Water-soluble block copolymer and use thereof as a support material for 3D printing

Patent metadata

Field	Value
Publication number	US-10487168-B2
Application number	US-201515538271-A
Country	US
Kind code	B2
Filing date	Dec 14, 2015
Priority date	Dec 23, 2014
Publication date	Nov 26, 2019
Grant date	Nov 26, 2019

Abstract

The invention relates to a novel type of sacrificial polymer or support material for 3D printing, comprising a block copolymer consisting of:
at least one partially or totally hydrophilic elastomeric block, with a Tg of less than 30° C. and comprising at least one hydrophilic monomer, and at least one water-soluble thermoplastic block with a Tg of greater than 30° C. and comprising at least one monomer bearing a carboxyl group,

said copolymer being extrudable and granulable, said copolymer being partially or totally soluble in water or in aqueous medium, and the mass proportion of the thermoplastic block being greater than 50% of the weight of said copolymer.

First claim

The invention claimed is:

1. A support material for an additive system for a digital manufacture of objects, said support material comprising a block copolymer, wherein the block copolymer comprises:
at least one partially or totally hydrophilic elastomeric block, wherein the elastomeric block has a Tg of less than 30° C. and comprises at least one hydrophilic monomer, and
at least one water-soluble thermoplastic block, wherein the thermoplastic block has a Tg of greater than 30° C. and comprises at least one monomer bearing a carboxyl group;
wherein the copolymer is partially or totally soluble in water or in aqueous medium, and a mass proportion of the thermoplastic block is greater than 50% of a weight of the block copolymer, and
wherein the block copolymer has a structure: P(BA-MPEGMA)-b-P(BA-S-MAA),
BA represents butyl acrylate,
MPEGMA represents methoxypolyethylene glycol methacrylate,
S represents styrene, and
MAA represents methacrylic acid.

2. The support material according to claim 1 , wherein the mass content of carboxyl functions in the block copolymer ranges from 10 to 40%, relative to the weight of the block copolymer.

3. The support material according to claim 1 , wherein the block copolymer is extrudable and granulable.

4. The support material according to claim 1 , wherein a mass proportion of the thermoplastic block is greater than or equal to 60% of a weight of said copolymer.

5. The support material according to claim 1 , wherein a Tg of said thermoplastic block of said block copolymer is between 50° C. and 250° C.

6. The support material according to claim 1 , wherein the block copolymer has a weight-average molecular mass of 10,000 to 1,000,000 g/mol.

7. The support material according to claim 1 , wherein the block copolymer has a weight-average molecular mass of 50,000 to 300,000 g/mol.

8. The support material according to claim 1 , wherein the block copolymer has a number-average molecular mass of 10,000 to 50,000 g/mol.

9. The support material according to claim 1 , wherein the block copolymer has a polydispersity index of less than 4.

10. The support material according to claim 1 , wherein the block copolymer has a polydispersity index of less than 2.

Assignees

• Arkema France

Inventors

• Inoubli Raber
• Bourrigaud Sylvain

Classifications

• C08F2438/02

  Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO] · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title

• C08F293/005 Primary

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

• B29C64/40 Primary

  Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof · CPC title

• B29C64/153

  using layers of powder being selectively joined, e.g. by selective laser sintering or melting · CPC title