Highly spherical polyamide microparticles and synthesis methods related thereto

Patent metadata

Field	Value
Publication number	US-12545762-B2
Application number	US-202218147633-A
Country	US
Kind code	B2
Filing date	Dec 28, 2022
Priority date	Jul 10, 2020
Publication date	Feb 10, 2026
Grant date	Feb 10, 2026

Abstract

A method of synthesizing polyamide microparticles may comprise: dehydrating and shearing a mixture comprising a matrix fluid, an emulsion stabilizer at about 0.01 wt % to about 50 wt % based on the weight of the matrix fluid, a solvent at about 13 wt % to about 75 wt % based on the weight of the matrix fluid, and a cyclic amide monomer at about 20 wt % to about 90 wt % based on the weight of the matrix fluid to yield an emulsion having a water content of about 1 wt % or less based on the total weight of the emulsion; adding a deprotonating agent to the emulsion at a concentration of about 0.01 wt % to about 1 wt % based on the weight of the matrix fluid; and contacting the emulsion with a polymerization initiator under conditions effective to polymerize the cyclic amide monomer into a plurality of polyamide microparticles.

First claim

What is claimed:

1 . A method of synthesizing polyamide microparticles comprising:
dehydrating and shearing a mixture comprising a matrix fluid, an emulsion stabilizer, a solvent, and a cyclic amide monomer to yield an emulsion having a water content of about 1 wt % or less based on a total weight of the emulsion, wherein the emulsion stabilizer comprises nanoparticles; adding a deprotonating agent to the emulsion at a concentration of about 0.01 wt % to about 1 wt % based on a weight of the matrix fluid; adding a polymerization initiator to the emulsion; and polymerizing the cyclic amide monomer into a plurality of polyamide microparticles;
wherein the polyamide microparticles have a D10 of about 0.5 μm to about 125 μm, a D50 of about 1 μm to about 200 μm, and a D90 of about 70 μm to about 300 μm, wherein D10<D50<D90.

2 . The method of claim 1 , wherein the emulsion stabilizer is at a concentration of about 0.01 wt % to about 50 wt % based on the weight of the matrix fluid.

3 . The method of claim 1 , wherein the solvent is at a concentration of about 13 wt % to about 75 wt % based on the weight of the matrix fluid.

4 . The method of claim 1 , wherein the cyclic amide monomer is at a concentration of about 20 wt % to about 90 wt % based on the weight of the matrix fluid.

5 . The method of claim 1 , wherein adding the deprotonating agent is before adding the polymerization initiator.

6 . The method of claim 1 , wherein adding the deprotonating agent is after adding the polymerization initiator.

7 . The method of claim 1 , wherein adding the deprotonating agent is at the same time as adding the polymerization initiator.

8 . The method of claim 1 , wherein the cyclic amide monomer is selected from the group consisting of azeridinone, 2-azetidinone, 2-pyrrolidinone, 2-piperidinone, ε-caprolactam, 2-azacyclooctanone, 2-azacyclononanone, 2-azacyclodecanone, 2-azacycloundecanone, 2-aza-cyclododecanone, laurolactam, and any combination thereof.

9 . The method of claim 1 , wherein a polyamide of the polyamide microparticles is selected from the group consisting of polycaproamide, poly(hexamethylene succinamide), polyhexamethylene adipamide, polypentamethylene adipamide, polyhexamethylene sebacamide, polyundecamide, polydodecamide, polyhexamethylene terephthalamide, nylon 10.10, nylon 10.12, nylon 10.14, nylon 10.18, nylon 6.10, nylon 6.18, nylon 6.12, nylon 6.14, and any copolyamide thereof.

10 . The method of claim 1 , wherein the matrix fluid comprises one selected from the group consisting of polysiloxanes modified with fatty acids, polysiloxanes modified with fatty alcohols, polysiloxanes modified with polyoxy alkylenes, polydimethylsiloxane (PDMS), methylphenylpolysiloxane, an alkyl modified polydimethylsiloxane, an alkyl modified methylphenylpolysiloxane, an amino modified polydimethylsiloxane, an amino modified methylphenylpolysiloxane, a fluorine modified polydimethylsiloxane, a fluorine modified methylphenylpolysiloxane, a polyether modified polydimethylsiloxane, a polyether modified methylphenylpolysiloxane, silicone oil, fluorinated silicone oils, perfluorinated silicone oils, polyethylene glycols, paraffins, liquid petroleum jelly, vison oils, turtle oils, soya bean oils, perhydrosqualene, sweet almond oils, calophyllum oils, palm oils, parleam oils, grapeseed oils, sesame oils, maize oils, rapeseed oils, sunflower oils, cottonseed oils, apricot oils, castor oils, avocado oils, jojoba oils, olive oils, cereal germ oils, esters of lanolic acid, esters of oleic acid, esters of lauric acid, esters of stearic acid, fatty esters, higher fatty acids, and fatty alcohols, and any combination thereof.

