Photopolymerizable thermoplastics and methods of making and using same

Patent metadata

Field	Value
Publication number	US-12410283-B2
Application number	US-202017616922-A
Country	US
Kind code	B2
Filing date	Jun 8, 2020
Priority date	Jun 7, 2019
Publication date	Sep 9, 2025
Grant date	Sep 9, 2025

Abstract

In one aspect, the disclosure relates to compositions comprising semicrystalline, linear photopolymers that possesses extraordinary mechanical properties for application in 3D printing. The photopolymers are rapidly fabricated using low viscosity liquids at ambient conditions.

First claim

What is claimed is:

1. A thermoplastic polymer of formula (I):

wherein:
each occurrence of R 1 is independently selected from the group consisting of:

each of which is independently optionally substituted;
each occurrence of R 2 is independently selected from the group consisting of optionally substituted C 1 -C 15 alkylene, optionally substituted C 1 -C 15 heteroalkylene, optionally substituted C 2 -C 15 alkenylene, optionally substituted C 2 -C 15 heteroalkenylene, optionally substituted C 2 -C 15 alkynylene, and optionally substituted C 2 -C 15 heteroalkynylene;
each occurrence of p is independently an integer from 1 to 25;
each occurrence of n is independently an integer from 2 to 200,000; and
the polymer is semi-crystalline and has a melting point of about 70° C. to about 120° C.

2. The polymer of claim 1 , which is prepared from:
a monomer of formula (II):

and
a monomer of formula (III):

3. The polymer of claim 1 , wherein at least one of the following applies:
(a) each occurrence of R 1 is independently selected from the group consisting of:

(b) the polymer is selected from the group consisting of

wherein is n is an integer ranging between 2 and 200,000.

4. The polymer of claim 2 , wherein at least one of the following applies:
(a) the monomer of formula (II) is selected from the group consisting of diallyl terephthalate and diallyl cyclohexane-1,4-dicarboxylate;
(b) the monomer of formula (III) is selected from the group consisting of

wherein each occurrence of m is independently an integer from 1 to 25;
(c) the monomer of formula (III) is selected from the group consisting of

wherein the molar ratio of the monomer of formula (II) and the monomer of formula (III) in the polymer is about 1:1.

5. The polymer of claim 1 , wherein at least one of the following applies:
(a) the polymer is a linear polymer;
(b) the polymer is a continuous-phase polymer;
(c) the polymer is suitable for 3D-printing;
(d) the polymer is suitable for stereolithography (SLA) printing;
(e) the polymer has tensile strength ranging from about 15 MPa to about 35 MPa;
(f) the polymer has a toughness ranging from about 80 MJ/m 3 to about 140 MJ/m 3 .

6. A method of synthesizing a semi-crystalline continuous-phase thermoplastic polymer of formula (I), wherein the method comprises;
irradiating a mixture of
a monomer of formula (II),

a monomer of formula (III),

and a photoinitiator, and
polymerizing the mixture to form the semi-crystalline continuous-phase thermoplastic polymer of formula (I),
wherein the semi-crystalline continuous-phase thermoplastic polymer of formula (I) has a melting point of about 70° C. to about 120° C.,
wherein the polymer of formula (I) has the formula

wherein:
each occurrence of R 1 is independently selected from the group consisting of:

each of which is independently optionally substituted;
each occurrence of R 2 is independently selected from the group consisting of optionally substituted C 1 -C 15 alkylene, optionally substituted C 1 -C 15 heteroalkylene, optionally substituted C 2 -C 15 alkenylene, optionally substituted C 2 -C 15 hetero alkenylene, optionally substituted C 2 -C 15 alkynylene, and optionally substituted C 2 -C 15 heteroalkynylene;
each instance of p is independently an integer from 1 to 25; and
each instance of n is independently an integer from 2 to 200,000.

7. The method of claim 6 , wherein the mixture is irradiated with UV radiation having wavelength of about 380 nm to about 410 nm.

8. The method of claim 7 , wherein at least one of the following applies:
(a) an irradiation time of the irradiation ranges from about 2 seconds to about 30 seconds;
(b) the irradiation comprises light having intensity of about 1 mW/cm 2 to about 20 mW/cm 2 ;
(c) the polymerization occurs predominantly via thiol-ene step-growth mechanism;
(d) the polymerization takes place at a temperature ranging from about 15° C. to about 40°.

Assignees

• Univ Colorado Regents

Inventors

• Bowman Christopher N
• Alim Marvin Dion
• Mcbride Matthew K
• Kay-Childress Kimberly
• Hernandez Juan J
• Stansbury Jeffrey W

Classifications

• C08F218/16 Primary

  with alcohols containing three or more carbon atoms · CPC title

• C08F2/50

  with sensitising agents · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08G75/045 Primary

  from mercapto compounds and unsaturated compounds · CPC title

• C08F2/46

  Polymerisation initiated by wave energy or particle radiation · CPC title