Source: https://patents.google.com/patent/US20100084607
Timestamp: 2018-04-26 11:34:30
Document Index: 485558485

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US20100084607A1 - Macromolecular antioxidants and polymeric macromolecular antioxidants - Google Patents
Macromolecular antioxidants and polymeric macromolecular antioxidants Download PDF
US20100084607A1
US20100084607A1 US12583012 US58301209A US2010084607A1 US 20100084607 A1 US20100084607 A1 US 20100084607A1 US 12583012 US12583012 US 12583012 US 58301209 A US58301209 A US 58301209A US 2010084607 A1 US2010084607 A1 US 2010084607A1
US12583012
Disclosed are macromolecular antioxidants represented by a structural formula selected from I-VI:
and polymeric macromolecular antioxidants comprises at least one repeating unit represented by a structural formula selected from VIIa, VIIb, VIIIa, VIIIb or a combination thereof:
possessing superior oxidative resistance and higher thermal stability than commercially available antioxidants, and synthesis and applications of these macromolecular antioxidants and polymeric macromolecular antioxidants.
This application is a divisional of U.S. application Ser. No. 11/588,824 filed on Oct. 27, 2006, which claims the benefit of U.S. Provisional Application No. 60/731,125 filed on Oct. 27, 2005. The entire teachings of the above applications are incorporated herein by reference.
In a particular embodiment, the present invention pertains to macromolecular antioxidants and polymeric macromolecular antioxidants possessing superior oxidative resistance and higher thermal stability than commercially available antioxidants.
In certain particular embodiments, the present invention pertains to macromolecular antioxidants represented by a structural formula selected from I-VI:
Z in each occurrence, independently is a bond, an optionally substituted alkylene group, —S—, —O— or —NH—;
k is a positive integer from 1 to 12;
q is a positive integer from 1 to 3;
s a positive integer from 1 to 6;
A in each occurrence, independently is a bond, —O—, —NH—, —S—, —C(O)—, —C(O)NH—, —NHC(O)—, —C(O)O—, —OC(O)—, —CH═N— or —N═CH—;
B in each occurrence, independently is a bond or an optionally substituted alkyl group;
C in each occurrence independently is —H, an optionally substituted alkyl group or
i and j in each occurrence, independently is 0, 1, 2, 3 or 4;
D in each occurrence, independently is a bond, an optionally substituted alkyl group, —(CH2)lC(O)O(CH2)h—, —(CH2)lNHC(O)(CH2)h—, —(CH2)lC(O)NH(CH2)h—, —(CH2)lOC(O)(CH2)h—, —(CH2)lCH═N(CH2)h—, —(CH2)lN═CH(CH2)h—, —(CH2)lNH(CH2)h—, —(CH2)lS—(CH2)h—, —(CH2)l(O)(CH2)h—, —(CH2)lC(O)(CH2)h—,
l is 0 or a positive integer from 1 to 12;
h is 0 or a positive integer from 1 to 12;
Da, for each occurrence, is independently —C(O)NRd—, —NRdC(O)—, —NRd—, —CRd═N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond, wherein Rd is independently H or optionally substituted alkyl;
Rc and Rc′ are independently H or an optionally substituted alkyl;
Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, —SH; alkyl;
p′, for each occurrence, is independently an integer from 0 to 4; and
m′ and n′, for each occurrence, are independently integers from 0 to 6.
In certain other particular embodiments the present invention pertains to polymeric macromolecular antioxidants comprising at least one repeating unit represented by a structural formula selected from VIIa, VIIb, VIIIa, VIIIb or a combination thereof:
R3 and R4 in each occurrence, independently is C1-C16 alkyl, —O—C1-C16 alkyl, —NHAr, —NH2, —OH, or —SH;
In another embodiment, the present invention pertains to methods of preventing oxidation. The method comprises combining an oxidizable material with a compound or polymer of the present invention.
In yet another embodiment, the present invention pertains to methods for preparing compounds represented by a structural formula selected from I-VI. The method comprises comprising the step of reacting R++, wherein R++ is:
with a compound selected from:
Q is a halogen or —Z—H.
D′ in each occurrence, independently is —H, an optionally substituted alkyl group, —(CH2)lC(O)O(CH2)hR*—, —(CH2)lNHC(O)(CH2)hR*—, —(CH2)lC(O)NH(CH2)hR*—, —(CH2)lC(O)O(CH2)hR*—, —(CH2)lOC(O)(CH2)hR*—, —(CH2)lCH═N(CH2)hR*—, —(CH2)lN═CH(CH2)hR*—, —(CH2)lNH(CH2)hR*—, —(CH2)lS—(CH2)hR*—, —(CH2)lO(CH2)hR*— or —(CH2)lC(O)(CH2)hR*—.
R* in each occurrence, independently is —CH3 or —H.
In yet another embodiment, the present invention pertains to methods for preparing polymers represented by a structural formula selected from VII and VIII. The method comprises comprising the step of polymerizing a monomer represented by a structural formula selected from:
or combinations thereof in the presence of an oxidative polymerization catalyst.
In yet another embodiment the present invention pertains to the use of the disclosed compounds and polymers as antioxidants in a wide range of materials including, but not limited to, food, plastics, elastomers, composites and petroleum based products.
