Basic Structure Properties

PKG 827.
POLYMERIC PACKAGING MATERIALS
Chapter 2 Basic Structure/Property Relationships - Regularity,

Conformational Flexibility, and Intermolecular Forces
This chapter is a complementary reading material to your required text material Paul C. Painter
and Michael M. Coleman. Fundamentals of Polymer Science. An Introductory Text. 2nd Ed.,
CRC Press. ISBN: 1-56676-559-5. The chapter provides a basic introduction to polymer
properties based on their chemical structures. Finally, at the end of the chapter a section is
including with most of the main polymer’s properties. This chapter has evolved through the
years of teaching PKG 827 by different SoP faculty.
PKG827- Polymeric Packaging Materials
Chapter 2 Basic Structure/Property Relationships
Table of Contents
Chapter 2 Basic Structure/Property Relationships - Regularity, Conformational Flexibility,
and Intermolecular Forces ........................................................................................................... 1!
2.0$Introduction$...............................................................................................................................$5!
2.1$Regularity$...................................................................................................................................$6!
2.1.1!Chemical!Regularity!...................................................................................................................!7!
2.1.2!Stereochemical!Regularity!.......................................................................................................!15!
2.2$Conformational$Flexibility$........................................................................................................$19!
2.2.1!Thermal!Transitions,!Tg!and!Tm!.................................................................................................!19!
2.2.2!Effect!of!Side!Groups!on!Rotation!of!CAC!Bonds!......................................................................!19!
2.2.3!Effect!of!Chain!Backbone!Linkages!on!Conformational!Flexibility!...........................................!23!
2.3$Intermolecular$Forces$..............................................................................................................$27!
2.3.1!Primary!and!Secondary!Bonds!.................................................................................................!27!
2.3.2!Effect!of!Secondary!Bonds!on!Polymer!Behavior!.....................................................................!29!
2.3.3!Quantifying!Intermolecular!Forces!..........................................................................................!31!
2.3.4!Effects!of!Hydrogen!Bonding!...................................................................................................!33!
2.4$Effects$of$Molecular$Weight$.....................................................................................................$33!
2.4.1!Effect!of!Molecular!Weight!on!Tg!.............................................................................................!33!
2.4.2!Effect!of!Molecular!Weight!on!Tm!............................................................................................!33!
2.4.3!Other!Effects!of!Molecular!Weight!..........................................................................................!34!
2.5$Relationship$between$Tm$and$Tg$...............................................................................................$35!
2.6$Other$Considerations$Involving$Crystallinity$and$Crystallization$...............................................$36!
2.6.1!Isomorphous!Groups!................................................................................................................!36!
2.6.2!Transparency/Opacity!..............................................................................................................!37!
2.7$Barrier$......................................................................................................................................$38!
2.8$Addition$polymer$properties$....................................................................................................$39!
2.8.1!Polyethylene!family!..................................................................................................................!40!
2.8.2!Polypropylene!..........................................................................................................................!43!
2.8.3!Polystyrene!..............................................................................................................................!44!
2.8.4!Polyvinyl!Chloride!.....................................................................................................................!45!
2.8.5!Polyvinylidene!Chloride!............................................................................................................!47!
2.8.6!Polyvinyl!Acetate!......................................................................................................................!49!
2.8.7!Polyvinyl!Alcohol!......................................................................................................................!50!
2.8.8!Polytetrafluoroethylene!...........................................................................................................!51!
2.8.9!Polychlorotrifluoroethylene!.....................................................................................................!52!
2.8.10!Polyacrylonitrile!.....................................................................................................................!53!
2.9$Condensation$polymer$properties$............................................................................................$54!
2.9.1!Polyethylene!Terephthalate!(PET)!...........................................................................................!55!
2.9.2!PET!Copolymers!.......................................................................................................................!57!
2.9.3!Polycarbonate!..........................................................................................................................!59!
2.9.4!Polyethylene!Naphthalate!(PEN)!..............................................................................................!61!
2.9.5!Nylons!(Polyamides)!.................................................................................................................!62!
2
Figures
Figure 2-1 Portion of a linear amylose starch molecule ................................................................. 6!
Figure 2-2 Free radical polymerization of ethylene ........................................................................ 9!
Figure 2-3 Initiation step in free radical polymerization ................................................................ 9!
Figure 2-4 Propagation step in free radical polymerization............................................................ 9!
Figure 2-5 Termination step in free radical polymerization ......................................................... 10!
Figure 2-6 Chain transfer reactions in free radical polymerization .............................................. 11!
Figure 2-7 Production of LLDPE ................................................................................................. 12!
Figure 2-8 Addition step in free radical polymerization; (1) is head to tail, (2) is head to head. . 13!
Figure 2-9 Head-to-tail addition polymer ..................................................................................... 14!
Figure 2-10 Addition polymer with random configuration .......................................................... 14!
Figure 2-11 Types of free radicals; (a) primary, (b) secondary, (c) tertiary ................................. 15!
Figure 2-12 The two mirror-image forms of a chiral carbon ........................................................ 15!
Figure 2-13 Isostatic polypropylene ............................................................................................. 16!
Figure 2-14 Syndiotactic polypropylene ....................................................................................... 16!
Figure 2-15 Atactic polypropylene ............................................................................................... 16!
Figure 2-16 Structural formula of PP............................................................................................ 17!
Figure 2-17 Illustrative structure of a 2-carbon molecule with 6 substituents ............................. 20!
Figure 2-18 Staggered configuration of a 2-carbon molecule with 6 substituents ....................... 20!
Figure 2-19 Eclipsed configuration on a 2-carbon molecule with 6 substituents ......................... 20!
Figure 2-20 Effect of rotation on potential energy in ethane ........................................................ 21!
Figure 2-21 Effect of rotation on potential energy in n-butane .................................................... 21!
Figure 2-22 Cis- and trans- configurations ................................................................................... 24!
Figure 2-23 Transfer of the free radical during polymerication of butadiene .............................. 25!
Figure 2-24 Cis- and trans- forms of polybutadiene ..................................................................... 25!
3
Tables
Table 2-1 Properties of some typical HDPE, LDPE and LLDPE................................................... 8!

Table 2-2 Sample HDPE homopolymer and copolymer blow molding resin properties ............. 13!
Table 2-3 Typical properties of polypropylene ............................................................................ 17!
Table 2-4 Examples of bond rotation energy barriers .................................................................. 22!
Table 2-5 Sample HDPE and PP properties ................................................................................. 22!
Table 2-6 Melting and glass transition temperature comparisons ................................................ 22!
Table 2-7. Sample PS properties ................................................................................................... 23!
Table 2-8 Properties of cis- and trans-polybutadiene ................................................................... 25!
Table 2-9 Typical primary bond lengths and energies for bonds commonly found in packaging
plastics................................................................................................................................... 28!
Table 2-10 Sample PVC and PP properties .................................................................................. 30!
Table 2-11 The cohesive energies of some common polymers, along with Tg and Tm ................ 32!
Table 2-12 Group contributions to cohesive energy and molar volume (Fedors, from Polymer
Handbook, 4th ed., J. Brandrup et al., Wiley, New York, 1999) ........................................... 32!
Table 2-13 Typical properties of HDPE and LDPE blown films ................................................. 41!
Table 2-14 Typical properties of LLDPE blown films ................................................................. 42!
Table 2-15 Typical properties of PP ............................................................................................. 43!
Table 2-16Typical properties of PS .............................................................................................. 44!
Table 2-17 Typical properties of rigid and flexible PVC ............................................................. 45!
Table 2-18 Typical properties of PVDC film ............................................................................... 48!
Table 2-19 Typical properties of PET .......................................................................................... 56!
Table 2-20 Typical properties of PC ............................................................................................. 60!
Table 2-21 Typical properties of PEN .......................................................................................... 61!
Table 2-22 Typical properties of nylons ....................................................................................... 63!
Table 2-23 Typical properties of nylons (cont.,) .......................................................................... 63!
Table 2-24 Tg and Tm for selected condensation polymers ........................................................... 64!
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2.0 Introduction
When we consider the chemical structure of polymers, three of the major influences on behavior
are:
• Regularity - both chemical and stereochemical

• Conformational flexibility, and
• Intermolecular forces
In addition, we need to consider:
• Chemical reactivity
• Elemental composition
• Structure, and
• Covalent bond strength
It is also useful to remind ourselves of a fundamental law of thermodynamics - spontaneous

change is always from a higher to a lower energy state.
These influences on polymer behavior impact the following polymer characteristics:
• Physical structure (microstructure), especially:

o Crystallinity
• Strength of secondary bonding
The polymer properties affected include: strength, elasticity, barrier, flow behavior, and many
others.
We will use common packaging polymers as examples of the relationships between these
characteristics and plastic performance, as we look at them in more depth.
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2.1$Regularity$$
Readings: Painter & Coleman, Chapter 1, Part B, pp. 3-16. (Yes, this is material that you should
have read for Unit 1. As I indicated, that was to be "once over lightly" and now we're taking a
more detailed look at some of the concepts.) Chapter 7, part A, pp. 207-208. Part E, pp. 237-
254.
Polymers differ considerably in amount of crystallinity. Some are totally amorphous, others are
predominantly crystalline. The amount of crystallinity is a profound influence on polymer
structure. Therefore, structural features of the polymer that affect crystallinity can have a major
impact on its properties.
Crystallinity requires the polymer molecules to be able to pack into a regular repeating array.
The structure of the polymer may or may not permit this to happen. If the next polymer
backbone unit (sometimes referred to as a "mer" or building block unit) has a size and shape that
do not allow it to fit into that regular array, then crystallinity is disrupted. So, structural
irregularities can significantly limit potential crystallinity. In general, the higher the degree of
irregularity, the less the polymer is able to crystallize.
Structural irregularity is not, however, the only influence on crystallinity of a polymer. Some
polymers have regular structures that are shaped in a way that does not permit them to form a
crystal lattice. One example is the difference between amylose starch and cellulose. Both are
formed from glucose units attached to each other in a regular linear pattern. Cellulose is joined in
a way that produces a straight chain, and is highly crystalline. The units in starch are attached at
a different point in the glucose ring, resulting in curling of the chain, producing a spiral-shaped
molecule, and a much less crystalline material.
Figure 2-1 Portion of a linear amylose starch molecule
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In addition, all polymers have a limited range of temperature over which they can crystallize. A
polymer cannot crystallize above its melting temperature (Tm), or below its glass transition
temperature (Tg). Above the melting point, the polymer molecules have too much energy to
"settle down" into a crystallite. In fact, the melting temperature is defined by the breakup of
crystallites. Below the glass transition temperature, the polymer molecules do not have enough
energy to move sufficiently to pack into a crystallite (they are "frozen" in place).
For some plastics, the range for crystallization to occur is considerably narrower than Tm to Tg. If
a plastic is cooled very quickly from the melt to a temperature below its crystallization
temperature range, it will develop little or no crystallinity. The same plastic, held within the
crystallization temperature range for an extended period of time, may become highly crystalline.
We will talk more about the influence of crystallinity on properties a bit later on.
2.1.1 Chemical Regularity
One fundamental type of regularity is chemical regularity, Here, we ask the question: "Is the
chemical structure such that it consists of the repetition of identical units?" If the answer is yes,
the polymer is chemically regular. If the answer is no, the polymer has at least some degree of
irregularity.
There are a number of characteristics to consider in determining whether the polymer is

chemically regular, in other words, a set of questions we can ask:
(A) Is the polymer linear or branched or cross-linked?
Branches interfere with the packing - at branch points the polymer won't "fit" into the crystal
lattice. Cross-links not only interfere with the fit, but also restrict the ability of molecular
segments to move in order to assume a regular order.
Example 1:
HDPE - linear homopolymer of ethylene - crystallinity 65-90%
LDPE - branched homopolymer of ethylene - crystallinity 40-60%
By decreasing the crystallinity, the presence of the branches results in less

efficient packing of the molecules into space, thus decreasing the density of the
plastic. This results in significant differences in behavior: flexibility, melting
temperature, impact strength, tensile strength, permeability, etc., between LDPE
and HDPE.
In the vast majority of materials, the spacing between adjacent molecules is smaller in crystalline
areas than in non-crystalline (amorphous) areas. (Water is one of the very few exceptions. Ice,
the crystalline form of water, floats in liquid water because it is less dense - the spacing between
molecules is greater in ice than in liquid water.)
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The following table gives examples of some of the differences in properties that can arise in
similar materials due in large part to differences in crystallinity.
Table 2-1 Properties of some typical HDPE, LDPE and LLDPE
Property HDPE LDPE LLDPE

