comprises the anionic group, and at least one monomer used to form the polymer comprises the phosphono-phosphate group. In another embodiment, the phosphono-phosphate groups are added during post-polymerization modification.

In one embodiment, when the at least one monomer used to form the polymer comprises the phosphono-phosphate group, said at least one monomer has the structure of formula 4:

wherein:

β is the site of attachment to the phosphono-phosphate group of formula 1;

R₈is selected from-H and-CH₃；

L₁A structure selected from the group consisting of a bond, an aryldiyl, and formula 5:

wherein:

α is the attachment site to the alkenyl group in formula 4;

β is the site of attachment to the phosphono-phosphate group of formula 1;

x is selected from the group consisting of structures in formulas 6 to 12;

wherein:

R₉selected from-H, alkyl_(C1-8)Phosphonoalkyl and phosphono (phospho) alkyl(ii) a And is

Y is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl.

In one embodiment, the anionic group is selected from phosphate, phosphonate, sulfate, sulfonate or carboxylate. In another embodiment, the anionic group is a sulfonate. In another embodiment, the anionic group is a carboxylate. In another embodiment, the anionic group is phosphonate.

In one embodiment, when at least one monomer used to form the polymer comprises an anionic group, the at least one monomer further comprises an alkenyl group having the structure of formula 13:

wherein:

R₁₀is selected from H or CH₃And L₂Is a linking group attached to the anionic group.

In one embodiment, when at least one monomer used to form the polymer comprises an anionic group, the at least one monomer further comprises an alkenyl group having the structure of formula 14:

wherein:

R₁₁selected from H and alkyl;

is a site of attachment to the anionic group;

L₃a structure selected from the group consisting of a bond, an aryldiyl, and formula 15;

wherein:

γ is the attachment site to the alkenyl group;

is a site of attachment to the anionic group;

w is selected from structures in formulas 16-22:

wherein:

R₁₂selected from-H and alkyl_(C1-8)(ii) a And is

V is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl.

In one embodiment, when at least one monomer used to form the polymer comprises an anionic group, the at least one monomer is selected from the group consisting of vinyl phosphonate, vinyl sulfonate, acrylate, methyl vinyl phosphonate, methyl vinyl sulfonate, methacrylate, styrene phosphonate, styrene sulfonate, vinyl benzene phosphonate, vinyl benzene sulfonate, 2-acrylamido-2-methylpropane sulfonate (AMPS) and 2-sulfopropyl acrylate (SPA).

In one embodiment, when the at least one monomer used to form the polymer comprises the anionic group and the at least one monomer used to form the polymer comprises the phosphono-phosphate group, the ratio of the at least one monomer comprising the phosphono-phosphate group to the at least one monomer comprising the anionic group is from 99.9:0.1 to 0.1:99.9, respectively.

These and other features, aspects, and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure.

Drawings

FIG. 1 is a graph showing polymer properties.

Fig. 2 is a graph showing polymer properties.

Fig. 3 is a graph showing polymer properties.

Fig. 4 is a graph showing polymer properties.

FIG. 5 is a GPC trace obtained from polymer analysis.

FIG. 6 is a GPC trace obtained from polymer analysis.

Detailed Description

While the specification concludes with claims particularly pointing out and distinctly claiming the present invention, it is believed that the present invention will be better understood from the following description.

All percentages herein are by mole of the composition, unless otherwise indicated.

All ratios are molar ratios unless otherwise indicated.

All percentages, ratios, and levels of ingredients referred to herein are based on the actual amount of the ingredient in moles, and do not include solvents, fillers, or other materials that may be used in combination with the ingredients in commercially available products, unless otherwise specified.

As used herein, "comprising" means that other steps and other ingredients that do not affect the end result can be added. The term encompasses the terms "consisting of …" and "consisting essentially of …".

All cited references are incorporated herein by reference in their entirety. The citation of any document is not an admission of its availability as prior art to the claimed invention.

Definition of

The terms "site" or "attachment point" each refer to an atom having an open valence state within a chemical group or defined structural entity, which atom is designated with a symbol such as a simple dash (-) or a lower case Greek letter (e.g., α -, β -, etc.) followed by a dash or straight line, indicating that the atom so designated is attached to another atom in a separate chemical group via a chemical bondWhen drawing vertically across keys

The point of attachment of the chemical group is also indicated. Note that this approach is typically only used to identify the point of attachment of a larger chemical group, in order to specifically assist the reader in identifying the point of attachment to the atom from which the chemical bond extends. The attachment site or point on the first chemical group or defined structural entity is linked to the attachment site or point on the second chemical group or defined structural entity by a single, double or triple covalent bond so as to satisfy the normal valency of the atom attached.

The term "group" when used with a chemical group means any attached atomic group, such as a methyl group, a carboxyl group, or a phosphono-phosphate group as part of a larger molecule.

When used in the context of chemical groups: "Hydrogen" means-H; "hydroxy" means-OH; "oxo" means ═ O; "carbonyl" refers to-C (═ O) -; "carboxy" and "carboxylate" refer to-C (═ O) OH (also written as-COOH or-CO 2H) or a deprotonated form thereof; "amino" means-NH 2; "hydroxyamino" refers to-NHOH; "nitro" means-NO 2; "imino" means ═ NH; "amine oxide" means N⁺O^-Wherein N has three covalent bonds with atoms other than O; "hydroxamic acid" or "hydroxamate" refers to-C (O) NHOH or a deprotonated form thereof; in the monovalent context, "phosphate" means-OP (O) (OH)₂Or a deprotonated form thereof; in the context of divalent, "phosphate" means-op (O) (oh) O-or a deprotonated form thereof; "phosphonate" means C-P (O) (OH)₂Or a deprotonated form thereof, wherein C has a normal tetravalent and three covalent bonds to atoms other than P; "Phosphonyl-phosphate group" means a phosphonate group chemically bonded to at least one phosphate by sharing an oxygen atom, such as, but not limited to, phosphono-monophosphate C-P (O) (OH) OP (O) (OH)₂Phosphono-diphosphonic acid C-P (O) (OP (O) (OH)₂)OP(O)(OH)₂Phosphono-cyclic diphosphonic acidsPhosphono-pyrophosphoric acid C-P (O) (OH) OP (O) (OH)₂And phosphono-polyphosphoric acid C-P (O) (OH) (OP (O) (OH))_nOP(O)(OH)₂(wherein n is an integer between 1 and 100Number) or a deprotonated form thereof, wherein C has a normal tetravalent and three covalent bonds to atoms other than P; "phosphinate" refers to C-P (O) (OH) (C) or a deprotonated form thereof, wherein two Cs each have a normal tetravalent and three additional bonds to atoms other than P; "sulfate" means-OS (O)₂OH or a deprotonated form thereof; "sulfonate" means CS (O)₂OH or a deprotonated form thereof, wherein C has a normal tetravalent and three additional bonds to atoms other than S; "sulfinate" refers to cs (o) OH or a deprotonated form thereof, where C has a normal tetravalent and three additional bonds to atoms other than S; "mercapto" means-SH; "thio" means ═ S; "sulfonyl" means-S (O) 2-; and "sulfinyl" means-S (O) -.