The macromolecular antioxidants and polymeric macromolecular antioxidants of the present invention generally can be synthesized more cost effectively than currently available antioxidants. Macromolecular antioxidants of the present invention can impart high antioxidant activities along with improved thermal stability and performance to a wide range of materials, including but not limited to plastics, elastomers, lubricants, petroleum based products (lubricants, gasoline, aviation fuels, and engine oils), cooking oil, cosmetics, processed food product, than commercially available antioxidants. The macromolecular antioxidants of the present invention generally have higher thermal stability, higher oxidative induction time lower changes in melt flow and diffusion rate than commercially available antioxidants.
FIG. 1, is an infrared (IR) spectrum of 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether of the invention.
FIG. 2 is an ultraviolet (UV) spectrum of 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether of the invention.
FIG. 3 is a comparison of an oxidative induction time (OIT) of one embodiment of the invention, namely, 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether, versus commercially available Irganox®.
FIG. 4 is a thermogravimetric analysis (TGA) of 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether of the invention.
FIG. 5 is an oxidative induction time (OIT) of polypropylene in combination with one embodiment of the invention, namely, 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether.
FIG. 6 is an oxidative induction time (OIT) of polyol ester based samples in combination with various polymeric macromolecular antioxidants of the present invention versus commercially used APAN (alkylated phenyl naphthalene amine) and DODP (di-octylated diphenyl amine).
FIG. 7 is an oxidative induction time (OIT) for polypropylene in combination with N-phenyl-para-phenylene-diamine versus polypropylene in combination with commercially available Irganox®.
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention. Unless otherwise stated, substituents identified represent options that can occur independently of other listed optional substituents in each occurrence.
In certain embodiments, the present invention pertains to macromolecular antioxidants represented by a structural formula selected from:
l is 0 or a positive integer from 1 to 20, and when D is —(CH2)lNHC(O)(CH2)h—, —(CH2)lOC(O)(CH2)h—, —(CH2)lS—(CH2)h—, or —(CH2)lO(CH2)h—, l is not 0. In one embodiment, l is 0 or a positive integer from 1 to 12. In another embodiment, l is 0 or a positive integer from 1 to 6.
In certain embodiments, the present invention is directed to macromolecular antioxidants represented by structural formula I.
In certain embodiments, the present invention is directed to macromolecular antioxidants represented by structural formula II.
In certain embodiments, the present invention is directed to macromolecular antioxidants represented by structural formula III.
In certain embodiments, the present invention is directed to macromolecular antioxidants represented by structural formula IV.
In certain embodiments, the present invention is directed to macromolecular antioxidants represented by structural formula V.
In certain embodiments, the present invention is directed to macromolecular antioxidants represented by structural formula VI.
In other certain embodiments, the present invention is directed to macromolecular antioxidants represented by a structural formula selected from Structural Formulas I-VI, wherein R is:
In certain particular embodiments, the present invention pertains to polymeric macromolecular antioxidants comprising at least one repeating unit represented by VIIa, VIIb, VIIIa, VIIIb or a combination thereof:
In another particular embodiment, the present invention pertains to a method for the synthesis of polymeric macromolecular antioxidants containing aromatic amine type antioxidant units where antioxidant units are, for example, but not limited to C-substituted anilines/dianilines, C-substituted napthylamines, N-substituted anilines/dianilines, N-substituted napthylamines and their combination in various ratios.
Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, or —SH. In certain other embodiments, each Ra is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl. In certain other embodiment each Ra is independently an alkyl or alkoxycarbonyl. In certain other embodiments each Ra is independently a C1-C6 alkyl or a C1-C6 alkoxycarbonyl. In certain other embodiments each Ra is independently tert-butyl or propoxycarbonyl. In certain other embodiments each Ra is independently an alkyl group. In certain embodiments each Ra is independently a bulky alkyl group. Suitable examples of bulky alkyl groups include butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like. In certain embodiments each Ra is tert-butyl. In certain embodiments at least one Ra adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In certain other embodiments both Ra groups adjacent to —OH are bulky alkyl groups (e.g., butyl, sec-butyl, tent-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In another embodiment, both Ra groups are tert-butyl. In another embodiment, both Ra groups are tert-butyl adjacent to the OH group.
In an additional embodiment, for formulas I-VI R is:
R′1 is an optionally substituted C1-C6 alkyl, an optionally substituted aryl, an optionally substituted aralkyl, —OH, —NH2, —SH, or C1-C6 alkyl ester wherein at least one R1 adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like).
In yet another embodiment, for formulas I-VI R is:
In a specific embodiment, M′ is
wherein p is 0, 1, 2, 3 or 4; and the values and preferred values for the remainder of the variables are as described above for formulas I-VI.
In an additional embodiment, the present invention is directed to macromolecular antioxidants of formulas I-VI, wherein:
R is represented by the following structural formula:
Db for each occurrence, is independently —O—, —NH—, —C(O)NH—, —NHC(O)—, —C(O)O—, —OC(O)— and —CH2—;
Ra′ for each occurrence, is independently H, optionally substituted alkyl or optionally substituted aryl;
A′, for each occurrence, is independently —O—, —NH—, —C(O)NH—, —NHC(O)—, —C(O)O—, —OC(O)— and —CH2—;
m″ and n″ are independently 0 or an integer from 0 to 12; and
p″, for each occurrence, is independently 0, 1, 2, 3 or 4.
