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US 10,118,989 B2Granted
Methods of forming block polymers for directed self-assembly
AssigneeInternational Business Machines Corporation
InventorsAnindarupa Chunder, Daniel P. Sanders, Ankit Vora
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Abstract
Block polymers are formed by ring opening polymerization (ROP) of a cyclic carbonate monomer using a polymeric initiator for the ROP that comprises repeating functionalized ethylene units. The block polymers are free of, or substantially free of, any polymer having a chemical structure that does not comprise the polymer backbone of the polymeric initiator. The block polymers are capable of directed self-assembly.
Claims21
A method, comprising:
- i) providing a mathematical function F(t) for a ring opening polymerization (ROP) of a cyclic carbonyl monomer, wherein
- F(t) expresses an amount of consumed cyclic carbonyl monomer as a function of ROP duration time t for a given set of reaction conditions,
- the ROP utilizes a reaction mixture initially comprising the cyclic carbonyl monomer, a polymeric initiator for the ROP, a ROP catalyst, and a solvent,
- the polymeric initiator comprises i) a polymer backbone comprising repeating functionalized ethylene units and ii) 1 to 2 nucleophilic groups linked to respective end groups of the polymer backbone, the nucleophilic groups capable of initiating the ROP of the cyclic carbonyl monomer,
- F(t) has a duration time t1>0 corresponding to 50% consumption of the cyclic carbonyl monomer,
- F(t) has duration times t2 and t3 wherein t3>t2>t1,
- F(t) has a first derivative designated F′(t),
- F′(t) at t1 has a value F′(t1)=m, wherein m is a number >0
- F′(t) at t2 has a value F′(t2)=0.9m, and
- F′(t) at t3 has a value F′(t3)=0.8m;
- ii) conducting the ROP of the cyclic carbonyl monomer using the given set of reaction conditions;
- and
- iii) stopping the ROP at a ROP duration time of about t1 to about t3, thereby forming a second mixture comprising a block polymer, wherein the block polymer comprises a first block linked to a second block, the first block comprises the polymer backbone comprising repeating functionalized ethylene units, the second block comprises a backbone derived from ROP of the cyclic carbonyl monomer, the first block is substantially immiscible with the second block, the second mixture is free of, or substantially free of, any polymer having a chemical structure that contains none of the polymer backbone of the polymeric initiator, and the block copolymer is capable of self-assembly to form a phase separated domain pattern comprising alternating domains of the first block and the second block.
10 more elements
A method, comprising:
- i) providing a mathematical function F(t) for a ring opening polymerization (ROP) of a cyclic carbonyl monomer, wherein
- F(t) expresses an amount of consumed cyclic carbonyl monomer as a function of ROP duration time t for a given set of reaction conditions,
- the ROP utilizes a reaction mixture initially comprising the cyclic carbonyl monomer, a polymeric initiator for the ROP, a ROP catalyst, and a solvent,
- the polymeric initiator comprises i) a polymer backbone comprising repeating functionalized ethylene units and ii) 1 to 2 nucleophilic groups linked to respective end groups of the polymer backbone, the nucleophilic groups capable of initiating the ROP of the cyclic carbonyl monomer, and
- F(t) has a first derivative F′(t);
- ii) providing a mathematical function D(t) expressing change in F′(t) between adjacent ROP duration times, designated ΔF′(t), as a function of ROP duration time t, wherein i) ΔF′(tn)=F′(tn)−F′(tn-1) for adjacent duration times tn and tn-1, tn>tn-1, and n is a positive integer greater than or equal to 1, ii) D(t) has a first derivative designated D′(t), and iii) D′(t) has a duration time t′>0 wherein D′(t′)=0;
- iii) conducting the ROP of the cyclic carbonyl monomer using the given set of reaction conditions;
- and
- iv) stopping the ROP at a polymerization duration time of 0.8t′ to t′, thereby forming a second mixture comprising a block polymer capable of self-assembly, wherein the block polymer comprises a first block comprising the polymer backbone comprising repeating functionalized ethylene units, the first block being linked by a polymer chain end group to a second block comprising a polymer backbone derived from the cyclic carbonyl monomer, the first block is substantially immiscible with the second block, the second mixture is substantially free of any polymer having a chemical structure that contains none of the polymer backbone of the polymeric initiator, and the block copolymer is capable of self-assembly to form a phase separated domain pattern comprising alternating domains of the first block and the second block.
6 more elements
Dependencies are inferred from the claim text.