Lecture 12

Question 1

What are polyolefins?

Answer 1

A polyolefin is a type of polymer with the general formula (CH2CHR)n where R is an alkyl group. They are usually derived from a small set of simple olefins (alkenes). Dominant in a commercial sense are polyethylene and polypropylene

Question 2

What are the general properties of PE and PP?

Answer 2

They are both semi-crystalline with typical properties as shown in the digital notes.

Important things to mention are:
- The Tg of both PE and PP are very small, therefore they would have some chain flexibility at room temp (for example plastic)

-Tm of both PE and PP are not that high, so they are limited to applications with low temperatures

• At high molecular weight PE shows a rubbery plateau, But pp doesn’t

Question 3

What are the different types of PE polymers and how are they formed?

Answer 3

Types of PE polymers are:
i) formed by coordination polymerization:

• High-density PE (HDPE) - Hardly has any branches, which allows for a larger crystallization making it have a higher density

-Linear Low-Density PE (LLDPE) - It has short chain branching, making it difficult to crystallize which leads to it having a lower density

ii) Free radical polymerization

Low-density PE - It has long and short branching making it much harder to crystallize leading to lower densities.

Note that the densities of LDPE are comparable to the densities of LLDPE.

Question 4

What are the two requirements needed for polymerization of polyolefins?

Answer 4

1. Symmetry:

For crystallite formation, close-packing in 3D is required. Any Irregularities (such as BRANCHING) which disturb linearity/symmetry will lower the packing efficiency thereby reducing the crystallinity (this is shown in digital notes)!

To show how important symmetry is, I put an image to see the top view of PE (it is really symmetrical)

2. Tacticity: Shown in the coming slides.

Question 5

What is tacticity?

Answer 5

Tacticity refers to the arrangement of side groups (or substituents) along the polymer chain in relation to the main polymer backbone.

These said side groups will affect the flexibility of the chain, the larger the are the more rigid the chain becomes, but the more difficult it is to pack!

There are three common arrangements:

• Isotactic: Same-side arrangements, can crystallize. Usually forms helical structures with the side groups sticking out, forming very nice crystals as shown in the notes
• Syntactic: Alternating side group arrangements, can crystallize
• Atactic: Random side group arrangements, can’t crystallize –> amorphous.

Question 6

What effect does branching have on Tm?

Answer 6

Generally branching of side groups, will lead to stiffer bonds that will then increase the Tm. The bulkier the side group the larger the Tm

Question 7

Important note

Answer 7

In the exam, we will be asked to compare between polymers. Which has a larger melting point and which is more likely to crystallize.

Question 8

What is the molar mass effect on the melting point?

Answer 8

Chains end in polymers are able to move freely. This mobility causes them to be in the amorphous region. The more chain ends present, the more amorphous character and therefore the lower the melting temperature is.

Therefore when the molar mass of the polymers is increased, the number of chain ends decreases. This of course leads to an increase in the melting temperature.

This is depicted within the notes

Question 9

How are HDPE and LLDPE made? (No mechanism yet)

Answer 9

HDPE - Coordination polymerization of ethylene

LLDPE - Coordination copolymerization
of ethylene with 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene

Question 10

How can we find the density of PE?

Answer 10

First, it is important to note that any semi-crystalline material is made up of both a crystalline region and an amorphous region. These regions have different densities (with crystalline ofc having larger densities). So from this, we can derive an equation that gives the value of the overall density:

ρ = φc⋅ρc + (1−φc)⋅ρa, where φc is the volume fraction of crystalline materials.

Question 11

What is the relationship between density, crystallinity and mol% comonomer?

Answer 11

As the percentage of comonomer increases, the stiffer the chains get, the lower the crystallinity will be and the lower the density will be.

This is depicted in digital notes

Question 12

What is the relation between Young’s modulus and crystallinity?

Answer 12

as the young modulus of the polymer increases the crystallinity increases exponentially

This is depicted in notes under flashcard 11

Question 13

Imp note

Answer 13

Okay, I am getting a bit confused so let’s make things clear:

As chain stiffness increases the polymers will be easier to back together increasing the crystallinity. BUT if comonomers are involved, even though they increase the stiffness, they will introduce steric hindrance that can completely disrupt the packing of the polymers, making it not crystallize

Question 14

In LLDPE and LDPE, where does the branching originate from?

Answer 14

In LLDPE Branches originate from the comonomer in coordination polymerization.

