Filamentous polymer particles and method for preparing same by means of controlled radical polymerisation in emulsion

Patent metadata

Field	Value
Publication number	US-9745399-B2
Application number	US-201113996703-A
Country	US
Kind code	B2
Filing date	Dec 16, 2011
Priority date	Dec 23, 2010
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

The invention relates to polymer particles in the form of filaments formed by block copolymers, as well as to the method for preparing same by means of controlled radical polymerization in emulsion in the presence of a specific living macroinitiator derived from a nitroxide. The invention is characterized in that the filamentous particles are obtained in a dispersed aqueous medium by means of the synthesis of said block copolymers, performed by heating the reaction medium at a temperature of 60 to 120° C., the final block copolymer containing between 10 and 50 mol. % of the macroinitiator which is water soluble and the hydrophobic monomer conversion rate being at least 50%. According to the invention, the weight ratio of hydrophilic fraction of the filamentous particles is less than 25 wt %.

First claim

The invention claimed is:

1. A method for preparing filamentous particles, said particles consisting of block copolymers, comprising the step of synthesizing by controlled radical emulsion polymerization at least one hydrophobic monomer in the presence of a living macroinitiator derived from a nitroxide, at a reaction temperature of 60 to 120° C., resulting in filamentous particles, wherein:
said macroinitiator is water-soluble and comprises a hydrophilic moiety, wherein the mass fraction of the hydrophilic moiety constituting the final block copolymer is less than 25%,
the mass percent of the water-soluble macroinitiator in the final block copolymer is between 10% and 50%, and
the degree of conversion by mass of the hydrophobic monomer is at least 50% and wherein said filamentous particles have a length of at least 10 microns.

2. The method as claimed in claim 1 , wherein the hydrophobic monomer is selected from the group consisting of vinylaromatic monomers alkyl, cycloalkyl, or aryl acrylates, alkyl methacrylates, cycloalkyl methacrylates, alkenyl methacrylates, aryl methacrylates, and vinylpyridine.

3. The method as claimed in claim 1 , wherein the percentage of the molar mass of the water-soluble macroinitiator in the final block copolymer is between 10% and 30%.

4. The method as claimed in claim 1 , wherein the initial pH of the reaction mixture is between 5 and 10.

5. The method as claimed in claim 1 , further comprising the step of admixing into the reaction mixture a crosslinking comonomer.

6. The method as claimed in claim 5 , wherein the crosslinking cornonomer is selected from the group consisting of divinylbenzenes, trivinylbenzenes, allyl (meth)acrylates, diallyl maleate polyol (meth)acrylates, and alkylene glycol di(meth)acrylates which have from 2 to 10 carbon atoms in the carbon chain.

7. The method as claimed in claim 1 , wherein said method is a “one pot” method comprising first synthesizing said water-soluble macroinitiator in aqueous medium, and then forming said block copolymer by addition of at least one hydrophobic monomer to the same medium.

8. The method of claim 2 , wherein said vinylaromatic monomers are selected from the group consisting of styrene and substituted styrenes; said alkyl, cycloalkyl, or aryl acrylates are selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and phenyl acrylate; and said alkyl, cycloalkyl, alkenyl, or aryl methacrylates are selected from the group consisting of methyl methacrylate, butyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, allyl methacrylate, 2-ethyl-hexyl methacrylate, and phenyl methacrylate.

Assignees

• Magnet Stephanie
• Inoubli Raber
• Couvreur Laurence
• Charleux Bernadette
• Brusseau Segolene
• Arkema France
• Centre Nat Rech Scient
• Univ Paris Curie

Inventors

• Magnet Stephanie
• Inoubli Raber
• Couvreur Laurence
• Charleux Bernadette
• Brusseau Segolene

Classifications

• C08F293/005

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

• C08F293/00 Primary

  Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02) · CPC title

• C08F2/22 Primary

  Emulsion polymerisation · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• D01F6/28

  from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title