Melting temperature (°C)* 130-137 98-115 122-124
Density (g/cm3) 0.950 0.921 0.918
Tensile strength (psi) - MD 4,600 2,900 5,000
Tensile strength (psi) - CD 6,500 2,700 3,800
Elongation (%) - MD 350 200 350-550
Elongation (%) - CD 550 600 750-850
Tear strength (gf/mil) - MD 15 160 140
Tear strength (gf/mil) - CD 100 110 340
*Melting temperature is range for resin category, not specific to resin density listed.
Remember: polymers are never 100% crystalline, they will have both crystalline and amorphous
areas. The structure affects how much crystallinity can develop. Processing affects how much
crystallinity actually develops.
In general, we can say that for a given polymer, increasing crystallinity:
• Increases sealing temperature

• Increases tensile strength
• Increases stiffness
• Decreases elongation
• Decreases permeability
• Decreases impact strength
• Decreases tear strength
Note: in general, significant structural irregularity will prohibit crystallinity - LDPE is an

exception. Because of its very small side-groups (hydrogens only), polyethylene crystallizes very
easily - so easily that even the irregularity imparted by the branch points does not prevent
crystallization.
Why do HDPE and LDPE differ in structure - why is one linear and the other branched? And
where does LLDPE fit in?
Recall that HDPE, LDPE, and LLDPE are all addition polymers - formed by free radical
polymerization reactions from a monomer with a double bond:
8
Figure 2-2 Free radical polymerization of ethylene
The reaction sequence can be seen as having three steps: initiation, propagation, and termination.
The initiation step has two substeps: the formation of the free radical and the addition of the first
monomer. The initial generation of a free radical is usually accomplished by the decomposition
of an initiator, which is a relatively unstable compound such as a peroxide (R-O-O-R'),
hydroperoxide (R-O-O-H) or azo compound (R-N=N-R'). Sometimes UV radiation or high
temperatures are used to generate free radicals. After the initiator free radical is formed, the
addition of the first monomer unit occurs as shown: (We are using X as a generic substitute on
one of the carbons. In the case of polyethylene, X is a hydrogen atom.)
Figure 2-3 Initiation step in free radical polymerization
In the propagation steps, monomer is added to the growing chain, producing an increase in the
size of the polymer molecule:
Figure 2-4 Propagation step in free radical polymerization
9
Finally, termination occurs when something happens to end the growth of the molecule. There
are a number of termination mechanisms. The one illustrated shows two large free radicals
recombining:
Figure 2-5 Termination step in free radical polymerization
If the reaction occurs as shown above, a linear polymer will result - giving us, in our example,
HPDE. However, these are not the only types of reaction that can occur. The free radicals can
also participate in chain transfer reactions, which lead to branching, as shown in Figure 2-6.
These reactions are favored by high-energy states in the free radicals - in other words, by high
temperature. The rate of the propagation reaction itself also generally increases as temperature
increases (provided that the temperature is not so high as to lead to decomposition).
LDPE is made under conditions of high temperature (high energy), which also necessitates the
use of high pressure to get adequate reaction rates, since the monomer is a gas. High pressure is
required for the concentration of the reacting monomer to be high. At these conditions, a
substantial number of chain transfer reactions will occur. The reaction leading to short chain
branching is more common than the one leading to long chain branching, since the free radical is
most likely to collide with a nearby part of the same molecule. Therefore, LDPE has lots of short
branches and some long ones.
10
Figure 2-6 Chain transfer reactions in free radical polymerization
HDPE is made under milder reaction conditions, where chain transfer reactions are much less
likely to occur. However, at these conditions, the ordinary free radical initiation and propagation
reactions are also very slow. Therefore, to manufacture the polymer, a catalyst is required. The
catalyst provides a lower energy pathway from reactants to products. We will discuss this further
later on in the course. The catalyst does not promote branching reactions, so HDPE is a mostly
linear molecule.
So, the answer to how we can get both branched and linear molecules starting from the same
monomer, ethylene, lies in using differing reaction conditions. Since the branching reduces
crystallinity, LDPE with its branched structure, has a lower density than HDPE, with its linear
structure. The answer to where LLDPE fits in comes next.
(B) Is the polymer a homopolymer or a copolymer?
Copolymer units are a source of structural irregularity. In most cases, the two different
monomeric units will not fit into the same crystalline arrangement, so the presence of the
comonomer disrupts crystallinity.
In rare circumstances, two different structures will fit into the same crystalline latice. Such
groups are referred to as isomorphous. We'll say more about these later.
Example 2:
LLDPE is a linear polyethylene copolymer, with comonomers of butene, hexene,

or octene. The amount and size of the comonomer units present affect the
11
crystallinity - and hence the density - of the plastic. In the reaction illustrated in
Fig. 2.1.6, LLDPE is produced if X sometimes represents H, and sometimes
represents other monomers as indicated.
If butene is the comonomer, X is CH2CH3

If hexene is the comonomer, X is CH2CH2CH2CH3
If octene is the comonomer, X is CH2CH2CH2CH2CH2CH3
Figure 2-7 Production of LLDPE
These side groups look and act like branches, interfering with crystallization by providing
disorder. People often refer to LLDPE as having "controlled branching" but in reality, LLDPE is
a linear polymer. It is formed at essentially the same conditions as HDPE, also using a catalyst to
provide a lower energy route for polymerization, so we can get reasonable reaction rates without
the chain transfer reactions that lead to branching (more on this later).
The differences between HDPE and LLDPE properties are in large part due to differences in
crystallinity. However, since LDPE and LLDPE of equal density have essentially equal percent
crystallinity, we cannot explain the differences between these two materials (see the previous
page) by differences in crystallinity. Differences in molecular weight and molecular weight
distribution are the major factors, as we will discuss later. You might also expect that there will
be differences between the 3 LLDPE families - those based on butene, on hexene, and on octene,
and indeed this is the case.
If a larger amount of comonomer is added in the polymerization process, the crystallinity, and
hence the density, is further reduced - giving us very low density polyethylene VLDPE or ultra
low density polyethylene ULDPE. These terms are essentially synonymous.
Example 3:
Copolymer HDPE is used for detergent bottles, to decrease environmental stress

cracking by decreasing crystallinity. Adding the comonomer also decreases
stiffness & tensile strength.
12
Table 2-2 Sample HDPE homopolymer and copolymer blow molding resin properties
Property! HDPE$homopolymer$ HDPE$copolymer$

Density (g/cm3) 0.961 0.954
Tensile strength at yield (psi) 4,400 3,800
Flexural modulus (psi) 200,000 165,000
Elongation (%) 800 750
Izod impact strength (ft-lbf/in 2.0 3.0
notch)
Tensile impact (ft-lbf/in2) 30 70
The third important question to ask in determining whether a polymer is structurally regular is
addressed next.
(C) In vinyl polymers, is the addition head-to-head or head-to-tail?
A vinyl polymer is one formed from a monomer which can be written as:
CH2=CHX
Since X is bigger than hydrogen (if it is not H), and a head is bigger than a tail, the CHX end is
the "head" of the monomer and the CH2 end is the "tail." (Note that if X is H, then this concept
does not apply, as the two ends of the monomer are identical.)
The addition of a vinyl monomer to a free radical can take place in either of two ways:
Figure 2-8 Addition step in free radical polymerization; (1) is head to tail, (2) is head to head.
If only reaction (1) occurs, the resulting polymer has a head-to-tail configuration, since the head
of one monomer is connected to the tail of the next:
13
Figure 2-9 Head-to-tail addition polymer
If both reactions (1) and (2) take place, both head-to-head and tail-to-tail configurations occur
randomly in the molecule, along with head-to-tail configurations:
Figure 2-10 Addition polymer with random configuration
In practice, we seldom need to worry about this cause of irregularity, because in most cases, free
radical polymerization of vinyl polymers, with or without a catalyst, results in head-to-tail
addition. The reason this is so is because the free radical that results from reaction (1) is more
stable - is at a lower energy level, so is more likely to be produced - compared to the free radical
that results from reaction (2).
This point can be confusing, so I want to reiterate it. The "more stable" free radical is the one that
is at lower energy. All of these intermediates are highly reactive. If the reaction has two
pathways, it is more likely to go by way of the pathway that requires less energy - there is less of
an energy "leap" that the molecule must make. As a rough analogy, you can think of these energy
barriers as hills of differing heights. If you pour out a stream of water, more water will go over
the lower hill than over the higher one. The hill represents the energy of the intermediate species.
The water on top of the lower hill has less potential energy (is more stable) than the water on the
higher hill.
Carbon free radicals are classified according to the number of carbon atoms attached to the
carbon with the unpaired electron. Primary free radicals (a) have only one carbon bonded to the
free radical carbon, secondary free radicals (b) have two, and tertiary free radicals (c) have three.
Tertiary free radicals are the most stable, secondary radicals the next, and primary free radicals
the least stable. The reason is that carbon atoms are more able than hydrogen atoms to share
electron-time with the electron-deficient C free radical. By "sharing" the lack of electron, the
neighboring carbon atoms stabilize the free radical.
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Figure 2-11 Types of free radicals; (a) primary, (b) secondary, (c) tertiary
Thus the energy conditions are most favorable for producing tertiary free radicals, followed by
secondary, and lastly by primary. Since reaction (1) above results in a secondary free radical, it is
favored energetically over reaction (2), which results in a primary free radical. Therefore, as a
rule vinyl polymerization produces predominantly head-to-tail addition.
2.1.2 Stereochemical Regularity
Readings: Painter & Coleman: Chapter 1, Part B, Section on Isomerism, pp. 8-13.
For molecules to pack into a crystal lattice, stereochemical regularity is required, as well as
structural regularity. Stereochemistry refers to the arrangement of molecules in space. If a
monomeric unit is chiral (if it contains a chiral carbon), it can add to the polymer in two distinct
orientations, as we will see below.
A chiral carbon is one that is attached to 4 different groups. It therefore can exist in two mirror
image forms, which cannot be interconverted without breaking primary bonds:
Figure 2-12 The two mirror-image forms of a chiral carbon
In a polymer, the ends of the polymer chain are always different from each other, so to be chiral,
a carbon need only be bonded to two different side groups or atoms (since the groups the carbon
is bonded to in the main chain of the molecule are different. Note that we look beyond the first
atom that is attached, and consider the entire molecular segment. If A is CH2CH3 and B is
CH2CH2CH3, these are different substituents.
15
If a polymer contains chiral carbons, it can exist in distinct stereochemical forms. As an example,
let's consider polypropylene. Polypropylene is a linear polymer that can exist in three different
stereochemical forms (symmetry patterns, patterns of stereo-regularity):
Figure 2-13 Isostatic polypropylene
In isotactic PP, when the PP molecule is laid out in its fully-extended-chain conformation, all the
methyl groups are on the same side of the chain. (Recall the difference between conformation
and configuration. Configuration refers to the pattern of bonding within the molecule - what
atoms are attached to what, and in what position. Conformation refers to the current arrangement
in space. Conformation changes every time there is rotation about a bond. Configuration cannot
be changed without disrupting and reforming primary chemical bonds (the bonds that make up
the molecule).)
Figure 2-14 Syndiotactic polypropylene
In syndiotactic PP, when the PP molecule is laid out in its fully-extended-chain conformation,
the position of the methyl group alternates from one side of the chain to the other.
Figure 2-15 Atactic polypropylene
In atactic PP, when the PP molecule is laid out in its fully-extended-chain conformation, the
position of the methyl group is random - there is no pattern to whether it is on one side of the
chain or the other.
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If the polymer is either isotactic or syndiotactic, it usually is able to crystallize, although the
differences in crystal structure often result in some differences in chemical properties between
the two forms. The atactic form, on the other hand, is generally not able to pack into a repeating
pattern, since the H and CH3 groups will not fit the same spot in the lattice, and there is no
predictability about which will occur. Therefore, atactic polymers are generally amorphous.
Note that all three forms of PP are structurally regular. They are linear homopolymers, with a
head-to-tail addition pattern. All can be represented, in 2 dimensions, by:
Figure 2-16 Structural formula of PP
Note that there is no way, in this 2-dimensional representation, to tell whether this, or a
similar, polymer is isotactic, syndiotactic, or atactic.
If we look at PP properties, we can see the result of the differences in crystallinity between these
three forms of PP, as shown in Table 2.3.
Table 2-3 Typical properties of polypropylene
Tacticity! Density$ Tm$(°C)$ Tg$(°C)$ Solubility$in$nCheptane$

