Polymer Schiff bases with ketone resins

Abstract

In some aspects, the polymer is represented by formula (VII): # imgabs0 # wherein: R5 and R8 are each independently hydrogen or-CH2OH; r6, R7, R6 ', R7', R5 ', R5' ', R8' and R8 ''are each independently a bond, aryl, alkyl, cycloalkyl or heteroaryl, wherein R6 and R7, R6 'and R7', R5 'and R5'' and R8' and R8 ''may be independently combined to form a cycloalkyl ring or aryl ring; q1 ''and Q1'' 'are each independently oxygen, sulfur, or # imgabs1 # R9, R10, and R11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl, or heteroaryl, Q1 and Q1 'are each independently oxygen or sulfur, x is a positive integer, z is 0 or a positive integer, and x + z is such that the polymer represented by Formula (VII) has a molecular weight of about 400 g / mol to about 20,000 g / mol.

Description

[0001] Related Applications

[0002] This application claims the benefit of and priority to U.S. Patent Application No. 63 / 452,322 filed on March 15, 2023 and Indian Patent Application No. 202211058873 filed on October 14, 2022, the entire contents of which are incorporated herein by reference.

[0003] Government funding

[0004] This invention was made with Government support under Grant No. W912HQ-21-C-0067 awarded by the Department of Defense. The Government has certain rights in this invention. Technical Field

[0005] Aspects of the invention relate to Schiff base polymers and methods of making the same. Background Art

[0006] Polymers can be used to prevent corrosion of metal surfaces (e.g., steel). Such polymeric materials can be applied as coatings to act as a barrier between a substrate and an external corrosive environment. However, simply applying a coating does not necessarily provide long-term corrosion protection, because a number of different variables (e.g., coating adhesion and hydrophobicity / hydrophilicity) may affect the rate and extent of corrosion of the metal substrate. In addition, some coating systems have received attention regarding their potential environmental impacts (e.g., toxic chemical composition, product life, and volatile organic content (VOC) requirements).

[0007] In some cases, these and other potential problems can be addressed by including reinforcing additives, flakes and particles. The addition of such materials not only improves the overall physical properties of the polymer, but they also increase the total amount of chemical components involved in producing sufficient coatings. In addition, including such additives in the coating composition can increase the tortuosity of the final coating, thereby improving the ability of the coating to resist the invasion of the surrounding acidic environment into the substrate. However, the addition of such materials may have an adverse effect on its intended application, such as increased brittleness and cost.

[0008] Therefore, there is a need for improved corrosion protection materials and methods. Summary of the invention

[0009] In some aspects, the polymer is represented by formula (VII):

[0010]

[0011] in:

[0012] R 5 and R 8 Each is independently hydrogen or -CH2OH;

[0013] R 6 , R 7 , R 6’ , R 7’ , R 5’ , R 5” , R 8’ and R 8” are each independently a bond, an aryl group, an alkyl group, a cycloalkyl group or a heteroaryl group, wherein R 6 and R 7 , R 6’ and R 7’ , R 5’ and R 5” and R 8’ and R 8” can independently combine to form a cycloalkyl ring or an aryl ring;

[0014] Q 1” and Q 1”’ are independently oxygen, sulfur or

[0015] R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl;

[0016] Q 1 and Q 1’ each independently is oxygen or sulfur;

[0017] x is a positive integer, z is 0 or a positive integer, x+z is such that the polymer represented by formula (VII) has a molecular weight of about 400 g / mol to about 20,000 g / mol, and is a block copolymer or a random copolymer.

[0018] In some aspects, the method of forming a polymer comprises introducing formaldehyde with a ketone to form an intermediate polymer, and then treating the intermediate polymer with a carbohydrazide / semicarbazide represented by the formula:

[0019] Where Q 1” is oxygen or sulfur, and R 15’ , R 16’ and R 17’ Each is independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl.

[0020] In some aspects, the polymer is represented by formula (XXV):

[0021]

[0022] in:

[0023] R1 is aryl, alkyl, cycloalkyl or heteroaryl;

[0024] R 10 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl;

[0025] R 8 and R 9 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl;

[0026] R 11 and R 13 Each is independently hydrogen or represented by the following formula:

[0027]

[0028] R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 2’ , R 3’ , R 4’ , R 5’ , R 6’ , R 7’ are each independently aryl, alkyl, cycloalkyl or heteroaryl, wherein R 2 and R 3 , R 4 and R 5 , R 6 and R 7 , R 2’ and R 3’ , R 4’ and R 5’ and R 6’ and R 7’ can independently combine to form a cycloalkyl ring or an aryl ring;

[0029] R 16 and R 16’ Each is independently hydrogen or -CH2OH;

[0030] Q 1 , Q 2 , Q 2’ and Q 4 each independently is oxygen or sulfur;

[0031] Q 3 , Q 3’ , Q 6 and Q 6’ are independently oxygen, sulfur or Where Q 1’are each independently oxygen or sulfur, and R 14 , R 15 and R 16 are each independently hydrogen, aryl, alkyl, cycloalkyl or heteroaryl,

[0032] n and n' are each independently a positive integer;

[0033] m and m' are each independently 0 or a positive integer, and

[0034] The polymer represented by formula (XXV) is a block copolymer or a random copolymer. DETAILED DESCRIPTION

[0035] Recent advances in materials and polymer science have shown that the implementation of certain chemical additives that are able to interact with potential corrosion sites provides promising results in inhibiting corrosion without the need for reinforcing additives, flakes and particles. As a result, Schiff base organic compounds are widely considered to be excellent corrosion inhibitors for metal substrates such as mild steel. Without being bound by theory, these inhibitors work through an adsorption mechanism on the metal surface, thereby blocking potential corrosion sites.

[0036] In some cases, it may be advantageous to chemically link a Schiff base organic compound to a polymer used in a coating composition to eliminate the use of additive materials. Although attempts have been made to do so, many existing Schiff base polymers are low molecular weight, linear, and contain functional groups typically as part of the backbone, all of which limit the accessibility of the polymer to metal surfaces having significant contours.

[0037] Therefore, there is a need to develop new Schiff base polymers and methods of forming the same for corrosion inhibition of metal surfaces, such that the polymers have high molecular weight, are optionally linear, and have pendant functional groups.

[0038] Aspects of the present invention relate to Schiff base polymers and methods for preparing the same. It has been found that ketone resins can be functionalized to form Schiff bases providing hanging functional groups, thereby providing high molecular weight polymers. Functional groups can be spaced apart from each other, which is advantageous because polar functional groups close together tend to associate with other polar functional groups, which promotes polymer aggregation, thereby reducing metal surface coverage. The spaced apart functional groups remain close to the metal surface, and also reduce the cost of the entire polymer, because the advantageous functional groups are more effectively utilized. Along with solvent evaporation during polymer application to a metal substrate, using a high molecular weight polymer (i.e., for example, about 400 g / mol to about 20,000 g / mol) also provides a faster viscosity build, which reduces sagging or dripping of a polymer layer disposed on a metal substrate.

[0039] For post-polymerization modification of Schiff base polymers

[0040] In general, post-polymerization modifications offer certain advantages for the production of polymeric materials, such as, but not limited to, the ability to formulate polymers composed of sensitive monomers, the ability to attach identification tags or tracers to polymers, and the ability to develop new polymers with different structures and chemical compositions.

[0041] The polymer for post-polymerization modification may include any one or more reactive functional groups along the polymer backbone.The polymer for post-polymerization modification includes one or more functional groups of ketone, aldehyde, or a combination thereof along the polymer backbone.

[0042] The polymeric Schiff bases are synthesized by post-polymerization modification. In this case, at least one ketone-containing polymer is contacted with one or more thiosemicarbazide molecules in the presence of a catalytic amount of an acid catalyst to form a polymer having one or more Schiff base moieties.

[0043] In some aspects, the ketone polymer subjected to post-polymerization modification is represented by Formula (I):

[0044]

[0045] in:

[0046] R1 and R 4 are each independently aryl, alkyl, cycloalkyl or heteroaryl;

[0047] R 2 and R 3 Each is independently aryl, alkyl, cycloalkyl, heteroaryl, a bond, or may be combined to form a cycloalkyl ring or an aryl ring;

[0048] Q 1 is oxygen or sulfur; and

[0049] n is a positive integer greater than 1 and about 30.

[0050] n of formula (I) may be a positive integer greater than 1, such as about 1.1 to about 30, such as about 5 to about 30, such as about 10 to about 30, such as about 15 to about 30, such as about 20.

[0051] R of formula (I) 2 and R 3 They may be combined to form a cycloalkyl ring or an aryl ring.

[0052] R of formula (I) 2 may be a bond, and R of formula (I) 3 Can be selected from any one or more of the following:

[0053]

[0054]

[0055] The Mw of the ketone polymer of formula (I) as determined by gel permeation chromatography (GPC) can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. In one or more aspects, the PDI of the ketone polymer of formula (I) as determined by GPC can be from about 1.01 to about 5.0, such as from about 1.1 to about 4, such as from about 1.5 to about 3.5, such as from about 2 to about 3.

[0056] The glass transition temperature (Tg) of the ketone polymer of formula (I) as determined by differential scanning calorimetry (DSC) may be from about 50°C to about 200°C, such as from about 55°C to about 100°C, such as from about 60°C to about 100°C, such as from about 65°C to about 80°C.

[0057] In some aspects, the ketone polymer subjected to post-polymerization modification is represented by formula (II):

[0058]

[0059] in,

[0060] R 5 , R 6 , R 7 and R 8 Each is independently an aryl group, an alkyl group, a cycloalkyl group, or a heteroaryl group, or can be combined to form a cycloalkyl ring or an aryl ring, wherein R 6 and R 7 can combine to form a cycloalkyl ring or an aryl ring;

[0061] Q 1 is oxygen or sulfur; and

[0062] n is a positive integer greater than 1 and about 30.

[0063] n of formula (II) may be a positive integer greater than 1, such as about 1.1 to about 30, such as about 5 to about 30, such as about 10 to about 30, such as about 15 to about 30, such as about 20.

