Process for the preparation of a diol
View Patent ↗There is provided a process for the preparation of a polymerizable composition comprising a cross-linker and a polymerizable monomer of formula (I) comprising (i) contacting a compound of formula (II) with an acid such as an imobilized acid; and (ii) neutralizing product of (i) such that a crosslinker is formed.
1. A process for the preparation of a polymerizable composition comprising polymerizable monomer of formula I:
said process comprising the steps of:
(i) contacting a compound of formula II
with an immobilized acid to thereby form a composition comprising the monomer of formula (I) and an acid by-product thereof,
wherein
X, Y, Z, P, and Q are independently selected from a hydrocarbyl group or hydrogen,
A is (CH 2 ) n , wherein n is 0 or 1;
R 1 corresponds to either formula IIIA or formula IIIB
where R 2 is selected from the group consisting of H, methyl, ethyl, propyl, and butyl, and
and
R 3 is an unsaturated C 2-5 alkyl; and
(ii) neutralizing the composition of step (i) with an immobilized hydroxide, to thereby provide a composition comprising the monomer of formula I and a cross-linker.
2. A process according to claim 1 wherein the immobilized acid is a strong acid.
3. A process according to claim 1 wherein the acid is immobilized on an ion exchange resin.
4. A process according to claim 1 wherein X and Y are independently selected from hydrocarbon groups having from 1 to 20 carbon atoms and hydrogen.
5. A process according to claim 1 wherein R1 corresponds to formula IIIA, and R 2 is CH 3 .
6. A process according to claim 1 wherein X is H; Y is H, Z is H, n=0, R 1 corresponds to formula IIIA, and R 2 is CH 3 .
7. A process according to claim 6 wherein prior to said said contacting, the immobilized acid is contained, and after said contacting, passing a gas through the contained immobilized acid.
8. A process according to claim 7 wherein the gas is air.
9. A process according to claim 7 wherein the immobilized acid is contacted with the compound of formula II in the absence of an organic solvent.
10. A process according to claim 1 wherein said contacting is performed in the presence of water.
11. A process according to claim 7 , wherein prior to said contacting, the immobilized acid is contained in a fluidized bed reactor.
12. A process according to claim 7 , further comprising after said passing step, extracting the gas from the contained immobilized acid.
13. A process according to claim 1 , further comprising, after said neutralizing, polymerizing the composition formed in step (ii), to thereby form a polymer.
14. A process according to claim 1 , wherein said acid by-product formed in step (i) is methacrylic acid.
15. A process according to claim 1 , wherein said acid by-product formed in step (i) is acrylic acid.
16. A process according to claim 13 , further comprising forming the polymer formed in said polymerizing step into an ocular device.
17. A polymerizable monomer or composition formed by the process of claim 1 .
18. A polymer formed by the process of claim 13 .
19. An ocular device comprising the polymer formed by the process of claim 13 .
20. A process for the preparation of a polymerizable composition comprising a polymerizable monomer of formula I:
said process comprising the steps of:
(i) contacting a compound of formula II
with an immobilized acid having a pK a of less than 3 to thereby form a composition comprising the monomer of formula (I) and an acid by-product thereof,
wherein
X and Y are independently selected from hydrocarbon groups having 1 to 20 carbon atoms and hydrogen,
Z, P, and Q are independently selected from a hydrocarbyl group or hydrogen, A is (CH 2 ) n , wherein n is 0 or 1;
R 1 corresponds to either formula IIIA or formula IIIB
where R2 is selected from the group consisting of H, methyl, ethyl, propyl, and butyl, and
R 3 is an unsaturated C 2-5 alkyl; and
(ii) neutralizing the composition of step (i) with an immobilized hydroxide, to thereby provide a composition comprising the monomer of formula I and a cross-linker.
21. The process of claim 1 , effective to form a composition comprising said monomer of formula (I) and about 0.50 percent or less of said cross-linker.
22. The process of claim 7 , wherein said contacting results in formation of P—C(O)-Q, and said passing step is effective to remove said P—C(O)-Q from said composition.
23. The process of claim 22 , wherein said process is effective to provide essentially quantitative conversion of the compound of formula (II) to the monomer of formula (I).
24. The process of claim 13 , wherein the resulting polymer comprises 5% or less of a polymer formed by polymerization of said cross-linker.
25. The process of claim 3 , wherein prior to said neutralizing, said immobilized acid is removed by filtration.
26. The process of claim 1 , wherein the polymerizable monomer of formula (I) is glycerine methacrylate (GMA), the compound of formula (II) is 2,2-dimethyl-1,3-dioxolan-4-yl methyl methacrylate (GMAK), the acid by-product is methacrylic acid (MA), and the cross-linker is glycerol dimethacrylate.