(g/cm3)$
isotactic 0.90-0.91 171 -20 insoluble
syndiotactic 0.88-0.90 138 -20 insoluble
atactic 0.85 - -20 soluble
Note that the melting temperature, Tm, is not defined for atactic PP. Recall that Tm is the
temperature at which the crystallites break up. Since atactic PP is amorphous, it has no
crystalline areas, and therefore the melting temperature is not defined. The differences in the
melting temperature and density between syndiotactic and isotactic PP reflect differences in
intermolecular spacing within the crystallites, as well as differences in the total amount of
crystallinity that develops.
As we know, the PP we use in packaging is a linear isotactic PP. If we had branched PP, it could
not crystallize, and would not have useful properties for packaging applications. Similarly,
atactic PP is a soft, weak material, which is not useful to us as a packaging material. (Actually,
atactic PP has some limited use as an adhesive, but it is a rather poor adhesive, so we do not use
it much even in that application.) Syndiotactic PP has properties somewhat inferior to isotactic
17
PP. Our usual polymerization methods give us isotactic PP in high yield. (Commercial grades of
isotactic PP typically contain up to about 5% atactic PP as an impurity.)
It has been much more difficult to produce syndiotactic PP, so, since its properties are not as
good for most applications, and it was much more expensive, there was little reason to use it.
While we still do not often use syndiotactic PP in packaging applications, the new single site
catalysts (we will discuss these in more detail later) make it possible to produce syndiotactic PP
much more economically than used to be the case, and they have a few niche market uses.
Syndiotactic PP films are softer and more flexible than isotactic PP films.
18
2.2 Conformational Flexibility
Readings for Sect. 2.2: Painter & Coleman, Chapter 7 Structure, Sect. A-C, pp. 207-224.
As we'll discuss, conformational flexibility refers to the ease of rotation around the main chain of
the polymer - in other words, how readily the polymer can move from one conformation to
another, how much energy this motion requires
2.2.1 Thermal Transitions, Tg and Tm
The ease of rotation of bonds in the polymer chain strongly affects its properties - in particular
the glass transition temperature, Tg.
Glass transition temperature - the temperature above which the polymer has segmental
mobility - above Tg the polymer tends to be soft and flexible, below Tg it tends to be stiff
and rigid
Segmental mobility - the coordinated crankshaft-type motion of 10-50 atoms
The basic requirement for segmental mobility is that there be rotation around single bonds in the
polymer backbone (the main chain).
At the glass transition temperature and above we have segmental mobility, so parts of the
molecule can change their position with respect to their neighbors. To get flow, where whole
molecules can slide past each other, the molecules must have even more energy - be at a higher
temperature. In general, we think about this type of behavior, liquid flow, as characterizing
materials that are above their melting temperature, Tm. Recall, however, that while all
thermoplastics can be made to flow at elevated temperatures, the melting temperature is defined
only for crystalline polymers, as it is defined as the temperature at which the crystallites break
up. Remember that this does not mean that amorphous polymers do not become liquid - it just
means that we cannot draw a clear distinguishing line between liquid and solid behavior for these
materials. The transition between "solid" and "liquid" is very gradual, so we cannot define Tm.
There is another relationship between these thermal transitions and crystallinity. As mentioned
earlier, below Tg, polymers cannot rearrange themselves into a crystal lattice. They do not have
enough energy, and hence mobility, to change the position of molecular segments to assume this
type of ordered arrangement. Since above Tm the crystallites will break up, crystallization can
only occur at temperatures between Tg and Tm. For some polymers, the range of temperatures at
which crystallization can occur is even more limited. As we will see later, PET is a polymer with
a limited crystallization range. Polyethylene, on the other hand, can crystallize at any
temperature between Tg and Tm.
2.2.2 Effect of Side Groups on Rotation of C-C Bonds
When atoms or groups of atoms get too close together, they interfere with each other. Consider a
two-carbon molecule with six substituents:
19
Figure 2-17 Illustrative structure of a 2-carbon molecule with 6 substituents
In a structure like this, the lowest energy state is where the groups A, B, D and E, F, G are, on
average, farthest apart. This is called the staggered conformation:
Figure 2-18 Staggered configuration of a 2-carbon molecule with 6 substituents
Rotation around the single C-C bond causes the side groups to move closer to one another as
they pass through an eclipsed conformation before again reaching the more stable staggered
conformation.
Figure 2-19 Eclipsed configuration on a 2-carbon molecule with 6 substituents
Because of interference of the side groups with each other, the eclipsed conformation is at a
higher energy level than the staggered conformation. Therefore, for rotation to occur, there must
be enough energy available to reach the energy levels required for the eclipsed conformation.
The molecule will then continue to rotate to reach a new staggered conformation.
For polymers, in general, the larger the side groups are, the more interference there will be when
they pass by each other, so the larger will be the amount of energy required for rotation.
20
We can see the beginnings of this trend by examining rotation in ethane and in n-butane.
In ethane rotation, the "side groups" passing near each other are all hydrogens.
Figure 2-20 Effect of rotation on potential energy in ethane
In n-butane rotation, the side groups passing near each other consist of both hydrogens and
methyl groups:
Figure 2-21 Effect of rotation on potential energy in n-butane
Note that the energy situation is more complex in n-butane, since within the staggered
conformations, the arrangements, which have the methyl groups close to one another (gauche
conformations,) are at higher energy levels than those in which the methyl groups are farthest
apart (anti conformation).
Note also that the energy barrier for rotation is considerably higher for rotation around the center
bond in n-butane than it is for rotation in ethane.
21
In most cases, the larger the group which must be rotated, the higher will be the energy required
for rotation, as shown in Table 2.2.1.
Table 2-4 Examples of bond rotation energy barriers
Bond! Rotation$Barrier$(kcal/mol)$
CH3-CH3 3.0
CH3-CH2CH3 3.4
CH3-CH2Cl 3.7
CH3-CH2F 3.3
If we translate this from these small molecules to polymers, we can examine the difference in
conformational flexibility of (linear) polyethylene and polypropylene. Polyethylene has only H's
as side groups, while PP has a CH3 on every other carbon. Rotation of PP, then, brings more
interference with adjacent groups, and consequently has a higher energy requirement, than
rotation of PE. Since Tg is an indication of how much energy is required for rotation, we would
expect the Tg for PP to be significantly higher than the Tg for PE. Also, at any given temperature
below Tm, we would expect PP to be stiffer than HDPE.
If we compare the properties of PP and HDPE, most of the differences are due to the difference
in conformational flexibility between the two polymers:
Table 2-5 Sample HDPE and PP properties
Property! HDPE$ PP$

Tg (°C) -120 -20 to -10
Tm (°C) 130-137 160-175
Density (g/cm3) 0.94-0.965 0.89-0.91
Tensile strength (psi) 3200-4500 3600-4500
Tensile modulus (psi) 89,900-158,000 165,000-225,000
Flexural modulus (psi) 145,000-225,000 170,000-250,000
Elongation (%) 10-1200 100-600
Izod impact (ft-lbf/in notch) 2.0 0.7
Tear strength (lb/mil) 0.04-0.13 0.11
Heat distortion temp (°C) 62-91 107-121
We can also examine polymers with larger side groups, for example, isotactic PS (note the PS we
normally use in packaging is atactic).
Table 2-6 Melting and glass transition temperature comparisons
Polymer! Tg$(°C)$ Tm$(°C)$

HDPE -120 130-137
PP, isotactic -10 to -20 160-175
PS, isotactic 100 239
22
To think about - before reading further: Why didn't we put our normal atactic PS in the table
above? What differences in these values, if any, would you expect to find between atactic and
isotactic PS?
If we compare the differences in behavior between HDPE and PS, we have a combination of
differences due to crystallinity and differences due to conformational flexibility. The PS we use
in packaging is a linear addition polymer, but the way we produce it gives us an atactic material.
Because PS is atactic, it cannot crystallize. (Note that isotactic and syndiotactic PS can be
produced, and these materials, despite the large size of the benzene ring side group, can and do
crystallize. The properties of isotactic and syndiotactic PS are markedly different from those of
atactic PS.)
Because of its high Tg, PS at room temperature is a material that is stiff and strong enough to
have useful properties for packaging applications - in contrast to atactic PP. Because it is
amorphous, it has high transparency.
Table 2-7. Sample PS properties
Property! PS$(atactic)$
Tg (°C) 74-105
Tm (°C) -
Density (g/cm3) 1.04-1.05
Tensile strength (psi) 5200-7500
Tensile modulus (psi) 330,000-475,000
Flexural modulus (psi) 400,000-500,000
Elongation (%) 1.2-2.5
Izod impact (ft-lbf/in notch) 0.3-0.5
Tear strength (lb/mil) 0.01-0.04
Heat distortion temp (°C) 66-110
Note: This "interference" conception of the reason for the differences in required energy for
rotation between ethane and propane was accepted for many years. New information, coming
from statistical mechanics within the last handful of years, reveals that it's not really quite correct
- that the differences are actually more to do with shapes of orbitals, etc. With apologies, I'm
sticking to this old way of viewing things, as I find it useful, and the more correct way doesn't
easily allow us to extrapolate to other molecular structures.
2.2.3 Effect of Chain Backbone Linkages on Conformational Flexibility
Up to now we have considered only polymers where the main chain (backbone) is comprised of -
C-C-C-linkages. However, there are a number of other possibilities.
23
2.2.3.1 Double Bonds in the Backbone
Double bonds are rigid structures and do not permit rotation. It might therefore be assumed that
polymers containing double bonds in the backbone would be more rigid than those with only
single bonds. However, this is not the case. If we have a -C=C- structure in the backbone of the
polymer, then each of those C atoms can be bonded only to one side group. Thus, if we look at
rotation - not around the double bond (since it cannot rotate) - but about the single bond adjacent
to the double bond, there is less interference with rotation. We can see this from the rotational
energy barrier:
CH2=CH - CH3 2.1 kcal/mol around the single bond (marked in red)
The effect is even more pronounced in larger molecules:
CH3CH2 - CH=CH2 <0.8 kcal/mol
CH3 - CH=CHCH3 <0.8 kcal/mol
What this means, in terms of polymer performance, is that polymers with double bonds in the
main chain tend to have low Tg's, and to be soft and flexible. It is in this group that elastomers
are usually found. Also note that the presence of the double bond means that the material retains
some reactivity, permitting subsequent cross-linking and other modification, if desired.
The presence of a double bond in the main chain also means we have two different isomers
which may be present, due to the rigid nature of that bond. If we think of the configuration of the
main chain, looking at it in its fully extended conformation, there are two possibilities,
depending on whether the monomer adds in a cis or trans form:
Figure 2-22 Cis- and trans- configurations
To examine this, as well as the effects of the low barrier to rotation on adjacent single bonds, we
can consider the case of polybutadiene.
Polybutadiene is prepared by polymerization of 1,4 butadiene
H2C=CH-CH=CH2
This can polymerize in 3 fashions. One is the standard addition polymerization which will add 2
C's into the main chain, and leave a -CH=CH2 side group. This results, with the usual
24
polymerization methods, in an atactic polymer, which consequently does not crystallize and has
a Tg of about -10°C, so is a soft rubbery material, with no particularly useful properties.
More commonly, there is a transfer of the free radical as follows:
Figure 2-23 Transfer of the free radical during polymerication of butadiene
so that all 4 of the carbons are added into the main chain. In this case, either cis- or trans-
isomers can result:
trans:
cis:
Figure 2-24 Cis- and trans- forms of polybutadiene
While both of these have regular structures and can crystallize, the compactness of the crystals
and ease of crystallization differ significantly, and consequently affect the material properties.
Table 2-8 Properties of cis- and trans-polybutadiene
Polymer! Tg$(°C)$ Tm$(°C)$ Behavior$

cis-1,4 polybutadiene -103 to -95 0-6 soft rubber
trans-1,4 polybutadiene -38 135-145 hard plastic
2.2.3.2 Ring Structures in the Backbone
Ring structures put rigid links in the backbone, as do double bonds. In contrast to double bonds,
rings provide no appreciable effect of easing rotation around adjacent single bonds.
25
Consequently, polymers containing backbone rings tend to be quite stiff, and have high Tg and
Tm.
Since we have no common examples of plastics with rings in the backbone which consist only of
C and H, we will wait to illustrate such structures.
2.2.3.3 Effect of Non-C atoms in the Backbone
If we examine the barrier to rotation about an O-C bond, we find that it is lower than that for
rotation around a C-C bond:
CH3 - CH3 3.0 kcal/mol
CH3 - OCH3 2.7 kcal/mol
Thus the presence of O in the main chain tends to increase the flexibility of a polymer structure,
lowering its Tg (and Tm, if applicable).
Whenever we have atoms other than C and H in the polymer, we need also to consider the effects
of the magnitude of secondary forces on properties. Intermolecular forces are also important in
considering the effect of molecular weight on polymer properties.
26
2.3 Intermolecular Forces