The following subscripts within parentheses further define the chemical groups/classes as follows for the following chemical groups and classes: "(Cn)" defines the exact number of carbon atoms (n) in a chemical group/class. "(C.ltoreq.n)" defines the maximum number of carbon atoms (n) that can be in a chemical group/class, wherein the minimum number of chemical groups under consideration is as small as possible, for example, it is to be understood that the chemical group "alkenyl"_(C≤8)Alkenes of "or chemical class_(C≤8)The minimum number of carbon atoms in "is 2. For example, "alkoxy group_(C≤8)"denotes those alkoxy groups having 1 to 8 carbon atoms. (Cn-n ') defines both the minimum (n) and maximum (n') numbers of carbon atoms in a chemical group. Similarly, alkyl radicals_(C2-8)Represent those alkyl groups having from 2 to 8 (including 2 and 8) carbon atoms.

The term "cation" refers to an atom, molecule or chemical group having a net positive charge, including both singly and multiply charged species. The cation may be a single atom such as a metal (non-limiting examples include Na)⁺Or Ca⁺²) Single molecule (non-limiting examples include (CH)₃)₄N⁺) Or a chemical group (non-limiting examples include-N (CH)₃)₃ ⁺). The term "amine cation" refers to NR₄ ⁺Form of a particular moleculeA cation in which the four substituted R moieties may be independently selected from H and alkyl, non-limiting examples including NH₄ ⁺(ammonium), CH₃NH₃ ⁺(methylammonium), CH₃CH₂NH₃ ⁺(ethylammonium), (CH)₃)₂NH₂ ⁺(dimethylammonium), (CH)₃)₃NH⁺(trimethylammonium) and (CH)₃)₄N⁺(tetramethylammonium).

The term "anion" refers to an atom, molecule, or chemical group having a net negative charge, including both singly and multiply charged species. The anion may be a single atom (such as, but not limited to, halogen F)^-、Cl^-、Br^-) Single molecule (non-limiting examples include CO)₃ ^-2、H₂PO₄ ^-、HPO₄ ^-2、PO₄ ^-3、HSO₄ ^-、SO₄ ^-2) Or a chemical group (non-limiting examples include sulfate, phosphate, sulfonate, phosphonate, phosphinate, sulfonate, sulfhydryl, carboxylate, amine oxide, hydroxamate, and hydroxylamino). A deprotonated form of a chemical group as defined previously is considered an anionic group if removal of a proton yields a net negative charge. In solution, according to Henderson-Hasselbach formula (pH ═ pKa + log)₁₀([A^-]/[HA]) (ii) a Wherein [ HA ]]Is the molar concentration of the undissociated acid, and [ A-]The molar concentration of the conjugate base of the acid), the chemical group can lose a proton and become an anion as a function of pH. When the pH of the solution is equal to the pKa value of the functional group, 50% of the functional groups will be anionic, while the remaining 50% will have protons. In general, a functional group in solution may be considered to be an anion if the pH is at or above the pKa of the functional group.

The term "salt" refers to a charge-neutral combination of one or more anions and cations. For example, when R is represented as the salt of a carboxylate group-COOR, it is understood that the carboxylate (-COO-) is an anion having a negative charge of-1, and R is a cation having a positive charge of +1 to form an electrically neutral entity with one anion having a charge of-1, or R is a cation having a positive charge of +2 to form an electrically neutral entity with two anions each having a charge of-1.

As used herein, the term "saturated" refers to a chemical compound or group so modified that does not have a carbon-carbon double bond and does not have a carbon-carbon triple bond, unless described below. In the case of substitution patterns of saturated chemical groups, one or more carbon-oxygen double bonds or carbon-nitrogen double bonds may be present. When such bonds are present, then there is no exclusion that the carbon-carbon double bond may occur as part of keto-enol tautomerism or imine/enamine tautomerism.

The term "aliphatic" when used without the modifier "substituted" means that the chemical compound/group so modified is acyclic or cyclic, but is a non-aromatic chemical compound or group. In an aliphatic chemical compound/group, the carbon atoms may be linked together in the form of straight, branched or non-aromatic rings (alicyclic hydrocarbons). Aliphatic chemical compounds/groups may be saturated, i.e. linked by single bonds (alkanes/alkyls); it may also be unsaturated, i.e. have one or more double bonds (alkene/alkenyl) or one or more triple bonds (alkyne/alkynyl).

The term "alkyl" when used without the modifier "substituted" refers to a monovalent saturated aliphatic group having a carbon atom as the point of attachment, which has a straight or branched chain, cyclic, or acyclic structure, and which has no atoms other than carbon and hydrogen. Thus, as used herein, a cycloalkyl group is a subset of alkyl groups in which the carbon atoms forming the point of attachment are also members of one or more non-aromatic ring structures in which the cycloalkyl group contains no atoms other than carbon and hydrogen. As used herein, the term does not preclude the presence of one or more alkyl groups (carbon number limitations allow) attached to the ring or ring system. group-CH₃(Me)、-CH₂CH₃(Et)、-CH₂CH₂CH₃(n-Pr or propyl), -CH (CH)₃)₂(i-Pr, ` Pr, or isopropyl), -CH (CH)₂)₂(cyclopropyl), -CH₂CH₂CH₂CH₃(n-Bu)、-CH(CH₃)CH₂CH₃(sec-butyl), -CH₂CH(CH₃)₂(isobutyl), -C (CH)₃)₃(tert-butyl, t-Bu or tBu), -CH₂C(CH₃)₃(neopentyl), cyclobutyl, cyclopentyl, cyclohexyl and cyclohexylmethyl are non-limiting examples of alkyl groups. The term "alkanediyl," when used without the modifier "substituted," refers to a divalent saturated aliphatic group having one or two saturated carbon atoms as the point of attachment, having a straight or branched chain, cyclic, or acyclic structure, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. group-CH₂(methylene), -CH₂CH₂-、-CH₂C(CH₃)₂CH₂-and-CH₂CH₂CH₂-is a non-limiting example of an alkanediyl group. The term "alkylidene" when used without the modifier "substituted" refers to a divalent radical, CRR ', wherein R and R ' are independently hydrogen, alkyl, or R and R ' taken together represent an alkanediyl group having at least two carbon atoms. Non-limiting examples of alkylidene groups include: CH (CH)₂、＝CH(CH₂CH₃) And ═ C (CH)₃)₂. "alkane" refers to the compound H-R, wherein R is alkyl, as defined above for this term. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been independently replaced by-OH, -F, -Cl, -Br, -I, -NH₂、-NO₂、-CO₂H、-CO₂CH3、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃、-S(O)₂NH₂、-P(O)(OH)₂、-P(O)(OH)OP(O)(OH)₂、-OP(O)(OH)₂、-OP(O)(OH)OP(O)(OH)₂、-S(O)₂(OH) or-OS (O)₂(OH) substitution. The following groups are non-limiting examples of substituted alkyl groups: -CH₂OH、-CH₂Cl、-CF₃、-CH₂CN、-CH₂C(O)OH、-CH₂C(O)OCH₃、-CH₂C(O)NH₂、-CH₂C(O)CH₃、-CH₂OCH₃、-CH₂OC(O)CH₃、-CH₂NH₂、-CH₂N(CH₃)₂、-CH₂CH₂Cl、-CH₂P(O)(OH)₂、-CH₂P(O)(OH)OP(O)(OH)₂、-CH₂S(O)₂(OH) and-CH₂OS(O)₂(OH). The term "haloalkyl" is a subset of substituted alkyl groups in which one or more hydrogen atoms have been replaced with a halogen group and no other atoms than carbon, hydrogen, and halogen are present. group-CH₂Cl is a non-limiting example of a haloalkyl group. The term "fluoroalkyl" is a subset of substituted alkyls in which one or more hydrogens have been replaced with a fluorine group, and no other atoms than carbon, hydrogen, and fluorine are present. group-CH₂F、-CF₃and-CH₂CF₃Are non-limiting examples of fluoroalkyl groups.