[0064] R of formula (II) 6 and R 7 Can be combined to form a cycloalkyl ring or an aryl ring, m represents the number of carbon atoms contained in the ring. In some aspects, m is 3 to 30, such as 4 to 20, such as 5 to 10, such as 5 to 7.6 and R 7 In one or more aspects that combine to form a cycloalkyl or aryl ring, the ring may be substituted at any one or more of the corresponding positions, and the substitution is any one or more of alkyl, aryl, cycloalkyl, and heteroalkyl.

[0065] R of formula (II) 6 and R 7 Can be combined to form a cycloalkyl ring, the cycloalkyl ketone is a limonene-derived ketone or a terpene-derived ketone. In at least one aspect, the cycloalkyl ketone is limonene-derived, which is camphor. In at least one aspect, the cycloalkyl ketone is a terpene-derived ketone selected from the group consisting of terpene ketone, leucosesterterpenone, farnesyl acetone, leucosesterlactone, pseudoionone and muqubilone.

[0066] The Mw of the ketone polymer of formula (II) measured by GPC can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. In one or more aspects, the PDI of the ketone polymer of formula (II) measured by GPC can be from about 1.01 to about 5.0, such as from about 1.1 to about 4, such as from about 1.5 to about 3.5, such as from about 2 to about 3.

[0067] The glass transition temperature (Tg) of the ketone polymer of formula (II) as determined by DSC may be about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0068] In some aspects, the post-polymerization modified ketone polymer formed from cyclohexanone and formaldehyde is represented by formula (III):

[0069]

[0070] Among them, R 5 Depend on Indicates that, and R 8 It is -OH.

[0071] The Mw of the ketone polymer of formula (III) determined by GPC can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. In one or more aspects, the PDI of the ketone polymer of formula (III) determined by GPC can be from about 1.01 to about 5.0, such as from about 1.1 to about 4, such as from about 1.5 to about 3.5, such as from about 2 to about 3.

[0072] As described above, polymeric Schiff bases can be synthesized by post-polymerization modification of a ketone polymer contacted with one or more thiosemicarbazides, thiocarbohydrazides, or any suitable thiocarbonyl-containing compound having one or more terminal (-NH2) groups in the presence of a catalytic amount of an acid catalyst to form pendant Schiff base structures along the polymer backbone.

[0073] In one or more aspects, the ketone polymer subjected to post-polymerization modification is contacted with a thiosemicarbazide represented by formula (IV):

[0074]

[0075] in:

[0076] Q 1 is oxygen or sulfur; and

[0077] R 9 , R 10 and R 11 Each is independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl.

[0078] The ketone polymer subjected to post-polymerization modification is contacted with a thiosemicarbazide of formula (IV) represented by the following formula:

[0079]

[0080] In some aspects (which may be combined with other aspects of this document), the post-polymerization modification reaction (PPM) is carried out as a solution phase reaction or a bulk phase reaction, comprising contacting a ketone polymer with one or more thiosemicarbazide molecules in the presence of a catalytic amount of an acid catalyst. When the PPM is carried out as a solution phase, the reaction can be carried out in any one or more solvents.

[0081] Typically, the equivalent ratio of reactants in a PPM reaction is determined relative to the functional equivalents of the ketone polymer, wherein the functional equivalents of the ketone polymer can be determined by any one or more suitable quantitative spectroscopic techniques (i.e., nuclear magnetic resonance spectroscopy (NMR)). For example, and without being bound by theory, if the ketone polymer is undergoing a PPM reaction with a thiosemicarbazide, the functional equivalent ratio will be determined as the number of ketone moieties input relative to the number of -NH-NH2 inputs. In one or more aspects, the equivalent ratio of ketone to -NH-NH2 used in the PPM reaction can be from about 100:1 to about 1:100, such as from about 75:1 to about 1:75, such as from about 50:1 to about 1:50, such as from about 25:1 to about 1:25, such as from about 10:1 to about 1:10. In at least one aspect, the equivalent ratio of ketone to -NH-NH2 is about 1:1.

[0082] The equivalent ratio of the ketone to the acid catalyst used in the PPM reaction can be from about 100: 1 to about 1: 100, such as from about 75: 1 to about 1: 75, such as from about 50: 1 to about 1: 50, such as from about 25: 1 to about 1: 25, such as from about 10: 1 to about 1: 10. In at least one aspect, the equivalent ratio of the ketone to -NH-NH2 is about 1: 0.1.

[0083] After the PPM reaction is completed, a Schiff base polymer is produced, which can be represented by formula (V):

[0084]

[0085] in:

[0086] R 1 and R 4 are each independently aryl, alkyl, cycloalkyl or heteroaryl;

[0087] R 2 , R 2 '、R 3 and R 3 ' are each independently a bond, an aryl, an alkyl, a cycloalkyl or a heteroaryl, or are combined to form a cycloalkyl ring or an aryl ring;

[0088] Q 1 each independently is oxygen or sulfur;

[0089] R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl;

[0090] x is the number of repeating units in which the parent ketone is converted to a Schiff base; and

[0091] z is the number of repeating units in which the parent ketone is unreacted.

[0092] R of formula (V) 2 and R 3 and R 2 ' and R 3 ' can be combined to form a cycloalkyl ring or an aryl ring.

[0093] When carrying out the PPM reaction, the order of addition, the rate of addition and the concentration of reactants can be considered, for example, for the purpose of preventing gelation. For example and without being bound by theory, if polyketones are added drop-wise to extremely excessive thiosemicarbazide molecules, the ketone functional group will be consumed in large quantities as a limiting agent (assuming fast reaction kinetics). In this case, the functional average value of each individual molecule will be conducive to forming a hanging Schiff base part. On the contrary, if thiosemicarbazide is added drop-wise to a solution containing a certain amount of polyketones, thiosemicarbazide will be consumed as a limiting agent. If the thiosemicarbazide molecules used in this case provide a reactive functionality of about more than 2, then unwanted side reactions may occur, thereby potentially causing gelation. In some aspects, polyketones are slowly added drop-wise to thiosemicarbazide.

[0094] As a result of the PPM reaction, the conversion of the ketone to the Schiff base can be from about 1% to about 100% conversion (mol %), such as from about 10% to about 95% conversion, such as from about 20% to about 90% conversion, such as from about 30% to about 85% conversion, such as from about 40% to about 80% conversion, such as from about 45% to about 75% conversion, such as from about 50% to about 70% conversion. The percentage conversion of the parent ketone to the Schiff base determines the corresponding values ​​of x and z.

[0095] The Mw of the ketone polymer of formula (V) measured by GPC can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. The PDI of the ketone polymer of formula (V) measured by GPC can be from about 1.01 to about 5.0, such as from about 1.1 to about 4, such as from about 1.5 to about 3.5, such as from about 2 to about 3.

[0096] The ratio of x to z of formula (V) may be from about 1:10 to about 10:1, such as from about 1:7.5 to about 7.5:1, such as from about 1:5 to about 5:1, such as from about 1:2.5 to about 2.5:1. In at least one aspect, the ratio of x to z is from about 1:1 to about 3:1. In at least one aspect, x consists of values ​​from about 10 to about 15, and z consists of values ​​from about 10 to about 15. The Schiff base polymer of formula (V) comprises a main chain framework of at least one of a random copolymer, a block copolymer, an alternating copolymer, or a gradient copolymer. In one or more aspects, the Schiff base polymer of formula (V) is a random copolymer. In one or more aspects, the Schiff base polymer of formula (V) is a block copolymer.

[0097] The glass transition temperature of the Schiff base polymer of formula (V) as determined by GPC may be about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0098] In at least one aspect wherein the conversion of the parent ketone of formula (V) to the Schiff base is 100%, the Schiff base polymer can be represented by the formula:

[0099]

[0100] in:

[0101] R 1 and R 4 are each independently aryl, alkyl, cycloalkyl or heteroaryl, wherein R 2 and R 3 can combine to form a cycloalkyl ring or an aryl ring;

[0102] R 2 and R 3 are each independently a bond, an aryl, an alkyl, a cycloalkyl or a heteroaryl ring, wherein R 2 and R 3 can combine to form a cycloalkyl ring or an aryl ring;

[0103] Q 1 is oxygen or sulfur;

[0104] R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl; and

[0105] n is a positive integer greater than 1, and is the sum of x and z.

[0106] In some aspects, the Schiff base polymer produced via the PPM reaction can be represented by Formula (VI):

[0107]

[0108] in:

[0109] R 5 , R 6 , R 6’ , R 7 , R 7’ and R 8 Each is independently an aryl, alkyl, cycloalkyl or heteroaryl ring, wherein R 6 and R 7 and R 6’ and R 7’ can combine to form a cycloalkyl ring or an aryl ring;

[0110] Q 1 each independently is oxygen or sulfur;

[0111] R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl;

[0112] x is the number of repeating units in which the parent ketone is converted to a Schiff base; and

[0113] z is the number of repeating units in which the parent ketone is unreacted.

[0114] R of formula (VI) 6 and R 7 They may be combined to form a cycloalkyl ring or an aryl ring, and m represents the number of carbon atoms contained in the ring. m in formula (VI) may be 3 to 30, such as 4 to 20, such as 5 to 10, such as 5 to 7. R in formula (VI) 6 and R 7 The groups may be combined to form a cycloalkyl ring or an aryl ring, the ring may be substituted at any one or more corresponding positions, and the substitution is any one or more of alkyl, aryl, cycloalkyl and heteroalkyl.

[0115] R of formula (VI) 6 and R 7 Can be combined to form a cycloalkyl ring, the cycloalkyl ketone is a limonene-derived ketone or a terpene-derived ketone. In at least one aspect, the cycloalkyl ketone is limonene-derived, which is camphor. In at least one aspect, the cycloalkyl ketone is a terpene-derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene ketone, pseudoionone and muqubilone.

[0116] The conversion of the parent ketone of formula (VI) to the Schiff base can be from about 1% to about 100% conversion, such as from about 10% to about 95% conversion, such as from about 20% to about 90% conversion, such as from about 30% to about 85% conversion, such as from about 40% to about 80% conversion, such as from about 45% to about 75% conversion, such as from about 50% to about 70% conversion. The percentage conversion of the parent ketone to the Schiff base determines the corresponding values ​​of x and z.

