Polymerisation question (1 Viewer)

bengosha60

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When a peroxide initiator is added in the initiation process and eventually becomes part of a polyethylene radical, does it remain part of the complete polymer at the end after termination? Or does it somehow just disappear...
For example:
R-O-C-C-C-C + C-C-C-C-O-R ----> R-O-C-C-C-C-C-C-C-C-O-R
 

QZP

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Yeah, during the termination reaction two ethylene-initiator radicals join as such in the equation you provided.
 

anomalousdecay

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The organic peroxide initiator does not join the chain.

Instead, it stays present in the mixture and allows the LDPE to keep on branching and allowing it hence to "Back-bite".

When the process is terminated, the removal of the organic peroxide is necessary to prevent the chain from growing more, although I'm not sure how this is done.

The organic peroxide is re-used again for making a new piece of LDPE I would imagine.
 

strawberrye

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The organic peroxide initiator does not join the chain.

Instead, it stays present in the mixture and allows the LDPE to keep on branching and allowing it hence to "Back-bite".

When the process is terminated, the removal of the organic peroxide is necessary to prevent the chain from growing more, although I'm not sure how this is done.

The organic peroxide is re-used again for making a new piece of LDPE I would imagine.
However, I have just consulted my HSC Conquering Chemistry textbook, initiators are mainly used for the production of Low Density Polyethylene(LDPE) and within the textbook, it clearly states that in this process the 'initiator' is not strictly a catalyst because it gets incorporated into the actual polymer formed-one initiator molecule per one or two polymer molecules, equivalent to 2000/3000 monomer units. Because by your deduction that it gets removed-then it will not be called an 'initiator' but rather a catalyst-since catalyst doesn't get consumed in the chemical reaction it is speeding up, and in this instance, I don't think the initiator can be classified as a catalyst in the scientific sense of defining a catalyst as a substance that accelerates the rate of a chemical reaction without being consumed by the reaction.

I think rather than the removal of the organic peroxide-addition of inhibitors or lowering the pressure and temperature, or when the free peroxide radicals attached monomer chains collide to combine to form non-activated species-which results in chain termination and stops the polymerisation process seems to be a more logical process. I have consulted with various HSC chemistry textbooks and they seem to suggest that the OP is on the right track.
 

anomalousdecay

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However, I have just consulted my HSC Conquering Chemistry textbook, initiators are mainly used for the production of Low Density Polyethylene(LDPE) and within the textbook, it clearly states that in this process the 'initiator' is not strictly a catalyst because it gets incorporated into the actual polymer formed-one initiator molecule per one or two polymer molecules, equivalent to 2000/3000 monomer units. Because by your deduction that it gets removed-then it will not be called an 'initiator' but rather a catalyst-since catalyst doesn't get consumed in the chemical reaction it is speeding up, and in this instance, I don't think the initiator can be classified as a catalyst in the scientific sense of defining a catalyst as a substance that accelerates the rate of a chemical reaction without being consumed by the reaction.

I think rather than the removal of the organic peroxide-addition of inhibitors or lowering the pressure and temperature, or when the free peroxide radicals attached monomer chains collide to combine to form non-activated species-which results in chain termination and stops the polymerisation process seems to be a more logical process. I have consulted with various HSC chemistry textbooks and they seem to suggest that the OP is on the right track.
Chemistry Contexts says this:

"Production and uses of low-density polyethylene
The polymerisation process consists of three stages: initiation, propagation
and termination. During the production of LDPE, the reaction is initiated
with a catalyst, usually an organic peroxide. These peroxides produce free
radicals (molecules with at least one unpaired electron). The radical R–O•,
where R represents an alkyl group and • represents an unpaired electron,
is electron defi cient and attacks the double bond in the ethylene. This
causes one of the bonds between carbon atoms in the CH2=CH2 molecule
to break, and a covalent bond is formed between one of the carbon atoms
and the radical. The resulting molecule, R–O–CH2CH2• , is itself a radical
and will attack the double bond in another ethylene molecule, resulting in
the ‘addition’ of another –CH2CH2– group. This process continues and so
the polymer chain rapidly grows. These reactions are referred to as chain
propagating reactions.
As the chains grow, they often curl back on themselves so that the radical end
of the chain removes a hydrogen atom from a CH2 group within the chain, as
shown in Figure 2.21. This leaves the within-chain group with an unpaired electron
which will react with an ethylene molecule, and so a new branch will begin to grow
from this point. This process, called ‘backbiting’, results in branches being formed
approximately every fifty or so atoms.
At various times it is possible for two free radical polymers to react to form
a covalent bond. This type of reaction is called a chain terminating reaction".


