Polymer Chemistry

The chemical structure and the nature of plas- prevent any additional boxcars from being
tics materials have a significant relationship not added to any of the trains being assembled.
only to the properties of the plastic but to the Thus, we ultimately end up with trains having
ways in which it can be processed, designed, a variety of lengths, yet all composed of the
or otherwise translated into an end-product. same kinds of boxcars.
Throughout this book the reader will find var- The railroad analogy described above is ba-
ious references to polymer chemistry (e.g., the sically what happens in an “addition” type of
section entitled “Theory of Injection Mold- polymerization.
ing,’’ in Chapter 5 on “Injection Molding”). The above process is characterized by the
This chapter therefore will provide a basic simple combination of molecules without the
review of polymer chemistry, with emphasis on generation of any by-products formed as a re-
the distinctions between various structures and sult of the combination. The molecules that
their influence on the engineering of plastics combine do not decompose to produce fission
products. products which then remain as part of the re-
action debris or need to be removed from the
reaction to either allow it to continue the mol-
Forming Polymers ecule-building process or to ensure the forma-
tion of a pure polymer.
Basically, all polymers are formed by the cre- In reality the addition-type process can occur
ation of chemical linkages between relatively in several ways. One way simply involves the
small molecules or monomers to form very external chemical activation of molecules that
large molecules or polymers; the same idea as causes them to start combining with each other
connecting boxcars on a railroad to form a train, in a chain-reaction-type fashion (by the bond-
the boxcars being monomers and the train a ing of atoms directly within the reacting mol-
polymer. Like boxcars, the molecules must ecule). Another way for an addition polymeri-
have the ability to be coupled at either end. zation to occur is through a rearrangement of
Actually, in polymer formation, the process atoms within both reacting molecules, but still
is more like forming many, many trains in a without the net loss of any atoms from the pol-
railroad yard simultaneously from the boxcars ymer molecule. And still a third way for addi-
available in the yard in a competitive fashion, tion polymerization to occur is for a molecule
so that the switching engine that moved the composed of a ring of atoms to open up and
fastest would form the longest train while the connect with other ring-type molecules being
slowest switching engine would form the short- opened up under the influence of the proper
est train, due to depletion of the available roll- catalytic activators, once again with no net loss
ing stock by the concurrent train-forming of any atoms from the polymer structure.
process. The train-forming process of In another type of polymerization reaction,
polymerization comes to a stop when factors which has been called “condensation” poly-

33
34 SPI PLASTICS ENGINEERING HANDBOOK

merization, the chemical union of two mole- Catalyst activated bond opening (ethylene
cules can be achieved only by the splitting out polymerization)
of a molecule (usually small) formed by the at-
2CHz=CH2 t R-R 2R+H2--CH2+
oms, which must be removed from the two
-+

molecules being joined to allow the coupling Initial reaction

process o r polymerization to continue. This is
R*H2-CH2-f t (n - 1)CH2=CH2
the type of polymerization involved in the for-
-+

mation of some nylons, phenolics, amino res-

ins, and polyester pre-polymers.
Normally the reaction by-product in a con- Propagation reaction
densation type of polymerization must be im-
R*H2--CH2k t R- -+
mediately removed from the reacting polymer
because it may either inhibit further polymer-
ization or appear as an undesirable impurity in R+H2---CHz-fR
the finished polymer. Termination reaction (combination)
There is yet another method by which poly- Rearrangement (polyurethane polymerization)
mers may be formed, but it is in reality simply
a sequential combination of the previous two I
nO=C=N-R-k=C=O t nH-0-R-OH -+

