HSP Application note #4
Hansen Solubility Parameters (HSP) of AntiOxidant2010.3.25
HSPiP Team Senior Developer, Dr. Hiroshi Yamamoto
Antioxidants are blended into polymers to provide resistance to heat, light and air.
But these chemicals elute out polymer and cause to environmental pollution. I start to analyze with HSP.
Hansen Solubility Parameters (HSP)Hansen Solubility Parameters(HSP) were developed by Charles M. Hansen as a way of predicting if one material will dissolve in another and form a solution. They are based on the idea that "like dissolves like" where one molecule is defined as being 'like' another if it bonds to itself in a similar way.
What can perhaps be surprising is that one can assign HSP to so many different things. Gases like carbon dioxide, solids like carbon-60, sugar, and biological materials like human skin, depot fat, DNA, and even some proteins all have HSP. The list can be continued with drugs, polymers, plasticizers, and in fact any organic material and even many inorganic materials like salts. The only requirement for an experimental confirmation is that the material must behave differently in a sufficient number of test solvents upon contact. Pirika JAVA Demo Applet calculate HSP. HSPLight is available here. |
I can say Similar HSP of AO will easily dissolve into similar HSP of polymer.
HSP DistanceTo calculate the distance (Ra) between Hansen parameters in Hansen space the following formula is used:
HSP distance(Ra)={4*(dD1-dD2)2 + (dP1-dP2)2 +(dH1-dH2)2 }0.5 |
I got the separation report from TOSOH (Japanese HPLC vender) and inside the report, they show the HPLC result of Antioxidants for polymer.
| NO | name | Hcode |
CAS# | RT |
1 |
Cyasorb UV-24 | 21881 |
131-53-3 | 6.897 |
2 |
BHA | 18988 |
25013-16-5 | 7.441 |
3 |
Ionox 100 | 10781 |
88-26-6 | 8.439 |
4 |
Seesorb 101 | 20389 |
131-57-7 | 9.71 |
5 |
Tinuvin P | 21882 |
50815-99-1 | 13.43 |
6 |
Yoshinox SR | 21883 |
96-69-5 | 15.064 |
7 |
Seesorb 202 | 20386 |
87-18-3 | 16.606 |
8 |
BHT | 7766 |
128-37-0 | 17.241 |
9 |
Noclizer M-17 | 20833 |
4130-42-1 | 18.603 |
10 |
Yoshinox 2246R | 20689 |
119-47-1 | 18.966 |
11 |
Topanol CA | 21884 |
1843-03-4 | 20.69 |
12 |
Yoshinox 425 | 21885 |
88-24-4 | 21.143 |
13 |
Cyanox 1790 | 21886 |
40601-76-1 | 21.869 |
14 |
Cyasorb UV-531 | 20384 |
1843-05-6 | 22.958 |
15 |
Ionox 220 | 21887 |
118-82-1 | 24.41 |
16 |
Nonflex CBP | 21888 |
77-62-3 | 25.045 |
17 |
Tinuvin 326 | 20394 |
3896-11-5 | 25.136 |
20 |
Uvtex OB | 21889 |
7128-64-5 | 28.131 |
21 |
Tinuvin 327 | 20830 |
3864-99-1 | 28.675 |
22 |
Tinuvin 328 | 20395 |
25973-55-1 | 29.492 |
25 |
Irganox 1076 | 21890 |
80693-11-4 | 41.379 |
18 |
Tinuvin 120 | 21891 |
4221-80-1 | 25.771 |
19 |
Irganox 3114 | 21892 |
27676-62-6 | 28.04 |
23 |
Irganox 1010 | 21893 |
98584-37-3 | 36.388 |
24 |
Irganox 1330 | 21894 |
1709-70-2 | 38.657 |
26 |
Irgafos 168 | 21895 |
69344-92-9 | 47.55 |
ChromatographyThe most popular column for HPLC is ODS column and this column contains Silica-gel covered by Octadecyl. When we insert some chemicals into this column, some chemicals dissolve to octadecyl alkyl chain deeply and some do not. So, highly interacted chemicals will delay to elute. Or some chemicals which are very easily dissolve to carrier liquid, elute very early.
We can evaluate these solubility with Hansen Solubility Parameters (HSP). Molecular size also play important role. Pirika Java Demo Applet design Carrier Solvent. HPLCDemo is available here. |
I calculated HSP of these AO and plot. (refer this article for details )
For almost all AO (Blue), Distance from OD(Octadecane) become short, retention time become large. This means that HSP of AO become similar to OD, it dissolve to OD easily and hard to elute. There are 2 type of exceptions, Triazole(Red) and HBP(green).
For Triazole, there are several structure notations.
I treat these nitrogens as “N3res” (Resonance Nitrogen with 3 connections).
1-Methyl Imidazole official HSP is [19.7, 15.6, 11.2] so the dD parameter of “N3res” become pretty high, and triazole have 3 “N3res”.
As the result, dD of triazole compounds become very high.
Maybe center nitrogen attach to aromatic make parameter worse.
If some one make experiment for solubility of triazole compounds, we can determine exact parameter for triazole.
If Ciba, Nagase or other vender researcher read this article, please contact us.
Thank to our contributor, I got solubility data of these triazole compounds. I gave them new parameter.
In version 4, everyone can use new parameter.
Other exception is HBP(green).
These compounds have hydroxy group and very near to hydroxy group, there is ketone.
So the solubility behavior slightly different.
For other AOs, I believe HSP calculated values are OK.
Once I have HSP of AOs, I can predict solubility AOs to polymer.
“Like seeks like”
If I calculate polymer HSP, then choose most similar HSP AO may improve properties.
2011.4.25
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If you are using HTML5 enable browser such as Chrome, Safari or FireFox (IE9 is out of support), you will see the Canvas.
With polymer HSP listed in HSPiP, I made 3D plot program with Anti Oxidants. If you pick Anti Oxidants (RED spheres), polymer (Blue sphere) name will appear. You can easily find nearest Anti Oxidants to the polymer.
If you draw several molecules and calculate each molecules' properties, program will simulate Retention Time (RT) of OSD column for HPLC. If you want to know how to draw molecules, please refer to Power Tools + applications. I have full version of this HPLC RT simulation program at Power Tools+ Applications.
Solubility of polymer.
Poly vinylidene fluoride based packing swelling
Electric Conducting Sulfur Containing Polymer for Solar Cell.
NBR rubber
AntiOxidant for polymer.
Plasticizer for polymer
Fungicide for Polymer
Cleaning of Mold Release agent from polymer.
Intrinsic Viscosity of polymer solution.
Retention time for HPLC
HPLC analysis of PAHs
HPLC analysis of medicine of Epilepsia
HPLC analysis of Anti-oxidant.
HPLC analysis of Sulfa Drugs.
HPLC analysis of Plasticizer