Examples of macromolecular antioxidants of the present invention, for example, high molecular weight dimers, and tetramers are shown below.
In a first specific embodiment, the present invention is directed to macromolecular antioxidants of Structural Formulas I-VI, wherein R is represented by Structural Formula B,
Da, for each occurrence, is independently —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —O— or —C(O)—;
n′ and m′, for each occurrence, are independently integers from 0 to 2;
p′, for each occurrence, is independently an integer from 0 to 2; and the remainder of the variables are as described above for Structural Formula B.
In a second specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula B, wherein:
Da, for each occurrence, is independently —NH—, —C(O)NH— or —NHC(O)—;
p′ is 2; and the remainder of the variables are as described in the first embodiment.
In a third specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula B, wherein:
In a fourth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula B1, wherein:
Da is —NH—, —C(O)NH— or —NHC(O)—;
p′, for each occurrence, is independently an integer from 0 to 4;
m′, for each occurrence, is independently an integer from 0 to 6; and
Rc and Rc′ are independently H or optionally substituted alkyl and at least one of Rc and Rc′ is H. In certain embodiments, Rc and Rc′ are H. In certain other embodiments, one of Rc and Rc′ is H and the other is an alkyl group. More specifically, the alkyl group is a C1-C10 alkyl. Even more specifically, the alkyl group is a C10 alkyl.
In a fifth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula B1, wherein:
p′, for each occurrence, is independently an integer from 0 to 2;
m′, for each occurrence, is independently an integer from 0 to 2; and the remainder of the variables are as described above in the fourth embodiment.
In a sixth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula B1, wherein each Ra is independently an alkyl group, and the remainder of the variables are as described above in the sixth embodiment. In certain embodiments each Ra is a bulky alkyl group. In certain embodiments two Ra groups are bulky alkyl groups adjacent to the —OH group. In certain embodiments the two R groups are tert-butyl groups adjacent to the —OH group.
In a seventh specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula B2, wherein:
Rc and Rc′ are independently H or optionally substituted alkyl and at least one of Rc and Rc′ is H.
In a eighth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula B2, wherein one of Rc and Rc′ is H and the other is an alkyl group. More specifically, the alkyl group is a C1-C10 alkyl. Even more specifically, the alkyl group is a C10 alkyl.
In a ninth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula B3:
wherein Z is a bond and Da is —NH—, —C(O)NH— or —NHC(O)—.
In a tenth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula A:
wherein Z is a bond and the remainder of the variables are as described above for Structural Formula A.
In a eleventh specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula A, wherein h is 0 and the remainder of the variables are as described in the tenth specific embodiment.
In a twelfth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula A1
wherein the variables are as described as in the tenth specific embodiment. More specifically, D is —(CH2)l—C(O)O—, —(CH2)l—C(O)NH— or a bond.
In a thirteenth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula A2:
wherein the variables are as described in the tenth specific embodiment. More specifically, D is —(CH2)l—C(O)O—, —(CH2)l—C(O)NH— or a bond.
In a fourteenth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula A3
wherein the variables are as described as in the tenth specific embodiment. More specifically, D is —(CH2)l—C(O)O—, —(CH2)l—C(O)NH— or a bond. Even more specifically, m is 2.
In a fifteenth specific embodiment, for macromolecular antioxidants of Structural Formulas I-VI, R is represented by Structural Formula A4
wherein the variables are as described in the tenth specific embodiment. More specifically, D is —(CH2)l—C(O)O—, —(CH2)l—C(O)NH— or a bond. Even more specifically, m is 2. Even more specifically, m is 2 and R2 is -Me.
In certain embodiments the present invention pertains to methods of synthesizing compounds represented by a structural formula selected from I-VI, comprising the step of reacting R++, wherein R++ is:
Q is an electrophilic group or a leaving group, such as for example, a halogen, for example, fluorine, chlorine, bromine or iodine, or Q is —Z—H where Z and the remainder of the variables are as described above.
In certain particular embodiments the reaction is carried out in a suitable solvents such as, for example, tetrahydrofuran, dichloromethane and toluene
In certain other particular embodiments the reaction is carried out in the presence of a suitable catalysts such as, for example, potassium carbonate, potassium hydroxide and sodium hydroxide.
In certain other particular embodiments the reaction is carried out under reflux conditions.
In certain other particular embodiments the reaction is carried out under a nitrogen atmosphere.
In certain other particular embodiments, the reaction is carried out at a temperature between about 50° C. and about 200° C. In certain other particular embodiments, the reaction is carried out at a temperature between about 80° C. and about 150° C. In certain other particular embodiments, the reaction is carried out at a temperature between about 100° C. and about 130° C.
In certain other particular embodiments, the reaction is carried for between 5 minutes and 60 hours, between 30 minutes and 36 hours, between 1 hours and 24 hours and between 2 hours and 12 hours.