The term "phosphonoalkyl" is a subset of substituted alkyl groups in which one or more hydrogens have been replaced with a phosphonate group, and no other atoms than carbon, hydrogen, phosphorus and oxygen are present. group-CH₂P(O)(OH)₂and-CH₂CH₂P(O)(OH)₂And their corresponding deprotonated forms are non-limiting examples of phosphonoalkyl groups.

The term "phosphono (phospho) alkyl" is a subset of substituted alkyl groups in which one or more hydrogens have been replaced with a phosphono-phosphate group and no other atoms than carbon, hydrogen, phosphorus and oxygen are present. group-CH₂P(O)(OH)OP(O)(OH)₂and-CH₂CH₂P(O)(OH)OP(O)(OH)₂And their corresponding deprotonated forms are non-limiting examples of phosphono (phospho) alkyl groups.

The term "sulfonylalkyl" is a subset of substituted alkyl groups in which one or more hydrogens have been replaced with a sulfonate group, and no atoms other than carbon, hydrogen, sulfur, and oxygen are present. group-CH₂S(O)₂OH and-CH₂CH₂S(O)₂OH and their corresponding deprotonated forms are sulfonic acidsNon-limiting examples of acyl alkyl groups.

The term "alkenyl", when used without the modifier "substituted", refers to a monovalent unsaturated aliphatic group having one carbon atom as the point of attachment, having a straight or branched chain, cyclic, or acyclic structure, at least one non-aromatic carbon-carbon double bond, no carbon-carbon triple bond, and no atoms other than carbon and hydrogen. Non-limiting examples of alkenyl groups include: -CH ═ CH₂(vinyl), -C (CH)₃)＝CH₂(methylethenyl), -CH ═ CHCH₃、-CH＝CHCH₂CH₃、-CH₂CH＝CH₂(allyl), -CH₂CH＝CHCH₃and-CH ═ CHCH ═ CH₂. The term "alkenediyl" when used without the modifier "substituted" refers to a divalent unsaturated aliphatic group having two carbon atoms as points of attachment, having a straight or branched chain, cyclic, or acyclic structure, at least one non-aromatic carbon-carbon double bond, no carbon-carbon triple bond, and no atoms other than carbon and hydrogen. Group > C ═ CH₂(vinylidene), -CH-, -CH-C (CH)₃)CH₂-and-CH ═ CHCH₂-is a non-limiting example of an alkenediyl group. It is noted that while the alkenediyl group is aliphatic, once attached at both ends, it is not excluded that the group forms part of an aromatic structure. The term "alkene" or "alkene" is synonymous and refers to a compound having the formula H-R, wherein R is alkenyl as defined above for the term. "terminal alkene" refers to an alkene having only one carbon-carbon double bond, wherein the bond forms a vinyl group at one end of the molecule. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been independently replaced by-OH, -F, -Cl, -Br, -I, -NH, -NO₂、-CO₂H、-CO₂CH₃、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃or-S (O)₂NH₂And (4) substitution. The radical-CH ═ CHF. -CH ═ CHCl and-CH ═ CHBr are non-limiting examples of substituted alkenyl groups.

The term "alkynyl", when used without the modifier "substituted", refers to a monovalent unsaturated aliphatic group having one carbon atom as the point of attachment, having a straight or branched chain, cyclic, or acyclic structure, at least one carbon-carbon triple bond, and no atoms other than carbon and hydrogen. As used herein, the term alkynyl does not preclude the presence of one or more non-aromatic carbon-carbon double bonds. The group-C.ident.CH, -C.ident.CCH₃and-CH₂C≡CCH₃Are non-limiting examples of alkynyl groups. "alkyne" refers to the compound H-R, where R is alkynyl. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been independently replaced by-OH, -F, -Cl, -Br, -I, -NH₂、-NO₂、-CO₂H、-CO₂CH₃、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃or-S (O)₂NH₂And (4) substitution.

The term "aryl," when used without the modifier "substituted," refers to a monovalent unsaturated aromatic group having, as the point of attachment, one aromatic carbon atom that forms part of one or more six-membered aromatic ring structures, wherein the ring atoms are all carbon, and wherein the group contains no atoms other than carbon and hydrogen. If more than one ring is present, the rings may be fused or unfused. As used herein, the term does not preclude the presence of one or more alkyl or aralkyl groups (carbon number limitations allow) attached to the first aromatic ring or any additional aromatic rings present. Non-limiting examples of aryl groups include phenyl (-Ph), methylphenyl, (dimethyl) phenyl, -C₆H₄CH₂CH₃(ethylphenyl), naphthyl and a monovalent radical derived from biphenyl. The term "aryldiyl," when used without the modifier "substituted," refers to a divalent group having two aromatic carbon atoms as the point of attachmentAn aromatic group, the carbon atoms forming part of one or more six-membered aromatic ring structures, wherein the ring atoms are all carbon, and wherein the monovalent group contains no atoms other than carbon and hydrogen. As used herein, the term does not preclude the presence of one or more alkyl, aryl or aralkyl groups (carbon number limitations allow) attached to the first aromatic ring or any additional aromatic rings present. If more than one ring is present, the rings may be fused or unfused. Unfused rings may be connected via one or more of the following (carbon number limitation allowed): a covalent bond, an alkanediyl or alkenediyl group. Non-limiting examples of aryldiyl groups include:

"arene" refers to the compound H-R, where R is aryl, as defined above for this term. Benzene and toluene are non-limiting examples of aromatic hydrocarbons. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been independently replaced by-OH, -F, -Cl, -Br, -I, -NH₂、-NO₂、-CO₂H、-CO₂CH₃、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃or-S (O)₂NH₂And (4) substitution.

The term "acyl" when used without the modifier "substituted" refers to the group-c (o) R, wherein R is hydrogen, alkyl, aryl, aralkyl, or heteroaryl as defined above for those terms. The radicals-CHO (formyl), -C (O) CH₃(acetyl, Ac), -C (O) CH₂CH₃、-C(O)CH₂CH₂CH₃、-C(O)CH(CH₃)₂、-C(O)CH(CH₂)₂、-C(O)C₆H₅、-C(O)C₆H₄CH₃、-C(O)CH₂C₆H₅-C (O) (imidazolyl) is a non-limiting representation of an acyl groupFor example. "thioacyl" is defined in a similar manner except that the oxygen atom of the group-C (O) R has been replaced with a sulfur atom to form-C (S) R. As defined above, the term "aldehyde" corresponds to an alkane in which at least one of the hydrogen atoms has been substituted by a-CHO group. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms (including the hydrogen atom directly attached to a carbonyl or thiocarbonyl group, if any) have been replaced independently with-OH, -F, -Cl, -Br, -I, -NH2, -NO₂、-CO₂H、-CO₂CH₃、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃or-S (O)₂NH₂And (4) substitution. group-C (O) CH₂CF₃、-CO₂H (carboxyl), -CO₂CH₃(methyl carboxyl), -CO₂CH₂CH₃、-C(O)NH₂(carbamoyl) and-CON (CH)₃)₂Are non-limiting examples of substituted acyl groups.