2.3.1 Primary and Secondary Bonds
Readings: Painter & Coleman, Ch. 7, Sect. B, pp. 208-217 (you should have read this earlier).
2.3.1.1 Primary Bonds
The process of polymerization is that of assembling the polymer molecules by forming primary
bonds between atoms. Primary bonds can be of three main types: covalent, ionic, and metallic.
Covalent bonds involve sharing of electrons between the two atoms being bonded. Electrons end
up paired with one another - a lower energy state than the unpaired state.
Ionic bonds involve the transfer of electrons from one atom (which results in the formation of a
positively charged ion) to another (resulting in the formation of a negatively charged ion). The
molecular fragments are then joined together by electrostatic attraction. Again electrons end up
in pairs.
Metallic bonds occur when electrons are very loosely held, and are therefore relatively free to
wander away from their originating atom. We can think of metallic bonds as involving a mobile
"sea" of electrons. This makes metals good conductors of electricity.
Metallic bonds are not found in polymers. Ionic bonds are found only rarely (such as in
ionomers). Thus nearly all polymer primary bonds are covalent in nature.
Covalent bonds can be further subdivided into those in which the electron sharing is equal, non-
polar bonds, and those in which the electron sharing is unequal, polar bonds. C-C and C-H bonds
are non-polar. Bonds involving C and O, N, Cl, and F (the other atoms commonly found in
polymers) are generally polar. O, N, Cl and F all have a higher electron affinity than C.
Therefore the two electrons being shared will spend a higher proportion of their time near the
electronegative atom (O, N, Cl, F) than near the C atom. As a result, we can think of the C as
having a partial positive charge and the O, N, Cl or F as having a partial negative charge.
The strength of the primary bonds is the prime determinant of the chemical reactivity of the
polymer. This largely determines what chemical species will react with the polymer, its
decomposition temperature, the type of products produced by reaction, speed of reaction, etc.
The bond length determines the basic spacing of the atoms in the molecule.
27
Table 2-9 Typical primary bond lengths and energies for bonds commonly found in packaging
plastics
Bond! Bond$Length$(Å)$ Dissociation$Energy$(kcal/mol)$

C-C 1.54 83
C=C 1.34 146
C-C triple bond 1.20 194
C-H 1.10 99
C-N 1.47 73
C=N 1.27 147
C-N triple bond 1.15 213
C-O 1.46 86
C=O 1.21 179
C-F* 1.32-1.39 103-123
C - Cl 1.77 81
C-S 1.81 62
N-H 1.01 93
O-H 0.96 111
S-H 1.35 81
O-O 1.32 35
* The bond length decreases and the dissociation energy increases as additional fluorine atoms are
substituted on the same carbon atom.
We can estimate, to a rough degree, the propensity of a molecule to undergo a chemical reaction
by comparing the energies of the bonds present before and after the reaction. Since spontaneous
processes always go from higher to lower energy states, if the end products are at a lower energy
than the reactants, there will be some thermodynamic driving force in the direction of that
reaction. We must note, however, that this does not mean the reaction will occur spontaneously.
In general, intermediate states have a higher energy level than either the reactants or the
products. This will prohibit the reaction from occurring unless something gives at least some of
the molecules enough energy to get over this energy barrier. Once this occurs, the liberation of
heat during the reaction will often tend to increase the likelihood of subsequent reaction -
sometimes catastrophically so.
2.3.1.2 Secondary Bonds
In contrast to primary bonds, which are the bonds making up the molecule, secondary bonds are
those which attract adjacent molecules to each other. If a substance had no secondary bonds, it
would behave like an ideal gas. In general, we can say that secondary bonds are strongest in
solids, somewhat weaker in liquids, and weakest in gases. Therefore, secondary bonds are
important in determining the properties of all solid materials we use, and polymers are no
exception. In fact, while the types and character of secondary bonds are the same in plastics as in
materials made from small molecules, the sheer number of secondary bonds between adjacent
molecules in polymers (due to the size of the polymer molecules and hence the number of
opportunities for such attractions) is primarily responsible for the unique characteristics of
polymers, including packaging plastics.
28
Secondary bonds can be classified as four major types: dispersion forces, induction forces, dipole
forces, and hydrogen bonds. The first three of these are grouped together as van der Waals
forces.
Dipole forces are due to electrostatic attractions between atoms with equal and opposite electric
charges. They are the strongest of the van der Waals forces, up to approximately 2 kcal/mol (8
kJ/mol). Dipole forces are found in polar molecules, where the electron sharing is unequal.
Induction forces occur when a polar molecule induces dipoles in surrounding nonpolar
molecules. They are weaker than dipole forces, but stronger than dispersion forces.
Dispersion forces are the attraction between neighboring molecules that results from
instantaneous configurations of electrons and nuclei that result in time-varying dipole moments
(which average to zero), which perturb the electronic clouds of neighbors and lead to attractive
forces. These are found in all molecules, and are the weakest of the secondary forces, with
strengths of 0.1-0.2 kcal/mol (0.4-0.8 kJ/mol). If all molecules in a substance are nonpolar, these
are the only secondary forces that are present.
Hydrogen bonds are a uniquely strong kind of intermolecular force, with values of 2-10
kcal/mol. They result from the attraction between a H atom bonded to an electronegative atom,
and a neighboring electronegative atom. Some H-bonds recently were found to have some
covalent nature, meaning that there is actually some electron-sharing which may occur between
the atoms connected by a hydrogen bond. Not all electronegative atoms are strong enough to
promote H-bonding. Those which can do so are, in decreasing order of strength, F, O, N, and to a
lesser extent S and Cl. Since we are talking about polymers, and F can bond to only one other
atom, F will only be a factor in polymer hydrogen bonding if there is also some other
electronegative atom present which is bonded to an H. Therefore, the atoms in polymers whose
presence is a cue to look for hydrogen bonding are O and N. A typical value for an O···H-O
bond is 5 kcal/mol. The bond length is typically 2.4-3.2 Å.
In understanding intermolecular attractions, it is important to remember that they are

proportional to r-6, where r is the distance between the atoms. Thus, the strength of the attractions
is influenced very strongly by the spacing between adjacent atoms. One of the ways in which
crystallinity influences polymer properties is by achieving a tighter packaging of the atoms, and
hence increasing intermolecular forces.
2.3.2 Effect of Secondary Bonds on Polymer Behavior
If the secondary bonds are what differentiate real substances from ideal gases, then it is obvious
that the type, strength, and number of secondary bonds in plastics are key to many of their
properties. In particular, as we have said, plastics are unlike substances made of small molecules
largely because of the great number of secondary bonds attracting polymer molecules to each
other.
To examine the effect of strong intermolecular forces on polymer behavior, we can look at PVC
as an example. Chlorine is a strongly electronegative atom. Therefore the C-Cl bonds in PVC are
29
strongly polar. We can compare properties of PP and PVC, which have side groups of a similar
size, so they are not very different in conformational flexibility. One thing we need to note is that
the way we commonly produce PVC yields a polymer which is predominantly atactic, though it
does have a slight syndiotactic character. Therefore PVC is a nearly amorphous plastic. It has
just enough crystallinity to allow us to define a Tm, but not enough to materially affect polymer
properties.
Table 2-10 Sample PVC and PP properties
Property! PVC$ PP$

Tg (°C) 75-105 -20 to -10
Tm (°C) 212 160-175
Density (g/cm3) 1.35-1.41 0.89-0.91
Tensile strength (psi) 6000-10,000 3600-4500
Tensile modulus (psi) to 600,000 165,000-225,000
Elongation (%) 5-135 100-600
Izod impact (ft-lbf/in notch) 0.65-1.6 0.7
Tear strength (lb/mil) 0.11
Heat distortion temp (°C) 57-82 107-121
Note the much higher Tg of PVC. This permits PVC to have usefulness as a packaging material
in its amorphous state, whereas amorphous PP does not have useful properties. The strong ability
of PVC to form secondary bonds is also responsible for its affinity for plasticizers, which permits
us to formulate PVC in a wide range of compositions, from the stiff, brittle nature of relatively
unmodified PVC to the soft flexible nature of highly plasticized PVC film.
Two of the properties, which are strongly influenced by secondary bonding, are the melting
temperature, Tm, and glass transition temperature, Tg.
2.3.2.1 Effect of Secondary Bonds on Tg
We have already discussed the importance of conformational flexibility in determining how

much energy is required for rotation around polymer bonds, to permit the segmental
mobility that is associated with temperatures above Tg. To that, we must add the idea that in
order for segmental mobility to occur, not only must we have enough energy for rotation within
the polymer backbone, we must also have enough energy to disrupt the secondary bonds that act
to restrain motion of a segment of the polymer molecule, by keeping it "tied" to neighboring
molecular segments.
We can conclude that (all else being equal) the stronger are the intermolecular attractions, the
more energy will be required for segmental mobility, and hence the higher will be Tg.
30
2.3.2.2 Effects of Conformational Flexibility and of Secondary Bonds on Tm
Our conclusions about effects on Tm parallel those for Tg. Within the crystallite, the stronger are
the attractions between neighbors, the greater will be the energy required to break up the
crystallites.
Going back to conformational flexibility and its effects on Tm, we expect that, in general, lower
conformational flexibility, as, for instance, associated with side groups, would tend to increase
Tm. This pattern certainly held for the HDPE/PP comparison. However, another effect of
increasing size of side groups (as well as some other factors, such as rings) is to increase the
average spacing between molecules in the crystal framework.As we discussed, intermolecular
attractions have a strength inversely proportional to the 6th power of the distance between the
atoms. Therefore, increasing the spacing acts to decrease the strength of secondary bonds in the
crystallite - which acts to lower Tm.
Consequently, the effect of conformational flexibility on Tm is less straight-forward than its

effect on Tg. If we examine the effect of increasing size of pendant groups in a series such as
HDPE, PP, polybutene, polypentene, etc. (assuming all are isotactic), we will see Tm first
increase and then decrease, as the effects of conformational flexibility and intermolecular forces
counteract each other.
2.3.3 Quantifying Intermolecular Forces
Complementary reading material: Rodriguez pp. 34-35 (30-31 4th ed)

The cohesive energy density is a measure of the strength of secondary forces. It is equivalent to
the energy required to separate molecules (in the close-spaced liquid state) from one another,
isothermally, to a spacing far enough apart that secondary bonding forces are insignificant (ideal
gas state - or infinite volume), per unit volume:
∆!!
!"# =
!!
It does not include attractions related to crystallization.
The solubility parameter, *, is the square root of the cohesive energy density.
We can conclude that, other factors being equal, a polymer with a higher cohesive energy density
will have a higher Tg (and Tm, if applicable).
31
Table 2-11 The cohesive energies of some common polymers, along with Tg and Tm
Polymer Cohesive Energy Solubility Tg (°C) Tm (°C)

(J/mol) parameter
(*) (MPa1/2)
Polyethylene (HDPE) 8200-9600 16.93 -120 128-138
Polypropylene 13,900-17,400 17.2-19.2 -20 to -10 160-175
Polystyrene 29,700-35,400 17.5-21 74-105 -
Polyvinyl chloride 16,700-22,100 19.2-21.5 75-105 212
Polyvinylidene chloride 23,900-36,300 25 -15 to 2 160-172
Polytetrafluoroethylene 8,000 12.7 -73 327-345
Polyvinyl alcohol 23,300-29,600 21.7-25.8 85 decomposes
Polyvinyl acetate 26,300-36,900 18.21 23-39 -
Polyacrylonitrile 29,400-44,500 25.2-31.5 85-104 ˜320
Polyethylene terephthalate 56,700-68,700 21.9 73-80 245-265
(PET)
Nylon 6 21.5 59-75 220-231
We can also look at the contribution various types of groups make to cohesive energy. In
general, the more polar the group, the stronger will be its contribution. WARNING: different
methods of calculating these contributions give substantially different values, although the trends
are generally similar.
Table 2-12 Group contributions to cohesive energy and molar volume (Fedors, from Polymer
Handbook, 4th ed., J. Brandrup et al., Wiley, New York, 1999)
Group Cohesive Energy Contribution, Group Molar Volume, V