In LDPE Branches originate from inter- and intramolecular chain transfer in free-radical polymerization.

Question 15

What are the different processing techniques that apply to LDPE, LLPDE, and HDPE?

Answer 15

Look at the digital notes

Question 16

Why is having control over the crystalline region important?

Answer 16

Because the number of crystalline regions determines the rubbery plateau, which is essential in many process techniques

Question 17

How do we make syndiotactic and isotactic polymers?

Answer 17

Syndiotactic is made via attack of the double bond from the monomer from under causing an alternating side groups

Isotactic is made via attack of the double bond from the monomer from above causing a same-side side group.

Atactic is formed when the attack has no stereoselectivity for the attack

Question 18

What does tacticity determine/influence?

Answer 18

i) tacticity determines the crystallinity - of course, as mentioned before that depends mainly on the fact that activity determines the structure of the polymer (atactic, syntactic, isotactic)

ii) tacticity determines the solubility - Again the more something is nicely packed, the harder it would be for the solvent molecule to disrupt its structure causing solubility to decrease.

iii) Tacticity determines the glass-transition temperature (Tg) - the more crystalline, the less space there is in the amorphous regions causing them to become less mobile, therefore the Tg increases

Question 19

What is the main analysis method of tacticity for molecules?

Answer 19

NMR:
i) Analysis via Dyads
ii) Analysis via Triads

Question 20

What are dyads?

Answer 20

A diad refers to the stereochemical relationship between two neighbouring monomer units in the polymer chain. There are two types of diads:

1. meso (m) diad: This occurs when two adjacent monomer units have the same stereochemistry — that is, their side groups are on the same side of the polymer backbone.
2. racemic (r) diad: This occurs when two adjacent monomer units have opposite stereochemistry — that is, their side groups are on opposite sides of the polymer backbone.

This is shown in the notes.

Question 21

How is a quantitative analysis of tacticity determined by Dyads?

Answer 21

¹³C-NMR (Carbon-13 NMR) is often used to analyze the diads because the chemical shifts of the carbon atoms will be different depending on whether the adjacent monomers form an m diad or an r diad.¹H-NMR (Proton NMR) can also detect diads by analyzing the chemical shifts of the hydrogen atoms in the polymer backbone or side groups.

m diads will produce distinct NMR peaks corresponding to the regular, same-side arrangement of the methyl groups.

r diads will produce different peaks because of the alternating stereochemistry of the adjacent methyl groups.

By integrating the peak areas in the NMR spectrum corresponding to m diads and r diads, you can quantify the proportion of each type of diad in the polymer, which gives insight into the polymer’s tacticity:

Isotactic polymers: Will predominantly show m diads in the NMR spectrum, since all the side groups are on the same side.

Syndiotactic polymers: Will predominantly show r diads, since the side groups alternate regularly.

Atactic polymers: Will show a mixture of m diads and r diads, reflecting the random placement of side groups.

Question 22

What are triads?

Answer 22

triads refer to groups of three consecutive monomer units in a polymer chain, and they are used to describe the stereoregularity (tacticity) of a polymer. There are three types of triads:

mm (meso-meso): Indicates two adjacent units with the same stereochemistry (both are on the same side, corresponding to isotactic configuration).

rr (racemic-racemic): Indicates two adjacent units with opposite stereochemistry (alternating pattern, corresponding to syndiotactic configurations).
(random orientation, corresponding to atactic configuration).

mr (meso-racemic): Indicates a mixed stereochemistry(random orientation, corresponding to heterotactic configuration).

This shown in the notes under flashcard 20

Question 23

How is a quantitative analysis of tacticity determined by Triads?

Answer 23

Very similar to dyads:

¹³C NMR is commonly used because it can detect the carbon atoms in the polymer backbone and side groups. ¹H NMR can also be used, especially to monitor the protons of the methyl or methylene groups along the polymer chain.

By integrating the areas under the peaks corresponding to different triads (mm, mr, and rr), the relative amounts of isotactic, syndiotactic, and atactic sequences in the polymer can be quantified

Question 24

What is the effect of tacticity on Tm?

Answer 24

The higher the stereoregularity (i.e the higher the isotacticity which in this case corresponds to the higher m ratio) the higher the Tm.

This is depicted within the notes.

The reason of course is due to better crystallization and more close packing

Question 25

What is coordination polymerization (just a refresh in case I forgot)?