The term "alkoxy" when used without the modifier "substituted" refers to the group-OR, wherein R is alkyl as defined above for the term. Non-limiting examples of alkoxy groups include: -OCH₃(methoxy), -OCH₂CH₃(ethoxy), -OCH₂CH₂CH₃、-OCH(CH₃)₂(isopropoxy), -O (CH)₃)₃(tert-butoxy), -OCH (CH)₂)₂-O-cyclopentyl and-O-cyclohexyl. The terms "alkenyloxy," "alkynyloxy," "aryloxy," "aralkoxy," "heteroaryloxy," "heterocycloalkoxy," and "acyloxy," when used without the modifier "substituted," refer to a group defined as-OR, wherein R is independently alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocycloalkyl, and acyl. The term "alkoxydiyl" refers to the divalent radicals-O-alkanediyl-, -O-alkanediyl-O-or-alkanediyl-O-alkanediyl-. The term "alkanediyl-alkoxy" refers to-alkanediyl-O-alkaneAnd (4) a base. A non-limiting example of an alkanediyl-alkoxy group is CH₂-CH₂-O-CH₂-CH₃. The terms "alkylthio" and "acylthio", when used without the modifier "substituted", refer to the group-SR, wherein R is alkyl and acyl, respectively. The term "alcohol" corresponds to an alkane as defined above, wherein at least one hydrogen atom has been replaced by a hydroxyl group. The term "ether" corresponds to an alkane as defined above, wherein at least one hydrogen atom has been substituted by an alkoxy group. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been independently replaced by-OH, -F, -Cl, -Br, -I, -NH₂、-NO₂、-CO₂H、-CO₂CH₃、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃or-S (O)₂NH₂And (4) substitution.

The term "alkylamino" when used without the modifier "substituted" refers to the group-NHR, wherein R is alkyl as defined above for the term. Non-limiting examples of alkylamino groups include: -NHCH₃and-NHCH₂CH₃. The term "dialkylamino", when used without the modifier "substituted", refers to the group-NRR ', where R and R ' may be the same or different alkyl groups, or R and R ' may be taken together to represent an alkanediyl group. Non-limiting examples of dialkylamino groups include: -N (CH)₃)₂、-N(CH₃)(CH₂CH₃) And N-pyrrolidinyl. The terms "alkoxyamino", "alkenylamino", "alkynylamino", "arylamino", "aralkylamino", "heteroaralkylamino", "heterocycloalkylamino", and "alkylsulfonylamino", when used without the modifier "substituted", refer to groups defined as — NHR, wherein R is alkoxy, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocycloalkyl, and alkylsulfonyl, respectively. A non-limiting example of an arylamino group is-NHC₆H₅. The term "acylAmino (acylamino) "when used without the modifier" substituted "refers to the group-NHR, wherein R is acyl as defined above for the term. A non-limiting example of an amido group is-NHC (O) CH₃. The term "alkylimino", when used without the modifier "substituted", refers to a divalent group, NR, where R is alkyl as defined above for the term. The term "alkylaminodiyl" refers to the divalent radical- -NH-alkanediyl- -, - -NH-alkanediyl-NH- -or- -alkanediyl-NH- -alkanediyl-. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been independently replaced by-OH, -F, -Cl, -Br, -I, -NH₂、-NO₂、-CO₂H、-CO₂CH₃、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃or-S (O)₂NH₂And (4) substitution. The group-NHC (O) OCH₃And NHC (O) NHCH₃Are non-limiting examples of substituted amido groups.

The terms "alkylsulfonyl" and "alkylsulfinyl", when used without the modifier "substituted", refer to the group-S (O), respectively₂R and-S (O) R, wherein R is alkyl as defined above for the term. The terms "alkenylsulfonyl", "alkynylsulfonyl", "arylsulfonyl", "aralkylsulfonyl", "heteroarylsulfonyl" and "heterocycloalkylsulfonyl" are defined in an analogous manner. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been independently replaced by-OH, -F, -Cl, -Br, -I, -NH2, -NO₂、-CO₂H、-CO₂CH₃、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃or-S (O)₂NH₂And (4) substitution.

The term "alkylphosphate" in the absence ofThe modifier "substituted", when used, refers to the group-op (o) (oh) (or) or a deprotonated form thereof, wherein R is alkyl, as that term is defined above. Non-limiting examples of alkyl phosphate groups include: (O) OP (O), (OH) (OMe) and (O) (OH) (OEt). The term "dialkylphosphate" when used without the modifier "substituted" refers to the group-OP (O) (OR '), wherein R and R ' may be the same OR different alkyl groups, OR R and R ' may be taken together to represent an alkanediyl group. Non-limiting examples of dialkyl phosphate groups include: -OP (O) (OMe)₂OP (O) (OEt) (OMe) and OP (O) (OEt)₂. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been independently replaced by-OH, -F, -Cl, -Br, -I, -NH₂、-NO₂、-CO₂H、-CO₂CH₃、-CN、-SH、-OCH₃、-OCH₂CH₃、-C(O)CH₃、-NHCH₃、-NHCH₂CH₃、-N(CH₃)₂、-C(O)NH₂、-OC(O)CH₃or-S (O)₂NH₂And (4) substitution.

A linking group refers to a covalent bond between two other defining groups, or a series of covalently bonded atoms linking two other defining groups, wherein in the series of covalently bonded atoms, except at the point of attachment to the two other defining groups, there is no open valence state. Non-limiting examples of linking groups include covalent bonds, alkanediyl, alkenediyl, aryldiyl, alkoxydiyl, and alkylaminodiyl groups.

As used herein, "chiral auxiliary" refers to a removable chiral group that is capable of affecting the stereoselectivity of a reaction. Those skilled in the art are familiar with such compounds, and many such compounds are commercially available.

Other abbreviations used herein are as follows: DMSO, dimethyl sulfoxide; DMF, dimethylformamide; MeCN, acetonitrile; MeOH, methanol; EtOH, ethanol; EtOAc, ethyl acetate; tBuOH, tert-butanol; iPrOH, isopropanol; cHexOH, cyclohexanol; ac of₂O, acetic anhydride; AcOOH, peracetic acid; HCO₂Et, AEthyl ester of acid; THF, tetrahydrofuran; MTBE, methyl tert-butyl ether; DME, dimethoxyethane; NBS, N-bromosuccinimide; CDI, carbonyldiimidazole; DIEA, diisopropylethylamine; TEA, triethylamine; DMAP, dimethylaminopyridine; NaOH, sodium hydroxide; AAPH, 2,2' -azobis (2-methylpropionamidine) dihydrochloride; CTA, 1-octanethiol; APS, ammonium persulfate; TMP, trimethyl phosphate; VPA, vinyl phosphonic acid; VPP, vinylphosphonyl-monophosphate; VPPP, vinylphosphonyl-pyrophosphate; MVPP, methyl-vinylphosphonyl-monophosphate; SVS, sodium vinyl sulfonate; AMPS, sodium 2-acrylamido-2-methylpropane sulfonate; potassium salt of SPA, 3-sulfopropyl acrylate; 22A2MPA2HCl, 2,2' -azobis (2-methylpropionamidine) dihydrochloride; VBPP, (4-vinylbenzyl) monophosphoryl-phosphate; VSME, methyl vinylsulfonate; NaOMe, sodium methoxide; NaCl, sodium chloride; DMVP, dimethylvinylphosphonate

The International Union of Pure and Applied Chemistry (IUPAC) defines a "monomeric molecule" as a "molecule that can undergo polymerization to contribute structural units to the basic structure of a macromolecule". The polymer is a macromolecule.

