阅读说明：本技术 可固化组合物 (Curable composition ) 是由 B.麦克格雷尔 W.沃尔夫 于 2018-12-04 设计创作，主要内容包括：杂环官能树脂比如环氧化物、氧杂环丁烷类、环状碳酸酯、丙交酯类和内酯与烯属不饱和材料比如(甲基)丙烯酸根化合物一起用于辐射固化性配方中,以与含有所述烯属不饱和材料但是没有杂环官能树脂的配方相比,在由其制备的固化组合物中实现改善的机械性质和/或更低的收缩率。使用不饱和羧酸或酸酐制备的可聚合烯属不饱和金属络合物比如Zn和Ca羧酸盐,可被用于实现这样的配方的杂环官能树脂的热固化,这在3D打印制品等的制造中是特别有用的。(Heterocyclic functional resins such as epoxides, oxetanes, cyclic carbonates, propionates, and lactones are used in radiation curable formulations with ethylenically unsaturated materials such as (meth) acrylate compounds to achieve improved mechanical properties and/or lower shrinkage in cured compositions prepared therefrom as compared to formulations containing the ethylenically unsaturated materials but without the heterocyclic functional resin. Polymerizable ethylenically unsaturated metal complexes prepared using unsaturated carboxylic acids or anhydrides, such as Zn and Ca carboxylates, can be used to effect thermal curing of heterocyclic functional resins of such formulations, which is particularly useful in the manufacture of 3D printed articles and the like.)

1. A curable composition comprising:

a) at least one polymerizable ethylenically unsaturated metal complex;

b) at least one polymerizable ethylenically unsaturated compound different from the polymerizable ethylenically unsaturated metal complex, and

c) at least one polymerizable heterocyclic moiety-containing compound different from the epoxy-containing compound.

2. The curable composition of claim 1 wherein the at least one polymerizable ethylenically unsaturated metal complex comprises at least one polymerizable ethylenically unsaturated metal complex comprising at least one (meth) acrylate group.

3. The curable composition of claim 1 wherein the at least one polymerizable ethylenically unsaturated metal complex comprises at least one polymerizable ethylenically unsaturated metal complex comprising a metal selected from the group consisting of Zn, Ti, Ca, Mg, Al, Zr, Hf, Ga, Cr, L a, Ce, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and L u.

4. The curable composition of any one of claims 1-3 wherein the at least one polymerizable ethylenically unsaturated metal complex comprises at least one polymerizable ethylenically unsaturated metal carboxylate salt prepared by reacting (A) a metal compound with (B) an acid functional compound which is the reaction product of a reactive mixture comprising (i) α to β ethylenically unsaturated hydroxyl functional compound and (ii) a carboxylic acid-based polyacid or anhydride.

5. The curable composition of any one of claims 1-4 wherein the at least one polymerizable ethylenically unsaturated metal complex comprises at least one polymerizable ethylenically unsaturated metal complex comprising an ethylenically unsaturated β -diketonate ligand.

6. The curable composition of any one of claims 1-5, wherein the at least one polymerizable heterocyclic moiety-containing compound c) comprises at least one polymerizable heterocyclic moiety-containing compound selected from oxetanes, cyclic carbonates, propionates, and lactones, or wherein the curable composition comprises a) at least one polymerizable heterocyclic moiety-containing compound selected from oxetanes, cyclic carbonates, propionates, and lactones, and b) at least one epoxide.

7. The curable composition of any one of claims 1 to 6, wherein the at least one polymerizable heterocyclic moiety-containing compound c) comprises at least one polymerizable heterocyclic moiety-containing compound selected from the group consisting of: caprolactone, propylene carbonate, 3-ethyl-3-hydroxymethyloxetane, 3' - [1, 4-phenylenebis (methyleneoxymethylene) ] bis [ 3-ethyloxetane ], 3-ethyl-3- [ [ (2-ethylhexyl) oxy ] methyl ] oxetane, ethylene carbonate, glycerol carbonate, lactide and valerolactone.

