Polyhydroxyurethane microparticles, and process for producing same

Patent metadata

Field	Value
Publication number	US-9416227-B2
Application number	US-201214111135-A
Country	US
Kind code	B2
Filing date	Apr 24, 2012
Priority date	May 2, 2011
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

Abstract

A problem is to provide polyhydroxyurethane microparticles, which have a narrow particle size distribution and are applicable to a wide range of use. Provided are polyhydroxyurethane microparticles which are spherical polymer microparticles having particle sizes of 0.1 μm to 300 μm. A polymer that makes up the polymer microparticles has in a structure thereof chemical structure units represented by the following formula (1) and/or chemical structure units represented by the following formula (2). In the chemical structure units (1) and (2), —O—CO— bonds have been derived from carbon dioxide.

First claim

The invention claimed is:

1. Polyhydroxyurethane microparticles,
wherein the polyhydroxyurethane microparticles are spherical polymer microparticles having a particle size in a range from 1 μm to 300 μm,
a polymer that forms the polymer microparticles is a product of an addition reaction between a first compound having at least three 5-membered cyclic carbonate groups as reactive groups and a second compound having at least two amino groups as reactive groups,
in a process of the addition reaction, both the first compound and the second compound are present at an equivalent ratio of functional groups in a range from 0.7 to 1.5 as defined by a following equation:
the equivalent ratio of functional groups =(mass of the first compound in a composition×a number of the carbonate groups in the first compound/molecular weight of the first compound)/ (mass of the second compound in the composition×a number of amino groups in the second compound/molecular weight of the second compound)

where the number of the carbonate groups as the functional groups in the first compound means a number of cyclic carbonate structures that the first compound has in a molecule thereof, and the number of the amino groups as the functional groups in the second compound means the number of amino groups that the second compound has in a molecule thereof, and

the polymer comprises therein at least one chemical structure unit selected from the group consisting of a unit of formula (1) and a unit of formula (2), and
—O—CO— bonds present in the chemical structure unit of the formula (1) and the chemical structure unit of the formula (2), respectively, are derived from carbon dioxide

2. The polyhydroxyurethane microparticles according to claim 1 ,
wherein the —O—CO— bonds present in the chemical structure unit of the formula (1) and the chemical structure unit of the formula (2), respectively, each are derived from, as the reactive group, the 5-membered cyclic carbonate group of the first compound that incorporates carbon dioxide as one of raw materials, and
the —O—CO— bonds derived from carbon dioxide are contained in an amount range from 1 to 30 mass % in the polymer that forms the polymer microparticles.

3. The polyhydroxyurethane microparticles according to claim 1 ,
wherein, the first compound is at least one compound selected from the group consisting of

4. The polyhydroxyurethane microparticle according to claim 1 ,
wherein the polyhydroxyurethane microparticles are in a powder form.

5. The polyhydroxyurethane microparticles according to claim 1 ,
wherein the polyhydroxyurethane microparticles have a degree of roundness of no lower than 0.94,
wherein the degree of roundness is obtained by a following formulae:
the degree of roundness=a perimeter of a circle as determined from an equivalent circle diameter/a perimeter of a projected microparticle image,

where the projected microparticle image is obtained with a particle shape image analyzer.

6. A process for producing the polyhydroxyurethane microparticles according to claim 1 , comprising:
forming the polymer microparticles being dispersed in an inert liquid by reacting the first compound that has at least three 5-membered cyclic carbonate groups as reactive groups with the second compound that has at least two amino groups as reactive groups, homogeneously dispersing these compounds in the inert liquid with a dispersant contained therein, and then heating the resulting dispersion,
wherein the reaction between the first compound and the second compound is the adding reaction,
in the reacting process, both the first and second compounds are present at an equivalent ratio of functional groups, as defined by a following equation, in a range from 0.7 to 1.5.

7. The process according to claim 6 ,
wherein the first compound having the 5-membered cyclic carbonate groups as the reactive groups has been synthesized using carbon dioxide as one of raw materials, and
the —O—CO— bonds are derived from carbon dioxide, and
the carbon dioxide is contained in an amount range from 1 to 30 mass % in the polymer obtained using the first compound in the reaction.

8. The process according to claim 6 ,
wherein as the dispersant, a compound that has a non-polar moiety and a polar moiety in a structure thereof is used, wherein said non-polar moiety has a polybutadiene skeleton, and said polar moiety has a 5-membered cyclic carbonate structure or a hydroxyurethane structure.

9. The process according to claim 6 , further comprising removing the inert liquid from the polymer microparticles being dispersed in the inert liquid so that the polymer microparticles in a powder form are collected.

10. The process according to claim 6 ,
wherein, the first compound is at least one compound selected from the group consisting of

11. Polyhydroxyurethane microparticles,
wherein the polyhydroxyurethane microparticles are spherical polymer microparticles having an average particle size in a range from 5.0 μm to 10.5 μm,
a polymer that forms the polymer microparticles is a product of an addition reaction between a first compound having at least three 5-membered cyclic carbonate groups as reactive groups and a second compound having at least two amino groups as reactive groups,
in a process of the addition reaction, both the first compound and the second compound are present at an equivalent ratio of functional groups in a range from 0.7 to 1.5 as defined by a following equation:
the equivalent ratio of functional groups =(mass of the first compound in a composition×a number of the carbonate groups in the first compound/molecular weight of the first compound)/ (mass of the second compound in the composition×a number of amino groups in the second compound/molecular weight of the second compound)

where the number of the carbonate groups as the functional groups in the first compound means a number of cyclic carbonate structures that the first compound has in a molecule thereof, and the number of the amino groups as the functional groups in the second compound means the number of amino groups that the second compound has in a molecule thereof, and

the polymer comprises therein at least one chemical structure unit selected from the group consisting of a unit of formula (1) and a unit of formula (2), and
—O—CO— bonds present in the chemical structure unit of the formula (1) and the chemical structure unit of the formula (2), respectively, are derived from carbon dioxide

12. The polyhydroxyurethane microparticles according to claim 11 ,
wherein the —O—CO— bonds present in the chemical structure unit of the formula (1) and the chemical structure unit of the formula (2), respectively, each are derived from, as the reactive group, the 5-membered cyclic carbonate group that incorporates carbon dioxide as one of raw materials, and
the —O—CO— bonds derived from carbon dioxide are contained in an amount range from 1 to 30 mass % in the polymer that forms the polymer microparticles.

13. The polyhydroxyurethane microparticles according to claim 11 ,
wherein, t

Assignees

• Uruno Manabu
• Takahashi Kenichi
• Kimura Kazuya
• Hanada Kazuyuki
• Dainichiseika Color Chem

Inventors

• Uruno Manabu
• Takahashi Kenichi
• Kimura Kazuya
• Hanada Kazuyuki

Classifications

• C08G71/04 Primary

  Polyurethanes · CPC title

• Y10T428/2982

  Particulate matter [e.g., sphere, flake, etc.] · CPC title