[0117] The Mw of the ketone polymer of formula (VI) determined by GPC can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. The PDI of the ketone polymer of formula (VI) determined by GPC can be from about 1.01 to about 5.0, such as from about 1.1 to about 4, such as from about 1.5 to about 3.5, such as from about 2 to about 3.

[0118] The ratio of x to z of formula (VI) can be from about 1:10 to about 10:1, such as from about 1:7.5 to about 7.5:1, such as from about 1:5 to about 5:1, such as from about 1:2.5 to about 2.5:1. In at least one aspect, the ratio of x to z is from about 1:1 to about 3:1. In at least one aspect, n consists of values ​​from about 10 to about 15, and m consists of values ​​from about 10 to about 15. The Schiff base polymer of formula (VI) comprises a main chain framework of at least one of a random copolymer, a block copolymer, an alternating copolymer, or a gradient copolymer. In one or more aspects, the Schiff base polymer of formula (VI) is a random copolymer. In one or more aspects, the Schiff base polymer of formula (VI) is a block copolymer.

[0119] The glass transition temperature of the Schiff base polymer of formula (VI) as determined by GPC may be about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0120] In at least one aspect wherein the conversion of the parent ketone of formula (VI) to the Schiff base is 100%, the Schiff base polymer can be represented by the formula:

[0121]

[0122] in:

[0123] R 5 , R 6 , R 7 and R8 Each is independently an aryl, alkyl, cycloalkyl or heteroaryl ring, wherein R 6 and R 7 can combine to form a cycloalkyl ring or an aryl ring;

[0124] Q 1 is oxygen or sulfur;

[0125] R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl; and

[0126] n is a positive integer greater than 1 and about 30.

[0127] In at least one aspect, the ketone polymer implemented in the PPM reaction is a cyclohexanone-formaldehyde polymer. In at least one aspect where the conversion of the parent ketone is 100%, the Schiff base polymer derived from the cyclohexanone-formaldehyde polymer can be represented by the following formula:

[0128]

[0129] in:

[0130] R 5 and R 8 is independently an aryl, alkyl, cycloalkyl or heteroaryl ring, and n is a positive integer greater than 1 to about 30.

[0131] In at least one aspect where the conversion of the parent ketone of formula (VI) to the Schiff base is 100%, the Mw measured by GPC can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. In addition, the PDI of the Schiff base polymer of formula (VI) measured by GPC can be from about 1.01 to about 5.0, such as from about 1.1 to about 4, such as from about 1.5 to about 3.5, such as from about 2 to about 3.

[0132] In at least one aspect wherein the conversion of the parent ketone of formula (VI) to the Schiff base is 100%, n consists of values ​​from about 10 to about 15. The Schiff base polymer of formula (VI) can comprise a backbone architecture of at least one of a random copolymer, a block copolymer, an alternating copolymer, or a gradient copolymer. In one or more aspects, the Schiff base polymer is a random copolymer.

[0133] The glass transition temperature of the Schiff base polymer of formula (VI) wherein the conversion of the parent ketone to the Schiff base is 100% may be from about 50°C to about 200°C, such as from about 55°C to about 100°C, such as from about 60°C to about 100°C, such as from about 65°C to about 80°C.

[0134] In some aspects (which may be combined with other aspects herein), the Schiff base polymer is represented by formula (VII):

[0135]

[0136] in:

[0137] R 5 and R 8 Each is independently hydrogen or -CH2OH;

[0138] R 6 , R 7 , R 6’ , R 7’ , R 5’ , R 5” , R 8’ and R 8” are each independently aryl, alkyl, cycloalkyl or heteroaryl, wherein R 6 and R 7 , R 6 ' and R 7’ , R 5’ and R 5” and R 8’ and R 8” can independently combine to form a cycloalkyl ring or an aryl ring;

[0139] R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl;

[0140] Q 1 and Q 1’ each independently is oxygen or sulfur;

[0141] Q 1” and Q 1”’ are independently oxygen, sulfur or Where Q 1’ are each independently oxygen or sulfur, and R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl,

[0142] x is a positive integer, z is 0 or a positive integer, x+z is such that the polymer represented by formula (VII) has a molecular weight of about 400 g / mol to about 2,000 g / mol, and is a block copolymer or a random copolymer.

[0143] In some aspects (which may be combined with other aspects of the present invention), the polymer represented by formula (VII) may include various components. In one or more alternative aspects, R 6 , R 6’ , R 5’ and R 8’ Each is phenyl, R 7 , R 7’ and R 5” Each is a methylene group, and R 8” is methyl or methylene substituted with -CH2OH. In one or more alternative aspects, Q 1 and Q 1’ Each is oxygen, and R 9 , R 10 and R 11 In one or more alternative aspects, R 6 and R 7 , R 6’ and R 7’ , R 5’ and R 5” and R 8’ and R 8” Each can independently combine to form a cycloalkyl ring, such as a cyclohexyl ring.

[0144] The Mw of the ketone polymer of formula (VII) measured by GPC can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. The PDI of the ketone polymer of formula (VII) measured by GPC can be from about 1.01 to about 5.0, such as from about 1.1 to about 4, such as from about 1.5 to about 3.5, such as from about 2 to about 3.

[0145] In some aspects (combinable with other aspects herein), the ratio of x to z of Formula (VII) is from about 0.1:1 to about 1:0.1, or from about 1:1 to about 3:1. In at least one alternative aspect, the value of x is from about 10 to about 15, and the value of m is from about 10 to about 15.

[0146] The glass transition temperature of the Schiff base polymer of formula (VII) as determined by DSC may be about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0147] Formation of Ketone Resins for Schiff Base Separation

[0148] In some aspects (which may be combined with other aspects of the present invention), the Schiff base polymer is formed by contacting a dicarbonyl group (e.g., a diketone or a dialdehyde) with one or more thiocarbazides, thiosemicarbazides, or any suitable thiocarbonyl-containing compound having one or more terminal (-NH2) groups.

[0149] In some aspects that may be combined with other aspects herein, the Schiff base can be represented by formula (VIII):

[0150]

[0151] in:

[0152] Q 1 and Q 1’ each independently is oxygen or sulfur;

[0153] R 12 is aryl, alkyl, cycloalkyl or heteroaryl; and

[0154] R 9 , R 9’ , R 10 , R 10’ , R 11 and R 11’ Each is independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl.

[0155] R of formula (VIII) 12 Can be represented by any one or more of the following:

[0156]

[0157]

[0158] Here, δ is an aliphatic carbon chain.

[0159] δ can be an aliphatic carbon chain. In one or more aspects (which can be combined with other aspects of this article), δ is a C1-C8 aliphatic carbon chain, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or an isomer thereof, or a combination thereof.

[0160] The Schiff base of formula (VIII) can be represented by the following formula:

[0161]

[0162] The Schiff base polymer can be formed using any one or more suitable polymerization, PPM, coupling reaction and combination thereof. In one or more aspects, the method for producing the Schiff base separated resin is selected from a sequential reaction method or an in situ reaction method. In at least one aspect, the Schiff base polymer is formed by an in situ method, wherein the Schiff base is contacted with formaldehyde, one or more ketone-containing monomers and a catalytic amount of a base catalyst. In at least one aspect, the Schiff base polymer is formed by a sequential reaction method, wherein the Schiff base is first reacted with formaldehyde to form a product having one or more alcohol moieties, and then a subsequent polymerization reaction is performed. In one or more aspects, the alcohol functionalized reaction product of the Schiff base and formaldehyde can be represented by formula (IX):

[0163]

[0164] in:

[0165] Q 1 and Q 1’ each independently is oxygen or sulfur;

[0166] R 12 is aryl, alkyl, cycloalkyl or heteroaryl; and

[0167] R 9 , R 9’ , R 10 and R 10’ Each is independently hydrogen, amino, aryl, alkyl, cycloalkyl, heteroaryl or hydroxymethyl.

[0168] In some aspects (which may be combined with other aspects herein), the Schiff base polymer is represented by formula (X):

[0169]

[0170] in:

[0171] R 12 is aryl, alkyl, cycloalkyl or heteroaryl;

[0172] R 9 , R 9’ , R 10 and R 10’ are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl; and

[0173] R 50 and R 50’ Independently are polymer chains formed by the reaction between one or more ketone-containing monomers, formaldehyde, and a catalytic amount of a base catalyst.

[0174] R of formula (X) 50 and R50’ can be independently represented by the following formula:

[0175]

[0176] in:

[0177] R 13 is -CH2-;

[0178] R 14 and R 15 Each is independently aryl, alkyl, cycloalkyl, heteroaryl, or combined to form a cycloalkyl ring or an aryl ring;

[0179] R 16 are independently -OH or -CH2OH; and

[0180] n is independently a positive integer greater than 1 to about 30.

[0181] R of formula (X) 14 and R 15 and R 14’ and R 15’ They may be combined to form a cycloalkyl ring or an aryl ring.

[0182] n of formula (X) may be a positive integer greater than 1, for example, from about 1.1 to about 30, for example, from about 5 to about 30, for example, from about 10 to about 30, for example, from about 15 to about 30, for example, about 20. The Mw of the ketone polymer of formula (X) measured by GPC may be from about 400 g / mol to about 20,000 g / mol, for example, from about 500 g / mol to about 15,000 g / mol, for example, from about 600 g / mol to about 10,000 g / mol, for example, from about 700 g / mol to about 5,000 g / mol, for example, from about 750 g / mol to about 1,000 g / mol, for example, from about 750 g / mol to about 850 g / mol. The PDI of the ketone polymer of formula (X) may be from about 1.01 to about 5.0, for example, from about 1.1 to about 4, for example, from about 1.5 to about 35, for example, from about 2 to about 3.

[0183] The glass transition temperature of the Schiff base polymer of formula (X) as determined by DSC may be about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0184] In some aspects that may be combined with other aspects herein, the ketone-containing monomer implemented in the formation of the Schiff base polymer of formula (X) can be a cycloalkyl ketone or an aryl ketone such that R 50 and R 50’ can be independently represented by the following formula:

[0185]

[0186] in:

[0187] R 17 Each is -CH2;

[0188] R 18 and R 19 Each combines to form a cycloalkyl ring or an aryl ring;

[0189] R 20 each is -OH; and

[0190] n is each independently a positive integer greater than 1 to 30.

