Hello, I'm trying to use an NMR spectrum to calculate the degree of acrylation define/calculate a "degree of acrylation" for a PLA-PEG-PLA block copolymer that is di-acrylated (one di-acrylated. The macromer or (macro-monomer) is symmetrical in nature (Acr-PLA-PEG-PLA-Acr) and looks like this:
(-CH2-CH-CO-)p-(O-CH[CH3]-CO-)x-(CH2-CH2-O-)m-(O-CH[CH3]-CO-)x-(-CH2-CH-CO)p
For the PEG block in the middle, m is large (I have 4 different samples with pre-defined PEG MWs of 2k, 4k, 8k, and 12k g/mol). For the PLA blocks on either side of the PEG block, I have been able to calculate the average values of x for each sample, using the known value of m for the PEG blocks and the NMR-integrated ratio of PLA CH peaks (at 5.2 ppm) to the main-chain PEG CH2 peaks (at 3.6 ppm). So the formula set-up for that looks like this:
m = (PEG MW) / (EG unit MW)
2x / m = PLA CH peak / PEG CH2 peak
x is typically small (x = 2 - 6 LA units per chain end).
Using two other peaks, I should be able to do something similar to calculate the average value of p and thereby define a "degree of acrylation." So I have two follow-up questions:
4) Since the desire in synthesizing these macromers is to obtain p = 1 (an average of one acrylate CH2=CH-COO- group per chain end). end) then does it make sense if I know its define the "degree of acrylation" as p/1?
5) To calculate p using the NMR peaks: This is supposed to be possible by integrating the three peaks in the 5.79-6.43 range associated with the acrylate end groups, peaks (~ 6ppm) compared to a shifted PEG peak at 4.3 that arises from the represents the PEG CH2 groups closest directly next to the PLA blocks. (PEG is [CH2-CH2-O]n with a known n).
However I have a few questions:
1) Why do the blocks (~ 4.3ppm). Since there are 2 such CH2 groups per chain as well as 2 acrylate groups gives 3 per chain, would the ratio of the two peaks even though they only contain two types of hydrogens (CH2 and CH)?
2) Is it correct to assume that the combined integration of the acrylate peaks proportionally represent (2H+1H) x 2 end groups = 6H's?
3) Would it be correct, assuming there are two PEG directly give me the value of p? For instance, if t refers to the number of CH2 groups per chain located directly next to PLA blocks, per chain, then using a formula similar to that the above:
2p / t = Acr group peaks / shifted PEG CH2 group peak at 4.3 proportionally represents 4 H's?
Thank you for any guidance/assistance.
Since we know t = 2, then I can directly calculate p?