In certain embodiments, macromolecular antioxidants of Structural Formulas I-VI are synthesized by reacting a compound represented R1 ++ represented by the following structural formula:
D1′ is D1a′, D1b′, D1c′ or D1d′;
Q1 is Q1a or Q1b; wherein when D1′ is D1a′ or D1c′, Q1 is Q1a and when D1′ is D1b′ or D1d′, Q1 is Q1b.
D1a′ is —(CH2)lC(O)—X and X is H or a leaving group. In a specific embodiment, X is H. In another specific embodiment, X is a halogen or —ORe, wherein Re is an alkyl group. In a more specific embodiment, X is —Cl or —Br. In another more specific embodiment, X is —ORe. Re is preferably -Me.
D1b′ is H, —(CH2)lNH2, —(CH2)lSH, or —(CH2)10H.
D1c′ is —(CH2)lNHC(O)(CH2)h—X′, —(CH2)lC(O)NH(CH2)h—X′, —(CH2)lC(O)O(CH2)h—X′, —(CH2)lOC(O)(CH2)h—X′, —(CH2)lCH═N(CH2)h—X′, —(CH2)lN═CH(CH2)h—X′, —(CH2)JNH(CH2)h—X′, —(CH2)lS—(CH2)h—X′, —(CH2)lO(CH2)h—X′ or —(CH2)lC(O)(CH2)h—X′, wherein h is not 0 and X′ is a leaving group. More specifically, X′ is a halogen.
D1d′ is —(CH2)lNHC(O)(CH2)h—X″, —(CH2)lC(O)NH(CH2)h—X″, —(CH2)lC(O)O(CH2)h—X″, —(CH2)lOC(O)(CH2)h—X″, —(CH2)lCH═N(CH2)h—X″, —(CH2)lN═CH(CH2)h—X″, —(CH2)lNH(CH2)h—X″, —(CH2)lS—(CH2)h—X″, —(CH2)lO(CH2)h—X″ or —(CH2)lC(O)(CH2)h—X″, wherein X″ is a nucleophile. More specifically, X″ is —NH2 or —OH.
Q1a is a nucleophile. More specifically, Q1b is —NH2 or —OH.
Q1b is a —W—X1, wherein X1 is a leaving group and W is a bond or —C(O)—.
The remainder of the variables are as described above.
In a more specific embodiment, R1 ++ is represented by the following structural formula A1′:
wherein D1′ is as described above and the remainder of the variables are as defined as for Structural Formula A1.
In another more specific embodiment, R1 ++ is represented by the following structural formula A2′
wherein D1′ is as described above and the remainder of the variables are as defined as for Structural Formula A2.
In another more specific embodiment, R1 ++ is represented by the following structural formula A3′
wherein D1′ is as described above and the remainder of the variables are as defined as for Structural Formula A3.
In another more specific embodiment, R1 ++ is represented by the following structural formula A4′
wherein D1′ is as described above and the remainder of the variables are as defined as for Structural Formula A4.
In certain embodiments, when R1 ++ is represented by A1′, A2′, A3′ and A4′, D1′ is D1a′ and Q1 is Q1a. In a more specific embodiment, X is H and Q1 is —NH2. In another more specific embodiment, X is a halogen or —ORe, wherein Re is an alkyl group and Q1 is —NH2 or —OH. Even more specifically, X is —Cl, —Br, or —OMe.
In certain embodiments, when R1 ++ is represented by A1′, A2′, A3′ and A4′, D1′ is D1b′ and Q1 is Q1b. In a more specific embodiment, W is a bond and X1 is a halogen. In another more specific embodiment, W is —C(O)— and X1 is a halogen or —ORe, wherein Re is an alkyl group. Even more specifically, X is —Cl, —Br, or —OMe.
In certain embodiments, when R1 ++ is represented by A1′, A2′, A3′ and A4′, D1′ is D1c′ and Q1 is Q1a. In a more specific embodiment, X′ is a halogen and Q1a is —NH2 or —OH.
In certain embodiments, when R1 ++ is represented by A1′, A2′, A3′ and A4′, D1′ is D1d′ and Q1 is Q1b. In a more specific embodiment, X″ is —NH2 or —OH. In a even more specific embodiment, W is a bond and X1 is a halogen. In another even more specific embodiment, W is —C(O)— and X1 is a halogen or —ORe, wherein Re is an alkyl group. Even more specifically, X is —Cl, —Br, or —OMe.
In certain embodiments, macromolecular antioxidants of Structural Formulas I-VI are synthesized by reacting a compound represented R2 ++ represented by the following structural formula:
wherein D2′ is D2a′ or D2b′;
Q1 is Q1a or Q1b; wherein when D2′ is D2a′, Q1 is Q1a and when D2′ is D2b′, Q1 is Q1b.
D2a′ is —C(O)—X and X is H or a leaving group. In a specific embodiment, X is H. In another specific embodiment, X is a halogen or ˜ORe, wherein Re is an alkyl group. In a more specific embodiment, X is —Cl or —Br. In another more specific embodiment, X is —ORe. Re is preferably -Me.
D2b′ is NHRd, —SH, or —OH, wherein Rd is H or optionally substituted alkyl.
