Determining the reaction progress of graft polymerization reactions
View Patent ↗A method of using Raman Spectra for determining the progress of a graft polymerization reaction is disclosed. The method entails (a) measuring at the beginning of the reaction and at a plurality of time intervals in the course of the reaction, continuously and on-site, the Raman spectrum in the wave number range of 100 to 4000 cm −1 of one or more of the monomers and/or polymers entailed in the reaction and of at least one internal standard and (b) recording the spectra and (c) adding reaction partners necessary to the reaction continuously and/or discontinuously and (d) calculating the change in concentration of the monomers and polymers by comparing the spectra of the monomers or polymers with the internal standard.
1. A method using Raman Spectra for determining the progress of a graft polymerization reaction comprising:
(a) measuring at the beginning of the reaction and at a plurality of time intervals in the course of the reaction, continuously and on-site, the Raman spectrum in the wave number range of 100 to 4000 cm −1 of one or more of monomers and/or polymers entailed in the reaction and a graft base, which is used as an internal standard; and
(b) calculating the change in concentration of the monomers and polymers from the spectra in consideration of the internal standard.
2. The method of claim 1 wherein the quantities of the monomers and polymers are calculated from the current Raman spectrum during the course of the reaction by weighted subtraction of the spectra of the monomers and the polymers.
3. The method of claim 1 , wherein said graft base is introduced in its entirely before the start of a batchwise reaction.
4. The method of claim 1 wherein the Raman spectra are measured in the wave number range of 500 to 2500 cm −1 .
5. The method of claim 1 wherein the Raman spectra are measured in the wave number range of 750 to 1800 cm −1 .
6. A process for the preparation of graft polymers comprising
a) adding at least one of the reactants in a continuous and/or discontinuous manner,
b) obtaining at a plurality of time in the course of the reaction the concentrations of the monomers and/or polymers using the method of claim 1 ,
c) comprising said concentrations with the required concentrations at the time and
d) adjusting the current quantities to the required quantities at the following time interval by varying the quantities of at least one of the monomers that are added or by increasing or decreasing the polymerization rates.
7. The method of claim 6 wherein the graft polymerization reaction entails grafting a mixture containing A.1 5 to 95 wt. % of at least one vinyl monomer onto A.2 95 to 5 wt. % of one or more graft bases having glass transition temperatures <10° C., the percent being relative to the total weight of A.1 and A2.
8. The method of claim 6 wherein A.1 is a mixture of
A.1.1 50 to 99 parts by weight of at least one compound selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene, p-chlorostyrene and methacrylic acid (C 1 –C 8 ) alkyl esters and
A.1.2 1 to 50 parts by weight of at least one compound selected from the group consisting of acrylonitrile, methacrylonitrile, (meth)acrylic acid (C 1 –C 8 ) alkyl esters and derivatives of unsaturated carboxylic acids.
9. The method of claim 6 wherein A.2 is selected from the group consisting of diene rubbers, EP(D)M rubbers, acrylate, polyurethane, silicone, chloroprene end ethylene/vinyl acetate rubber.
10. The method of claim 6 wherein the reaction is initiated with at least one inorganic or organic peroxide.
11. The method of claim 6 wherein the reaction is initiated by a system that contains an organic hydroperoxide and ascorbic acid.