It says catalyst but it doesn't refer to anything about it becoming engulfed. Then again, Contexts could have possibly not included that piece of information that it is engulfed in the chain.

Need a few more confirmations :/
 
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QZP

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The organic peroxide initiator does not join the chain.

Instead, it stays present in the mixture and allows the LDPE to keep on branching and allowing it hence to "Back-bite".

When the process is terminated, the removal of the organic peroxide is necessary to prevent the chain from growing more, although I'm not sure how this is done.

The organic peroxide is re-used again for making a new piece of LDPE I would imagine.
A lot of misleading information here.

"The organic peroxide initiator does not join the chain."
Yes it does. And you can find it in the extract out of Chemistry Contexts you posted.

"Instead, it stays present in the mixture and allows the LDPE to keep on branching and allowing it hence to "Back-bite"."
Again, if you look at what you posted: there is nothing that says the initiator is what causes back-biting. Back-biting is an almost random process in the production of LDPE. As the polymer chain grows, it just happens to curl back onto itself, resulting in back-biting.

"When the process is terminated, the removal of the organic peroxide is necessary to prevent the chain from growing more, although I'm not sure how this is done."
Remove the initiator and then you created a radical site where you removed it. Thus, the chain would continue growing from there. You need two initiator radicals on both sides of the polymer chain if you want termination. Example: R-O-C-C• + •C-C-O-R ----> R-O-C-C-C-C-O-R (of course the reactants would be two very long polymer chains). Note: The termination reaction can happen at any time (not perfectly controlled).

"The organic peroxide is re-used again for making a new piece of LDPE I would imagine."
If follows from my above points that the organic peroxide is not reused.

~~~~~~~~~~~~~~~~~~~~~~~~~~

As for catalyst vs initiator, the peroxide radical is an initiator in a stricter sense (i.e. more correct). Confirmed by my old teacher who had friends working in the industry (he actually brought back the resulting LDPE product. They're like small balls haha kinda cool.)
 

strawberrye

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No wonder I got B5 :'(
Don't let your performance in an exam despair you from Chemistry-it really is a fascinating discipline of science and it is by making mistakes, that you will remember the content for a lot longer in your head. That's how we all learn-from our own mistakes and observing other people for that matter. And anyways, just because you had some misconceptions on one module in chemistry does not mean you are weak in the many other branches of chemistry. I had many misconceptions and made many mistakes once-and I would say I was grateful since I learnt from them:). Don't define yourself by a band, you've tried your very best-and you had mostly independent learning-and you should be proud of your result.

Anyways, I am sure OP really appreciates all the input-it will help him/her to avoid having that misconception later on in the year:) And you've gained something from this as well-you will probably not be making the same mistake/misconception again, so it has been a really beneficial experience on both sides:)
 
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anomalousdecay

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Don't let your performance in an exam despair you from Chemistry-it really is a fascinating discipline of science and it is by making mistakes, that you will remember the content for a lot longer in your head. That's how we all learn-from our own mistakes and observing other people for that matter. And anyways, just because you had some misconceptions on one module in chemistry does not mean you are weak in the many other branches of chemistry. I had many misconceptions and made many mistakes once-and I would say I was grateful since I learnt from them:). Don't define yourself by a band, you've tried your very best-and you had mostly independent learning-and you should be proud of your result.

Anyways, I am sure OP really appreciates all the input-it will help him/her to avoid having that misconception later on in the year:) And you've gained something from this as well-you will probably not be making the same mistake/misconception again, so it has been a really beneficial experience on both sides:)
Absolutely. At least by showing others my misconceptions they can learn from them. Everyone learns in the end from a little discussion.
 

SuchSmallHands

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It really just stays in there. At first this confused me as well, and while other people have explained it with varying degrees of success thus far the thing that really got me to understand how there could be these organic initiators floating around in LDPE, not removed but not harming anything, is when I considered the length of the chain vs. the size of a single benzoyl peroxide ring (or similar). You've got multiple thousands of monomers in this huge chain, and at the end, a single molecule of the initiator. Is it going to make a big difference to the end product? It's like 0.1% (if that) of the LDPE you end up with. When you're looking at a diagram with five monomers and this huge organic ring it seems like a big deal, but add another couple of thousand monomers and suddenly it doesn't seem so weird to let it slide :)
 

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