Co-crystallizable diacetylenic monomer compositions, crystal phases and mixtures, and related methods
View Patent ↗Solid polymerizable diacetylenic monomer compositions, including compositions co-crystallized from a diversity of solvent systems under diverse cooling conditions, can exhibit diffraction patterns associated with the color development reactivities of the compositions. High reactivity compositions are disclosed and high reactivity and low reactivity phases can be identified. A low angle powder X-ray diffraction peak can indicate the presence of one or more crystal phases in a composition. A fingerprint region can exhibit fingerprint patterns of diffraction peaks associated with different reactivities. Information about polymerization of the diacetylenic monomers is disclosed using 13 C nuclear magnetic resonance (“NMR”) characterization. Diacetylenic monomer compositions useful in ambient condition indicators, for example time-temperature indicators are disclosed.
1. A solid monomer composition comprising a first monomer and a second monomer, each said monomer having the formula:
CH 3 (CH 2 ) m1 NHCONH(CH 2 )(—C≡C—) 2 (CH 2 ) NHCONH(CH 2 ) m5 CH 3 ;
wherein
in the first monomer m1 and m5 are both 1;
in the second monomer m1 and m5 are both 2;
the solid monomer composition can exhibit an X-ray powder diffraction spectrum having three reflection peaks between a d spacing of about 4.28 Å and a d spacing of about 3.81 Å, the diffraction spectrum being collected using CuK α1 radiation;
the three reflection peaks comprise a long spacing peak at a d spacing in the range of from about 4.28 Å to about 4.18 Å, an intermediate spacing peak at a d spacing in the range of from about 4.11 Å to about 3.99 Å, and a short spacing peak at a d spacing in the range of from about 3.94 Å to about 3.81 Å; and
the solid monomer composition is thermally polymerizable to have a changed visual appearance.
2. The solid monomer composition of claim 1 wherein the X-ray powder diffraction spectrum comprises a separation between the long spacing peak and the intermediate spacing peak of from about 0.10 Å to about 0.27 Å, and a separation between the intermediate spacing peak and the short spacing peak of from about 0.07 Å to about 0.26 Å.
3. The solid monomer composition of claim 1 wherein the three reflection peaks are the highest intensity peaks for the diffraction spacing range between about 4.28 Å and 3.81 Å and wherein the intensity of the intermediate spacing peak is higher than the intensity of either the long spacing peak or the short spacing peak.
4. The solid monomer composition of claim 1 comprising a ratio of the first monomer to the second monomer in the range of from about 3:1 to about 1:1 by weight.
5. The solid monomer composition of claim 4 comprising a ratio of the first monomer to the second monomer of about 2:1 by weight.
6. The solid monomer composition of claim 4 comprising a ratio of the first monomer to the second monomer of about 1:1 by weight.
7. The solid monomer composition of claim 5 , wherein the X-ray powder diffraction spectrum comprises a longest spacing peak and a second longest spacing peak, the longest and second longest spacing peaks being singlet peaks at d spacings of about 17.80 Å and about 8.91 Å respectively.
8. A solid monomer composition comprising a first monomer and a second monomer, each said monomer having the formula:
CH 3 (CH 2 ) m1 NHCONH(CH 2 )(—CC—) 2 (CH 2 )NHCONH(CH 2 ) m5 CH 3 ;
wherein:
in the first monomer m1 and m5 are both 1;
in the second monomer m1 and m5 are both 2;
the solid monomer composition can exhibit an X-ray powder diffraction spectrum having two reflection peaks between a d spacing of about 4.40 Å and a d spacing of about 3.95 Å, and being collected using CuK α1 radiation;
the two reflection peaks comprise a long spacing peak at a d spacing in the range of from about 4.43 Å to about 4.37 Å, and a short spacing peak at a d spacing in the range of from about 3.99 Å to about 3.92 Å; and
the solid monomer composition is thermally polymerizable to have a changed visual appearance.
9. The solid monomer composition of claim 8 wherein the two reflection peaks are the highest intensity peaks in the diffraction spacing range of from about 4.43 Å to about 3.92 Å and wherein the intensities of the two peaks are similar.
10. The solid monomer composition of claim 8 comprising a ratio of the first monomer to the second monomer of about 2:1 by weight.
11. The solid monomer composition of claim 10 , wherein the X-ray powder diffraction spectrum comprises a longest spacing peak and a second longest spacing peak, the longest and second longest spacing peaks being essentially singlets at d spacings of about 17.80 Å and about 8.91 Å respectively.
12. A thermally polymerizable co-crystallized solid monomer composition comprising a first monomer, and a second monomer, each said monomer having the formula:
CH 3 (CH 2 ) m1 NHCONH(CH 2 )(—CC—) 2 (CH 2 )NHCONH(CH 2 ) m5 CH 3 ,
wherein
in the first monomer m1 and m5 are both 1;
in the second monomer m1 and m5 are both 2;
the solid monomer composition can exhibit an X-ray powder diffraction spectrum collected using CuK α1 radiation comprising a longest spacing peak and a second longest spacing peak;
the longest and second longest spacing peaks are essentially singlets; and
the second longest spacing peak is at a d spacing of about half the d spacing of the longest spacing peak.
13. The solid monomer composition of claim 12 wherein the longest spacing peak is at a d spacing of from about 16.4 Å to about 20.1 Å.
14. The solid monomer composition of claim 12 comprising a ratio of the first monomer to the second monomer of about 2:1 by weight.
15. The solid monomer composition of claim 12 comprising a ratio of the first monomer to the second monomer of about 1:1 by weight.
16. A crystal phase composition comprising a first crystal phase and a second crystal phase, wherein the first crystal phase comprises at least about 20 weight percent of a first monomer, the balance consisting essentially of a second monomer, and the second crystal phase comprises at least about 20 weight percent of the second monomer, the balance consisting essentially of the first monomer and wherein the first monomer and the second monomer have differing molecular structures of formula:
CH 3 (CH 2 ) m1 NHCONH(CH 2 ) m2 (—CC—) m3 (CH 2 ) m4 NHCONH(CH 2 ) m5 CH 3 ;
wherein
m1 is 0 or is a positive integer in the range of from 1 to about 17;
m2 is a positive integer in the range of from 1 to about 10;
m3 is a positive integer in the range of from 2 to 4;
m4 is a positive integer in the range of from 1 to about 10;
m5 is 0 or is a positive integer in the range of from 1 to about 17;
in each of the two monomers m2, 3, and m4 are the same integer;
at least one of m1 and m5 in the first monomer differs by one from m1 or m5, respectively, in the second monomer; and
the crystal phase composition can exhibit an X-ray powder diffraction spectrum having a longest spacing peak being a singlet peak and a second longest spacing peak being a shoulder peak or a doublet peak, the diffraction spectrum being collected using CuK α1 radiation.
17. The crystal phase composition of claim 16 , wherein m3 is two and wherein in the first monomer, m1 and m5 are both 1, and in the second monomer, m1 and m5 are both 2.
18. The crystal phase composition of claim 16 wherein, in the first monomer, m1 and m5 are both 1 and in the second monomer m1 and m5 are both 2, the longest spacing peak is at a d spacing of about 17.80 Å, and the second longest spacing peak is at a d spacing of about 8.91 Å.
19. The crystal phase composition of claim 16 wherein the first crystal phase comprises at least about 50 weight percent of the first monomer and the second crystal phase comprises at least about 50 weight percent of the second monomer.
20. A time-temperature indicator comprising a composition according to claim 1 .