In certain embodiments, R2 ++ is represented by the following structural formula:
and Q1 is a —W—X1, wherein X1 is a leaving group and W is a bond or —C(O)—. The remainder of the variable and their specific values are as described for Structural Formula B1. In a more specific embodiment, W is a bond and X1 is a halogen. In another more specific embodiment, W is —C(O)—X1 and X1 is a halogen or —ORe, wherein Re is an alkyl. Preferably, Re is methyl.
and Q1 is a —W—X1, wherein X1 is a leaving group and W is a bond or —C(O)—. The remainder of the variable and their specific values are as described for Structural Formula B2. In a more specific embodiment, W is a bond and X1 is a halogen. In another more specific embodiment, W is —C(O)—X1 and X1 is a halogen or —ORe, wherein Re is an alkyl. Preferably, Re is methyl.
Examples of reactions for synthesizing macromolecular antioxidants of Structural Formulas I-VI, where R is represented by Structural Formula A, are illustrated in the following schemes:
In certain other particular embodiments the reaction is carried out without solvent in bulk reaction conditions using a suitable catalyst such as, for example, sodium acetate or lithium carbonate.
In certain other particular embodiments the reaction is carried out under melt conditions or in heterogeneous melt.
In certain other particular embodiments the reaction is carried out under a nitrogen atmosphere or under vacuum.
In certain other particular embodiments, the reaction is carried for between 30 minutes and 96 hours, between 1 hour and 72 hours, between 2 hours and 60 hours between 4 hours and 48 hours and between 12 hours and 24 hours.
In certain embodiments, D′ as defined above acts as a linker group which can act as a remote handle in coupling of an R group to form the macromolecular antioxidant of the present invention. The addition of a linker D′ to a phenol can be carried out in a similar fashion as shown below:
In certain particular embodiments the reaction is carried out in a suitable solvent such as, for example, acetone, acetonitrile and tetrahydrofuran.
In certain other particular embodiments the reaction is carried out in the presence of a suitable catalysts such as, for example, potassium carbonate and sodium carbonate.
In certain other particular embodiments the reaction is carried out under reflux conditions
In certain other particular embodiments the reaction is carried out under a nitrogen atmosphere
In certain other particular embodiments, the reaction is carried out at a temperature between about 5° C. and about 200° C. In certain other particular embodiments, the reaction is carried out at a temperature between about 10° C. and about 150° C. In certain other particular embodiments, the reaction is carried out at a temperature between about 50° C. and about 100° C. In certain other particular embodiments, the reaction is carried out at a temperature between about 60° C. and about 80° C.
In certain other particular embodiments, the reaction is carried out for between 30 minutes and 72 hours, between 1 hour and 48 hours, between 2 hours and 24 hours between 4 hours and 18 hours and between 10 hours and 14 hours.
Examples of reactions for synthesizing macromolecular antioxidants of Structural Formula I-VI, wherein R is represented by Structural Formula B are shown in the following schemes:
Y is represented by the following structural formula:
Q1 is —W—X1;
W is a bond or —C(O); and
X1 is a leaving group. More specifically, X1 is a halogen.
Macromolecular antioxidants of Structural Formula I-VI of the present invention can be prepared in a similar fashion according to the reactions described above.
In certain embodiments, the macromolecular antioxidants contain both C—N—C and C—C couplings in the backbone.
In certain embodiments, the process involves the polymerization of aromatic amine type monomeric system such as C-substituted anilines/dianilines, C-substituted napthylamines, N-substituted anilines/dianilines, N-substituted napthylamines, their combination in various ratios and other active aromatic amines leading to the formation of polymeric macromolecular antioxidants.
In one example, the polymeric macromolecular antioxidant based on N-substituted anilines/dianilines type monomer may contain Structures VIIa, VIIb or both.
In another example, the polymeric macromolecule based on napthylamine type monomer may contain Structures VIIIa, VIIIb or both.
In certain embodiments, the present invention pertains to methods of synthesizing polymer represented by structural formulas VIIa, VIIb, VIIIa and VIIIb.
In certain other embodiments these polymers are synthesized by polymerizing a monomer represented by a structural formula selected from:
or combinations thereof using an oxidative polymerization catalyst.
In certain embodiments, the oxidative polymerization catalyst is a biocatalyst or a biomimetic catalyst selected from Iron(II)-salen complexes, horseradish peroxidase, soybean peroxidase, hematin, laccase, tyroniase, ferric chloride and ammonium persulphate and a tyroniase-model complex.
In certain other embodiments, the oxidative polymerization catalyst is an inorganic or organometallic catalyst.
In yet another particular embodiment, the present invention pertains to a method for the synthesis of polymeric macromolecules, where catalysts used for polymerization are for example, but not limited to enzyme or enzyme mimetic catalysts.
Examples of enzyme or enzyme mimetic used for polymerization include Iron(II)-salen complexes, horseradish peroxidase (HRP), soybean peroxidase (SBP), hematin, laccase, tyroniase, tyroniase-model complexes and other peroxidases.