processes. Such a process is used in the for- H O

mation of plastics such as the polyesters and I II
O=C=N+R-N-C--O-R+H
the polyurethanes.
In such a polymerization, a condensation re- &ng-opening reaction (nylon 6 from capro-
action usually is carried out first to form a rel- lactam)
atively small polymer, which is then capable of
nH-r;i--(CH2)5T=0 -+
undergoing further reaction by addition poly-
merization to form larger polymer molecules H 0
with a third ingredient. This is what is done
when a polyester is formed first by a conden-
sation reaction, and the then still-active polyes-
ter is reacted with styrene to form what is es- Fig. 2-la. Typical addition polymerizations (no by-
products).
sentially a polyester-styrene copolymer.
The various types of polymerization reac- them in some form of extraneous media such
tions are shown in Figs. 2 - l a , 2-lb, and 2-lc. as is done in the other types of polymeriza-
tions.
Polymerization Techniques Two types of behavior are observed in bulk
polymerizations. In one case, the polymer is
In actual practice there are many different tech- soluble in the monomer during all stages of the
niques used to carry out polymerization reac- polymerization, and a monomer-soluble initia-
tions. However, most involve one of four tor is used. As polymerization progresses, vis-
general methods of polymerization: the cosity increases significantly, and chain growth
polymerization of the monomer o r reactants in takes place in the monomer o r polymers dis-
bulk, in solution, in suspension, and in emul- solved in the monomer until all of the monomer
sion forms. The bulk and solution methods are is consumed.
used for the formation of both addition and In the second case, the polymer is insoluble
condensation type polymers, whereas suspen- in the monomer system. In such systems, the
sion and emulsion techniques are used largely polymerization is believed to occur within the
for addition polymerizations. growing polymer chains because very high mo-
Bulk Polymerization. This type of poly- lecular weights are formed even though the
merization involves the reaction of monomers polymer chain drops out of the monomer so-
or reactants among themselves without placing lution.
 POLYMER CHEMISTRY 35

Phenol-aldehyde reaction
OH OH

o \ t CH2O 4

or
OH
w H 2 0 H + [6CH2--..-i]j] tnH20
n
Polyesterification (reaction between organic acids and alcohols)
0
II
n HO--R--COOH + HOt-R-C-OkH t (H - 1)H20
or
0 0
n HO-R-OH t n HOOC-R'-COOH -+

Reaction when byproduct is other than water (polycarbonate)

Bisphenol A Phosgene Polycarbonate ch loriie

Fig. 2-lb. Typical condensation polymerizations (production of by-product)

Step 1: Condensation reaction

n HO-R-OH t
H H
I I
n HOOC-C=C-COOH -+ n HO+R-O-C-C=C-c
O H H O
I' ' 'I+ t nH20

Step 2 : Addition reaction

O H H O O H H 0
II I I II
n HO-R-O-C-C=C-C~--H + n CH2=CHC6H6 -+

)I

Fig. 2-lc. Combination polymerizations (curing of polyesters).

