Flame retardant acrylic/PLA copolymer

Patent metadata

Field	Value
Publication number	US-9422386-B2
Application number	US-201414513349-A
Country	US
Kind code	B2
Filing date	Oct 14, 2014
Priority date	Oct 14, 2014
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

A flame retardant acrylic/polylactic acid (PLA) copolymer is synthesized which contains a FR-PMMA block that includes either a poly(MMAP) block or a poly(MMA-co-MMAP) block, wherein MMA is methyl methacrylate and MMAP is a MMA-like monomer that is functionalized with a phosphorus-containing moiety. In some embodiments, the flame retardant acrylic/PLA copolymer is a diblock copolymer containing a PLA block and a FR-PMMA block. In other embodiments, the flame retardant acrylic/PLA copolymer is a triblock-graft copolymer containing a PLA block, a PMMA block and a FR-PMMA block.

First claim

What is claimed is:

1. A flame retardant acrylic/polylactic acid (PLA) copolymer, comprising:
a diblock copolymer containing a PLA block and a poly(MMA-co-MMAP) block, wherein MMA is methyl methacrylate and MMAP is a MMAP monomer represented by the following formula:

wherein FR is a phosphorus-containing moiety.

2. The flame retardant acrylic/PLA copolymer as recited in claim 1 , wherein the diblock copolymer is represented by the following formula:

wherein FR is the phosphorus-containing moiety.

3. The flame retardant acrylic/PLA copolymer as recited in claim 1 , wherein the diblock copolymer is represented by the following formula:

wherein Ph is a phenyl group.

4. A flame retardant acrylic/polylactic acid (PLA) copolymer, comprising:
a diblock copolymer containing a PLA block and a poly(MMAP) block, wherein MMAP is a MMAP monomer represented by the following formula:

wherein FR is a phosphorus-containing moiety, wherein the diblock copolymer is synthesized by a method comprising the steps of:
reacting 2-hydroxyethyl 2-bromoisobutyrate (HEBIB) and lactide in the presence of tin(II) 2-ethylhexanoate (Sn(Oct) 2 ) via ring-opening polymerization (ROP) to prepare a PLA-based polymer;
reacting the PLA-based polymer and the MMAP monomer in the presence of CuBr and N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) via atom transfer radical polymerization (ATRP) to prepare the diblock copolymer containing the PLA block and the poly(MMAP) block.

5. The flame retardant acrylic/PLA copolymer as recited in claim 2 , wherein the diblock copolymer is synthesized by a method comprising the steps of:
reacting 2-hydroxyethyl 2-bromoisobutyrate (HEBIB) and lactide in the presence of tin(II) 2-ethylhexanoate (Sn(Oct) 2 ) via ring-opening polymerization (ROP) to prepare a PLA-based polymer;
reacting the PLA-based polymer, MMA and the MMAP monomer in the presence of CuBr and N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) via atom transfer radical polymerization (ATRP) to prepare the diblock copolymer containing the PLA block and the poly(MMA-co-MMAP) block.

6. An article of manufacture comprising the flame retardant acrylic/PLA copolymer as recited in claim 1 , wherein the flame retardant acrylic/PLA copolymer is blended with at least one of PLA and PMMA.

7. A flame retardant acrylic/polylactic acid (PLA) copolymer, comprising:
a triblock-graft copolymer containing PLA grafted outer blocks, linear PMMA outer blocks, and either a linear poly(MMAP) inner block or a linear poly(MMA-co-MMAP) inner block, wherein the linear PMMA outer blocks and either the linear poly(MMAP) inner block or the linear poly(MMA-co-MMAP) inner block define the backbone of the triblock-graft copolymer, wherein the PLA grafted outer blocks are grafted to the linear PMMA outer blocks, wherein MMA is methyl methacrylate and MMAP is a MMAP monomer represented by the following formula:

wherein FR is a phosphorus-containing moiety.

8. The flame retardant acrylic/PLA copolymer as recited in claim 7 , wherein the triblock-graft copolymer contains the linear poly(MMAP) inner block, and wherein the triblock-graft copolymer is represented by the following formula:

wherein FR is the phosphorus-containing moiety.