Ecoh (J/mol) (cm3/mol)
-CH3 4,710 33.5
-CH2- 4,940 16.1
>CH- 3,430 -1
>C< 1,470 -19.2
phenyl 31,940 71.4
-F 4,190 18.0
-CF2- 4,270 23.0
-Cl 11,550 24.0
-CN 25,530 24.0
-OH 29,800 10.0
-O- 3,350 3.8
-CHO, aldehyde 21,350 22.3
-CO- 17,370 10.8
-COOH 27,630 28.5
-COO- 18,000 18.0
-NH2 12,560 19.2
-NH- 8,370 4.5
32
2.3.4 Effects of Hydrogen Bonding
As we have seen, hydrogen bonds are the strongest intermolecular forces. Because water is
capable of strong hydrogen bonding, polymers which have intermolecular hydrogen bonds are
often strongly affected by the presence of water. One example is polyvinyl alcohol, which
interacts so strongly that it is soluble in water.
More commonly, polymers with significant hydrogen bonding show changes in their behavior in
the presence of water. Nylons, for example, typically are better barriers when dry than in high
moisture conditions. The same is true for ethylene vinyl alcohol.
2.4 Effects of Molecular Weight
Important note: All of the discussion below assumes the polymer has not changed - only its
molecular weight has changed. In other words, the polymer chain has gotten longer.
Readings: Painter & Coleman, Chapter 1, Section C, pp. 16-24; Chapter 7, Section F, pp. 255-
256.
We will come back to a more detailed look at the effects of molecular weight on polymer
properties in Unit 5. For now, we'll look briefly at the following:
2.4.1 Effect of Molecular Weight on Tg
One effect of increasing molecular weight is to increase the average number of secondary bonds
per molecule. We can also conceptualize increasing molecular size as putting some "restraint" on
overall levels of segmental mobility, and thus as increasing the amount of energy required for
such mobility.
In general, there is an empirical correlation for Tg of the form:
!!
!! = !!,! −
!!
where Tg is at a finite molecular weight Mn, and Tg,∞ is Tg for an infinitely long polymer. Kg is an
empirical correlation coefficient, which is found by fitting the equation to experimental data for a
particular polymer.
2.4.2 Effect of Molecular Weight on Tm
The effect of molecular weight on Tm is complex. If we look at the effect of molecular weight
alone, with crystallinity held constant, everything is straightforward. Increasing molecular
weight increases Tm.
33
Increasing molecular weight generally makes it more difficult to pack the polymer molecule into
a crystalline arrangement, because it is harder to move around and rearrange the bigger chain. On
the other hand, chain ends are a disrupting influence in crystallinity. Therefore, crystallinity first
increases with molecular weight and then decreases.
Increasing percent crystallinity generally increases Tm, and decreasing percent crystallinity
generally decreases Tm slightly. (Note that there is an effect of the size of the crystallites as well
as of the percent crystallinity, to further complicate matters.)
When we put these effects together, if we are below the molecular weight region where %
crystallinity starts to decrease, Tm increases as molecular weight and crystallinity increase. When
we get to the point where further increases in molecular weight begin to decrease crystallinity,
we have competing influences, and the result will depend on which predominates - the increase
due to molecular weight or the decrease due to crystallinity effects. In any case, the effect will
likely be small.
2.4.3 Other Effects of Molecular Weight
Increasing molecular weight also tends to increase impact resistance, toughness, and tensile
strength of polymers. Since materials are more likely to fail through disruption of secondary
bonding than through rupture of primary (covalent) bonds, increasing the chain length makes it
more difficult (requires more energy) to pull chain ends out of the material, causing cracking.
Increasing molecular weight also increases viscosity. Two effects occur. First, the preferred
conformation of a polymer molecule in the melt is as a random coil. The larger the molecule, the
larger will be the random coil. It takes more energy to move larger coils. Second, an important
factor in the high viscosity characteristic of polymers is chain entanglement. Longer chains
tangle more, thus increasing viscosity. Heat resistance and required sealing temperature will also
increase, and the sealing range tends to decrease.
Chemical resistance tends to increase somewhat with increasing molecular weight - chain ends
are generally more vulnerable to attack than the chain body.
Increasing molecular weight itself has little effect on barrier. Changes in crystallinity do affect
barrier, however, so there may be an indirect effect.
It must be remembered that the molecular weight distribution has effects which are independent
of those of molecular weight average. In general, a broad distribution of molecular weight
improves flow properties but decreases strength properties. In practice, it is possible to add a
relatively small amount of low molecular weight polymer to significantly improve flow
properties (decrease viscosity) while at the same time reducing the weight average molecular
weight and related strength properties by only a small amount.
34
2.5 Relationship between Tm and Tg
Readings: no assignment. You are welcome to read Painter & Coleman, Ch. 8, if you wish, but it
goes into quite a bit of thermodynamics. We'll cover thermodynamics a little bit towards the end
of the course, but not now.
As we have seen, many factors about polymer structure tend to affect both Tg and Tm. For many
homopolymers, the following general relationship holds (T must be in absolute temperature (e.g.
K):
!!
1.4 < < 2.0
!!
Note that this relationship is not exact, and does not hold at all for some polymers, as can be seen
in the following table:
Table 2.5 Tg and Tm for Selected Addition Polymers
Polymer Tg (°C) Tg (K) Tm (°C) Tm (K) Tm/Tg

HDPE -120 153 137 410 2.7
PP, isotactic -20 253 176 449 1.8
PP, atactic -35 238 - - -
PVC 87 360 190 463 2.4
PS, isotactic 90-100 363-373 190 463 1.2
PVDC -18 255 190 463 1.8
Polyvinyl acetate (PVA) 29 302 - - -
Polyvinyl alcohol (PVOH) 70 343 decomposes at - -
T>150; est 212-
267 485- 1.8-2.5
540
Polytetrofluoroethylene -120 to - 153-176 327 600 3.4-3.9
(PTFE) 97
Polychlorotrifluoroethylene 45 318 - - -
(PCTFE)
Polyacrylonitrile 90 363 - - -
35
2.6 Other Considerations Involving Crystallinity and Crystallization
We will come back to some more discussion in this area in Section 7, morphology. For now,
some basic observations:
As we have discussed, polymers are never totally crystalline (although they may, of course, be
totally amorphous). The large size of polymer molecules acts against their ability to be totally
arranged in a repeating way. Also, chain ends act as irregularities. Polymers typically assume a
zigzag or helical arrangement within crystallites. Crystallites grow from an initiation point, and,
if conditions permit, continue to grow until their growth is interfered with by the presence of
another crystallite. Patterns of crystal growth (and the forms of the crystallites) under stress, such
as during orientation, often are very different from patterns during quiescent growth conditions.
Crystallites cannot form at temperatures below Tg, since there is no ability for the rearrangement
of the molecules which is necessary for them to assume an ordered arrangement. There is no
crystal growth at temperatures above Tm, since (by definition) there is too much mobility and the
molecules will not stay arranged. Therefore crystallization rates increase as one moves away
from Tg and Tm. Consequently, there is some intermediate temperature at which crystallization
rates reach a maximum. The range over which crystallization can occur may extend from Tg to
Tm, or may be much more restricted, depending on the polymer.
2.6.1 Isomorphous Groups
When we have discussed irregularities of structure which interfere with crystallinity, there is one
concept which we have omitted until now. Irregularities interfere with crystallinity if they
prohibit the molecular segment from packing into the crystalline arrangement determined by the
composition of the polymer. There are some groups which are able to "fit" the same crystal
lattice spaces as other, chemically different, groups. Such groups are known as isomorphous.
For the purpose of understanding the properties of packaging polymers, there is one set of
isomorphous groups which is significant. The groups:
CH2 CHOH CF2 C=O
are isomorphous to each other. They will fit the same spaces in the crystal lattice. Therefore if
the only irregularity is that related to not knowing which among these groups will be present in a
given location, there is no interference with crystallization. We will see an example of the
effect of isomorphous groups when we discuss polyvinyl alcohol in Sect. 2.8, and will find
unpredictability about whether a CH2 or CHOH group will be present. The group above is the
only set of isomorphous groups that we are likely to encounter in our study of packaging plastics.
Note: Chemical groups are never "ismorophous" without qualification. Rather, two groups may
be isomorphous to each other. The groups identified above are all isomorphous to each other.
However, it would certainly not be true to say, for instance, that CF2 is isomorphous, or to say
that it is isomorphous to CCl2.
36
2.6.2 Transparency/Opacity
In general, the presence of crystallites leads to differences in refractive index between the
crystallites and the noncrystalline regions of a polymer. This causes light scattering at the crystal
boundaries, which renders materials hazy or opaque. Therefore, the general rule is that
amorphous polymers have better transparency than crystalline polymers.
However, the degree of light scattering is dependent on the size of the crystallites. If the
crystallites are small enough, they do not interfere with light transmission as much as if they are
larger. Thus a polymer with a large number of small crystallites is likely to have better
transparency than the same polymer with the same percent crystallinity, but with larger
crystallites.
Consequently, transparency of a semicrystalline plastic can be improved by either reducing the

overall amount of crystallinity (such as by cooling it faster to reduce the time available to
crystallize, or by introducing irregularities to inhibit crystallization), or by manipulating the
conditions to favor the growth of small crystallites over large ones. Of course, these techniques
can also be used together.
A common way to favor the growth of small crystallites is by "seeding" the polymer with
inclusions around which crystal growth can occur - nucleating agents. This is employed
(sometimes in conjunction with copolymerization to reduce overall levels of crystallinity) in
producing clear grades of polypropylene, for example.
37
2.7 Barrier
The ability of a polymer to retard permeation of substances through it is composed of two parts -
solubility, which determines how much of the permeant will be present within the plastic, and
rate of diffusion, which determines how rapidly the permeant will be able to travel within the
plastic.
In general, permeation requires the presence of "holes" in the polymer matrix of an appropriate
size for the penetration of the permeant. Therefore, all else being equal, larger molecules will
permeate at slower rates than smaller molecules. We would expect, therefore, permeation rates
for oxygen to be higher than permeation rates for carbon dioxide.
(Be careful to note that "all else being equal." Unfortunately for our ease of drawing conclusions,
that's often not the case. As stated above, it's not just the size of the permeant molecules that
matters but also how many of them get into the polymer - the solubility of the permeant. What
we find in comparing oxygen and carbon dioxide permeation rates is that because solubility may
be a more important influence than diffusion rates, just the opposite is true for many polymers;
the rate of carbon dioxide permeation is higher than the rate of oxygen permeation. Perhaps a
better example is that permeation rates for water are generally higher than those for oxygen, due
in part to the water molecule being much smaller than the oxygen molecule.)
Further, since within crystallites molecules are tightly packed, most permeation will occur
through amorphous regions. Therefore, a polymer with a higher extent of crystallinity will be a
better barrier than the same polymer with lower crystallinity. Similarly, strong intermolecular
forces decrease permeability.
Permeation rates generally increase with increasing temperature. While solubility may increase
or decrease, the increase in diffusion rate with increasing temperature usually dominates.
Polymers above their Tg are significantly poorer barriers than the same polymers below their Tg -
there is an increase in slope of the P v T curve at Tg. This is primarily due to the phenomenon
known as "activated diffusion." Below Tg, the permeant is limited to traveling through existing
spaces between polymer molecules. Above Tg, segmental mobility acts to create spaces through
which the permeant molecule can travel.
38
2.8 Addition polymer properties
This section deals with application of the principles of regularity, conformational flexibility, and
intermolecular forces in order to understand the properties of some important packaging
polymers. We will first look at addition or carbon-chain polymers.
General readings: Painter & Coleman, Chapter 2, Sect. A (pp. 29-31) and Sect. C (pp. 40-54).
Note: For each polymer, to understand the relationship between structure and properties, it is
obviously important to know something about the properties themselves. As I note in the
polyethylene page, our textbook does not contain this type of discussion, so to refresh our
recollection of properties, we need to depend on other readings. If you have the supplemental
text (the text for PKG 323 and PKG 801) you should find sufficient detail in there. If you're
fortunate enough to have access to the Wiley Encyclopedia of Packaging Science and
Technology, that is a great source of information. I've put links in to Wikipedia articles, which
are very good for some polymers, and almost useless for some of the others. Another general
source is Macrogalleria, http://pslc.ws/mactest/index.htm but it’s too elementary for us in most
cases. Many polymer science textbooks have a reasonable discussion of the plastics we’re
interested in.
An excellent source that you can access online through the MSU Library’s electronic resources is
the Encyclopedia of Polymer Science and Technology. To get to it, go to
http://mrw.interscience.wiley.com.proxy2.cl.msu.edu:2047/emrw/9780471440260/search/firstpa
ge
When you go to this link, you should be redirected to a login page, and once you’ve logged in,
you should get to the encyclopedia. If this doesn’t work, go to the Library’s Electronic Resources
page at http://er.lib.msu.edu/ and search for the Encyclopedia.
I am not listing the particular articles for each polymer, as the articles are longer and more
detailed than I’m really expecting you to need, but feel free to read them if you wish!
39
2.8.1 Polyethylene family
Reading assignment: Read something that provides a general description of polyethylene and its
properties. There are a number of options. Here is one: Wikipedia,
http://en.wikipedia.org/wiki/Polyethylene. Another option, if you have the supplemental text
(from PKG 801 or 323, for example), is to read about polyethylene there. There are a number of
other ways to get this information, too. This is going to be the general practice in this section.
The text does not contain detailed descriptions of the polymers we will discuss, so we'll look
for more detailed information elsewhere. You should have previous exposure to these materials
and their properties, so this is in the nature of a refresher on properties, so that we can connect
them more closely to structure.
Because of its extremely low Tg, polyethylene, at all typical use conditions, is a soft, flexible
polymer. HDPE, with its higher crystallinity, is stiffer than LDPE and LLDPE. This
characteristic is a deficiency when we want to use PE at elevated temperatures, since its Tm is
also relatively low (but this is an asset in heat sealing).
PE is quite inert, since C-C and C-H bonds are strong and stable. It is a relatively good water
vapor barrier, since it is totally nonpolar so has low solubility for water. HDPE, with its
increased crystallinity, is a better barrier than LDPE. Both are relatively poor gas barriers, since
intermolecular forces are weak and the materials are above their Tg at use conditions and hence
have segmental mobility.
40
Table 2-13 Typical properties of HDPE and LDPE blown films
Property HDPE - MMW HDPE - HMW LDPE