36 SPI PLASTICS ENGINEERING HANDBOOK

One of the disadvantages of carrying out a monomer, polymer, and solvent in the system,
polymerization in bulk is the fact that the rise the way in which the ingredients are fed to the
in viscosity can interfere with keeping reaction system can have a significant effect on how the
conditions under control because of the diffi- polymerization proceeds, and hence the struc-
culty of maintaining proper agitation and re- ture of the finished polymer.
moving heat from exothermic polymerization Suspension Polymerization. Often called
reactions which give off heat. However, the “pearl” polymerization, this technique nor-
process is widely used. mally is used only for catalyst-initiated or free-
Solution Polymerization. Solution poly- radical addition polymerizations. The mono-
merization is similar to bulk polymerization ex- mer is mechanically dispersed in a liquid, usu-
cept that the solvent for the forming polymer ally water, which is a nonsolvent for the mon-
in bulk polymerization is the monomer, omer as well as for all sizes of polymer mole-
whereas the solvent in solution polymerization cules that form during the reaction.
is usually a chemically inert medium. The sol- The catalyst initiator is dissolved in the
vents used may be complete, partial, or non- monomer, and it is preferable that it does not
solvents for the growing polymer chain. dissolve in the water so that it remains with the
When the monomer and the polymer are both monomer. The monomer and polymer being
soluble in the solvent, initiation and propaga- formed from it remain within the beads of or-
tion of the growing polymer chains take place ganic material dispersed in the phase. Actually
in the oil or organic phase. Because of the mass- suspension polymerization is essentially a finely
action law, rates of polymerization in solvents divided form of bulk polymerization. The ad-
are slower than in bulk polymerizations, and vantage of suspension polymerization over the
the molecular weight of the polymers formed bulk type is that it allows the operator to effec-
is decreased. tively cool exothermic polymerization reac-
In another case, when the monomer is solu- tions and thus maintain closer control over the
ble in the solvent but the polymer is only par- chain building process. Other behavior is the
tially soluble or completely insoluble in the sol- same as that of bulk polymerization.
vent, initiation of the polymerization takes By controlling the degree of agitation,
place in the liquid phase. However, as the monomer-to-water ratios, and other variables,
polymer molecules grow, some of the propa- it is also possible to control the particle size of
gation of polymers takes place within monomer the finished polymer, thus eliminating the need
swollen molecules, which are beginning to pre- for re-forming the material into pellets from a
cipitate from the reaction. When this occurs, it melt, as is usually necessary with bulk poly-
again becomes possible to build up molecular merizations.
weights because of the decreased dilution Emulsion Polymerization. This is a tech-
within the polymers. Thus, molecular weights nique in which addition polymerizations are
as high as those possible with bulk polymer- camed out in a water medium containing an
izations can also be achieved in solution poly- emulsifier (a soap) and a water-soluble initia-
merizations, provided the polymer precipitates tor. It is used because emulsion polymerization
out of solution as it is formed and creates a is much more rapid than bulk or solution
propagation site. polymerization at the same temperatures and
In the third case, in which the polymer is produces polymers with molecular weights
completely insoluble in the solvent and the much greater than those obtained at the same
monomer is only partially soluble in the sol- rate in bulk polymerizations. The polymeriza-
vent, rates of reaction are reduced, and lower tion reaction in emulsion polymerization in-
molecular weights, below those possible in bulk volves causing the reaction to take place within
polymerizations, are formed. However, the a small hollow sphere composed of a film of
formation of relatively high molecular weight soap molecules, called a micelle. Monomer dif-
polymers is still possible in such a system. fuses into these micelles, and control of the
In addition to the relative solubilities of soap concentration, overall reaction-mass rec-
 POLYMER CHEMISTRY 37