In yet another particular embodiment, the present invention relates to a simple process for the synthesis of polymeric macromolecular antioxidants based on aromatic amine type antioxidant units using typical biocatalysts such as peroxidases e.g. horse radish peroxidase (HRP), biomimetic type catalysts (e.g. hematin) or other inorganic catalysts such as Fe-Salen.
In certain embodiments the polymeric antioxidants of the present invention are synthesized as follows:
In certain other particular embodiments the reaction is carried out in the presence of a suitable solvent such as, for example, tetrahydrafurna (THF), dioxane, acetonitrile, DMF and methanol.
In certain embodiments, the reaction is carried out in the presence of an oxidative polymerization catalyst selected from Iron(II)-salen complexes, horseradish peroxidase, soybean peroxidase, hematin, laccase, tyroniase, ferric chloride and ammonium persulphate and a tyroniase-model complex.
In certain other particular embodiments, the reaction is carried out at a temperature between about 2° C. and about 120° C. In certain other particular embodiments, the reaction is carried out at a temperature between about 5° C. and about 100° C. In certain other particular embodiments, the reaction is carried out at a temperature between about 10° C. and about 60° C. In certain other particular embodiments, the reaction is carried out at a temperature between about 20° C. and about 40° C.
In certain other embodiments the polymeric antioxidants of the present invention are synthesized as follows:
In certain other particular embodiments the reaction is carried out in the presence of a suitable solvent such as, for example, tetrahydrafurna (THF), dioxane, methanol, diimethylformamide (DMF) and acetonitrile
In certain embodiments, the reaction is carried out in the presence of an oxidative polymerization catalyst selected from Iron(II)-salen complexes, horseradish peroxidase, soybean peroxidase, hematin, laccase, tyroniase, ferric chloride, ammonium persulfate and a tyroniase-model complex.
The term “alkyl” as used herein means a saturated straight-chain, branched or cyclic hydrocarbon. When straight-chained or branched, an alkyl group is typically C1-C8, more typically C1-C6; when cyclic, an alkyl group is typically C3-C12, more typically C3-C7 alkyl ester. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and tent-butyl and 1,1-dimethylhexyl.
The term “alkyl ester” as used herein means a group represented by C(O)OR**, where R** is an alkyl group as defined above.
Examples of suitable substituents on a substitutable ring nitrogen atom of an aryl group include C1-C3 alkyl, NH2, C1-C3 alkylamino, C1-C3 dialkylamino, —C(O)NH2, —C(O)NH(C1-C3 alkyl), —C(O)(C1-C3 alkyl), —CO2R**, —C(O)C(O)R**, —C(O)CH3, —C(O)OH, —C(O)O—(C1-C3 alkyl), —SO2NH2—SO2NH(C1-C3alkyl), —SO2N(C1-C3alkyl)2, NHSO2H, NHSO2(C1-C3 alkyl), —C(═S)NH2, —C(═S)NH(C1-C3 alkyl), —C(═S)N(C1-C3 alkyl)2, —C(═NH)—N(H)2, —C(═NH)—NH(C1-C3 alkyl) and C(═NH)—N(C1-C3 alkyl)2,
A “leaving group” is a group which can readily be displaced by a nucleophile. Examples of a good leaving group include but not limited halogen, alkoxy group and a tosylate group.
A “nucleophile” is a reagent that brings an electron pair. Typical nucleophile include but not limited amines and alcohols.
In certain embodiments, the present invention pertains to the use of the disclosed compounds to inhibit oxidation in an oxidizable material. This process involves contact the oxidizable material with a compound or polymer of the present invention.
Antioxidant compounds and polymers of the present invention can be used to prevent oxidation in a wide variety of compositions where free radical mediated oxidation leads to deterioration of the quality of the composition, including edible products such as oils, foods (e.g., meat products, dairy products, cereals, etc.), and other products containing fats or other compounds subject to oxidation. Antioxidant compounds and polymers can also be present in plastics and other polymers, elastomers (e.g., natural or synthetic rubber), petroleum products (e.g., fossil fuels such as gasoline, kerosene, diesel oil, heating oil, propane, jet fuel), lubricants, paints, pigments or other colored items, soaps and cosmetics (e.g., creams, lotions, hair products). The antioxidant compounds and polymers can be used to coat a metal as a rust and corrosion inhibitor. Antioxidant compounds and polymers additionally can protect antioxidant vitamins (Vitamin A, Vitamin C, Vitamin E) and pharmaceutical products from degradation. In food products, the antioxidant compounds can prevent rancidity. In plastics, the antioxidant compounds and polymers can prevent the plastic from becoming brittle and cracking.
Antioxidant compounds and polymers of the present invention can be added to oils to prolong their shelf life and properties. These oils can be formulated as vegetable shortening or margarine. Oils generally come from plant sources and include cottonseed oil, linseed oil, olive oil, palm oil, corn oil, peanut oil, soybean oil, castor oil, coconut oil, safflower oil, sunflower oil, canola (rapeseed) oil and sesame oil. These oils contain one or more unsaturated fatty acids such as caproleic acid, palmitoleic acid, oleic acid, vaccenic acid, elaidic acid, brassidic acid, erucic acid, nervonic acid, linoleic acid, eleosteric acid, alpha-linolenic acid, gamma-linolenic acid, and arachidonic acid, or partially hydrogenated or trans-hydrogenated variants thereof. Antioxidant compounds and polymers of the present invention are also advantageously added to food or other consumable products containing one or more of these fatty acids.