Density (g/cm3) 0.950 0.950 0.921-0.923
Tensile strength (psi) 6100-6500 7000-7500 2700-3000
Tensile modulus (psi) 125,000- 125,000-
125,000 130,000
Flexural modulus (psi) 128,000-
260,000*
Elongation at break (%) 350-550 450-550 200-600
Izod impact (ft-lb/in) 2.0*
Tear strength (gf/mil) 15-100 20-150 90-160
Dart drop impact strength (gf/mil) 75-185
Heat-distortion temp. (oC)
Use temp. (oC) -51 to 121* -51 to 65*
o
Heat-seal temp. ( C) 135-155 121-177*
O2 permeability 100-200* 250-350*
(cm3 mil/100 in2 d atm)
WVTR (g mil/100 in2 d at 38oC, 0.8 0.8 (1.38)*
90% RH) (0.38)*
Haze (%) 78 78
*General property for material, not specific to blown film listed
41
Table 2-14 Typical properties of LLDPE blown films
LLDPE - butene LLDPE - hexene LLDPE - octene
Property
Density (g/cm3) 0.918 0.918 0.920
Tensile 3800-5000 4700-5200 5100-6500
strength (psi)
Tensile
modulus (psi)
Elongation at 350-850**
break (%)
Izod impact (ft-
lb/in)
Tear strength 140-340 340-585 370-800
(gf/mil)
Dart drop 100 200 250
impact strength
(gf/mil)
Heat-distortion
temp. (oC)
Service temp.
(oC)
Heat-seal temp.
(oC)
O2 permeability
(cm3 mil/100 in2
d atm)
WVTR (g
mil/100 in2 d at
38oC, 90% RH)
Haze (%)
** Not specific to butene-based LLDPE, or to blown film of density listed
42
2.8.2 Polypropylene
Reading Assignment: Read a discussion of PP properties. One option:

http://en.wikipedia.org/wiki/Polypropylene.
The PP we commonly use in packaging is isotactic, and therefore crystalline. Because its Tg is
only about -20oC, PP, while reasonably soft and flexible at room temperature, tends to be brittle
at low (freezer) temperatures. It is a stiffer material than HDPE, and can be used at higher
temperatures, due to its higher Tm. PP is somewhat less inert than HDPE, because breaking the
C-C bond to produce free radicals on the methyl group and the polymer molecule is energetically
favored over breaking the C-H bond to produce a H free radical and a radical on the polymer
molecule. Like HDPE, PP is a relatively poor gas barrier but a good water vapor barrier.
Syndiotactic PP has a lower Tm than isotactic PP, lower density, and somewhat better impact
resistance and transparency.
PP does not heat seal well. Modification (coating, coextrusion, or copolymerization) is required
to produce a heat-sealable film. Without modification, the oriented film (which is what is usually
used) undergoes excessive distortion. Also, hot-tack strength is low.
Table 2-15 Typical properties of PP
Property isotactic - unoriented isotactic - biaxially

oriented
Density (g/cm3) 0.89-0.91 0.89-0.91
Tensile strength (psi) 3600-4900 18,000-35,000
Elongation at break (%) 100-600 30-150
Izod impact (ft-lb/in) 0.7
Tear strength (gf/mil) 50 4-6
Heat-distortion temp. (oC) 107-121
Service temp. (oC)
Heat-seal temp. (oC)
O2 permeability 150-250 80-150

WVTR (g mil/100 in2 d at 38oC, 90% 0.63 0.25-0.3
RH)
Haze (%) 2.0
43
2.8.3 Polystyrene
Readings: Something on PS. One option: http://en.wikipedia.org/wiki/Polystyrene.
PS is an atactic linear addition polymer, which consequently is amorphous. The bulk of the side
group increases Tg. Because only non-polar bonds are present, intermolecular attractions are
relatively weak. Due to the lack of crystallinity and weak intermolecular forces, and typical use
conditions below Tg, the polymer is a stiff, brittle, and relatively weak material.
Impact grades of PS have been modified to improve their impact strength. We will discuss these
materials further in Sect. 5 on copolymers. The unmodified, unfoamed versions of PS are called
crystal PS.
Table 2-16Typical properties of PS
Property crystal PS impact PS

Density (g/cm3) 1.04-1.05
Elongation at break (%) 1.2-2.5 40
Izod impact (ft-lb/in) 0.3-0.5 1-5
Tear strength (gf/mil) 4.5-18
Service temp. (oC)
O2 permeability 250-400
WVTR (g mil/100 in2 d at 7.1
38oC, 90% RH)
44
2.8.4 Polyvinyl Chloride
Readings: Something on PVC. One option: http://en.wikipedia.org/wiki/Polyvinyl_chloride.
PVC is a slightly syndiotactic addition polymer. C-Cl bonds are strongly polar. The polymer is
nearly totally amorphous, and has strong intermolecular forces. A range of grades of PVC is
available, differing primarily in the amount and type of modifying ingredients, particularly
plasticizer, which have been added.
The effect of plasticizers is to reduce intermolecular forces and increase chain flexibility, thereby
reducing Tg, by putting small molecules in between the PVC molecules. Plasticizers are
generally high boiling point organic liquids. The polar bonding in PVC gives it strong attractions
to the plasticizer molecules, reducing their tendency to be lost through migration and
evaporation.
The use of plasticizers permits us to manufacture PVC resins with a wide range of properties.
Relatively unmodified PVC is a stiff material with generally good barrier properties. Flexible
PVC film, which may be 50 percent plasticizer by weight, is soft and flexible, and a relatively
poor barrier.
Table 2-17 Typical properties of rigid and flexible PVC
Property Rigid PVC Flexible PVC film, unoriented

Density (g/cm3) 1.30-1.36 1.23-1.27
Izod impact (ft-lb/in) 0.5-20.0
Tear strength (gf/mil) 300-500
Heat-distortion temp. (oC) 70-76 (57-82)
Service temp. (oC) -29 - 66
Heat-seal temp. (oC) 143-171
O2 permeability 5-20 340-860
WVTR (g mil/100 in2 d at 0.02-0.04 10-16
38oC, 90% RH)
One element of PVC properties that we have not addressed is its lack of good thermal stability.
PVC is prone to thermal degradation at temperatures comparable to standard processing
temperatures. The basic reaction is:
-(CH2CHCl)n-CH2-CHCl-(CH2CHCl)m- → -(CH2CHCl)n-CH=CH-(CH2CHCl)m- + HCl
45
This reaction is especially likely to occur at locations in the molecule where head-to-head
addition has occurred (instead of the normal head-to-tail) and also at sites with an adjacent set of
double-bonded carbons. This leads to the formation of conjugated double bonds:
-(CH2CHCl)p-CH2=CH-CH=CH-CH=CH-(CH2CHCl)q-
One result is a color change. The PVC first yellows and then becomes brown. All varieties of
available PVC resins contain heat stabilizers to help prevent such degradation.
Exposure to ultraviolet light can also initiate degradation reactions. If PVC is to be used
outdoors, it will contain UV stabilizers in addition to heat stabilizers.
The presence of chlorine makes PVC a generally fire-resistance polymer. It burns only with
difficulty, and does not sustain a flame. (Polyolefins, on the other hand, burn readily - much like
the petrochemicals, which serve as their feedstock.)
46
2.8.5 Polyvinylidene Chloride
Readings: The Wikipedia entry for PVDC is

http://en.wikipedia.org/wiki/Polyvinylidene_chloride but it isn't very thorough. I haven't located
a really good on-line source yet.
The structure of PVDC is:
-(CH2-CCl2)n-
Because every other carbon has 2 chlorines attached, instead of 1 as in PVC, the bonds are not
able to be as polar - the carbon will not “accept” withdrawal of twice as much electron-time. The
bonds are still polar, but not as highly polar as in PVC. Addition is linear, and predominantly
head-to-tail, as usual. We no longer have a chiral carbon (no carbon bonded to two different side
groups), so PVDC is both structurally and stereochemically regular. This regularity, coupled
with relatively small side groups (single atom) and relatively strong intermolecular forces, mean
PVDC is highly crystalline. The combination of strong intermolecular forces and high
crystallinity makes PVDC an excellent barrier for many compounds, including water vapor,
oxygen, carbon dioxide, and odors and flavors. The barrier qualities are not affected by the
presence of water vapor.
The relatively strong intermolecular forces (compared to PE, PP, PS, etc.) give PVDC a
relatively high melting temperature. However, PVDC undergoes the same type of thermal
degradation reactions described for PVC. Hence, processing of PVDC is difficult. We could
improve processability by incorporating plasticizers, as we do for PVC. However, the reason we
usually use PVDC is to achieve good barrier properties. The use of plasticizers in amounts
sufficient to improve processability significantly reduces barrier. Therefore, our prime mode of
improving processability is to incorporate structural irregularity, and hence reduce crystallinity.
In practice, therefore, we never use homopolymer PVDC, and instead rely on copolymer PVDCs
of various types. (Saran Wrap household film is a plasticized PVDC copolymer.) A typical
copolymer composition is 15% vinyl chloride, 85% vinylidene chloride.
We will return to a discussion of copolymerization in Sec. 4.
47
Table 2-18 Typical properties of PVDC film
Property General purpose PVDC High barrier PVDC

Density (g/cm3) 1.60-1.71 1.73
Tensile strength (psi) 7,000-14,500 12,000-21,500
Izod impact (ft-lb/in)
Tear strength (gf/mil) 10-<100 10-<100
Service temp. (oC) -13 - 135 -13 - 135
Heat-seal temp. (oC) 121-149 121-149
O2 permeability 0.8-1.1 0.06
WVTR (g mil/100 in2 d at 0.2 0.05
38oC, 90% RH)
Haze (%) 2-3
48
2.8.6 Polyvinyl Acetate
Readings: The Wikipedia article for PVA (or PVAc) is very short:
http://en.wikipedia.org/wiki/Polyvinyl_acetate. I'll keep looking for a good on-line discussion.
Polyvinyl acetate has the following structure:
Vinyl acetate polymerizes in an atactic manner. Additionally, the way we make it is by an