IUPAC defines a "polymer backbone" or "backbone" as "all other chains (long or short or both) can be considered linear chains of their pendant groups", noting that "where two or more chains can be considered equivalently a backbone, the choice is such that the molecule represents the simplest chain. "the backbone may have a different chemical composition depending on the starting materials from which it is made. Common backbones of polymers from chemical synthesis and biosynthesis include alkanes (typically from vinyl or methyl vinyl polymerization or cationic and anionic polymerization), polyesters (from polycondensation), polyamides (such as from polypeptides that involve polymerization of amidation reactions), and polyethoxylates from epoxide ring opening.

IUPAC defines a "pendant group" or "side group" as a "branch from the main chain, neither an oligomer nor a polymer". Such side groups do not include linear repeat units.

IUPAC defines "polymeric side chains" or "side chains" as "oligomeric or polymeric branches from a macromolecular chain," it being further noted that "oligomeric branches may be referred to as short-chain branches" and "polymeric branches may be referred to as long-chain branches.

"post-polymerization modification" is defined as any reaction or treatment of the polymer that occurs after polymerization. Post-polymerization modification includes reaction of chemical groups within or attached to the polymer backbone, pendant group, or side chain.

The use of the words "a" or "an" when used in conjunction with the term "comprising" in the claims and/or the specification may mean "one," but is also consistent with the meaning of "one or more," at least one, "and" one or more than one.

Throughout this application, the term "about" is used to indicate that a value includes inherent variations in the apparatus, method errors used to determine the value or variations that exist between study subjects.

The terms "comprising," "having," and "including" are open-ended linking verbs. Any form or tense of one or more of these verbs, such as "comprising," "having," and "including," is also open-ended. For example, any method that "comprises," "has," or "includes" one or more steps is not limited to possessing only those one or more steps and also encompassing other unlisted steps.

The above definitions supersede any conflicting definition in any reference incorporated herein by reference. However, the fact that certain terms are defined should not be taken as indicating that any undefined terms are undefined. Rather, all terms used are to be construed as terms describing the invention so that one of ordinary skill can appreciate the scope of the invention and practice the invention.

Polymers containing phosphono-phosphate and anions

The present invention relates to novel polymers comprising phosphono-phosphate groups and anionic groups. It is recognized that the phosphono-phosphate groups may be anionic, depending on the substituents on the phosphono-phosphate group and the environment in which it is located. For the sake of clarity, anionic groups in this application refer to anionic groups other than phosphono-phosphate.

In one embodiment, the present invention relates to novel polymers containing a phosphono-phosphate group and an anionic group, wherein the phosphono-phosphate group has the structure of formula 1:

wherein:

is a site of attachment to a carbon atom in a main, pendant, or side chain of the polymer;

R₁a metal salt selected from the group consisting of-H, alkyl, alkanediylalkoxy, a metal salt having a Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cation, an amine cation salt, and a structure of formula 2:

wherein:

theta is the attachment site to formula 1,

R₄and R₅Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts;

R₂a metal salt selected from-H, alkyl, alkanediylalkoxy, a metal salt having a Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cation, an amine cation salt, and a structure of formula 3:

wherein:

theta is the attachment site to formula 1,

R₆and R₇Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts; and is

n is an integer from 1 to 22; and is

R₃Selected from the group consisting of-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts,

In one embodiment, at least one monomer used to form the polymer comprises a phosphono-phosphate group. In another embodiment, at least one monomer used to form the polymer comprises an anionic group. In another embodiment, at least one monomer used to form the polymer comprises the anionic group, and at least one monomer used to form the polymer comprises the phosphono-phosphate group. In another embodiment, the phosphono-phosphate groups are added during post-polymerization modification.

In one embodiment of the polymer, R₁、R₂And R₃Independently selected from the group consisting of H, Na salts and K salts. In one embodiment of the polymer, R₁、R₂And R₃Independently selected from the group consisting of H, Na salts, K salts, Zn salts, Ca salts, Sn salts, and amine cation salts.

In another embodiment of the polymer, R₁Has the structure of formula 2. In another embodiment of the polymer, R₁Has the structure of formula 2, and R₄And R₅Independently selected from the group consisting of H, Na salts and K salts. In another embodiment of the polymer, R₁Has the structure of formula 2, and R₄And R₅Independently selected from the group consisting of H, Na salts, K salts, Zn salts, Ca salts, Sn salts, and amine cation salts.

In another embodiment of the polymer, R₂Has the structure of formula 3. In another embodiment of the polymer, R₂Has a structure of formula 3, and n is an integer of 1 to 3. In another embodiment of the polymer, R₂Has the structure of formula 3, and n is 1. In the polymerization ofIn another embodiment of this invention, R₂Has the structure of formula 3, and R₆And R₇Independently selected from the group consisting of H, Na salts and K salts. In another embodiment of the polymer, R₂Has the structure of formula 3, and R₆And R₇Independently selected from the group consisting of H, Na salts, K salts, Zn salts, Ca salts, Sn salts, and amine cation salts. In another embodiment of the compounds, R₂Has the structure of formula 3, and R₆And R₇Independently selected from the group consisting of H, Na salts, K salts, Zn salts, Ca salts, Sn salts, and amine cation salts, and n is 1.

In one embodiment, when the at least one monomer used to form the polymer comprises the phosphono-phosphate group, said at least one monomer has the structure of formula 4:

wherein:

β is the site of attachment to the phosphono-phosphate group of formula 1;

R₈is selected from-H and-CH₃；

L₁A structure selected from the group consisting of a bond, an aryldiyl, and formula 5:

wherein:

α is the attachment site to the alkenyl group in formula 4;

β is the site of attachment to the phosphono-phosphate group of formula 1;

x is selected from the group consisting of structures in formulas 6 to 12;

wherein:

R₉selected from-H, alkyl_(C1-8)Phosphonoalkyl and phosphono (phospho) alkyl; and Y is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl.