[0191] R of formula (X) 18 and R 19 They can be combined to form a cycloalkyl ring or an aryl ring. 18 and R 19 In one or more aspects that combine to form a cycloalkyl or aryl ring, the ring may be substituted at any one or more of the corresponding positions, and the substitution is any one or more of alkyl, aryl, cycloalkyl, or heteroalkyl.

[0192] R of formula (X) 18 and R 19 Can be combined to form a cycloalkyl ring, the cycloalkyl ketone is a limonene-derived ketone or a terpene-derived ketone. In at least one aspect, the cycloalkyl ketone is limonene-derived, which is camphor. In at least one aspect, the cycloalkyl ketone is a terpene-derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene ketone, pseudoionone and muqubilone.

[0193] In some aspects, wherein R of formula (X) 18 and R 19 Combining to form a cycloalkyl ketone, n is a positive integer greater than 1, such as from about 1.1 to about 30, such as from about 5 to about 30, such as from about 10 to about 30, such as from about 15 to about 30, such as about 20. In one or more aspects, wherein R of formula (X) 18 and R 19 The ketone polymer has an Mw of about 400 g / mol to about 20,000 g / mol, such as about 500 g / mol to about 15,000 g / mol, such as about 600 g / mol to about 10,000 g / mol, such as about 700 g / mol to about 5,000 g / mol, such as about 750 g / mol to about 1,000 g / mol, such as about 750 g / mol to about 850 g / mol, as determined by GPC. In one or more aspects, wherein R 18 and R19 The PDI of the ketone polymers of formula (X) that combine to form the cycloalkyl ketone may be from about 1.01 to about 5.0, such as from about 1.1 to about 4, such as from about 1.5 to about 3.5, such as from about 2 to about 3.

[0194] The R 18 and R 19 The ketone polymers of formula (X) that combine to form the cycloalkyl ketone may have a glass transition temperature of about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0195] The Schiff base polymer may be formed via a PPM reaction by contacting a ketone resin represented by formula (X) with one or more thiosemicarbazide molecules. The resulting ketone resin represented by formula (X) may have R independently represented by formula (XI): 50 and R 50’ :

[0196]

[0197] in:

[0198] R 13 Each is -CH2;

[0199] R 16 Each is independently -CH2OH or -OH;

[0200] R 14 and R 15 each independently is an aryl, alkyl, cycloalkyl or heteroaryl ring;

[0201] Q 2 are each independently selected from oxygen and sulfur;

[0202] R 21 , R 22 and R 23 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl;

[0203] Each x is independently the average number of repeating units of the parent ketone unit converted to a Schiff base; and

[0204] Each z is independently the average number of unreacted repeating units of the parent ketone unit.

[0205] R of formula (XI) 14 and R 15 They may be combined to form a cycloalkyl ring or an aryl ring.

[0206] The conversion of the parent ketone of formula (X) to the Schiff base can be from about 1% to about 100% conversion, such as from about 10% to about 95% conversion, such as from about 20% to about 90% conversion, such as from about 30% to about 85% conversion, such as from about 40% to about 80% conversion, such as from about 45% to about 75% conversion, such as from about 50% to about 70% conversion. The percentage conversion of the parent ketone to the Schiff base determines the corresponding values ​​of x and z.

[0207] The R 50 and R 50’ The Mw of the Schiff base polymer of formula (X) independently represented by formula (XI) can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. 50 and R 50’ The Schiff base polymer of formula (X), independently represented by formula (XI), may have a PDI of about 1.01 to about 5.0, such as about 1.1 to about 4, such as about 1.5 to about 3.5, such as about 2 to about 3.

[0208] Where R 50 and R 50’ The ratio of x to z of formula (X) independently represented by formula (XI) can be from about 1:10 to about 10:1, such as from about 1:7.5 to about 7.5:1, such as from about 1:5 to about 5:1, such as from about 1:2.5 to about 2.5:1. In at least one aspect, the ratio of x to one or more of z is from about 1:1 to about 3:1. In at least one aspect, x is each independently composed of values ​​from about 10 to about 15, and z is independently composed of values ​​from about 10 to about 15. Where R 50 and R 50’ The Schiff base polymer of formula (X) independently represented by formula (XI) can comprise a main chain framework of at least one of a random copolymer, a block copolymer, an alternating copolymer, a gradient copolymer or a combination thereof. In one or more aspects, the Schiff base polymer is a random copolymer. In one or more aspects, the Schiff base polymer is a block copolymer.

[0209] The R 50 and R 50’The Schiff base polymer of formula (X) independently represented by formula (XI) may have a glass transition temperature of about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0210] In one or more alternative aspects, the Schiff base can be represented by formula (XV):

[0211]

[0212] in:

[0213] Q 1 and Q 1’ are each independently oxygen or sulfur; and

[0214] R 12 is aryl, alkyl, cycloalkyl or heteroaryl.

[0215] In some aspects (which may be combined with other aspects herein), the Schiff base polymer is represented by formula (XVI):

[0216]

[0217] in:

[0218] R 12 is aryl, alkyl, cycloalkyl or heteroaryl; and

[0219] R 25 , R 25’ , R 25” and R 25”’ Each is independently a polymer chain formed by the reaction between one or more ketone-containing monomers, formaldehyde, and a catalytic amount of a base catalyst.

[0220] In some aspects (which may be combined with other aspects of this document), R 25 , R 25’ , R 25” and R 25”’ Independently represented by the following formula:

[0221]

[0222] in:

[0223] R 13 Each is -CH2-;

[0224] R 14 and R 15 Each is independently alkyl, cycloalkyl or combined to form a cycloalkyl ring or an aryl ring;

[0225] R 16are each independently -OH or -CH2OH; and

[0226] n is a positive integer greater than 1 and about 30.

[0227] R of formula (XVI) 14 and R 15 , R 14’ and R 15’ , R 14” and R 15” and R 14”’ and R 15”’ They may be combined to form a cycloalkyl ring or an aryl ring.

[0228] Where R 14 and R 15 R of formula (XVI) is independently an alkyl group, a cycloalkyl group, or a group that combines to form a cycloalkyl ring or an aryl ring. 25 , R 25’ , R 25” and R 25”’ Each n may independently be a positive integer greater than 1, such as from about 1.1 to about 30, such as from about 5 to about 30, such as from about 10 to about 30, such as from about 15 to about 30, such as about 20.

[0229] Where R 14 and R 15 The Mw of the ketone polymer of formula (XVI) each independently being an alkyl group, a cycloalkyl group, or combining to form a cycloalkyl ring or an aryl ring can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. 14 and R 15 The ketone polymers of formula (XVI) each independently being an alkyl group, a cycloalkyl group, or combining to form a cycloalkyl ring or an aryl ring may have a PDI of about 1.01 to about 5.0, such as about 1.1 to about 4, such as about 1.5 to about 35, such as about 2 to about 3.

[0230] Where R 14 and R 15 The ketone polymer of formula (XVI) which is independently an alkyl group, a cycloalkyl group, or combines to form a cycloalkyl ring or an aryl ring may have a glass transition temperature of about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0231] The ketone-containing monomer employed in the formation of the Schiff base polymer is a cycloalkyl ketone or an aryl ketone such that R of formula (XVI) 25 , R 25’ , R 25” and R 25”’ can be independently represented by the following formula:

[0232]

[0233] in:

[0234] R 17 Each is -CH2-;

[0235] R 18 and R 19 Each combines to form a cycloalkyl ring or an aryl ring;

[0236] R 20 each is -OH; and

[0237] Each n is a positive integer greater than 1.

[0238] R of formula (XVI) 18 and R 19 Each may combine to form a cycloalkyl ring or an aryl ring, the ring may be substituted at any one or more corresponding positions, and the substitution is any one or more of alkyl, aryl, cycloalkyl and heteroalkyl.

[0239] In which R of formula (XVI) 18 and R 19 One or more of the can be combined to form one or more aspects of the cycloalkyl ring, the cycloalkyl ketone is a limonene-derived ketone or a terpene-derived ketone. In at least one aspect, the cycloalkyl ketone is limonene-derived, which is camphor. In at least one aspect, the cycloalkyl ketone is a terpene-derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene ketone, pseudoionone and muqubilone.

[0240] Where R 18 and R 19 R of formula (XVI) each combines to form a cycloalkyl ring or an aryl ring 25 , R 25’ , R 25” and R 25”’ Each n may independently be a positive integer greater than 1, such as about 1.1 to about 30, such as about 5 to about 30, such as about 10 to about 30, such as about 15 to about 30, such as about 20. 18 and R 19The Mw of the ketone polymer of formula (XVI) each combining to form a cycloalkyl ring or an aryl ring can be from about 400 g / mol to about 20,000 g / mol, such as from about 500 g / mol to about 15,000 g / mol, such as from about 600 g / mol to about 10,000 g / mol, such as from about 700 g / mol to about 5,000 g / mol, such as from about 750 g / mol to about 1,000 g / mol, such as from about 750 g / mol to about 850 g / mol. 18 and R 19 The PDI of the ketone polymer of formula (XVI) each combining to form a cycloalkyl ring or an aryl ring may be about 1.01 to about 5.0, such as about 1.1 to about 4, such as about 1.5 to about 35, such as about 2 to about 3.

[0241] Where R 18 and R 19 The ketone polymer of formula (XVI) each combining to form a cycloalkyl ring or an aryl ring may have a glass transition temperature of about 50°C to about 200°C, such as about 55°C to about 100°C, such as about 60°C to about 100°C, such as about 65°C to about 80°C.

[0242] The Schiff base polymer can be formed via a PPM reaction by contacting a ketone resin of formula (XVI) with one or more thiosemicarbazide molecules. The resulting ketone resin can be represented by formula (XVI), wherein R 25 , R 25’ , R 25” and R 25”’ Represented by formula (XVII):

[0243]

[0244] in:

[0245] R 13 Each is -CH2;

[0246] R 14 and R 15 Each is independently aryl, alkyl, cycloalkyl, heteroaryl, or combined to form a cycloalkyl ring or an aryl ring;

[0247] R 16 Each independently is -OH or -CH2OH;

[0248] Q 2 each independently oxygen and sulfur;

[0249] R 21 , R 22 and R 23 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl;

[0250] Each x is independently the average number of repeating units in which the parent ketone unit is converted to a Schiff base; and

[0251] Each z is independently the average number of repeating units in which the parent ketone unit is unreacted.