ipe, and reaction conditions provides additional molecule and is estimated by dividing the num-
controls over the reaction. ber-average molecular weight of the polymer
Polymerization techniques can have a signif- by the molecular weight of the monomer. The
icant effect on the number, size, and character- relationship can be expressed as:
istics of the polymer molecules formed and thus
will have a significant effect on the properties
MW of polymer = DP x MW of monomer
of the polymer. Thus, batches of a polymer
such as polystyrene, which can be made by any
of the four polymerization techniques de- And, finally, it is important to know some-
scribed above, will differ, depending on which thing about the molecular weight distribution
type of polymerization method was used to within the polymer, that is, the relative pro-
make the material. portions of molecules of different weight. Ob-
viously, if one could create a mono-disperse
Weight, Size, and Distribution of Molecules polymer, all of the molecules would be of a
single size. This has not been achieved com-
Because there is such diversity among polymer mercially, however, and so another parameter
molecules, a number of techniques for defining of definition used to describe polymers is the
and quantifying these characteristics are in use distribution of the various sizes of molecules
by the industry-and are also of value to pro- within a poly-disperse polymer, that is, the
cessors and end-users as a determinant of breadth of distribution o r ratio of large, me-
polymer properties. dium, and small molecular chains in the resin.
One such parameter relates to the size of the If the resin is made up of chains close to the
molecules in the polymer and is known as mo- average length, it is called narrow; if it is made
lecular weight (MW). MW refers to the aver- up of chains of a wider variety of lengths, it is
age weight of the molecules in the mixture of called broad.
different size molecules that make up the poly- In general, narrow-range resins have better
mer. It is expressed either as a number average, mechanical properties than broad-range resins,
based on the sum of the number fractions of the although, as with the case of the higher molec-
weight of each species or size of molecule pres- ular weight materials, they are somewhat more
ent, or as a weight average, based on the weight difficult to process.
fractions of each species or size of molecule The molecular weights of polymers and the
present in the polymer. molecular weight distribution are determined
The molecular weight of a polymer has a sig- indirectly by measuring the properties of the
nificant effect on its properties. Thus, higher polymers themselves or of their solutions and
molecular weight polymers tend to be tougher correlating this information with the type of
and more chemically resistant, whereas low molecular weight believed to correspond to the
molecular weight polymers tend to be weaker type of property measured.
and more brittle. In the polyethylene family, For example, chemical analysis of the end-
for example, low molecular weight polyethyl- groups present in polymer molecules, studies
enes are almost waxlike in characteristics, of the boiling points and freezing points of so-
whereas ultra-high molecular weight polyeth- lutions of polymers, and osmotic pressure stud-
ylenes offer outstanding chemical resistance ies on polymer solutions yield data on the num-
and toughness (although, conversely, the higher ber-average molecular weight of the polymer.
the molecular weight is, the more energy in the Light scattering in polymer solutions and sedi-
form of temperature and pressure required to mentation methods in the ultra-centrifuge yield
process the material.) data related to the weight-average molecular
Another expression applicable to molecular weights of polymers. Such methods yield the
weight is the degree of polymerization (DP). overall average molecular weight of the poly-
This refers to the number of monomer mole- mer samples. To get direct data on molecular
cules that combine to form a single polymer weight distributions, the polymers first must be
38 SPI PLASTICS ENGINEERING HANDBOOK

separated by fractionation methods into rather ume changes when solidifying from the melt,
sharp fractions of samples of relatively mono- or when the solid softens and becomes fluid.
disperse molecular weight. Crystalline polymers, on the other hand, have
considerable order to the molecules in the solid
state, indicating that many of the other atoms
Polymer Structure are regularly spaced; have a true melting point
with a latent heat of fusion associated with the
In addition to the size of molecules and the dis- melting and freezing process; and have a rela-
tribution of sizes in a polymer, the shapes or tively large volume change during the transi-
structures of individual polymer molecules also tion from melt to solid.
play a major role in determining the properties Thus, many different structures are possible
of a plastic. with plastics-and each will affect the basic
Earlier, in the discussion of the analogy be- properties of the polymer. For example, linear
tween the connecting of railroad boxcars to polymers, such as high-density polyethylene,
form a train and the formation of polymers, it are made of molecules that resemble spaghetti
was implied that polymers form by aligning in a bowl and are relatively free to slide over
themselves into long chains of molecules with- one another or to pack more closely together
out any side protrusions or branches, or lateral (in the absence of steric hindrances due to large
connections, between molecules. Some poly- pendant side groups). Branched polymers, such
mers do largely this and nothing more; how- as low-density polyethylene, on the other hand,
ever, it is also possible for polymers to form have side appendages and interconnections that
more complex structures. Thus, polymer mol- cause the molecules to resemble clumps of tree
ecules may form in the shape of branched mol- branches that cannot be easily compressed or
ecules, in the form of giant three-dimensional compacted. Thus, branched polymers (with
networks, in the form of linear molecules with more voids) are more permeable to gases and
regular lateral connections to form “ladder- solvents than linear polymers, lower in density
type” polymers, in the form of two-dimen- (since the molecules are not compacted to-
sional networks or platelets, and so forth, de- gether), and more flexible. Linear polymers, on
pending on how many connections or bonds can the other hand, are higher in tensile, stiffness,
exist between the mono-disperse monomeric and softening temperatures.
molecules that were used to form the polymer Cross-linked structures, in which the indi-
and between sites on the forming or already vidual chain segments are strongly bound to-
formed polymer molecules. See Fig. 2-2. gether by chemical unions, also have special
Because of the geometry of such molecules, characteristics (as in the family of thermoset-
some can come closer together than others in ting plastics). They do not exhibit creep or re-
which the structure prevents more intimate laxation unless such primary bonds actually are
contact. The structural obstruction to close ap- broken by continually applied stress or by ele-
proach is called steric hindrance. Thus, poly- vated temperatures high enough to cause chem-
mers that can be packed closely or exhibit little ical decomposition of the polymer. Cross-
steric hindrance ordinarily can more easily form linked polymers also are fairly resistant to sol-
crystalline structures in which the molecules are vent attack; solvents may swell such polymers,
aligned in some regular pattern; others, such as but seldom cause complete rupture or dissolu-
polymers that are cross-linked prior to crystal- tion.
lization, are prohibited from aligning them- Ladder structures have unusual stability and
selves in crystals because of the hindrance cre- have become important in terms of the new
ated by the multiple interconnections and hence heat-resistant plastics. Aromatic compounds
tend to be amorphous, or noncrystalline. (such as benzene) and heterocyclic compounds
Amorphous polymers do not have melting (such as benzimidazole) that have semiladder,
points, but rather softening ranges; are nor- ladder, or spiro structures offer heat stabilities
mally transparent; and undergo only small vol- in excess of 900°F.
 POLYMER CHEMISTRY 39

