Polymers (Topics 1-3) Flashcards
Dp is the
Degree of polymerisation
p (greek ro) is
conversion of a polymer synthesis
p (greek ro) is expressed as
either a percentage, or a number between 0 and 1 with 1 being full monomer consumption
Dm (funky line through the bottom of D) is called the
polydispersity index
Dm (funky line through the bottom of D) tells us
how broad the distribution is
Mn is the
number average of the polymer weights (true average calculated by the total dived by how many)
Mw is the
Weight average
What will a polymer look like on a graph of Mw vs number of molecules
a bell curve to represent that some chains are long and some are short but the majority are in the middle.
Where would you find Mn on a graph of Mw vs number of molecules ?
at the highest point of the bell curve. Then read down to the x axis to get the weight of that partiucular length.
Dm =
Mw/Mn
Mw is always —– than Mn
bigger / larger
true or false:
it is possible to have two polymers with different Dm but the same Mn?
true
true or false:
it is possible to have two polymers with different Mn but the same Dm?
True
Number averaged molecular mass (Mn) =
(sumNi)
Weight averages molecular mass (Mw) =
(sumNiMi)
Dm is always —— than 1
bigger/ larger
due to Mw being larger than Mn
Dm= Mw/Mn
Polymers in solution:
In solution polymers coil or kink, why?
its beneficial for energy
Polymers in solution:
We can measure the size of a polymer by its ….
hydrodynamic volume (Dh)
Polymers in solution:
In a bad solvent, what does the polymer look like?
In a bad solvent the polymer would look like a really small tight contracted ball of string. This is due to bad solvent/polymer interactions so it contracts and coils away to limit the amount of these interactions.
Polymers in solution:
In a good solvent, what does the polymer look like?
In a good solvent the polymer is extended and takes a much loser ball of string type form. This is because the solvent/polymer interactions are good so the polymer doesnt have to coil away to avoid these interactions, it is a bit more open to allow for these interactions to occur throughout the chain.
Polymers in solution:
what is the usual trend between Mw and Average diameter, what effect does this have on transparency of solutions?
usually a larger Mw means a larger diameter in the same solvent. The larger Mw polymers will be cloudy in solution as they scatter the light more as they are larger.
Polymers in solution:
GPC/SEC:
What do GPC and SEC stand for?
Gel permeation chromatography
size exclusion chromatography
Polymers in solution:
GPC/SEC:
What do we use GPC and SEC for?
To calculate Mw and dispersity of a polymer.
From this we can calculate Mn
Polymers in solution:
GPC/SEC:
Basic Principle of GPC/SEC
A polymer solution is washed down a chromatographic column with porous particles.
Polymers in solution:
Polymer size in solution is dependent on what two factors ??
solvent and
temperature
Polymers in solution:
GPC/SEC:
How does GPC/SEC work?
A polymer solution is washed down a chromatographic column with porous particles.
The porous particles have a rough surface with lots of little gaps for the polymers to permeate into. Depending on the size of the polymer, some will fully permeate, others will partially permeate and some will be excluded and continue past the porous particles.
the small polymers will get embedded into the porous particles and fully permeate whilst the larger ones will be too big and move past.
Polymers in solution:
GPC/SEC:
What order do polymers of different size and the solvent come out of GPC/SEC ?
Largest polymers come out first as they pass the porous particles as they are too large to be embedded.
Then the smaller ones will come after as they have been slowed by being embedded into the porous particles.
The solvent will come out last as it is super small and is very permeable into the pores.
Polymers in solution:
GPC/SEC:
We need to use a calibration curve to obtain a value of Mw from our sample, how would we interpret this curve to do this?
We would get a calibration curve of retention time (x) logM (y). We would measure the retention time of a certain polymer given by GPC/SEC and read off the calibration line to get logM which can be used to get Mw.
Polymers in solution:
GPC/SEC:
True or false, when doing a calibration, it is important to match the calibration polymer to the one being measured.
why?
true because different polymers will interact differently in the same solution and have different sizes (different Rms) which will effect their retention times.
Polymers in the solid state:
Polymers are rarely fully crystalline as they often have a mix of crystalline and ——- regions
amorphous
Polymers in the solid state:
What does Tg indicate?
Glass transition temperature
Polymers in the solid state:
What does Tm indicate ?
Crystalline Melting (transition) temperature
Polymers in the solid state:
What is Tg?