The shelf life of many materials and substances contained within the materials, such as packaging materials, are enhanced by the presence of an antioxidant compound or polymer of the present invention. The addition of an antioxidant compound or polymer to a packaging material is believed to provide additional protection to the product contained inside the package. In addition, the properties of many packaging materials themselves, particularly polymers, are enhanced by the presence of an antioxidant regardless of the application (i.e., not limited to use in packaging). Common examples of packaging materials include paper, cardboard and various plastics and polymers. A packaging material can be coated with an antioxidant compound or polymer (e.g., by spraying the antioxidant polymer or by applying as a thin film coating), blended with or mixed with an antioxidant compound or polymer (particularly for polymers), or otherwise have an antioxidant polymer present within it. In one example, a thermoplastic such as polyethylene, polypropylene or polystyrene can be melted in the presence of an antioxidant polymer in order to minimize its degradation during the polymer processing. An antioxidant polymer can also be co-extruded with a polymeric material.
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Docket No. 3805.1001-000; Provisional Patent Application No. 60/633,197, filed Dec. 3, 2004, Title: Synthesis Of Sterically Hindered Phenol Based Macromolecular Antioxidants, by Ashish Dhawan, et al.;
Docket No. 3805.1001-003; patent application Ser. No. 11/293,050, filed Dec. 2, 2005, Title: Synthesis Of Sterically Hindered Phenol Based Macromolecular Antioxidants, by Ashish Dhawan, et al.;
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Docket No. 3805.1002-003; patent application Ser. No. 11/293,049, filed Dec. 2, 2005, Title: One Pot Process For Making Polymeric Antioxidants, by Vijayendra Kumar, et al.;
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Docket No. 3805.1003-003; patent application Ser. No. 11/293,844, filed Dec. 2, 2005, Title: Synthesis Of Aniline And Phenol-Based Macromonomers And Corresponding Polymers, by Rajesh Kumar, et al.;
Docket No. 3805.1004-000; Provisional Patent Application No. 60/590,575, filed Jul. 23, 2006, Title: Anti-Oxidant Macromonomers And Polymers And Methods Of Making And Using The Same, by Ashok L. Cholli;
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Docket No. 3805.1004-002; patent application Ser. No. 11/184,724, filed Jul. 19, 2005, Title: Anti-Oxidant Macromonomers And Polymers And Methods Of Making And Using The Same, by Ashok L. Cholli;
Docket No. 3805.1004-005; patent application Ser. No. 11/184,716, filed Jul. 19, 2005, Title: Anti-Oxidant Macromonomers And Polymers And Methods Of Making And Using The Same, by Ashok L. Cholli;
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EXEMPLIFICATION Example 1 Synthesis of 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether
Two moles of N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl) propionamide and one mole of 1,6-dibromo hexane were dissolved in acetone in a round bottom flask under nitrogen. To the reaction mixture was added oven dried potassium carbonate and the reaction mixture was refluxed till the completion of the reaction (monitored by HPLC/TLC). After completion, the potassium carbonate was filtered off and acetone was removed by distillation to obtain solid residue. The solid residue after washing with water gave the desired compound as a white powder with melting point 195-197° C. The product was characterized by its IR and UV spectral analysis which can be seen in FIG. 1 and FIG. 2 respectively.
Example 2 Stabilization of polypropylene by 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether
5000 ppm of 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether was added to unstabilized polypropylene powder and extruded with single screw extruder in the form wires which was palletized. The pelltized sample of polypropylene was subjected to DSC to test for the stabilization (or Oxidative Induction Time determination). The results are shown in FIG. 3, which shows that 1,6-bis[N-(4-hydroxyphenyl)-3-(2,6-di-tert-butyl, 4-hydroxyphenyl)propionamide]hexyl ether has a significantly higher oxidative induction time than commercially available Irganox®.
Example 3 Macromolecular Antioxidants Linked Via Linkers
3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide was synthesized by the method described in our earlier work (Provisional Patent Application No. 60/633,196, filed Dec. 3, 2004) A linker was attached to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide at the phenolic hydroxyl using methylbromoacetate. The reaction was done in dry acetone and in presence of potassium carbonate at refluxing condition.
Scheme 2, synthesis of methyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide
3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide, methylbromoacetate and potassium carbonate were taken in equal molar ratio and dissolved in dry acetone. The reaction was conducted at refluxing condition and under nitrogen atmosphere. The reaction was monitored by TLC. After the consumption of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide, the reaction mixture was filtered to remove the potassium carbonate and then acetone was removed on rota-vapor. Now the solid reaction mixture was dumped into ice-cooled water to get the precipitate of methyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide. Methyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide was characterized by NMR. Performance was checked in polypropylene at 5000 ppm using DSC which shows 28.8 min of OIT (FIG. 5).