Answer 25

Coordination polymerization is a type of polymerization process that involves the formation of polymers through the coordination of monomers to a central metal atom or ion, typically in the presence of a catalyst. This process is particularly important in the production of olefinic polymers and is characterized by the use of transition metal complexes as catalysts.

Question 26

What are the requirements set for a catalyst to be used in coordination polymerization?

Answer 26

• Electrophilic metal centre (can be cationic)
• Vacant coordination site
• Polarized metal-polymer bond
• Robust ancillary* ligand system
• Sometimes a cocatalyst is required

This is depicted in the notes

*The term “ancillary” generally refers to something that provides support or assistance to a primary function or entity.

Question 27

What are the different Coordination polymerization catalysts?

Answer 27

1. Ziegler-Natta: Heterogeneous - planar- a class of transition metal catalysts widely used in the polymerization of olefins (alkenes) to produce polyolefins. They are known for their ability to control the molecular weight, structure, and stereochemistry of the resulting polymers.
2. Phillips - Heterogeneous - Cr based - a type of catalyst system used primarily for the polymerization of ethylene to produce polyethylene. They are particularly known for their ability to produce high-density polyethylene (HDPE) and are characterized by their simplicity and effectiveness.
3. Metallocene catalysts - Homogeneous - single sight - are a specific class of catalysts widely used in the polymerization of olefins to produce various types of polymers, including polyolefins. They are notable for their unique structure, efficiency, and ability to control polymer properties.

Question 28

What is the initiation step in coordination polymerization?

Answer 28

Found in digital notes

Question 29

What are the two different propagating mechanisms?

Answer 29

Note that we were told to ignore the backflip. But in my notes, I have that if the chains are more flexible a backflip won’t occur.

It is more important to memorize it and draw it out BECAUSE he will ask for mechanisms. Luckily in the written notes, I show an easy way to picture it.

one more thing….we basically insert the monomer in between the metal and the alkyl chain

Question 30

What is the main chain-stopping event in coordination polymerization?

Answer 30

Chain transfer:

1. β-hydrogen elimination: Whereupon the elimination of the β-hydrogen bond forms an unsaturated (double bond) end group. This will cause the termination product formed to act as a big monomer that can form a large branching point.
2. H2 as chain transfer agent: where you end up with a saturated end-group.

This is depicted in the notes.

Question 31

How is tacticity controlled in Ziegler-natta and Metallocene catalysts?

Answer 31

Ziegler-Natta: The catalyst starts as a nice spherical powder upon which polymerization will take place on the edges of the crystal. The Different catalytic sites
will give rise to different tacticities. this is depicted in the notes

Metallocene catalyst - Tacticity is determined by the structure/symmetry of the homogeneous catalyst. This will be demonstrated in the upcoming flashcards

Question 32

What is all the important information about the Heterogeneous Ziegler-Natta?

Answer 32

Look at the notes

Question 33

What are the different types(3yani structures) of Metallocene catalysts and how do they affect tacticity?

Answer 33

By designing the catalyst’s ligand system, the tacticity of polypropylene can be controlled:

• Dh: gives atactic polymer
• C2: gives isotactic polymer

-Cs: gives syntactic polymer

All the structures are shown in the notes

Question 34

How do the Dh Metallocene catalysts give atactic polymers?

Answer 34

Dh catalysts are symmetric. This symmetry brings about no steric hindrances upon the insertion of the monomer, which leads to no preferred addition and, therefore, forms atactic polymers.

Question 35

How do the C2 Metallocene catalysts give isotactic polymers?

Answer 35

C2 is symmetric only across the x-axis. Therefore when it’s rotated across the x-axis it will give the same structure.

thus, the same steric leads to the same preferential alignment which results in an isotactic polymer

This is depicted in the notes

Question 36

How do the Cs Metallocene catalysts give syntactic polymers?

Answer 36

Cs is symmetric across the y-axis. This leads to “mirror” symmetries which will lead to “mirror” preferential alignment resulting in a syntactic polymer. This is shown in the notes

Question 37

What is all the important information about the Metallocene catalysts?

Question 38

What is Ring Opening Metathesis Polymerization (ROMP)?

Answer 38

Go to digital notes I’ll explain everything their

Question 39

What are ionic and Catalytic Ring-opening Polymerization?

Answer 39

Go to digital notes I’ll explain everything their