[0252] Regarding formula (XVII), R 14 and R 15 One or more of them are combined to form a cycloalkyl ring or an aryl ring.

[0253] The conversion of the parent ketone of formula (XVI) to the Schiff base can be from about 1% to about 100% conversion, such as from about 10% to about 95% conversion, such as from about 20% to about 90% conversion, such as from about 30% to about 85% conversion, such as from about 40% to about 80% conversion, such as from about 45% to about 75% conversion, such as from about 50% to about 70% conversion. The percentage conversion of the parent ketone to the Schiff base determines the corresponding values ​​of x and z.

[0254] In one or more alternative aspects, the Schiff base polymer can be represented by formula (XXV):

[0255]

[0256] in:

[0257] R 1 is aryl, alkyl, cycloalkyl or heteroaryl;

[0258] R 10 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl;

[0259] R 8 and R 9 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl;

[0260] R 11 and R 13 Each is independently hydrogen or represented by the following formula:

[0261]

[0262] R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 2’ , R 3’ , R 4’ , R 5’ , R6’ , R 7’ are each independently aryl, alkyl, cycloalkyl or heteroaryl, wherein R 2 and R 3 , R 4 and R 5 , R 6 and R 7 , R 2’ and R 3’ , R 4’ and R 5’ and R 6’ and R 7’ can independently combine to form a cycloalkyl ring or an aryl ring;

[0263] R 16 and R 16’ Each is independently hydrogen or -CH2OH;

[0264] Q 1 , Q 2 , Q 2’ and Q 4 each independently is oxygen or sulfur;

[0265] Q 3 , Q 3’ , Q 6 and Q 6’ are independently oxygen, sulfur or Where Q 1’ are each independently oxygen or sulfur, and R 14 , R 15 and R 16 are each independently hydrogen, aryl, alkyl, cycloalkyl or heteroaryl,

[0266] n and n' are each independently a positive integer;

[0267] m and m' are each independently 0 or a positive integer, and

[0268] The polymer represented by formula (XXV) is a block copolymer or a random copolymer.

[0269] R of formula (XXV) 1 is an aryl group, for example Q in formula (XXV) 1 , Q 2 , Q 2’ , Q 4 , Q 3 , Q 3’ , Q 6 and Q 6’ Each is oxygen. Q of formula (XXV) 1 , Q 2 , Q 2’ and Q4 Each is oxygen, Q 6 and Q 6’ Each independently Where Q 1’ Each is oxygen, and R 14 , R 15 and R 16 Each is hydrogen.

[0270] With respect to Formula (XXV), the ratio of n to m is from about 0.1:1 to about 1:0.1, such as from about 1:1 to about 3:1. 2 and R 3 , R 4 and R 5 , R 6 and R 7 , R 2’ and R 3’ , R 4’ and R 5’ and R 6’ and R 7’ Each independently combines to form an alkyl ring. In some aspects, the alkyl rings are each a cyclohexyl ring.

[0271] In some aspects, the metal substrate includes a polymer of formula (XXV) disposed thereon.

[0272] In some aspects, the method of forming a polymer of formula (XXV) comprises forming an intermediate polymer by introducing formaldehyde and a ketone with a first semicarbazide represented by the formula:

[0273] Q 1 and Q 4 are independently oxygen or sulfur, R 1 is aryl, alkyl, cycloalkyl or heteroaryl; R 8 and R 9 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; R 10 , R 11 , R 12 and R 13 Each is independently hydrogen, aryl, alkyl, cycloalkyl or heteroaryl. In some aspects, the method may further include introducing the intermediate polymer with a second semicarbazide represented by the formula:

[0274] Among them, Q 1” is oxygen or sulfur, and R 15’ , R 16’ and R 17’ Each is independently hydrogen, aryl, alkyl, cycloalkyl or heteroaryl. In some aspects, R 1 is an aromatic group, such as In some aspects, the ketone is a cyclic alkyl ketone, such as cyclohexanone or acetophenone. In some aspects, the ketone is a limonene-derived ketone or a terpene-derived ketone. In some aspects, the ketone is a terpene-derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene ketone, pseudoionone and muqubilone.

[0275] Deposition of Schiff base polymers on substrates

[0276] In some aspects, the method includes applying a Schiff base polymer of the present invention (e.g., dispersed in a solvent) to a substrate (e.g., a metal substrate). The Schiff base polymer can be applied to the metal by spraying, brushing, rolling or dipping, for example, to completely coat the surface. The materials that can be applied by a range of methods expand the use of this technology. The aircraft industry may use spraying, while automobile companies may use dip tanks for automobile frames, and rail vehicle manufacturers may use rollers or brushes. The Schiff base polymer can be dispersed in an aqueous solvent, an organic solvent, or an aqueous solvent-organic solvent blend. The functional groups of the Schiff base ketone polymer can react with other ingredients, for example, to improve its dispersibility.

[0277] In certain aspects, the Schiff base ketone polymer provides corrosion protection for a long time, as determined by a pass / fail test of 3000 hours of ASTM B117 salt spray exposure. The Schiff base ketone polymer can form a continuous film that provides corrosion inhibition to the metal surface for a long time. The Schiff base polymer can form a coating to inhibit corrosion of metal surfaces of aerospace vehicles, automobiles, trucks, trains, boats, ships, buildings, bridges, and other metal parts.

[0278] Schiff base polymers and metals

[0279] The Schiff base ketone polymers of the present invention can be dispersed in a solvent. The Schiff base polymer can be in a composition having (e.g., dispersed with or ionically bonded to) one or more metals. Such metals can promote corrosion inhibition. For example, the metal can be a cationic species of a transition metal.

[0280] The metal can be in the form of a cation or a metal salt. For example, the metal can be selected from alkaline earth metals, transition metals and rare earth metal salts, such as selected from the group consisting of Zn, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ce, Co, Y, Bi, Cd, Pb, Ag, Sb, Sn, Cu, Fe, Ni, Li, Ca, Sr, Mg, Zr, Nd, Ba, Sc and any combination thereof. For example, the metal can be selected from the group consisting of Zn, La, Pr, Ce, Co, Y, Ca, Sr, Ba, Sc and Zr. The metal can be selected from at least one of Zn, Pr and Ce. The metal can be Zn. The metal can be Ce. The metal can be Pr. Some examples of salts that can be used are nitrates, chloride salts, acetates or any combination thereof.

[0281] It should be understood that the metal can have any suitable oxidation state. For example, the typical oxidation state of Zn is +2. The typical oxidation state of Pr is +2, +3 and / or +4. The typical oxidation state of Ce is +2, +3 and +4. It should be understood that various combinations and groups of the above metal salts can be used in the compositions of the present invention.

[0282] Substrates for corrosion protection

[0283] The substrate that can be protected from corrosion by the Schiff base ketone polymer or its composition can be any suitable substrate, such as a metal substrate or a plastic substrate. The metal substrate can include any substrate material whose surface is at least partially metal, for example, a portion of its outer surface is metal. The metal substrate can include any metal that needs corrosion protection. The metal substrate can include a metal or alloy selected from aluminum, such as an aluminum alloy. The metal substrate can be an aluminum alloy, such as an alloy of aluminum and one or more metals selected from the group consisting of copper, magnesium, manganese, silicon, tin, zinc and a combination thereof. The aluminum alloy can be an alloy containing copper. The metal substrate can be a copper-containing alloy, such as a copper-containing aluminum alloy. The amount of copper in the alloy can be about 1 weight % to about 20 weight %, about 1 weight % to about 18 weight %, about 1 weight % to about 10 weight % or about 1 weight % to about 6 weight %. The aluminum alloy can be an aerospace alloy, such as AA2XXX and AA7XXX types. For example, the aluminum alloy can be AA2024 and AA7075 types. The aluminum alloy can be an automotive alloy, such as AA6XXX type. The aluminum alloy can be a marine alloy, such as AA5XXX type.

[0284] Example

[0285] Synthesis of polymer Schiff bases via PPM reaction

[0286] A solution of thiosemicarbazide in 750 mL of ethanol was heated at 60 ° C under stirring until the thiosemicarbazide was completely dissolved. A solution consisting of 0.9 mL of HCl in 10 mL of ethanol was added dropwise to the thiosemicarbazide solution. A solution consisting of 10 g of ketone resin in 50 mL of ethanol was added to the thiosemicarbazide solution at 78 ° C for 30 minutes, and the solution was then refluxed for about 2-3 hours. The solution was then slowly cooled to room temperature to produce a yellow solid precipitate. The solid was collected and further washed with ethanol. It will be appreciated by those of ordinary skill in the art that, as contemplated herein, one or more of thiosemicarbazide, ethanol, HCl and ketone resins of greater / lesser volumes or concentrations may be used without departing from the experimental procedure.

[0287] Formation of alcohol-functionalized Schiff bases

[0288] A solution consisting of 24.3 g of formalin (37%), 1.4 g of Schiff's base and 15 mL of ethanol was heated and mixed at 60° C., and then 0.025 mL of 20% NaOH was added. The temperature of the solution was then brought to about 75° C. to about 80° C., and refluxed for 2-3 hours. A powdered product was then obtained, washed with water and ethanol, and dried under vacuum at 50° C. It will be appreciated by one of ordinary skill in the art that, as contemplated herein, one or more of formalin, Schiff's base, ethanol and NaOH in greater / lesser volumes or concentrations may be used without departing from the experimental procedure.