LDPE-type free radical polymerization, which produces some branching. Consequently PVA is
both structurally and stereochemically irregular, so it is amorphous. The C = O (carbonyl) group
is polar, so intermolecular forces are relatively high. Tg for this polymer is about 29oC, so it is
tough and form stable at room temperature, but becomes sticky and undergoes severe cold flow
at only slightly elevated temperatures.
Its primary packaging use is in adhesives, both emulsion types and hot-melts. Lower molecular
weight PVA is used in chewing gums.
PVA cannot hydrogen-bond (no H attached to an electronegative atom), but it is water-sensitive,

in strength and in adhesion. Often, instead of PVA we use ethylene vinyl acetate, EVA, a
copolymer of vinyl acetate and ethylene.
49
2.8.7 Polyvinyl Alcohol
Readings: Wikipedia article is at http://en.wikipedia.org/wiki/Polyvinyl_alcohol. It's reasonably

good.
The monomer unit represented by the polyvinyl alcohol structure, CH2 - CHOH, is unstable.
Therefore PVOH cannot be polymerized in the usual addition polymer manner. Instead, it is
produced by hydrolysis (to be more technically correct, alcoholysis or saponification) of PVA,
using methanol or ethanol with an acid or base catalyst:
Since this polymer was formed from a branched, atactic polymer, it will also be branched and
atactic. However, the OH groups are similar enough in size to H atoms that they will fit the same
spots in the crystal lattice - they are isomorphous, as we discussed earlier . Therefore PVOH can
crystallize, even though it is stereochemically irregular. Further, we saw that LDPE crystallizes
despite its structural irregularity (branching). The same is true of PVOH.
PVOH exhibits strong intermolecular hydrogen bonding, as we have an abundance of OH

groups. As we mentioned already, this causes it to be water-soluble. The intermolecular
attractions in PVOH are so strong that we cannot melt this polymer. At temperatures above
150oC, it decomposes by loss of H2O from adjacent carbons, leaving double bonds in the main
chain (analogous to PVC decomposition).
These strong intermolecular forces lead to a high Tg, about 70oC. At normal temperatures, then,
PVOH cannot crystallize, since it is below its Tg, so it does not have the segmental mobility
needed to assume a crystalline structure.
PVOH film is usually produced by casting from a water solution. The film, as produced, will be
predominantly amorphous. On stretching, however, there is rearrangement of the molecules
which enables some crystallinity to develop.
PVOH is a very good barrier for oxygen, carbon dioxide, and many odors and flavors.
Obviously, it is not a very good barrier for water vapor, as it will strongly interact with water.
The presence of water significantly decreases its barrier to other permeants.
PVOH can be modified by changing the degree of hydrolysis of the acetate groups, and thus the
extent of hydrogen bonding in the polymer, affecting its water solubility and its barrier. If some
acetates are left, a film can be produced which will be soluble in hot water but not in cold.
50
2.8.8 Polytetrafluoroethylene
Readings: Wikipedia article is at http://en.wikipedia.org/wiki/Polytetracfluoroethane. (Yes, I

know this is misspelled, but that's how you get there!)
PTFE has the structure -(CF2 - CF2)n-. F is strongly electronegative, but as is the case with
PVDC, the presence of 2 F’s on the carbon (each carbon in this case), makes the bonds less polar
than would be the case if the structure had HCF groups. Nonetheless, it results in very high
viscosity for the polymer, due to restricted rotation around the bonds, coupled with the high
molecular weight which is typical of this polymer. With its regularity, lack of bulky side groups,
and high intermolecular forces, it tends to be highly crystalline, 85-98%. This makes it an
excellent barrier to permeants.
PTFE is unaffected by water. The C-F bonds are very strong, so the polymer is highly inert. At
elevated temperatures, it decomposes to monomer. It will not burn, and can withstand elevated
temperatures for an extended period.
The very high viscosity of the polymer leads to very low melt flow rates. Therefore the polymer
is very difficult to process.
51
2.8.9 Polychlorotrifluoroethylene
Readings: Wikipedia has almost nothing:

http://en.wikipedia.org/wiki/Polychlorotrifluoroethylene.
PCTFE has the structure -(CF2 - CFCl)n-. This polymer has a chiral carbon, and as usually
produced is predominantly atactic. Therefore it is predominantly amorphous (sometimes
classified as semicrystalline). Because intermolecular forces are still very strong, it is a
reasonably good barrier for gases, and is regarded as the best transparent water vapor barrier.
The lack of crystallinity renders it melt processable, though with difficulty. Its Tg is 45oC.
PCTFE has some use in pharmaceutical packaging (although usually as a copolymer, Aclar, to
improve processability).
Typical Aclar films have WVTRs in the range 0.025-0.45 g mil/100 in2 d at 38oC, 90% RH.
Oxygen permeation values are 7-15 cm3 mil/100 in2 d atm.
As is the case for PTFE, PCTFE does not burn, instead decomposing to fluorochlorocarbon gas.
52
2.8.10 Polyacrylonitrile
Readings: Again, Wikipedia has very little: http://en.wikipedia.org/wiki/Polyacrylonitrile.
Polyacrylonitrile, PAN, has the structure:
The acrylonitrile group:
is highly polar. Thus intermolecular attractions are very strong, as evidenced by the cohesive
energy density of 237 cal/cm3. The polymer, as usually made, is atactic and therefore amorphous.
It tends to pack as rigid twisted rods, and is sometimes referred to as paracrystalline, since there
is a considerable degree of order, but not true crystallinity. There is lateral order between chains,
but no longitudinal order along chains.
Because of the strong intermolecular attractions, a lot of energy is required to get the polymer to
flow. Heat stability is a concern, as this polymer undergoes decomposition reactions which
involve formation of ring structures with the nitrogen, and its softening temperature is only
slightly below its decomposition temperature. Therefore it has no packaging uses as a
homopolymer, although a variety of copolymers containing acrylonitrile are used.
Copolymers containing substantial amounts of acrylonitrile are very good barriers to gases and
hydrocarbons. Their water vapor permeability is moderately high, but they maintain their gas
barrier even when wet. Typical oxygen permeabilities for high nitrile content barrier resins are
0.9-1.0 cm3 mil/100 in2 d atm. WVTR is 5.9 g mil/100 in2 d at 38oC, 90% RH.
The strong intermolecular attractions cause this to be a very brittle polymer.
The Barex families of resins are copolymers with high acrylonitrile content
53
2.9 Condensation polymer properties
Readings: Painter & Coleman, Ch. 2, Sect. B, pp 31-40.
Condensation polymers are formed by reaction of bifunctional (or higher) monomers -

monomers containing two or more functional (reactive) groups, such as acids (COOH), alcohols
(C - OH), and amines (NH2). Generally, two different types of monomers are used, although it is
possible to use a single type of monomer containing two different types of (mutually reactive)
functional groups. In most cases, a small byproduct molecule is formed during each reaction
step. Typical byproduct molecules are water, HCl, NaCl, CH2O (formaldehyde), CH3OH.
Bifunctional monomers yield linear polymers. Trifunctional (or higher) monomers typically
yield branched or cross-linked polymers.
The major classes of condensation polymers used in packaging are polyesters and polyamides.
Polyesters contain the functional group:
Polyamides contain the group:
54
2.9.1 Polyethylene Terephthalate (PET)
Readings: Wikipedia, PET http://en.wikipedia.org/wiki/Polyethylene_terephtalate; polyester

http://en.wikipedia.org/wiki/Polyester.
PET is formed by reaction of terephthalic acid or dimethyl terephthalate with ethylene glycol,
producing water as the byproduct if terephthalic acid is used, and methanol as the byproduct if
dimethyl terephthalate is used. The reaction using terephthalic acid is the following:
A typical value for n is 100-200.
The ring in the main chain imparts stiffness, somewhat compensated for by the presence of O in
the main chain. The C=O (carbonyl) groups are polar, and thus generate reasonably strong
intermolecular attractions. There is no significant hydrogen-bonding, since the only place we
might have H attached to an electronegative atom would be at the ends of the molecules.
Inertness of PET is significantly less than inertness of most addition polymers. As is generally
the case for condensation polymers, the condensation reactions are reversible. Thus PET will
tend to decompose in the presence of water at high temperatures, resulting in the potential for
substantial reduction in molecular weight.
Despite the complexity of the structure, there are no chiral carbons, and the polymer is
crystalline. PET has a limited temperature range over which it will crystallize. Therefore, it is
possible, by varying processing conditions, to substantially affect the degree of crystallinity of
the resulting polymer. Similarly, the limited mobility of polymer chains makes it possible,
through orientation, to impart a significant degree of molecular order. This phenomenon is the
basis of our ability to make transparent bottles with reasonably good barrier properties. At higher
levels of crystallinity, PET is opaque. The rate of crystallization can be enhanced by addition of
nucleating agents. In PET, in contrast to PP, the presence of nucleating agents generally leads to
opaque polymers, since they serve to increase the overall levels of crystallinity, rather than
primarily to suppress crystallite size as is the case with PP.
55
PET as polymerized has a molecular weight, which is below that desired for most applications. A
subsequent reaction step, known as “solid-stating” or solid-state polycondensation is employed
to increase the molecular weight of the solid polymer. At the range of molecular weights
commonly used in packaging applications, the viscosity of PET is still relatively low, which
causes the melted resin to have low melt strength, and prohibits extrusion blow molding of
containers, as well as production of blown film. Therefore PET film is produced by the cast film
process, and usually biaxially oriented. PET bottles are usually produced by injection stretch
blow molding, which imparts biaxial orientation to the bottles, improving their barrier and
strength properties. High molecular weight resins, with higher viscosity, can be successfully
extrusion blow-molded. The cost of these resins is significantly higher than that of “normal”
grades of PET. One of the major advantages is the ease of producing bottles with handles. Some
novel processes have been developed which provide handles on injection blow molded PET
bottles.
In October, 1999, Sekisui Plastics Co. in Japan started shipping sample quantities of expandable
PET beads, intended for use as foam. Full-scale production was scheduled to start in fall 2000.
Reportedly, the beads can be processed on standard EPS foaming machinery modified to
accommodate the higher pressures required. Packaging is one of the target markets. Cellpet
foamed PET sheet for food-contact applications has been marketed by the company for 5 years,
but price has limited its application.
Table 2-19 Typical properties of PET
Property PET PET film (biaxially PETG

oriented)
Density (g/cm3) 1.29-1.40 1.40 1.27
Tensile strength (psi) 7000-10,500 42,000
Dart impact, g (10 mil 425
film)
Tear strength (gf/mil) 30
Service temp. (oC)
O2 permeability 3.0-6.1 2.9
WVTR (g mil/100 in2 d at 1.0-1.3 1.3
38oC, 90% RH)
Haze (%) 3.6% for 48 gauge 0.5% for 10 mil
film (0.48 mil) film
Typical uses for PET
56
The most common single use for PET is in carbonated soft drink bottles. However, PET is
increasingly being used for a variety of other plastic bottles – both food and non-food. Much of
the market share lost by glass has gone to PET. Generally these containers are produced by
injection stretch blow molding, to achieve biaxial orientation.
2.9.2 PET Copolymers

A variety of PET-based copolymers can be produced by adding a third monomer to the reaction
mix. If an additional acid is used, the resulting copolymers are called acid-modified. If an
additional alcohol is used, the resulting copolymers are called glycol-modified. It is also possible
to produce combination acid and glycol modified copolymers by incorporating an additional acid
and an additional glycol.
2.9.2.1 PETG
PETG is the most common PET copolymer, and, as its name suggests, is formed by adding an
additional glycol, in this case 1,4-cyclohexane dimethanol:
to the standard monomers. The number-average molecular weight for PETG is typically about
26,000.
The presence of the additional ring structure, in place of the -CH2- CH2-, imparts additional
rigidity, as can be seen in the increased Tg, 81oC compared to about 70 oC for PET. More
importantly for processing, the irregularity introduced by the comonomer prevents
crystallization, so PETG is a clear amorphous polymer. It is typically processed at temperatures
of 230-250 oC, and has good melt strength, so it can be extruded readily, and extrusion-molded
bottles, as well as sheet, can be produced.
The main advantage of PETG over PET in bottles is the ability to use extrusion blow molding.
For sheet, a major advantage is that it is more easily thermoformed. Both of these properties are
related to its higher melt strength.
57
2.9.2.2 DuPont’s Biomax