I 1

I I

Fig. 2-2. Types of molecular stmctures in polymers.

Effect of Time and Temperature it can produce a polymer that is far more amor-
phous or noncrystalline in structure than the
It should also be noted that whereas the effect original polymeric sample. Such a quenched
of molecular weight and molecular weight dis- material can have properties that are signifi-
tribution on properties is relatively fixed and cantly different from the properties of a sample
stable with temperature (barring decomposition that is cooled slowly and allowed to recrystal-
of the polymer), the arrangement of the mole- lize.
cules within the structure of a polymer mass is The effects of time on a polymer structure
in most cases relatively sensitive to tempera- are similar to those of temperature in the sense
ture. Thus, the structure of any given polymer that any given polymer has a “most preferred”
can be significantly changed by exposing it to or equilibrium structure in which it would pre-
different temperatures and thermal treatments. fer to arrange itself, but it is prevented from
For example, heating a crystalline-type poly- doing so instantaneously on short notice by
mer above its melting point and then quenching steric hindrances. However, given enough
40 SPI PLASTICS ENGINEERING HANDBOOK

time, the molecules in a polymer ultimately mi- Chemical Composition

grate to arrange themselves in this form. Ele-
vating the temperature and making the mole- In addition to all the variations in the makeup
cules more mobile o r spreading them apart of the polymer discussed above and having to
allows them to accomplish this in a shorter time do largely with extra- or intermolecular phe-
and vice versa. nomena, polymer properties also are heavily
Thus over an extended period of time, the dependent on such factors as the intramolecular
properties of a polymer can become signifi- chemical composition of the polymer
cantly different from those measured earlier if For example, as shown in Fig. 2-3, polyeth-
the structure of the polymer was in an unstable ylene consists (except for catalyst or extra-
form when the properties were initially evalu- neous impurities) completely of atoms of car-
ated bon and hydrogen. This internal makeup of the

fefll H H

Polyethylene Polypropylene Polystyrene

+E$ H C1
#4+ H OOCCH,
+;-I* H CN

Polyvinyl chloride Polyvinyl acetate Polyacrylonitrile

H OH H COOCH3
Methyl pentene Polyvinyl alcohol Polymethyl acrylate
polymer (TPX)