[0289] Synthesis of polyketone resins for Schiff base separation via sequential reaction method

[0290] A mixture of 49.1 g of cyclohexanone and 5 g of alcohol functionalized Schiff base was prepared, followed by a mixture consisting of 16 g of formalin (37%) and 10 g of cyclohexane. The mixture was brought to a temperature of about 65° C. to about 70° C. and refluxed, followed by a mixture consisting of 100 mL of formalin (37%) and 3.64 mL of 20% NaOH. The reaction was allowed to proceed for 2 hours under alkaline conditions (e.g., pH=about 11-12). The viscous product was recovered by decanting the aqueous layer and washing with hot water until the filtrate became neutral. The resin was then dried in vacuo at 110° C. One of ordinary skill in the art will appreciate that, as contemplated herein, one or more of cyclohexanone, alcohol functionalized Schiff base, formalin, and NaOH may be used in greater / lesser volumes or concentrations without departing from the experimental procedure.

[0291] In situ Synthesis of Polyketone Resins Separated by Schiff Base

[0292] A mixture of 49.1 g of cyclohexanone and 1.4 g of Schiff's base is prepared, followed by a mixture consisting of 16 g of formalin (37%) and 10 g of cyclohexane. The mixture is brought to a temperature of about 65° C. to about 70° C. and refluxed, followed by a mixture consisting of 100 mL of formalin (37%) and 3.64 mL of 20% NaOH. The reaction is allowed to proceed for 2 hours under alkaline conditions (e.g., pH=about 11-12). The viscous product is recovered by decanting the aqueous layer and washing with hot water until the filtrate becomes neutral. The resin is then vacuum dried at 110° C. One or more of cyclohexanone, alcohol-functionalized Schiff's base, formalin, and NaOH may be used, as contemplated herein, without departing from the experimental procedure.

[0293] Other aspects

[0294] The present invention provides, inter alia, the following aspects, each of which may be considered to optionally include any alternative aspects.

[0295] Item 1. A polymer represented by formula (V):

[0296]

[0297] in:

[0298] R 1 and R 4 are each independently a bond, an aryl group, an alkyl group, a cycloalkyl group or a heteroaryl group, wherein R 2 and R 3 and / or R 2’ and R 3’ can independently combine to form a cycloalkyl ring or an aryl ring;

[0299] R 2 , R 2’ , R 3 and R 3’ are each independently a bond, an aryl group, an alkyl group, a cycloalkyl group or a heteroaryl group, wherein R 2 and R 3 and / or R 2’ and R 3’ can independently combine to form a cycloalkyl ring or an aryl ring;

[0300] Q 1 is oxygen or sulfur;

[0301] R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl; and

[0302] x is a positive integer, z is 0 or a positive integer, x+z is such that the polymer represented by formula (V) has a molecular weight of about 400 g / mol to about 20,000 g / mol, and the polymer represented by formula (V) is a block copolymer, a random copolymer, an alternating copolymer or a gradient copolymer.

[0303] Item 2. The polymer of Item 1, wherein the polymer represented by Formula (V) has a molecular weight of about 500 g / mol to about 15,000 g / mol and is a block copolymer or a random copolymer.

[0304] Item 3. The polymer according to Item 1 or 2, R 2 and R 2’ is a key, and R 3 and R 3’ Any one or more of the following:

[0305]

[0306] Item 4. The polymer according to Item 1 or 2, wherein R 2 and R 2’ Each is phenyl, R 3 and R 3’ Each is ethylene, and R 1 and R 4 are independently phenyl or -CH2OH.

[0307] Item 5. The polymer according to Item 1 or 2, R 2 and R 3 and R 2’ and R 3’ Each combines to form a cycloalkyl ring or an aryl ring, so that the polymer can be represented by formula (VI):

[0308]

[0309] in:

[0310] R 5 and R 8 are each independently aryl, alkyl, cycloalkyl or heteroaryl,

[0311] R 6 and R 7 and R 6’ and R 7’ Each of them combines to form a cycloalkyl group or an aryl group;

[0312] Q 1 is oxygen or sulfur;

[0313] R 9 , R 10 and R11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl; and

[0314] x is a positive integer, z is 0 or a positive integer, x+z is such that the polymer represented by formula (VI) has a molecular weight of about 400 g / mol to about 20,000 g / mol, and the polymer represented by formula (VI) is a block copolymer, a random copolymer, an alternating copolymer or a gradient copolymer.

[0315] Item 6. The polymer according to Item 5, wherein R 6 and R 7 and R 6’ and R 7’ The ring formed is a cycloalkyl ring.

[0316] Clause 7. The polymer of Clause 6, wherein the cycloalkyl ring is a cyclohexyl ring.

[0317] Clause 8. A polymer as described in any one of Clauses 1 to 7, wherein R 9 , R 10 and R 11 Each is hydrogen.

[0318] Clause 9. The polymer of any one of Clauses 1 to 8, wherein the ratio of x to z is from about 0.1:1 to about 1:0.1.

[0319] Clause 10. The polymer of any one of Clauses 1 to 9, wherein the ratio of x to z is from about 1:1 to about 3:1.

[0320] Item 11. A metal substrate comprising the polymer of any one of Items 1 to 10 disposed thereon.

[0321] Clause 12. A method of forming a polymer as described in any one of Clauses 1 to 11, comprising introducing formaldehyde together with a ketone to form an intermediate polymer, and then treating the intermediate polymer with a carbohydrazide / semicarbazide represented by formula (IV):

[0322]

[0323] in:

[0324] Q 1 is oxygen or sulfur; and

[0325] R 9 , R 10 and R 11 Each is independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl.

[0326] Clause 13. The process of any one of clauses 1 to 2, 5 to 6 and 8 to 12, wherein the ketone is a cycloalkyl ketone.

[0327] Clause 14. The process of any one of clauses 1 to 2, 5 to 6 and 8 to 13, wherein the cycloalkyl ketone is cyclohexanone or acetophenone.

[0328] Clause 15. The method of any one of Clauses 1 to 2, 5 to 6 and 8 to 14, wherein the ketone is a limonene-derived ketone or a terpene-derived ketone.

[0329] Clause 16. The process of any one of Clauses 1 to 2, 5 to 6 and 8 to 15, wherein the ketone is a limonene-derived ketone which is camphor.

[0330] Clause 17. The method of any one of clauses 1 to 2, 5 to 6 and 8 to 16, wherein the ketone is a terpene-derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene ketone, pseudoionone and muqubilone.

[0331] Item 18. A polymer represented by formula (X):

[0332]

[0333] in:

[0334] R 12 is aryl, alkyl, cycloalkyl or heteroaryl;

[0335] R 9 , R 9’ , R 10 and R 10’ are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl; and

[0336] R 50 and R 50’ Independently, a polymer chain formed by the reaction between one or more ketone-containing monomers, formaldehyde, and a catalytic amount of a base catalyst.

[0337] Item 19. The polymer according to Item 18, wherein R 12 Selected from:

[0338]

[0339]

[0340] Item 20. The polymer according to Item 18 or 19, wherein R 50 and R 50’Respectively represented by formula (XI):

[0341]

[0342] in:

[0343] R 13 Each is -CH2;

[0344] R 16 Each is independently -CH2OH or -OH;

[0345] R 14 and R 15 Each is independently aryl, alkyl, bond, cycloalkyl or heteroaryl ring, wherein R 14 and R 15 can independently combine to form a cycloalkyl ring or an aryl ring;

[0346] Q 2 each is oxygen or sulfur;

[0347] R 21 , R 22 and R 23 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl;

[0348] Each x is independently a positive integer, z is independently 0 or a positive integer, the sum of x and z is such that the polymer represented by formula (XI) has a molecular weight of about 400 g / mol to about 20,000 g / mol, and the polymer represented by formula (XI) is a block copolymer, a random copolymer, an alternating copolymer, or a gradient copolymer.

[0349] Clause 21. The polymer of any one of Clauses 18 to 20, wherein the polymer represented by formula (X) has a molecular weight of about 500 g / mol to about 15,000 g / mol and is a block copolymer or a random copolymer.

[0350] Item 22. The polymer according to Item 20 or 21, R 14 and R 14’ is a key, and R 15 and R 15’ Any one or more of the following:

[0351]

[0352]

[0353] Item 23. The polymer according to Item 20 or 21, wherein R 14 and R 14’ Each is phenyl, R 15Each is ethylene, and R 13 and R 16 are independently phenyl or -CH2OH.

[0354] Item 24. The polymer according to Item 20 or 21, wherein R 14 and R 15 Each combines to form a cycloalkyl ring or an aryl ring.

[0355] Item 25. The polymer according to Item 24, wherein R 18 and R 19 The ring formed is a cycloalkyl ring.

[0356] Clause 26. The polymer of Clause 25, wherein the cycloalkyl ring is a cyclohexyl ring.

[0357] Clause 27. A polymer as described in any one of Clauses 20 to 26, wherein R 21 , R 22 and R 23 Each is hydrogen.

[0358] Clause 28. The polymer of any one of Clauses 20 to 27, wherein the ratio of x to z is from about 0.1:1 to about 1:0.1.

[0359] Item 29. The polymer of any one of Items 20 to 28, wherein the ratio of x to z is from about 1:1 to about 3:1.

[0360] Item 30. A metal substrate comprising the polymer of any one of Items 18 to 29 disposed thereon.

[0361] Item 31. The polymer of Item 25, wherein the cycloalkyl ketone is cyclohexanone or acetophenone.

[0362] Item 32. The polymer of Item 25 or 31, wherein the ketone is a limonene-derived ketone or a terpene-derived ketone.

[0363] Item 33. The polymer of any one of Items 25 and 31 to 32, wherein the ketone is a limonene-derived ketone, and the limonene-derived ketone is camphor.

[0364] Item 34. The polymer of any one of Items 25 and 31 to 33, wherein the ketone is a terpene derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene lactone, pseudoionone and muqubilone.

[0365] Clause 35. A polymer as described in any one of Clauses 18 to 34, wherein R 12 yes

[0366] Clause 36. A method of forming a polymer as described in any one of Clauses 18 to 36, comprising:

[0367] The Schiff base is formed by introducing a diketone or a dialdehyde into one or more thiosemicarbazides;

[0368] introducing the Schiff base into one or more compositions comprising formaldehyde or comprising formaldehyde and a ketone-containing monomer; and

[0369] The polymer is introduced into an excess of thiosemicarbazide to produce a modified polymer having pendant Schiff base moieties.