DuPont produces a biodegradable polyester, tradenamed Biomax, that is based on PET with up
to 3 proprietary aliphatic monomers - the properties depend on the formulation. Tensile strength
of film ranges from 2,000-7,000 psi, modulus from 9,000-300,000 psi. Elongation ranges from
40 to 500%. The polymer biodegrades after initial hydrolysis in composting operations. Tm is
about 200 oC, density about 1.35 g/cm3
Currently, a Biomax resin is being sold by DuPont that is targeted for blending with PLA to
reduce the brittleness of PLA while maintaining the biodegradability of the packaging material.
58
2.9.3 Polycarbonate
Readings: Wikipedia http://en.wikipedia.org/wiki/Polycarbonate.
Polycarbonates can be considered polyesters of carbonic acid:
but they are generally classified separately because of the resulting
group.
The member of this family used in packaging is based on bisphenol A, properly known as
2,2’(4,4’ hydroxyphenyl) propane:
Rather than using carbonic acid, the other monomer used is phosgene:
so the byproduct molecule produced in each step is HCl rather than H2O. NaOH is used as a
catalyst. The resulting structure is:
59
The presence of two ring structures, as well as the two methyl groups on the carbon between the
rings, along with the lack of any sequences of CH2 groups, makes the polymer very stiff and
rigid. The carbonyl groups, since they are polar, impart some stronger than average
intermolecular forces. The result is a polymer that, even in the absence of crystallinity, has useful
properties. Structurally, PC is able to crystallize, but it is generally used in the amorphous form.
Development of crystallinity is retarded by the high stiffness of the structure, and, especially, by
the very bulky nature of the chain.
Table 2-20 Typical properties of PC
Property PC PC film
Density (g/cm3) 1.20 1.20
Tensile strength (psi) 9,100-10,500 10,000-10,735
Tensile modulus (psi) 345,000
Dart impact, g (10 mil film)
Izod impact (ft-lb/in) 12-17
Tear strength (gf/mil) 10-16 16
Service temp. (oC) -135 to 115-130
O2 permeability 300 240

WVTR (g mil/100 in2 d at 38 oC, 4.9-5.9 6.5
90% RH)
Haze (%) 1% at 0.125 in. 0.5 at 1 mil
PC does not require orientation to achieve useful properties. Amorphous PC has a wide softening
range, excellent strength for thermoforming, excellent dimensional stability, rigidity, and
transparency. Of particular importance is its excellent impact resistance over a wide range of
temperatures. It has very low water absorption, and is unlikely to pick up stains or odors.
Applications include 5 gal. water bottles, medical packaging, and refillable milk bottles (a small
and dying market). Non-packaging applications include compact disks, glazing for windows,
eyeglass lenses, appliances, baby bottles, etc.
60
2.9.4 Polyethylene Naphthalate (PEN)
Polyethylene naphthalate (PEN) is a polyester formed by polymerization of naphthalate

dicarboxylate (NDC) and ethylene glycol:
Thus PEN is a close cousin of PET. However, the additional ring structure in the main chain
makes the polymer considerably more rigid than PET. This can be seen in its higher Tg, as well
as its increased tensile strength (35% higher) and flexural modulus (50% higher). The polymer is
still regular, so can crystallize. Its barrier properties are better than PET - 4-5 times as good a
barrier for oxygen and water vapor.
PEN can be hot-filled without the distortion (sidewall deformation) characteristic of PET (stable
at temperatures up to 113 oC). It has excellent chemical and UV resistance. Like PET, it is
normally processed by injection stretch blow molding. Molding and blowing cycles are shorter
than for PET. The higher cost of NDC monomer means PEN is about 4-5 times as costly as PET.
We will discuss more about PEN when we consider copolymers:
Table 2-21 Typical properties of PEN
Property PEN (film)

Density (g/cm3) 1.36
Tensile strength (psi) 31,900
Tensile modulus (psi) 871,000
Elongation at break (%) 60-65
Tear strength (gf/mil) 8-12.5
Service temp. (oC)
O2 permeability
61
2.9.5 Nylons (Polyamides)
Readings: Wikipedia http://en.wikipedia.org/wiki/Nylon.
Nylons are formed by condensation polymerization of organic diamines and organic dicarboxylic
acids, or by condensation polymerization of amino acids. For aliphatic nylons, a numbering
system is commonly used, denoting the number of carbons in, first, the amine and, second, the
carboxylic acid. Only one number is used if the monomer is an amino acid. The properties of the
nylon are influenced by the length of the -CH2- repeating structure, which impacts the flexibility
of the chain directly, and also by impacting the “concentration” of polar groups.
Nylons contain hydrogen-bonding units, so are characterized by strong intermolecular forces and
water sensitivity (in most cases). They are good gas barriers when dry, and generally have
excellent thermal stability, low temperature flexibility, and yield strength, with good burst and
flex strength, as well. Nylons are particularly good barriers to many odor and flavor compounds.
The general amine-acid reaction for formation of a nylon is the following:
where R and R1 are of the form (CH2)x and (CH2)y. The nylon would be named Nylon x+2,y+2.
For example, Nylon 6,6 is formed from hexamethylene diamine H2N-(CH2)6-NH2 and adipic
acid HOOC(CH2)4COOH, while Nylon 6,10 is formed from the same amine and sebacic acid,
HOOC(CH2)8COOH.
For formation with an amino acid, the reaction is the following:
where, again, R is of the form (CH2)x. The name of the nylon in this case would be Nylon x+1.
Thus Nylon 6 is made from H2N(CH2)5COOH and Nylon 11 from H2N(CH2)10COOH. (Note:
again, we're taking some liberties - actually a ring-opening type of polymerization is generally
used for these types of nylons - but we could make them the way that is described here.)
These nylons are linear, and have regular structures, so they can crystallize.
62
Table 2-22 Typical properties of nylons
Property Nylon 6 Nylon 11 Nylon 12

Density (g/cm3) 1.13-1.16 1.03-1.05 1.02
Tensile strength (psi) 6000-24,000 8000-9500 50-55 MPa
78 MPa 44 MPa
Tensile modulus (psi) 100,000-247,000 185,000
2.6-3.0 GPa 1.5 GPa
Flexural modulus (psi)
Elongation at break (%) 300 300-400 290-300
Izod impact (ft-lb/in) 30-250 J/m 96 J/m
Tear strength (gf/mil) 35 (propagating) 400-500 (initial)
Heat-distortion temp. (oC) 80-200 55-150 48-135
Service temp. (oC) -40 to 80-160 -50 to 70-130
O2 permeability 1.2-2.6 32
WVTR (g mil/100 in2 d at 9.9-11 2.5-5.1
38oC, 90% RH) 18
Haze (%) 1.5-4.5
Table 2-23 Typical properties of nylons (cont.,)
Property Nylon 4,6 Nylon 6,6 MXD6, biaxially

oriented
Density (g/cm3) 1.18 1.14 1.20-1.25
Tensile strength (psi) 55-100 MPa 82 MPa 32,000-33,000
220-230 MPa
Tensile modulus (psi) 3.1-3.3 GPa 3.3 GPa 550,000-600,000
3.8-4.1 GPa
Flexural modulus (psi)
Elongation at break (%) 300 72-76
Izod impact (ft-lb/in) 80 J/m 40-110 J/m
Tear strength (gf/mil) 35
Heat-distortion temp. (oC) 160-220 100-200
Service temp. (oC) -40 to 100-200 -30 to 80-180
-73 to 232
O2 permeability 3.5 0.15-0.66
WVTR (g mil/100 in2 d at 19 1.6
38oC, 90% RH)
Haze (%) 1.5
Nylons, like PET, crystallize over a fairly narrow range of temperatures. Therefore it is possible
to modify the extent of crystallization by the rate of cooling of the nylon. Materials that are
nearly amorphous or that are highly crystalline can be produced, depending on the rate of
cooling.
63
Polyamides can also be made from non-aliphatic amines and acids. In this case, their naming
becomes more complex. One example is MXD-6 Nylon, made from meta-xylene diamine and
adipic acid:
MXD-6 is named by a combination of initials representing the ring-containing diamine, and

number representing the aliphatic (straight chain) carboxylic acid.
MXD-6 crystallizes to a relatively small extent. It has a Tg of 64oC, and a Tm of 243oC. As you
would expect, the ring structure adds rigidity. However, the increased average intermolecular
spacing, due to the structure of the main chain, moderates the effects of intermolecular forces.
Table 2-24 Tg and Tm for selected condensation polymers
Polymer Tg (oC) (K) Tm (oC) (K) Tm/Tg

PET 69 342 267 540 1.6
PETG 81 354 - - -
PEN 120 393 262 535 1.4
PC 105 378 265 538 1.4
Nylon 6 60 333 210-220 483-493 2.2-2.3
Nylon 6,6 266 539
Nylon 6,12 197-200 470-473
Nylon 11 180-190 453-463
MXD-6 Nylon 64 337 243 516 1.5
Typical uses for nylons:
In packaging applications, nylons are most commonly used either for their barrier properties,
their high strength, or their heat stability – or some combination. Applications include boil-in-
bag pouches for frozen vegetables, vacuum packaging, sterilizable medical packaging, etc.
64

Basic Structure Properties

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Basic Structure Properties

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PKG 827.

POLYMERIC PACKAGING MATERIALS

Chapter 2 Basic Structure/Property Relationships - Regularity,

Figure 2-1 Portion of a linear amylose starch molecule ................................................................. 6!

Figure 2-2 Free radical polymerization of ethylene ........................................................................ 9!

Figure 2-3 Initiation step in free radical polymerization ................................................................ 9!

Figure 2-4 Propagation step in free radical polymerization............................................................ 9!

Figure 2-5 Termination step in free radical polymerization ......................................................... 10!

Figure 2-7 Production of LLDPE ................................................................................................. 12!

Figure 2-9 Head-to-tail addition polymer ..................................................................................... 14!

Figure 2-10 Addition polymer with random configuration .......................................................... 14!

Figure 2-13 Isostatic polypropylene ............................................................................................. 16!

Figure 2-14 Syndiotactic polypropylene ....................................................................................... 16!

Figure 2-15 Atactic polypropylene ............................................................................................... 16!

Figure 2-16 Structural formula of PP............................................................................................ 17!

Figure 2-20 Effect of rotation on potential energy in ethane ........................................................ 21!

Figure 2-21 Effect of rotation on potential energy in n-butane .................................................... 21!

Figure 2-22 Cis- and trans- configurations ................................................................................... 24!

Figure 2-24 Cis- and trans- forms of polybutadiene ..................................................................... 25!

Table 2-1 Properties of some typical HDPE, LDPE and LLDPE................................................... 8!

• Regularity - both chemical and stereochemical

In addition, we need to consider:

It is also useful to remind ourselves of a fundamental law of thermodynamics - spontaneous

These influences on polymer behavior impact the following polymer characteristics:

• Physical structure (microstructure), especially:

Figure 2-1 Portion of a linear amylose starch molecule

2.1.1 Chemical Regularity

There are a number of characteristics to consider in determining whether the polymer is

(A) Is the polymer linear or branched or cross-linked?

HDPE - linear homopolymer of ethylene - crystallinity 65-90%

LDPE - branched homopolymer of ethylene - crystallinity 40-60%

By decreasing the crystallinity, the presence of the branches results in less

Table 2-1 Properties of some typical HDPE, LDPE and LLDPE

Property HDPE LDPE LLDPE

In general, we can say that for a given polymer, increasing crystallinity:

• Increases sealing temperature

Note: in general, significant structural irregularity will prohibit crystallinity - LDPE is an

Figure 2-2 Free radical polymerization of ethylene

Figure 2-3 Initiation step in free radical polymerization

Figure 2-4 Propagation step in free radical polymerization

Figure 2-5 Termination step in free radical polymerization

Figure 2-6 Chain transfer reactions in free radical polymerization

(B) Is the polymer a homopolymer or a copolymer?

LLDPE is a linear polyethylene copolymer, with comonomers of butene, hexene,

If butene is the comonomer, X is CH2CH3

Figure 2-7 Production of LLDPE

Copolymer HDPE is used for detergent bottles, to decrease environmental stress

Property! HDPE$homopolymer$ HDPE$copolymer$

(C) In vinyl polymers, is the addition head-to-head or head-to-tail?

Figure 2-9 Head-to-tail addition polymer

Figure 2-10 Addition polymer with random configuration

2.1.2 Stereochemical Regularity

Figure 2-12 The two mirror-image forms of a chiral carbon

Figure 2-13 Isostatic polypropylene

Figure 2-14 Syndiotactic polypropylene

Figure 2-15 Atactic polypropylene

Figure 2-16 Structural formula of PP

Table 2-3 Typical properties of polypropylene

Tacticity! Density$ Tm$(°C)$ Tg$(°C)$ Solubility$in$nCheptane$

2.2 Conformational Flexibility

2.2.1 Thermal Transitions, Tg and Tm

Segmental mobility - the coordinated crankshaft-type motion of 10-50 atoms

2.2.2 Effect of Side Groups on Rotation of C-C Bonds