9. The flame retardant acrylic/PLA copolymer as recited in claim 7 , wherein the triblock-graft copolymer contains the linear poly(MMA-co-MMAP) inner block, and wherein the triblock-graft copolymer is represented by the following formula:

wherein FR is the phosphorus-containing moiety.

10. The flame retardant acrylic/PLA copolymer as recited in claim 7 , wherein the triblock-graft copolymer contains the linear poly(MMA-co-MMAP) inner block, and wherein the triblock-graft copolymer is represented by the following formula:

wherein Ph is a phenyl group.

11. The flame retardant acrylic/PLA copolymer as recited in claim 8 , wherein the triblock-graft copolymer is synthesized by a method comprising the steps of:
reacting HEMA and MMA in the presence of methyl a-bromoisobutyrate, CuBr and N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) via atom transfer radical polymerization (ATRP) to prepare a MMA-based copolymer;
reacting the MMA-based copolymer and the MMAP monomer in the presence of CuBr and PMDETA via ATRP to prepare a diblock copolymer containing a linear PMMA block and a linear poly(MMAP) block;
reacting the diblock copolymer, MMA and HEMA in the presence of CuBr and PMDETA via ATRP to prepare a triblock polymer containing the linear PMMA outer blocks and the linear poly(MMAP) inner block;
reacting the triblock copolymer and lactide in the presence of tin(II) 2-ethylhexanoate (Sn(Oct) 2 ) via ring-opening polymerization (ROP) to prepare the triblock-graft copolymer containing the PLA grafted outer blocks, the linear PMMA outer blocks, and the linear poly(MMAP) inner block.

12. The flame retardant acrylic/PLA copolymer as recited in claim 9 , wherein the triblock-graft copolymer is synthesized by a method comprising the steps of:
reacting HEMA and MMA in the presence of methyl α-bromoisobutyrate, CuBr and N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) via atom transfer radical polymerization (ATRP) to prepare a MMA-based copolymer;
reacting the MMA-based copolymer, MMA and the MMAP monomer in the presence of CuBr and PMDETA via ATRP to prepare a diblock copolymer containing a linear PMMA block and a linear poly(MMA-co-MMAP) block;
reacting the diblock copolymer, MMA and HEMA in the presence of CuBr and PMDETA via ATRP to prepare a triblock copolymer containing the linear PMMA outer blocks and the linear poly(MMA-co-MMAP) inner block;
reacting the triblock copolymer and lactide in the presence of tin(II) 2-ethylhexanoate (Sn(Oct) 2 ) via ring-opening polymerization (ROP) to prepare the triblock-graft copolymer containing the PLA grafted outer blocks, the linear PMMA outer blocks, and the linear poly(MMA-co-MMAP) inner block.

13. An article of manufacture comprising the flame retardant acrylic/PLA copolymer as recited in claim 7 , wherein the flame retardant acrylic/PLA copolymer is blended with at least one of PLA and PMMA.

14. A flame retardant acrylic/polylactic acid (PLA) copolymer, comprising:
a triblock-graft copolymer containing PLA grafted outer blocks, a linear PMMA inner block, linear PMMA outer blocks, and either poly(MMAP) grafted inner blocks or poly(MMA-co-MMAP) grafted inner blocks, wherein the linear PMMA blocks define the backbone of the triblock-graft copolymer, and wherein the PLA grafted outer blocks are grafted to the linear PMMA outer blocks and either the poly(MMAP) grafted inner blocks or the poly(MMA-co-MMAP) grafted inner blocks are grafted to the linear PMMA inner block, wherein MMA is methyl methacrylate and MMAP is a MMAP monomer represented by the following for

Assignees

• IBM

Inventors

• Boday Dylan J
• Kuczynski Joseph
• Mauldin Timothy C

Classifications

• C08F291/06

  on to oxygen-containing macromolecules · CPC title

• C08F291/08

  on to macromolecules containing hydroxy radicals · CPC title

• C08F293/005 Primary

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08G63/08

  Lactones or lactides · CPC title

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title