Temperature at which a material undergoes a transition from a glass state to a rubbery state or vice versa. Allows molecular chains to slide past eachother when a force is applied.
Polymers in the solid state:
What is Tm?
The temperature at which the material melts . in polymers this will be from a rubbery state to melting.
Polymers in the solid state:
As temperature increases how does the rigidity of a polymer material change?
low temps - glassy until tg.
after tg - rubbery until tm
after tm- melted
Polymers in the solid state:
Useful rubbers will have a Tg of what?
more than 0
Polymers in the solid state:
What is the definition of a rubber/ elastomer?
a material that can undergo much more elastic deformation under stress than most materials can and still return to its previous size without permanent deformation.
Polymers in the solid state:
Useful plastics will have a Tg of what?
they are ofeten molded into shape above this temperature and cooled below it to harden.
above 60 degrees celcius
Polymers in the solid state:
Crystalline polymers:
A polymer can crystallise when …
total E of the molecules has dropped to a point when translational and rotational energies are zero.
Symmetry requirements need to be met also.
Polymers in the solid state:
Crystalline polymers:
True or false ?
A completely crystalline polymer will only have a Tm and not a Tg?
True
Polymers in the solid state:
Crystalline polymers:
True or false ?
A fully amorphous polymer will only have a Tg and not a Tm?
True
Polymers in the solid state:
At Tg, what properties about the polymer change ? (2)
specific heat capacity and specific volume changes.
Polymers in the solid state:
What would we see on a graph of temperature vs specific volume chnage of a polymer to represent Tg?
there would be a point on the line in which a change in gradient will occur.
Polymers in the solid state:
At what point do we consider the polymer frozen?
at Tg
Polymers in the solid state:
How does the concept of free volume explain the glass transition temperature?
free volume is the space in a solid or liquid that is not occupied by polymer molecules.
As temperature decreases, free volume decreases until there is not enough free volume to allow for molecular rotation or translation.
It is at this te,perature where no movement is possible that we say the polymer is frozen.
This is Tg as it has become hard and glassy.
Polymers in the solid state:
More glassy polymers have —- free volume.
less /low/ small amounts of
Polymers in the solid state:
More rubbery polymers have —- free volume.
more/ high/ larger amounts of
Polymers in the solid state:
Factors that effect Tg?
(8)
Sterics
Tacticity
Mw
Polarity
Symmetry
Branching
Crosslinking
Stereochemistry of polymer
Polymers in the solid state:
How do sterics effect Tg?
Increased steric bulk means it is harder for polymer chains to move past eachother which means they have a higher Tg as it needs much more energy to move past eachother.
Polymers in the solid state:
How does Mw effect Tg?
Assumption that there is more free volume at an end of a polymer than in the middle parts. Shorter polymers have more ends so more free volume.
More free volume lower Tg.
Polymers in the solid state:
How does tacticity effect Tg?
Polymers in the solid state:
How does polarity effect Tg?
Increase in polarity increases Tg.
Due to an increased amount of polar bonding. Bonds are stronger , less free volume, Tg increased
(i havent checked this logic but it does make sense)
Polymers in the solid state:
How does symmetry effect Tg?
(not to be confused with symmetry eg a1g t2g etc but rather symmetry across a polymer)
increase in symmetry reduces Tg.
harder to pack therefore larger free volume
reduces Tg
eg
h h h cl
-c c - - c c -
h cl h cl
Tg = 87C Tg= -17C
Polymers in the solid state:
How does branching effect Tg?
Low levels of branching increases free volume as it leads to more end groups. therefore reduces Tg
High levels of branching restricts chain mobility and has the same effect as steric bulking so raises tg.
Polymers in the solid state:
How does crosslinking effect Tg?
Crosslinking reduces volume of the polymer overall and therefore reduces the amount of free volume.
less free volume higher Tg.
Polymers in the solid state:
More free volume, —— Tg
lower
Polymers in the solid state:
How does the sterochemistry of the polymer as a whole effect Tg?
Growing polymer chain can attack from one of two sides so we end up with three posibilities of polymer:
Isotactic, syndiotactic and atactic.
isotactic polymers in which all same groups are on the same side means that layers are easier to move past one another
therefore a lower Tg than syndiotactic and atactic polymers.
Tg of mixtures formula:
Tgmix(AB)= ( wa/Tga + wb/Tgb ) ^-1