8. The curable composition of any one of claims 1 to 7, wherein the at least one polymerizable ethylenically unsaturated compound b) different from the polymerizable ethylenically unsaturated metal complex comprises at least one (meth) acrylate functional compound.

9. The curable composition as claimed in any of claims 1 to 8, wherein the at least one polymerizable ethylenically unsaturated compound b) different from the polymerizable ethylenically unsaturated metal complex comprises at least one (meth) acrylate-and hydroxy-functional compound.

10. The curable composition as claimed in any of claims 1 to 9, wherein the at least one polymerizable ethylenically unsaturated compound b) different from the polymerizable ethylenically unsaturated metal complex comprises at least one (meth) acrylate-and epoxy-functional compound.

11. The curable composition as claimed in any one of claims 1 to 10, wherein the at least one polymerizable ethylenically unsaturated compound b) different from the polymerizable ethylenically unsaturated metal complex comprises at least one compound selected from the group consisting of: caprolactone adducts of hydroxyalkyl (meth) acrylates, tricyclodecane dimethanol diacrylate, cyclic trimethylolpropane formal acrylate, tricyclodecane methanol (meth) acrylate, tris ((meth) acryloyloxyethyl) isocyanurate, glycerol carbonate (meth) acrylate and aliphatic polyurethane acrylates.

12. The curable composition of any one of claims 1-11, additionally comprising at least one photoinitiator.

13. The curable composition of any one of claims 1-12 additionally comprising at least one impact modifier selected from the group consisting of core-shell impact modifiers and block copolymer impact modifiers.

14. The curable composition of any one of claims 1-13 having a viscosity of no greater than 1000(mpa.s) (cP) at 25 ℃.

15. A two-component system for preparing a curable composition as claimed in any one of claims 1 to 14, the two-component system comprising: a first component comprising a); and a second component comprising b) and c).

16. A curable composition comprising:

a) at least one polymerizable ethylenically unsaturated metal complex;

b) at least one polymerizable ethylenically unsaturated compound different from the polymerizable ethylenically unsaturated metal complex, and

c) at least one polymerizable heterocyclic moiety-containing compound.

17. A cured composition obtained by curing the curable composition of any one of claims 1-14 or 16.

18. A method of making a cured composition comprising exposing the curable composition of any one of claims 1-14 to radiation to obtain a partially cured composition, and heating the partially cured composition to obtain the cured composition.

19. A method of making an article comprising printing an article in a three-dimensional manner using a curable composition comprising:

a) at least one polymerizable ethylenically unsaturated metal complex;

b) at least one polymerizable ethylenically unsaturated compound different from the polymerizable ethylenically unsaturated metal complex, and

c) at least one polymerizable heterocyclic moiety-containing compound.

20. The method of claim 19, wherein the article is cured using both radiation curing and thermal curing.

21. The method of claim 19 or 20, wherein the at least one polymerizable heterocyclic moiety-containing compound comprises at least one polymerizable heterocyclic moiety-containing compound selected from the group consisting of: epoxides, oxetanes, cyclic carbonates, lactides and lactones.

22. Use of the curable composition according to any one of claims 1-14 or 16 or the two-component system according to claim 15 for the manufacture of a three-dimensional article using 3D printing techniques.

A 3D printed article, wherein it results from curing of the curable composition according to any of claims 1-14 or 16 or from use according to claim 22.

Examples

General Experimental procedures

Dynamic mechanical analysis was performed using a TA Instruments Q2000 dynamic mechanical analyzer at 0.1% strain, 5 ℃/min temperature ramp and a deformation frequency of 1Hz between-150 and 200 ℃. Samples with smaller display temperature windows become too soft outside the window shown to be measured accurately. The curable composition was photopolymerized in a mold by: passing under a lamp (e.g., a medium pressure mercury vapor lamp of microwave power commercially available from Heraeus Noblelight) at 100 feet per minute on a conveyor belt; or a 3D printer to manufacture an article of a desired shape. Cleaning the article by: wipe with a cloth wetted with isopropyl alcohol to remove residual uncured resin. The heat cured ('baked') samples were left at 125 ℃ for 16 hours in a muffle furnace or a circulating air oven unless otherwise noted.