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US 2003/0149208 A1Published application
Method of controlling polymer molecular weight and structure
OwnerAlbert G. Anderson, Alexei Gridnev +3inventors
InventorsAlbert G. Anderson, Alexei Gridnev, Graeme Moad, Ezio Rizzardo, San Hoa Thang
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Abstract
This invention concerns the preparation of polymers of low polydispersity and/or controlled molecular weight and architecture employing living free radical polymerization initiated by an alkoxyamine initiator or nitroxide plus, optionally, a free radical initiator; the polymer produced thereby; selected nitroxide and alkoxyamine initiators; and a process for making the initiators; the polymeric products being useful in protective coatings.
Claims12
A polymer of the formula:
- 20
- wherein:
- R, R1, R2, R3 are each independently selected from the group consisting of C1 to C18 alkyl, substituted C1 to C18 alkyl, C6 to C18 aryl, C6 to C18 substituted aryl;
- R groups in a geminal position with respect to each other can together form a 4-8 membered ring;
- and R groups in a cis position with respect to each other can together form a 4-8 membered ring;
- X is selected from the group consisting of hydrogen, C1 to C18 alkyl, substituted C1 to C18 alkyl, C6 to C18 aryl, C6 to C18 substituted aryl;
- acyl;
- X and R can form a 5-8 membered ring;
- and X and R3 can form a 5-8 membered ring;
- M is one or more monomer units selected from the group consisting of styrene, substituted styrene, alkyl acrylate, alkyl methacrylate, substituted alkyl acrylate, substituted alkyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethacrylamide, N,N-dialkylacrylamide, N,N-dialkylmethacrylamide, isoprene and butadiene;
- n is an integer greater than 1;
- Y is a residue derived from a species that initiates free radical polymerization or is selected from the group consisting of C1 to C18 alkyl, substituted C1 to C18 alkyl, C1 to C18 alkoxy, substituted C1 to C18 alkoxy, C6 to C18 aryl, C6 to C18 substituted aryl, C6 to C18 aroyloxy, C6 to C18 substituted aroyloxy;
- and
- all substituents are independently selected from the group that consists of epoxy, hydroxy, C1 to C18 alkoxy, acyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, cyano, silyl, halo, and C1 to C18 dialkylamino.
11 more elements
Nitroxides of the formula
- 23
- wherein:
- R, R1, R2, R3 are each independently selected from the group consisting of C1 to C18 alkyl, substituted C1 to C18 alkyl, C6 to C18 aryl, C6 to C18 substituted aryl;
- R groups in a geminal position with respect to each other can together form a 4-8 membered ring;
- and R groups in a cis position with respect to each other can together form a 4-8 membered ring;
- and
- X is selected from the group consisting of C1 to C18 alkyl, substituted C1 to C18 alkyl, C6 to C18 aryl, C6 to C18 substituted aryl;
- acyl;
- X and R can form a 5-8 membered ring;
- and X and R3 can form a 5-8 membered ring;
- with the proviso that at least one of R, R1, R2, R3 and X is not methyl.
8 more elements
An alkoxyamine of the formula
- 26
- wherein:
- R, R1, R2, R3 are each independently selected from the group consisting of C1 to C18 alkyl, substituted C1 to C18 alkyl, C6 to C18 aryl, C6 to C18 substituted aryl;
- R groups in a geminal position with respect to each other can together form a 4-8 membered ring;
- and R groups in a cis position with respect to each other can together form a 4-8 membered ring;
- X is selected from the group consisting of hydrogen, C1 to C18 alkyl, substituted C1 to C18 alkyl, C6 to C18 aryl, C6 to C18 substituted aryl;
- acyl;
- X and R can form a 5-8 membered ring;
- X and R3 can form a 5-8 membered ring;
- and
- Z is a group having at least one carbon atom and is such that the carbon centered radical Z. is capable of initiating free radical polymerization of the monomer (M).
8 more elements
A method for making the nitroxide of Formula (1):
- 27
- wherein:
- R, R1, R2, R3 are each independently selected from the group consisting of C1 to C18 alkyl, substituted C1 to C18 alkyl, C6 to C18 aryl, C6 to C18 substituted aryl;
- R groups that are in a geminal position with respect to each other can together form a 4-8 membered ring, and R groups that are in a cis position with respect to each other can together form a 4-8 membered ring;
- X is selected from the group consisting of hydrogen, C1 to C18 alkyl, substituted C1 to C18 alkyl, C6 to C18 aryl, C6 to C18 substituted aryl;
- acyl;
- X and R can form a 5-8 membered ring;
- X and R3 can form a 5-8 membered ring;
- comprising the steps:
- (i) preparing a colorless aqueous ammonium sulfide solution containing sodium thiocyanate by titrating an aqueous ammonium sulfide solution containing ammonium polysulfide with sodium cyanide under nitrogen;
- (ii) sequentially adding an aminonitrile and a ketone to the aqueous ammonium sulfide solution under nitrogen;
- (iii) adding base and then neutralizing;
- and (iv) oxidizing the reaction product of step (iii) to form the nitroxide.
10 more elements
A colorless aqueous ammonium sulfide solution containing sodium thiocyanate and substantially no ammonium polysulfide.
Dependencies are inferred from the claim text.