[0370] Item 37. A polymer represented by formula (VII):

[0371]

[0372] in:

[0373] R 5 and R 8 Each is independently hydrogen or -CH2OH;

[0374] R 6 , R 7 , R 6’ , R 7’ , R 5’ , R 5” , R 8’ and R 8” are each independently a bond, an aryl group, an alkyl group, a cycloalkyl group or a heteroaryl group, wherein R 6 and R 7 , R 6’ and R 7’ , R 5’ and R 5” and R 8’ and R 8” can independently combine to form a cycloalkyl ring or an aryl ring;

[0375] Q 1” and Q 1”’ are independently oxygen, sulfur or

[0376] R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl;

[0377] Q 1 and Q 1’ each independently is oxygen or sulfur;

[0378] x is a positive integer, z is 0 or a positive integer, x+z is such that the polymer represented by formula (VII) has a molecular weight of about 200 to about 2,000 Daltons, and the polymer represented by formula (VII) is a block copolymer or a random copolymer.

[0379] Clause 38. The polymer according to clause 37, wherein R 6 , R 6’ , R 5’ and R 8’ Each is phenyl, R 7 , R 7’ and R 5” Each is a methylene group, and R 8” It is a methyl group or a methylene group substituted with -CH2OH.

[0380] Item 39. A polymer as described in Item 37 or 38, wherein Q 1 and Q 1’ Each is oxygen, and R 9 , R 10 and R 11 Each is hydrogen.

[0381] Clause 40. The polymer of any one of clauses 37 to 39, wherein R 6 and R 7 , R 6’ and R 7’ , R 5’ and R 5” and R 8’ and R 8” They can independently combine to form a cycloalkyl ring, such as a cyclohexyl ring.

[0382] Clause 41. The polymer of any one of Clauses 37 to 40, wherein the cycloalkyl ring is a cyclohexyl ring.

[0383] Clause 42. The polymer of any of Clauses 37 to 41, wherein the ratio of x to z is from about 0.1:1 to about 1:0.1.

[0384] Clause 43. The polymer of any of Clauses 37 to 42, wherein the ratio of x to z is from about 1:1 to about 3:1.

[0385] Clause 44. The polymer of any of Clauses 37 to 43, wherein x is from about 10 to about 15, and z is from about 10 to about 15.

[0386] Item 45. A metal substrate comprising the polymer of any one of Items 37 to 44 disposed thereon.

[0387] Clause 46. A method of forming a polymer as described in any of Clauses 37 to 45, comprising introducing formaldehyde together with a ketone to form an intermediate polymer, and then treating the intermediate polymer with a carbohydrazide / semicarbazide represented by the formula:

[0388] Among them, Q 1” is oxygen or sulfur, and R 15’ , R 16’ and R 17’ Each is independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl.

[0389] Clause 47. The process of any one of Clauses 37 to 46, wherein the ketone is a cycloalkyl ketone.

[0390] Clause 48. The process of any one of Clauses 37 to 47, wherein the cycloalkyl ketone is cyclohexanone or acetophenone.

[0391] Clause 49. The method of any one of Clauses 37 to 48, wherein the ketone is a limonene-derived ketone or a terpene-derived ketone.

[0392] Clause 50. The method of any one of Clauses 37 to 49, wherein the ketone is a limonene-derived ketone, and the limonene-derived ketone is camphor.

[0393] Clause 51. The method of any one of Clauses 37 to 50, wherein the ketone is a terpene-derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene ketone, pseudoionone and muqubilone.

[0394] Item 52. A polymer represented by formula (XXV):

[0395]

[0396] in:

[0397] R 1 is aryl, alkyl, cycloalkyl or heteroaryl;

[0398] R 10 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl;

[0399] R 8 and R 9 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl;

[0400] R 11 and R 13 Each is independently hydrogen or represented by the following formula:

[0401]

[0402] R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 2’ , R 3’ , R 4’ , R 5’ , R 6’ , R 7’ are independently aryl, alkyl, cycloalkyl or heteroaryl, wherein R 2 and R 3 , R 4 and R 5 , R 6 and R 7 , R 2’ and R 3’ , R 4’ and R 5’ and R 6’ and R 7’ can independently combine to form a cycloalkyl ring or an aryl ring;

[0403] R 16 and R 16’ Each is independently hydrogen or -CH2OH;

[0404] Q 1 , Q 2 , Q 2’ and Q 4 each independently is oxygen or sulfur;

[0405] Q 3 , Q 3’ , Q 6 and Q 6’ are independently oxygen, sulfur or Among them, Q 1’ are each independently oxygen or sulfur, and R 14 , R 15 and R 16 are each independently hydrogen, aryl, alkyl, cycloalkyl or heteroaryl,

[0406] n and n' are each independently a positive integer;

[0407] m and m' are each independently 0 or a positive integer, and

[0408] The polymer represented by formula (XXV) is a block copolymer or a random copolymer.

[0409] Item 53. The polymer according to Item 52, wherein R 1 It is an aromatic group.

[0410] Item 54. The polymer according to Item 52 or 53, wherein R 1 yes

[0411] Clause 55. A polymer as described in any one of Clauses 52 to 54, wherein Q 1 , Q 2 , Q 2’ , Q 4 , Q 3 , Q 3’ , Q 6 and Q 6’ Each is oxygen.

[0412] Clause 56. A polymer as described in any one of Clauses 52 to 55, wherein Q 1 , Q 2 , Q 2’ and Q 4 Each is oxygen, and Q 6 and Q 6’ Each independently Where Q 1’ Each is oxygen, and R 14 , R 15 and R 16 Each is hydrogen.

[0413] Clause 57. The polymer of any of Clauses 52 to 56, wherein the ratio of n to m is from about 0.1:1 to about 1:0.1.

[0414] Clause 58. The polymer of any of Clauses 52 to 57, wherein the ratio of n to m is from about 1:1 to about 3:1.

[0415] Clause 59. A polymer as described in any one of Clauses 52 to 58, wherein R 2 and R 3 , R 4 and R 5 , R 6 and R 7 , R 2’ and R 3’ , R 4’ and R 5’ and R 6’ and R 7’ Each independently combines to form an alkyl ring.

[0416] Clause 60. The polymer of any one of Clauses 52 to 59, wherein each of the alkyl rings is a cyclohexyl ring.

[0417] Item 61. A metal substrate comprising the polymer of any one of Items 52 to 60 disposed thereon.

[0418] Clause 62. A method of forming a polymer as described in any of Clauses 52 to 61, comprising forming an intermediate polymer by introducing formaldehyde and a ketone together with a first semicarbazide represented by the formula:

[0419] Among them, Q 1 and Q 4 are independently oxygen or sulfur, R 1 is aryl, alkyl, cycloalkyl or heteroaryl; R 8 and R 9 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; R 10 , R 11 , R 12 and R 13 Each is independently hydrogen, aryl, alkyl, cycloalkyl or heteroaryl.

[0420] Clause 63. The method of any one of Clauses 52 to 62, further comprising introducing the intermediate polymer with a second semicarbazide represented by the formula:

[0421] Among them, Q 1” is oxygen or sulfur, and R 15’ , R 16’ and R 17’ Each is independently hydrogen, aryl, alkyl, cycloalkyl or heteroaryl.

[0422] Clause 64. A polymer as described in any one of Clauses 52 to 63, wherein R 1 It is an aromatic group.

[0423] Clause 65. A polymer as described in any one of Clauses 52 to 64, wherein R 1 yes

[0424] Clause 66. The process of any one of Clauses 52 to 65, wherein the ketone is a cyclic alkyl ketone.

[0425] Clause 67. The process of any one of Clauses 52 to 66, wherein the cyclic alkyl ketone is cyclohexanone or acetophenone.

[0426] Clause 68. The method of any one of Clauses 52 to 67, wherein the ketone is a limonene-derived ketone or a terpene-derived ketone.

[0427] Clause 69. The method of any one of Clauses 52 to 68, wherein the ketone is a terpene-derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene ketone, pseudoionone and muqubilone.

[0428] As used herein, a wavy line in a chemical structure indicates the point of attachment between the depicted portion and the rest of the molecule.

[0429] As used herein, the term "composition" can include the components of the composition (eg, an oligomer and a metal and / or a metal salt) and / or the reaction product of two or more components.

[0430] As used herein, the term "catalytic amount" is the amount of a catalyst and / or composition used to catalyze a reaction of one or more components of a reaction mixture.

[0431] As used herein, the term "post-polymerization modification" is a process in which a previously formed polymer having one or more reactive functional moieties dispersed along the polymer chain is added to a composition and reacted with one or more structurally different molecules to structurally modify the previously formed polymer.

[0432] Unless otherwise specified / claimed, the groups / moieties of the Schiff base polymers described in the present invention are unsubstituted or substituted. The term "substituted" means that the group is substituted at any available position. The substitution can be selected from, for example, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, heteroaryl, formyl, alkanoyl, cycloalkanoyl, aroyl, heteroaroyl, carboxyl, alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, heteroaryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, arylaminocarbonyl, heterocyclylaminocarbonyl, heteroarylaminocarbonyl, cyano, alkoxy, cycloalkoxy, aryloxy, heterocyclyloxy, The term "substituted" refers to any one or more of heteroaryloxy, alkanoate, cycloalkanoate, aromatic ester, heterocyclic ester, heteroaromatic ester, alkylcarbonylamino, cycloalkylcarbonylamino, arylcarbonylamino, heterocyclylcarbonylamino, heteroarylcarbonylamino, nitro, hydroxyl, halogen (-F, -Cl, -Br, -I), haloalkyl, halogenated aryl, halogenated heterocyclyl, halogenated heteroaryl, haloalkoxy, silylalkyl, alkenylsilylalkyl, alkynylsilylalkyl or amino. In some aspects, the substitution may be halogen, alkyl, formyl or amino. Optional substituents may include salts of groups, such as carboxylates. It should be understood that "substituted" may include other groups not specifically described.

[0433] "Alkyl", whether used alone or in compound terms such as alkoxy, alkylthio, alkylamino, dialkylamino or haloalkyl, means a straight or branched chain hydrocarbon having a size of 1 to about 10 carbon atoms or more. Thus, unless specifically limited to smaller groups, alkyl moieties include moieties having a size of, for example, 1 to about 6 carbon atoms or more, such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl and higher isomers, including, for example, those straight or branched chain hydrocarbons having a size of about 6 to about 10 carbon atoms or more.