In one embodiment, when at least one of the monomers used to form the polymer comprises a phosphono-phosphate group and has the structure of formula 4, R of formula 4₈Is H. In one embodiment, when the at least one monomer used to form the polymer comprises a phosphonyl-phosphate group and has the structure of formula 4, R of formula 4₈Is CH₃。

In one embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group and the at least one monomer has the structure of formula 4, L₁In another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group and the at least one monomer has the structure of formula 4, L₁Having the structure of formula 5 in another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer has the structure of formula 4, and L₁Having the structure of formula 5, the structure of X is selected from the group consisting of formula 6, formula 9, and formula 11 in another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer having the structure of formula 4, and L₁In another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer has the structure of formula 4, and L₁In another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer has the structure of formula 4, and L₁When the structure of formula 5 is provided, X has the structure of formula 9. In another embodiment, when the at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer comprises a phosphono-phosphate groupOne monomer has the structure of formula 4, and L₁In another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer has the structure of formula 4, and L₁Having the structure of formula 5, X has the structure of formula 6, and Y is an alkanediyl group in another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer having the structure of formula 4, and L₁Having the structure of formula 5, X has the structure of formula 7 and Y is selected from the group consisting of alkanediyl and alkoxydiyl in another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer having the structure of formula 4, and L₁Having the structure of formula 5, X has the structure of formula 9, and Y is an alkanediyl group in another embodiment, when at least one monomer used to form the polymer comprises a phosphono-phosphate group, the at least one monomer having the structure of formula 4, and L₁When having the structure of formula 5, X has the structure of formula 11, and Y is an alkanediyl group.

In one embodiment, when at least one monomer used to form the polymer comprises an anionic group, the at least one monomer further comprises an alkenyl group having the structure of formula 13:

wherein:

R₁₀is selected from H or CH₃And L₂Is a linking group attached to the anionic group.

In one embodiment, when at least one monomer used to form the polymer comprises an anionic group, the at least one monomer further comprises an alkenyl group having the structure of formula 14:

wherein:

R₁₁selected from H and alkyl;

is a site of attachment to the anionic group;

L₃a structure selected from the group consisting of a bond, an aryldiyl, and formula 15;

wherein:

γ is the attachment site to the alkenyl group;

is a site of attachment to the anionic group;

w is selected from structures in formulas 16-22:

wherein:

R₁₂selected from-H and alkyl_(C1-8)(ii) a And is

V is selected from alkanediyl, alkoxydiyl, alkylaminodiyl or alkenediyl.

In one embodiment, when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14, R₁₁Is H. In another embodiment, when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14, R₁₁Is CH₃In another embodiment, L when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14₃Is a covalent bond. In another embodiment, when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14, R₁₁Is H and L₃Is a covalent bond. In another embodiment, when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14, R₁₁Is CH₃And L₃Is a covalent bond.

In one embodiment, L when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14₃In another embodiment, L when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14, 8915₃In another embodiment, L when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14, the at least one monomer comprises a carboxylic acid group having the structure of formula 15 and W has the structure of formula 19₃Has the structure of formula 15 and W has the structure of formula 21. In one embodiment, when used to formL when at least one monomer of the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14₃Having the structure of formula 15 and W has the structure of formula 16 and V is an alkanediyl group in another embodiment, when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14, L₃Having the structure of formula 15 and W has the structure of formula 19 and V is an alkanediyl group in another embodiment, when at least one monomer used to form the polymer comprises an anionic group and the at least one monomer further comprises an alkenyl group having the structure of formula 14, L₃Has the structure of formula 15 and W has the structure of formula 21 and V is an alkanediyl group.

Another embodiment of the invention is a novel polymer, which in this context is intended to include oligomers such as dimers, trimers and tetramers. The polymer comprises a phosphono-phosphate group and an anionic group, having the structure of formula 23:

wherein:

R₁a metal salt selected from the group consisting of-H, alkyl, alkanediylalkoxy, a metal salt having a Na, K, Ca, Mg, Mn, Zn, Fe, or Sn cation, an amine cation salt, and a structure of formula 2:

wherein:

theta is the attachment site to formula 23,

R₄and R₅Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts;

R₂selected from-H, alkyl, alkanediylalkoxy, with Na, K, Ca, Mg, Mn, Zn, Fe or SA metal salt of an n cation, an amine cation salt, and a structure of formula 3:

wherein:

theta is the attachment site to formula 23,

R₆and R₇Independently selected from-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts; and is

n is an integer from 1 to 22; and is

R₃Selected from the group consisting of-H, alkyl, alkanediylalkoxy, metal salts with Na, K, Ca, Mg, Mn, Zn, Fe or Sn cations, and amine cation salts,

R₈is selected from-H and-CH₃；

L₁A structure selected from the group consisting of a bond, an aryldiyl, and formula 5:

wherein:

α is a point of attachment to the polymer backbone;

β is the site of attachment to the phosphono-phosphate;

x is selected from the group consisting of structures in formulas 6 to 12;

wherein:

R₉selected from-H, alkyl_(C1-8)Phosphonoalkyl and phosphono (phospho) alkyl; and is

Y is selected from the group consisting of alkanediyl, alkoxydiyl, alkylaminodiyl and alkenediyl;

R₁₁is selected from-H and-CH₃；

Is a site of attachment to the anionic group;

L₃a structure selected from the group consisting of a bond, an aryldiyl, and formula 15;

wherein:

γ is a linkage site to the polymer backbone;

is a site of attachment to the anionic group;

w is selected from structures in formulas 16-22:

wherein:

R₁₂selected from-H and alkyl_(C1-8)(ii) a And is

V is selected from alkanediyl, alkoxydiyl, alkylaminodiyl or alkenediyl;

R₁₃is a chemical group initiated by the polymer;

R₁₄is a chemical group that causes chain termination;

m is an integer from 2 to 450; and is

p is an integer from 2 to 450.

In another embodiment of the polymer, R₂Has the structure of formula 3. In another embodiment of the polymer, R₂Has a structure of formula 3, and n is an integer of 1 to 3. In another embodiment of the polymer, R₂Has the structure of formula 3, and n is 1. In another embodiment of the polymer, R₂Has the structure of formula 3, and R₆And R₇Independently selected from the group consisting of H, Na salts and K salts. In another embodiment of the polymer, R₂Has the structure of formula 3, and R₆And R₇Independently selected from the group consisting of H, Na salts, K salts, Zn salts, Ca salts, Sn salts, and amine cation salts. In another embodiment of the compounds, R₂Has the structure of formula 3, and R₆And R₇Independently selected from the group consisting of H, Na salts, K salts, Zn salts, Ca salts, Sn salts, and amine cation salts, and n is 1.

In one embodiment of the polymer, R₈Is H. In another embodiment, R₈Is CH₃。

In one embodiment of the polymer, L₁Is a covalent bond, in another embodiment, L₁Having the structure of formula 5. in another embodiment, L₁Has a structure of formula 5, and the structure of X is selected from the group consisting of formula 6, formula 9, and formula 11. At another placeIn one embodiment, L₁Having the structure of formula 5, X has the structure of formula 6, in another embodiment, L₁Having the structure of formula 5, X has the structure of formula 7, in another embodiment, L₁Having the structure of formula 5, X has the structure of formula 9, in another embodiment, L₁Having the structure of formula 5, X has the structure of formula 11, in another embodiment, L₁Having the structure of formula 5, X has the structure of formula 6, and Y is an alkanediyl radical, in another embodiment, L₁Having the structure of formula 5, X has the structure of formula 7, and Y is selected from the group consisting of alkanediyl and alkoxydiyl in another embodiment, L₁Having the structure of formula 5, X has the structure of formula 9, and Y is an alkanediyl radical, in another embodiment, L₁Has the structure of formula 5, X has the structure of formula 11, and Y is an alkanediyl group.

