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US 10,329,369 B2Granted
Process for making branched reactive block polymers
AssigneeHenkel IP & Holding GmbH
InventorsQinyan Zhu, John G. Woods
Life of this patent
Estimating the term…
Abstract
The present invention relates to controlled radical polymerization processes for making branched-functionalized block polyacrylate polymers and compositions formed therefrom. In particular, such reaction products are formed by ensuring that the reaction products are substantially flowable and non-gelling, indicating that substantially no polymerization has occurred. The branched-functionalized block polyacrylates may be further functionalized and/or polymerized.
Claims32
A polymer composition comprising:
- (i) a linear or star-shaped block polyacrylate copolymer comprising the structure:
- Ri-[{Aa}-{BbCc}—X]z (Structure III),
- wherein A is a polyacrylate block derived from a monofunctional (meth)acrylate monomer or monofunctional (meth)acrylamide monomer, BC is a random functionalized polyacrylate block, wherein portion B of the BC block contains a polymerizable group derived from a difunctional (meth)acrylate monomer or a difunctional (meth)acrylamide monomer and portion C of the BC block is derived from a monofunctional (meth)acrylate monomer or monofunctional (meth)acrylamide monomer;
- and
- (ii) a linear or star-shaped block polyacrylate copolymer comprising the structure:
- Ri-[{Aa}-{Bb-dCcDd}-X]z (Structure IV),
- wherein A is a polyacrylate block derived from a monofunctional (meth)acrylate monomer or monofunctional (meth)acrylamide monomer, and BCD is a random functionalized polyacrylate block, wherein portion B of the BCD block contains a polymerizable group derived from a difunctional (meth)acrylate monomer or a difunctional (meth)acrylamide monomer, portion C of the BCD block is derived from a difunctional (meth)acrylate monomer or a difunctional (meth)acrylamide monomer, and portion D of the BCD block includes a polymer branched-structure;
- and wherein, in each of Structures III and IV the following definitions apply:
- Ri is an initiator fragment derived from halogenated compounds which initiate metal-catalyzed controlled radical polymerization;
- X is a halogen;
- z is an integer from 1-6;
- a is 10 to 10,000;
- b is an integer in the range from a/100 to a/10;
- c is an integer in the range from a/200 to a/2;
- and
- d is an integer greater than 0 and less than b.
13 more elements
A controlled radical polymerization method for making polymerizable branched-functionalized polyacrylates comprising:
- a) in a reaction vessel, reacting an initiator having the formula
- with a monofunctional monomer having the structure
- to form a macro-initiator having a structure:
- b) Sequentially reacting in the same reaction vessel the macro-initiator Structure I with a difunctional monomer having the structure:
- wherein in each of the structures of this claim the following definitions apply;
- Ri is an initiator fragment derived from halogenated compounds which initiate metal-catalyzed controlled radical polymerization;
- R is —CH3 or H;
- a is from 10 to 10,000;
- R1 is a hydrocarbyl group C1-20 which may be interrupted by one or more heteroatoms and is substantially free of radically polymerizable groups, and which may contain one or more functional groups selected from the group consisting of hydroxyl, alkoxy, epoxy, ether, ester, amine, carbamate, amide and combinations thereof;
- G is a divalent hydrocarbyl group C1-20 which may contain one or more heteroatoms and is selected from the group consisting of alkylenes, alkylene oxides, alkylene esters and combinations thereof and;
- Q is O or NR2, wherein R2 is H or C1-4 alkyl
- X is a halogen;
- z is and integer from 1-6;
- and
- wherein the sequentially reacting is conducted for a time and at a temperature to prevent complete conversion of the difunctional monomer.
12 more elements
A polymerizable branched-functionalized polyacrylate composition comprising the controlled radical polymerization reaction products of:
- (i) a macro-initiator having the structure:
- wherein Ri is an initiator fragment derived from halogenated compounds which initiate metal-catalyzed controlled radical polymerization;
- X is a halogen;
- a is from 10 to 10,000;
- z is 1-6;
- and
- (ii) a difunctional monomer having the structure:
- wherein R in both structures I and II may be the same or different and may be —CH3 or H;
- and
- R1 is a hydrocarbyl group C1-20 which may be interrupted by one or more heteroatoms and is substantially free of radically polymerizable groups, and which may contain one or more functional groups selected from the group consisting of hydroxyl, alkoxy, epoxy, ether, ester, amine, carbamate, amide and combinations thereof;
- G is a divalent hydrocarbyl group C1-20 which may contain one or more heteroatoms and is selected from the group consisting of alkylenes, alkylene oxides, alkylene esters and combinations thereof;
- and
- Q is O or NR2, wherein R2 is H or C1-4 alkyl.
10 more elements
A controlled radical polymerization process for making flowable, branch-functionalized polyacrylates comprising:
- (i) forming a reaction mixture by feeding a mixture of one or more monofunctional (meth)acrylate monomers and at least one amine ligand at a defined flow-rate into a reaction vessel containing a solvent, and adding at least one halogenated initiator and a metal catalyst;
- (ii) sequentially feeding at least one difunctional (meth)acrylate monomer into the reaction mixture and allowing a reaction to proceed to obtain a desired degree of branch functionalized polyacrylate polymer to form, whereby the branch-functionalized polyacrylate is flowable.
Dependencies are inferred from the claim text.