[0434] "Cycloalkyl" refers to a monocyclic or polycyclic carbocyclic ring system of varying sizes (e.g., about 3 to about 10 carbon atoms), such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl. The term cycloalkoxy refers to the same group attached via an oxygen atom, such as cyclopentyloxy and cyclohexyloxy. The term cycloalkylthio refers to the same group attached via a sulfur atom, such as cyclopentylthio and cyclohexylthio.

[0435] As will be understood, an aromatic group refers to a cyclic group having 4m+2 π electrons, where m is an integer equal to or greater than 1. As used herein, "aromatic" and "aryl" are used interchangeably to refer to aromatic groups, regardless of the valence of the aromatic group. Thus, aryl refers to monovalent aromatic groups, divalent aromatic groups, and higher valent aromatic groups.

[0436] "Aryl" includes aryl groups used alone or in compound words such as arylalkyl, aryloxy or arylthio. When used alone, aryl represents: (i) an optionally substituted monocyclic or polycyclic aromatic carbocyclic moiety, such as phenyl, naphthyl or fluorenyl, having from about 6 to about 60 carbon atoms; or (ii) an optionally substituted partially saturated polycyclic carbocyclic aromatic ring system in which an aryl and a cycloalkyl or cycloalkenyl group are fused together to form a cyclic structure, such as tetrahydronaphthyl, indenyl, indanyl or fluorenyl.

[0437] "Heterocyclyl" or "heterocyclic", whether used alone or in compound words such as heterocyclyl, means: (i) an optionally substituted cycloalkyl or cycloalkenyl radical, such as having from about 3 to about 60 ring members, which may contain one or more heteroatoms, such as nitrogen, oxygen or sulfur (examples include pyrrolidinyl, morpholinyl, thiomorpholinyl, or fully or partially hydrogenated thienyl, furanyl, pyrrolyl, thiazolyl, oxazolyl, oxazinyl, thiazinyl, pyridinyl and azepinyl); (ii) an optionally substituted partially saturated polycyclic ring system in which an aryl (or heteroaryl) ring and a heterocyclic group are fused together to form a cyclic structure (examples include chromanyl, dihydrobenzofuranyl and dihydroindolyl); or (iii) an optionally substituted fully or partially saturated polycyclic fused ring system having one or more bridges (examples include quinuclidinyl and dihydro-1,4-epoxynaphthyl).

[0438] A heteroaromatic group is an aromatic group or aromatic ring containing one or more heteroatoms such as N, O, S, Se, Si or P. As used herein, "heteroaromatic" and "heteroaryl" are used interchangeably, and heteroaryl refers to monovalent aromatic groups, divalent aromatic groups and higher valent aromatic groups containing one or more heteroatoms. "Heteroaryl" is considered a non-limiting type of "heterocyclyl".

[0439] "Heteroaryl", whether used alone or in compound words such as heteroaryloxy, means: (i) an optionally substituted monocyclic or polycyclic aromatic organic moiety, e.g., having from about 1 to about 10 ring members, one or more of which is an element other than carbon, e.g., nitrogen, oxygen, sulfur, or silicon; heteroatoms interrupting the carbocyclic structure and having a sufficient number of delocalized pi electrons to provide aromatic character, provided that the ring does not contain adjacent oxygen and / or sulfur atoms. Typical 6-membered heteroaryl groups are pyrazinyl, pyridazinyl, pyrazolyl, pyridinyl, and pyrimidinyl. All regioisomers are contemplated, e.g., 2-pyridinyl, 3-pyridinyl, and 4-pyridinyl. Typical 5-membered heteroaryl rings are furanyl, imidazolyl, oxazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, pyrrolyl, 1,3,4-thiadiazolyl, thiazolyl, thienyl, triazolyl, and silole. All regioisomers are contemplated, for example 2-thienyl and 3-thienyl. The bicyclic radical is typically a benzo-fused ring system derived from the above heteroaryl radicals, for example benzofuranyl, benzimidazolyl, benzothiazolyl, indolyl, indolizinyl, isoquinolyl, quinazolinyl, quinolyl and benzothienyl; or (ii) an optionally substituted partially saturated polycyclic heteroaryl ring system in which a heteroaryl radical and a cycloalkyl or cycloalkenyl radical are fused together to form a cyclic structure, for example a tetrahydroquinolyl or pyridyl ring.

[0440] "Hydroxyl" and "hydroxy" are used interchangeably to refer to the -OH moiety.

[0441] "Alkoxy" and "alkoxyl" are used interchangeably and refer to -O-alkyl groups, wherein alkyl is as defined above. Examples include methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy, pentoxy, hexoxy and higher isomers.

[0442] "Aryloxy" and "aryloxy" are used interchangeably to refer to an -O-aryl group, wherein aryl is as defined above. Examples include, but are not limited to, phenoxy and naphthoxy.

[0443] The compounds described herein may include salts, solvates, hydrates, isomers, tautomers, racemates, stereoisomers, enantiomers or diastereomers of those compounds. For example, the salt may include sodium, potassium, calcium, nitrate, phosphate, sulfate, chloride or a combination thereof.

[0444] While the foregoing is directed to various aspects of the present invention, other and further aspects of the invention may be devised without departing from the basic scope of the invention, which is determined by the claims that follow.

Claims

1. A polymer represented by formula (VII): in: R 5 and R 8 Each is independently hydrogen or -CH2OH; R 6 , R 7 , R 6’ , R 7’ , R 5’ , R 5” , R 8’ and R 8” are each independently a bond, an aryl group, an alkyl group, a cycloalkyl group or a heteroaryl group, wherein R 6 and R 7 , R 6’ and R 7’ , R 5’ and R 5” and R 8’ and R 8” can independently combine to form a cycloalkyl ring or an aryl ring; Q 1” and Q 1”’ are independently oxygen, sulfur or R 9 , R 10 and R 11 are each independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl; Q 1 and Q 1’ each independently is oxygen or sulfur; x is a positive integer, z is 0 or a positive integer, x+z is such that the polymer represented by formula (VII) has a molecular weight of about 400 g / mol to about 20,000 g / mol, and is a block copolymer or a random copolymer.

2. The polymer according to claim 1, wherein R 6 , R 6’ , R 5’ and R 8’ Each is phenyl, R 7 , R 7’ and R 5” Each is a methylene group, and R 8” It is methyl or methylene substituted with -CH2OH.

3. The polymer according to claim 1, wherein Q 1 and Q 1’ Each is oxygen, R 9 , R 10 and R 11 Each is hydrogen.

4. The polymer according to claim 1, wherein R 6 and R 7 , R 6’ and R 7’ , R 5’ and R 5” and R 8’ and R 8” Each can independently combine to form a cycloalkyl ring, such as a cyclohexyl ring.

5. The polymer according to claim 1, wherein The cycloalkyl ring is a cyclohexyl ring.

6. The polymer according to claim 1, wherein The ratio of x to z is from about 0.1:1 to about 1:0.

1.

7. The polymer according to claim 1, wherein The ratio of x to z is from about 1:1 to about 3:

1.

8. The polymer according to claim 1, wherein x is from about 10 to about 15, and z is from about 10 to about 15.

9. A metal substrate comprising the polymer of claim 1 disposed thereon.

10. A method of forming the polymer of claim 1 comprising introducing formaldehyde with a ketone to form an intermediate polymer and then treating the intermediate polymer with a carbohydrazide / semicarbazide represented by the formula: in, Q 1” is oxygen or sulfur, and R 15’ , R 16’ and R 17’ Each is independently hydrogen, amino, aryl, alkyl, cycloalkyl or heteroaryl.

11. The method of claim 10, wherein: The ketone is a cycloalkyl ketone.

12. The method of claim 10, wherein: The cycloalkyl ketone is cyclohexanone or acetophenone.

13. The method of claim 10, wherein: The ketone is a limonene-derived ketone or a terpene-derived ketone.

14. The method of claim 10, wherein: The ketone is a limonene-derived ketone, and the limonene-derived ketone is camphor.

15. The method of claim 10, wherein: The ketone is a terpene derived ketone selected from the group consisting of terpene ketone, terpene ketone, farnesyl acetone, terpene ketone, pseudoionone and muqubilone.

16. A polymer represented by formula (XXV): in: R 1 is aryl, alkyl, cycloalkyl or heteroaryl; R 10 and R 12 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; R 8 and R 9 are each independently hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; R 11 and R 13 Each is independently hydrogen or represented by the following formula: R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 2’ , R 3’ , R 4’ , R 5’ , R 6’ , R 7’ are each independently aryl, alkyl, cycloalkyl or heteroaryl, wherein R 2 and R 3 , R 4 and R 5 , R 6 and R 7 , R 2’ and R 3’ , R 4’ and R 5’ and R 6’ and R 7’ can independently combine to form a cycloalkyl ring or an aryl ring; R 16 and R 16’ Each is independently hydrogen or -CH2OH; Q 1 , Q 2 , Q 2’ and Q 4 each independently is oxygen or sulfur; Q 3 , Q 3’ , Q 6 and Q 6’ are independently oxygen, sulfur or Where Q 1’ are each independently oxygen or sulfur, and R 14 , R 15 and R 16 are each independently hydrogen, aryl, alkyl, cycloalkyl or heteroaryl, n and n' are each independently a positive integer; m and m' are each independently 0 or a positive integer, and The polymer represented by formula (XXV) is a block copolymer or a random copolymer.

17. The polymer according to claim 16, wherein R 1 It is an aromatic group.

18. The polymer according to claim 16, wherein R 1 yes 19. The polymer according to claim 16, wherein Q 1 , Q 2 , Q 2’ , Q 4 , Q 3 , Q 3’ , Q 6 and Q 6’ Each is oxygen.

20. The polymer of claim 16, wherein Q 1 , Q 2 , Q 2’ and Q 4 Each is oxygen, and Q 6 and Q 6’ Each independently Among them, Q 1’ Each is oxygen, and R 14 , R 15 and R 16 Each is hydrogen.

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