In one embodiment of the polymer, the anionic group is selected from phosphate, phosphonate, sulfate, sulfonate or carboxylate. In another embodiment, the anionic group is a sulfonate. In another embodiment, the anionic group is a carboxylate. In another embodiment, the anionic group is phosphonate.

In one embodiment of the polymer, R₁₁Is H. In another embodiment, R₁₁Is CH₃In another embodiment, L₃Is a covalent bond. In another embodiment, R₁₁Is H, and L₃Is a covalent bond. In another embodiment, R₁₁Is CH₃And L₃Is a covalent bond.

In one embodiment, L₃Having the structure of formula 15 and W has the structure of formula 16 in another embodiment, L₃Having the structure of formula 15, and W has the structure of formula 19 in another embodiment, L₃Having the structure of formula 15, and W has the structure of formula 21 in one embodiment, L₃Having the structure of formula 15, and W has the structure of formula 16, and V is an alkanediyl, in another embodiment, L₃Having the structure of formula 15, and W has the structure of formula 19, and V is an alkanediyl, in another embodiment, L₃Has the structure of formula 15, and W has the structure of formula 21, and V is an alkanediyl group.

In one embodiment of the compound, the chemical group R is derived from polymer initiation₁₃A structure selected from formula 24 to formula 28:

wherein:

R₁₅selected from-H, Na, K and amine cation salts;

τ is the attachment site to the polymer backbone; and is

Q is the non-olefinic residue of the monomer used for polymerization.

In another embodiment, Q has the structure of formula 29:

wherein L₁、R₁、R₂And R₃As previously described, and κ represents the attachment site to formula 28.

In another embodiment, Q has the structure of formula 30:

wherein L₃And as described previously, and κ represents the attachment site to formula 28.

In another embodiment, Q is phosphono-phosphate. In another embodiment, Q is sulfonate. In another embodiment, Q is phosphonate.

In one embodiment of the compound, the chemical group R is generated by polymer termination₁₄Is selected from-H. Chemical groups R resulting from termination of the polymer in one embodiment of the compound₁₄To have a head pairAnother polymer chain attached to the head.

In a preferred embodiment of the compounds, R₁、R₂And R₃Independently selected from the group consisting of H, Na salts, K salts, and amine cation salts, R₈Is H, L₁Being a covalent bond, L₃Is a covalent bond, the anionic group is a sulfonate group, R₁₃Is a structure of formula 28, Q is a structure of formula 29 or formula 30, and R₁₄Is H.

Process for preparing polymers

Embodiments of the invention can be made using these general methods as follows.

The polymers of the present invention may be prepared by a variety of techniques, including bulk, solution, emulsion or suspension polymerization. The polymerization method and techniques for polymerization are outlined in Encyclopedia of Polymer science and Technology (Interscience Publishers, New York) volume 7, page 361-. General reaction techniques suitable for use in the present invention are also described in preparation Methods of Polymer chemistry, 2 nd edition (Interscience Publishers, New York, 1968) at pages 248-251 of Sorenson, W.P. and Campbell, T.W., which are incorporated herein by reference. In one example, the polymer is prepared by free radical copolymerization using a water soluble initiator. Suitable free radical initiators include, but are not limited to, thermal initiators, redox pairs, and photochemical initiators. Redox and photochemical initiators may be used for the polymerization process initiated at temperatures below about 30 ℃. Such initiators are summarized in Kirk-Othmer Encyclopedia of Chemical Technology 3 rd edition (John Wiley & Sons, New York) volume 13, page 355-373 (1981), which is incorporated herein by reference. Typical water-soluble initiators that can provide free radicals at temperatures of 30 ℃ or less include redox couples such as potassium persulfate/silver nitrate, and ascorbic acid/hydrogen peroxide. In one example, the method uses a thermal initiator during the polymerization carried out at above 40 ℃. Water soluble initiators that can provide free radicals at temperatures of 40 ℃ or higher can be used. These include, but are not limited to, hydrogen peroxide, ammonium persulfate, and 2,2' -azobis (2-amidinopropane) dihydrochloride. In one example, the water-soluble starting monomer is polymerized in water at 60 ℃ using ammonium persulfate as an initiator.

The type of chemical functional group at the end of a linear polymer depends on how the polymerization of the polymer chain is initiated and terminated. For free radical polymerization, any free radical in the system can start a new chain. The free radical may be a direct derivative of the initiator, such as a sulfate group from persulfate salts, or an alkyl group from azo-type initiators (such as, but not limited to, 2' azobis (2-amidinopropane) dihydrochloride). The free radical may also be the result of a transfer reaction, for example between water and another free radical to produce a hydroxyl radical or between phosphate and another free radical to produce a phosphate radical. Non-limiting examples of these resulting structures are given below, where R represents H or a suitable counterion such as Na, K or an amine, and τ represents the attachment site to the polymer.

Free radicals can also be the result of chain transfer reactions, where a free radical is transferred from a growing polymer chain to start a new chain. Chain transfer has been specifically noted in the polymerization of vinylphosphonate monomers.Et al, Macromolecules, Vol.41, p.1634-1639 (2008), which is incorporated herein by reference, describe how polymerization of alkyl esters of vinylphosphonates results in chain transfer on the alkyl group. The transfer eventually begins with a new polymer chain having an olefin-containing chemical group at the beginning. Strand transfer stops the growth of one strand and starts a new strand.

In the phosphono-phosphate containing polymers, vinyl CH is observed in the final polymer composition₂A group. Assuming these vinyl groupsThe clusters are formed by one of two mechanisms. The first mechanism isPhenomena similar to those observed, however similar toIn contrast, the olefin is not from the alkyl ester of the phosphonate, but may be from a vinyl monomer on the newly initiated chain. Without wishing to be bound by theory, the following scheme is given as a possible pathway by which chain transfer can produce an olefin at the initiation site of a universal free radical polymerizable monomer, where for clarity the non-olefin portion of the monomer is described simply as Q. Q may represent any number of chemical functional groups and is not limited to a single chemical entity. Olefin end-capping groups based on vinylphosphonate and vinylphosphonyl-phosphate have been observed.

The second mechanism for introducing vinyl groups involves a back-biting reaction and β cleavage, which has been widely indicated in the literature for acrylate polymers β generates vinyl groups and primary radicals upon cleavage.

Using the nomenclature used previously to denote the site of attachment to the polymer by τ, the initial functional group can be written as follows it should be noted that chain transfer and back-biting and subsequent β cleavage mechanisms will produce a vinyl group with two protons on the same carbon atom.

The chemical groups on the ends of the polymer chains depend on how the chains are terminated. The most common termination is the chain transfer and back-biting reactions mentioned above, as well as combinations and disproportionations. In chain transfer and reverse cleavage, the terminal group is usually hydrogen. In combination, the chain propagating radicals on both chains react to form a new chain. This reaction results in a "head-to-head" configuration at the point of attachment.

In disproportionation, hydrogen is exchanged from one radical chain to another. The result is that one chain is unsaturated and the other chain is saturated. Note that the resulting unsaturated group is not a vinyl group. The unsaturated group has only one hydrogen per carbon.

