High temperature performance polymers for stereolithography

• US 6,054,250 A
• Filed: 01/26/1998
• Issued: 04/25/2000
• Est. Priority Date: 02/18/1997
• Status: Expired due to Fees

• Current Assignee: Alliedsignal Inc.
• Original Assignee: Alliedsignal Inc.
• Inventors: Koljack, Mathias P., Sitzmann, Eugene V., Anderson, Russell F., Cruz, Julietta G., Srivastava, Chandra M.
• Primary Examiner(s): Hamilton, Cynthia
• Application Number:
  US09/013,159
• Time in Patent Office: 820 Days
• Field of Search: 430/280.1, 522/103, 522/170
• US Class Current: 430/280.1
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08F 283/10 on to polymers containing more than one epoxy radical per molecule C08F283/004 takes precedence
• CPC Class Codes: C08F 283/105 on to unsaturated polymers containing more than one epoxy radical per molecule
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence

Abstract

The present invention relates to polymer precursors used in sterolithography. Specifically, the invention provides a novel resin having a glass transition temperature (Tg) that is substantially higher than any existing resins. The polymer precursors comprise an admixture of at least one vinyl ether, functionalized compound and at least one epoxy functionalized compound, at least one acrylate functionalized compound, and a photoinitiator, wherein the polymer precursor composition cures by a dual cure mechanism utilizing a free radical pathway as well as a cationic pathway thus yielding improved green strength.

Claims

1. A liquid polymer precursor comprising:

from about 5 to about 15 weight percent of at least one vinyl ether functionalized compound;

an amount of at least one epoxy functionalized compound ranging from about 2 to about 10 times the weight of vinyl ether functionalized compound in the precursor composition;

an amount of at least one acrylate functionalized compound ranging from about 2 to about 8 times the weight of vinyl ether functionalized compound in the precursor composition; and

at least one photoinitiator wherein the epoxy functionalized compounds, the vinyl ether functionalized compounds and the acrylate functionalized compounds are present in the composition in an amount sufficient to ensure that upon photoinitiation, the epoxy functionalized compounds polymerize primarily by cationic chain transfer polymerization and wherein the vinyl ether functionalized compounds polymerize primarily by radical polymerization and combine with the acrylate functionalized compounds to form a copolymer.

2. The liquid polymer precursor of claim 1 wherein the photoinitiator is from about 1.0 to about 3.0 pph of a cationic photoinitiator and from about 0.4 to about 4.0 wt % of a free radical photoinitiator.

3. The liquid polymer precursor of claim 2 wherein the cationic photoinitiator is selected from the group consisting of Ar₃ S⁺ SbF₆^- and Ar₂ I⁺ coupled with phosphate or antiminate counterions, and mixtures thereof.

4. The liquid polymer precursor of claim 1 wherein the vinyl ether functionalized compounds are selected from the group consisting of difunctional and polyfunctional vinyl ether terminated monomers, oligomers, and mixtures thereof.

5. The liquid polymer precursor of claim 1 wherein the epoxy functionalized compound is present in the precursor in an amount ranging from about 4 to about 7 times the weight of the vinyl ether functionalized compound in the precursor.

6. The liquid polymer precursor of claim 5 wherein the epoxy functionalized compound includes cycloaliphatic diepoxies.

7. The liquid polymer precursor of claim 1 wherein the acrylate functionalized compound is present in the precursor composition in an amount ranging from about 3 to about 5 times the weight of vinyl ether functionalized compound in the precursor.

8. The liquid polymer precursor of claim 7 wherein the acrylate functionalized compound is at least on non-volatile diacrylate having a viscosity of from about 300 to about 1000 centipoise.

9. The liquid polymer precursor of claim 8 including from about 5.0 to about 15 wt % of at least one diol.

10. The liquid polymer precursor of claim 1 further including at least one compound selected from the group consisting of alcohols, diols, polyols, and mixtures thereof.

11. The liquid polymer precursor of claim 1 having a viscosity of from about 200 to about 10,000 centipoise.

12. The liquid polymer precursor of claim 1 including pyrene.

13. The liquid polymer precursor of claim 12 including from about 0.05 to about 0.5 pph pyrene.

14. A liquid polymer precursor comprising:

from about 5 to about 15 weight percent of difunctional, and polyfunctional vinyl ether terminated monomers, oligomers and mixtures thereof;

at least one cycloaliphatic diepoxy in an amount of from 4 to 7 times the amount of the vinyl ether present in the polymer precursor;

at least one non-volatile diacrylate in an amount of from 3 to 5 times the amount of vinyl ether present in the polymer precursor;

at least one cationic photoinitiator;

at least one free radical photoinitiator; and

at least one compound selected from the group consisting of alcohols, diols, polyols, and mixtures thereof wherein the epoxy functionalized compounds, the vinyl ether functionalized compounds and the acrylate functionalized compounds are present in the composition in an amount sufficient to ensure that upon photoinitiation, the epoxy functionalized compounds polymerize primarily by cationic chain transfer polymerization and wherein the vinyl ether functionalized compounds polymerize primarily by radical polymerization and combine with the acrylate functionalized compounds to form a copolymer.

15. A liquid polymer precursor comprising:

from about 5 to about 15 weight percent bis-(4-vinyl oxy butly)isophthalate vinyl ether;

at least one cycloaliphatic diepoxy having the following composition;

##STR2## in an amount of from 4 to 7 times the amount of the vinyl ether present in the polymer precursor;

ethoxylated bis phenol A diacrylate in an amount of from 3 to 5 times the amount of vinyl ether present in the polymer precursor;

at least one cationic photoinitiator;

at least one free radical photoinitiator; and

at least one diol or polyol having a molecular weight greater than 200.