11 . The method of claim 1 , wherein the solvent has a boiling point greater than about 150° C.

12 . The method of claim 1 , wherein the dehydrating is performed such that about 10% to about 15% of the solvent is distilled off during the dehydrating.

13 . The method of claim 1 , wherein the polymerization initiator comprises one selected from the group consisting of toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), and any combination thereof.

14 . The method of claim 1 , wherein the deprotonating agent comprises a Group I or Group II metal hydroxide, a Group I or Group II metal hydride, potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium t-butoxide, sodium t-butoxide, lithium t-butoxide, sodium caprolactamates, ε-caprolactam magnesium bromides, sodium dicaprolactamato-bis-(2-methoxyethoxo)-aluminate, or any combination thereof.

15 . The method of claim 1 further comprising:
washing the polyamide microparticles.

16 . The method of claim 1 , wherein the polyamide microparticles have a diameter span of about 0.2 to about 10.

17 . The method of claim 1 , wherein the polyamide microparticles have a circularity of about 0.8 or greater.

18 . A method of synthesizing polyamide microparticles comprising:
dehydrating and shearing a mixture comprising a matrix fluid, an emulsion stabilizer at a concentration of about 0.01 wt % to about 50 wt % based on a weight of the matrix fluid, and a solvent at a concentration of about 13 wt % to about 75 wt % based on the weight of the matrix fluid, wherein the emulsion stabilizer comprises nanoparticles; while shearing, adding a cyclic amide monomer at a concentration of about 20 wt % to about 90 wt % based on the weight of the matrix fluid to the mixture to yield an emulsion; dehydrating the emulsion to a water content of about 1 wt % or less based on a total weight of the emulsion to yield a dehydrated emulsion; adding a deprotonating agent to the dehydrated emulsion at a concentration of about 0.01 wt % to about 1 wt % based on the weight of the matrix fluid; and contacting the dehydrated emulsion with a polymerization initiator under conditions effective to polymerize the cyclic amide monomer into a plurality of polyamide microparticles, wherein the nanoparticles are associated with an outer surface of the polyamide microparticles, and wherein the polyamide microparticles have a D10 of about 0.5 μm to about 125 μm, a D50 of about 1 μm to about 200 μm, and a D90 of about 70 μm to about 300 μm, wherein D10<D50<D90.

19 . A method of synthesizing polyamide microparticles comprising:
dehydrating and shearing a mixture comprising a matrix fluid, an emulsion stabilizer at a concentration of about 0.01 wt % to about 50 wt % based on a weight of the matrix fluid, and a solvent at a concentration of about 13 wt % to about 75 wt % based on the weight of the matrix fluid, wherein the emulsion stabilizer comprises oxide nanoparticles; while shearing, adding a cyclic amide monomer at a concentration of about 20 wt % to about 90 wt % based on the weight of the matrix fluid to the mixture to yield an emulsion; dehydrating the emulsion to a water content of about 1 wt % or less based on a total weight of the emulsion to yield a dehydrated emulsion; adding a deprotonating agent to the dehydrated emulsion at a concentration of about 0.01 wt % to about 1 wt % based on the weight of the matrix fluid; and contacting the dehydrated emulsion with a polymerization initiator under conditions effective to polymerize the cyclic amide monomer into a plurality of polyamide microparticles, wherein the oxide nanoparticles are embedded in an outer surface of the polyamide microparticles, and wherein the polyamide microparticles have a D10 of about 0.5 μm to about 125 μm, a D50 of about 1 μm to about 200 μm, and a D90 of about 70 μm

Assignees

• Xerox Corp

Inventors

• Jamali Hojjat Seyed

Classifications

• B29B2009/125

  Micropellets, microgranules, microparticles · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08J3/12

  Powdering or granulating · CPC title

• C08G69/46 Primary

  Post-polymerisation treatment · CPC title

• C08G69/20

  characterised by the catalysts used · CPC title