Example 4 Coupling of methyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide with pentaerythritol
The reaction was performed in bulk. The reaction was started at 100° C. under vacuum and in nitrogen atmosphere. The temperature was raised to 120° C. after melting of the reaction mixture. The reaction was monitored by TLC. After complete conversion of pentaerythritol, the reaction was worked-up to get the pentaerythritol coupled with 13-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-(4-hydroxyphenyl)propanamide and characterized by NMR.
Example 5 Fe-Salen Biomimetic Catalyzed Synthesis of Polymeric Macromolecular antioxidant N-phenyl-para-phenylene-diamine (AO-1)
N-phenyl-p-phenylenediamine (5 g) was dissolved in THF (50 ml) and 100 mg of Fe-Salen was added to it. To the reaction mixture 25% hydrogen peroxide (equimolar) solution was added incrementally over the period of 1 hour. After completion of addition, the reaction mixture was stirred for additional 24 hours. After completion of reaction THF was removed, product washed with water and dried
Example 6 Fe-Salen Biomimetic Catalyzed Synthesis of Polymeric Macromolecular antioxidant diaminonapthlene (AO-2)
1,5-diamino-napthalene (5 g) was dissolved in THF (50 ml) and 100 mg of Fe-Salen was added to it. To the reaction mixture 25% hydrogen peroxide (equimolar) solution was added incrementally over the period of 1 hour. After completion of addition, the reaction mixture was stirred for additional 24 hours. After completion of reaction THF was removed, product washed with water and dried.
Example 7 HRP Catalyzed Synthesis of Copolymeric Macromolecular Antioxidant n-phenyl-para-phenylene-diamine and napthylamine (AO-3)
N-phenyl-p-phenylenediamine (3 g) and 1-amino-napthalene (2 g) were dissolved in MeOH: pH=4.3 (100 ml) phosphate buffer and 100 mg of HRP enzyme was added to it. To the reaction mixture 5% hydrogen peroxide (equimolar) solution was added incrementally over the period of 3 hours. After completion of addition, the reaction mixture was stirred for additional 24 hours. After completion of reaction methanol and water were removed, and the product was washed with water and dried.
Example 8 Evaluation of Polymeric Macromolecular Antioxidants in Synthetic Ester Based Lubricant Oil
The oxidative stability of the polyol ester base stock samples containing 200 ppm by weight of polymeric macromolecular antioxidants were evaluated on the basis of their OIT values. FIG. 6 shows the isothermal DSC curves representing the exothermic thermal-oxidative degradation at 200° C. for polyol ester base stock. Data in FIG. 6 suggests that the sample containing commercially used APAN (alkylated phenyl naphthalene amine) and DODP (di-octylated diphenyl amine) have significantly lower resistance to oxidative degradation compared to polymeric macromolecular antioxidants. The OIT values for the samples containing 200 ppm of commercial antioxidants are 14.8 min and 16.5 min, respectively. On the other hand, the samples containing 200 ppm polymeric macromolecular antioxidants AO1, AO2 and AO3 showed significantly higher OIT values of 78 min, 92 min and 58 min, respectively.
Example 9 Evaluation of Polymeric Macromolecular Antioxidants in Polyolefins
The isothermal oxidative induction time (OIT) is used to compare the performance macromolecular antioxidant in polyolefins. The polypropylene (PP) samples were extruded into small pellets by mixing with 5000 ppm by weight of antioxidants. The OIT values for PP containing macromolecular antioxidant AO1 and Irganox® 1010 are 90 minutes and 39 minutes, respectively (FIG. 7)
1. A method of preventing oxidation comprising combining an oxidizable material with a polymer comprises at least one repeating unit represented by a structural formula selected from VIIa, VIIb, VIIIa, VIIIb or a combination thereof:
2. The method of claim 1, wherein the polymer comprises at least one repeating unit represented by a structural formula selected from VIIa, VIIb or a combination thereof.
i and j are 0.
4. The method of claim 1, wherein the polymer comprises at least one repeating unit represented by a structural formula selected from VIIIa, VIIIb or a combination thereof.
i is 0; and
j is 1.
6. The method of claim 1, wherein the polymer comprises at least one repeating unit represented by a structural formula selected from:
US12583012 2005-10-27 2009-08-12 Macromolecular antioxidants and polymeric macromolecular antioxidants Abandoned US20100084607A1 (en)
US73112505 true 2005-10-27 2005-10-27
US11588824 US20070106059A1 (en) 2005-10-27 2006-10-27 Macromolecular antioxidants and polymeric macromolecular antioxidants
US12583012 US20100084607A1 (en) 2005-10-27 2009-08-12 Macromolecular antioxidants and polymeric macromolecular antioxidants
US20100084607A1 true true US20100084607A1 (en) 2010-04-08
ID=38004683
US11588824 Abandoned US20070106059A1 (en) 2005-10-27 2006-10-27 Macromolecular antioxidants and polymeric macromolecular antioxidants
US12583012 Abandoned US20100084607A1 (en) 2005-10-27 2009-08-12 Macromolecular antioxidants and polymeric macromolecular antioxidants
US (2) US20070106059A1 (en)
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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHOLLI, ASHOK L.;KUMAR, RAJESH;DHAWAN, ASHISH;AND OTHERS;SIGNING DATES FROM 20061118 TO 20070105;REEL/FRAME:023643/0543