Polymers comprising phosphono-phosphate groups and anionic groups may have phosphono-phosphate groups and anionic groups attached directly to the polymer side groups or side chains, but not on the polymer backbone. The phosphono-phosphate groups can be incorporated into the polymer by addition of the phosphono-phosphate groups by polymerization of monomers having phosphono-phosphate groups, or by polymerization of monomers not having phosphono-phosphate groups and subsequent post-polymerization modification of the resulting polymer. Similarly, anionic groups can be incorporated into the polymer by polymerization of monomers having anionic groups, or by addition of anionic groups by polymerization of monomers having no anionic groups followed by post-polymerization modification of the resulting polymer. The examples in the subsequent paragraphs will describe different methods of incorporating phosphono-phosphate groups into polymers, where anionic groups are introduced as comonomers or as a result of incomplete reaction of the phosphonate when attempting to form phosphono-phosphate groups. This section will not describe all possible anionic monomers nor the various methods of introducing anionic groups into the polymer after polymerization, as they are well known to those skilled in the art.

As an example of a polymer comprising phosphono-phosphate groups attached to the polymer backbone, consider a polymer made from monomeric vinyl phosphonate or methyl-vinyl phosphonate. The vinyl phosphonate or methyl-vinyl phosphonate can be chemically reacted to form the phosphono-phosphate monomer as shown in reaction 1 in scheme 1. These phosphono-phosphate-containing monomers can then be copolymerized with anionic group-containing monomers, as shown in reaction 2 of the same scheme, to give phosphono-phosphate-containing polymers having phosphono-phosphate groups directly attached to the polymer backbone. Alternatively, the vinylphosphonate or methyl-vinylphosphonate may first be copolymerized as shown in reaction 3 to give the polymer. After polymerization, the phosphono-phosphate groups can be produced by post-polymerization modification by reacting the attached phosphonate moieties as shown in reaction 4, thereby producing phosphono-phosphate groups directly attached to the polymer backbone.

The second way of producing phosphono-phosphate groups and anionic groups directly attached to the backbone by post-polymerization modification can be illustrated by starting from polyethylene. See m.anbar, g.a.st.john and a.c Scott, J Dent Res, vol 53, No. 4, p.867-878, 1974 for an example of the first reaction in such modifications. As shown in scheme 2, the polyethylene is first oxidized with oxygen and PCl₃Oxidative phosphorylation is performed to form a random phosphonated polymer. The phosphonated polymer may then be modified to produce a randomly substituted phosphono-phosphate/phosphonate polymer. The reaction products shown are intended to show the random nature of the attachment points of the phosphonate groups and the phosphono-phosphate groups in the resulting polymer. The phosphonate groups are anionic.

As an example of preparing a polymer having phosphono-phosphate groups attached to pendant groups, consider the vinylbenzyl Chemistry shown in scheme 3. 4-vinylbenzyl chloride can be reacted with diethylphosphite to form vinylbenzyl phosphonate as shown in reaction 1 of scheme 3. for an example of this reaction, see Frantz, Richard, Durand, Jean-Olivier, Carre, Francis; L anneau, Gerard F.; L e Bideau, Jean; Alonso, Bruno; Massiot, Dominique, Chemistry-A European Journal, Vol.9, Vol.3, p.770-775, p.2003. vinylbenzyl phosphonate can be reacted to form vinylbenzyl-phosphono phosphate as shown in reaction 2. this monomer can then be copolymerized to form the polymer containing phosphono-phosphate and alternative anions shown in reaction 5, where the phosphono-phosphate groups are attached to the pendant groups, where polymer is modified by polymerization of phosphonic acid groups, see, e.7. after polymerization of phosphonic acid groups, see polymer having phosphono-benzyl chloride groups attached to the pendant groups, see, Bucky-benzyl phosphonate, reaction, JUN-phosphonic acid groups, see, JUN, 7, where the polymer can be reacted to form a polymer shown in reaction to form a polymer having pendant groups, where the pendant groups, shown in reaction, see, 7, where the polymer shown in reaction, 7, 5, where the polymer having pendant groups, 5, where the pendant groups, 7, where the pendant groups can be reacted to produce a polymer can be polymerized to produce a polymer having pendant groups, where the polymer can.

As a first example of a polymer comprising a phosphono-phosphate group attached to a side chain, consider the polyethylene glycol (PEG) side chain shown in scheme 4. The phosphonate containing PEG chain can be reacted with acryloyl chloride to produce an acrylate with PEG terminated phosphonate. After the reaction to produce the phosphono-phosphate, the phosphono-phosphate monomer may be copolymerized with the anion-containing monomer to produce the phosphono-phosphate and anion-containing polymer, wherein the phosphono-phosphate is attached to the side chains of the polymer.

As a second example of a polymer comprising phosphono-phosphate groups attached to side chains, consider the polyvinyl alcohol shown in scheme 5. The hydroxyl groups can be reacted with ethylene oxide to produce a polymer with PEG side chains. The capped hydroxyl groups on the side chains can be reacted with vinyl phosphonate groups and then partially reacted to form a phosphono-phosphate/phosphonate polymer. Thus, this example describes phosphono-phosphate-containing polymers in which the phosphono-phosphate is attached to the side chains of the polymer and added via post-polymerization modification. The phosphonate is an anionic group.

The schemes are not intended to be exhaustive in nature, but are intended to convey the various ways in which the phosphono-phosphate-containing and anionic polymers can be produced. These examples provide synthetic technical details and numerous variations of polymers containing phosphono-phosphate and anionic groups, including polymers in which the phosphono-phosphate groups are directly attached to the polymer backbone and polymers in which the phosphono-phosphate groups are attached to side groups. For additional examples of phosphonate containing monomers and polymers that can be converted to phosphonate containing monomers and polymers, see Sophie Monge, Benjamin Canicini, Ghislain David and Jean-Jacques Robin, RSC Polymer Chemistry Series No.11, Phosphorus-base polymers: From Synthesis to Applications, edited by Sophie Monge and Ghislain David, The Royal Society of Chemistry 2014, published by Royal Society of Chemistry www.rsc.org.

Use of polymers containing phosphono-phosphate groups

The phosphono-phosphate containing polymers according to the present invention can be incorporated into a variety of compositions. These compositions include both aqueous and non-aqueous compositions. These compositions are useful for treating teeth, hair, body, fabric, paper, non-wovens, and hard surfaces. These compositions are useful in water treatment, boiler treatment, treating ship hulls, oil wells, batteries, baking, fermentation, ceramics, plastic stabilizers, glass making, cheese making, buffering agents in food, abrasives in dentifrices, binders in meat, coffee creamer, antifreeze, dispersants in paint liquid soaps, metal cleaners, synthetic rubbers, textiles, and flame retardants. These compositions may also be used to treat materials containing polyvalent metal cations including, but not limited to, calcium, tin, magnesium, and iron. Examples of such materials include hydroxyapatite, calcium carbonate (amorphous, calcite, aragonite), calcium phosphate, calcium hydroxide, magnesium carbonate, magnesium phosphate, soap scum (a mixture of calcium, magnesium and iron salts of stearic acid and carbonates), and hard water stains. In one embodiment, the composition comprising the phosphono-phosphate containing polymer is non-aqueous. In another embodiment, the composition is aqueous.

The phosphono-phosphate containing compounds and polymers can be applied to a variety of substrates. Embodiments of the substrate include biomaterials, textiles, nonwovens, paper products, and hard surface materials. In one embodiment, the biological material comprises teeth. In another embodiment, the biological material comprises keratin, such as hair or skin.

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