H F
#4$ H F
+J+ H C1

Polyvinyl fluoride Polyvinylidene fluoride Polyvinyl dichloride

Polymethyl methacrylate Chlorotnfluoroe thylene Poly tetrafluoroethylene

Fig. 2-3. Polymers based on the ethylene chain

 POLYMER CHEMISTRY 41

polymer molecule affects in turn all the previ- tive amounts of each monomer used in the re-
ously discussed variables and hence contributes action also may be varied to produce a literally
its own basic characteristics to the overall prop- unlimited number of possible permutations and
erties of the polymer. combinations of types and amounts of mono-
Going further, if one takes every fourth hy- mers. The ability of the polymer chemist to
drogen atom occurring in polyethylene and re- react different monomers together in different
places it with a methyl (CH3) group in regular amounts has given rise to the concept of “tai-
intervals along the length of the chainlike mol- lor-making’’ plastic materials.
ecule as shown in Fig. 2-3, the polyethylene is Figure 2-4 illustrates some of the more com-
transformed into polypropylene. In such a case,< mon copolymers now available commercially.
the degree of polymerization and the molecular The subscripts of x , y , and z denote differing
weight distribution remain roughly the same; amounts of each of the structural units in the
but the spacing of the molecules in the polymer polymer chain. It should be noted that the
matrix or the morphology of the polymer structural formulas in Fig. 2-4 are somewhat
changes, and thus its macroscopic physical fictional, in the sense that there is an implica-
properties also change. tion that a long chain of one group is connected
Similarly, if every fourth hydrogen atom of to a long chain of another group, and succes-
the polyethylene were substituted with a ben- sively to a long chain of still a third type of
zene ring structure (C,H,), or with a chlorine polymer. Actually, the distribution of each of
atom (Cl), as shown in Fig. 2-3, the ethylene the species within the chain will depend both
would become either polystyrene or polyvinyl on the amount present and how the polymer-
chloride, respectively, ization was carried out.
The simple substitution of a single hydrogen For example, an acrylonitrile-styrene co-
atom with another atom or chemical group can polymer might be made by first reacting a good
cause a drastic change in the properties of a portion of the acrylonitrile to form polyacry-
polymer. Whereas polyethylene is translucent, lonitrile and then adding the styrene and re-
flexible, and crystalline, polystyrene is trans- maining acrylonitrile to complete the polymer-
parent, brittle, and amorphous. ization of the desired end product. Or, in
another case, both ingredients might be added
to a reactor simultaneously and allowed to react
Copolymers concurrently.
In addition to making changes in the basic re-
peating unit by substitution, as illustrated Other Polymers
above, it is possible to change the chemical
composition and hence the morphology and From a study of Figs. 2-3 and 2-4, it will be
properties of a polymer by mixing the types of noted that all of the polymers listed there are
structural groups or basic repeating units within formed by combinations made possibly by re-
the chain of a polymer. This is done by a pro- action of the double bonds that exist between
cess called copolyrnerizarion. In such a reac- adjacent carbon atoms in the monomers used
tion, for example, monomers of styrene and as starting materials. However, as mentioned
acrylonitrile can react to form styrene-acrylo- earlier, this is not the only way in which pol-
nitrile copolymers; or styrene may react with ymers are formed. When polymers are created
butadiene to form styrene-butadiene copoly- by rearrangements or condensation reactions,
mers; or acrylonitrile, butadiene, and styrene other types of polymeric chains can be formed.
may all react simultaneously to form the ABS Figure 2-5 lists the structural formulas of sev-
(acrylonitrile-butadiene-styrene) copolymers. eral commercially important polymers in which
Any of the polymerization techniques previ- oxygen (0) is an integral part of the bonds
ously discussed can be used. holding the polymer together. Similarly, Fig.
In addition to varying the types of starting 2-6 lists several types of polyamides and a
ingredients used to form copolymers, the rela- polyurethane in which nitrogen (N) atoms form
42 SPI PLASTICS ENGINEERING HANDBOOK

Acrylonitrile Styrene Butadiene Styrene

Acrylonitrile-styrene copolymer Butadiene-styrene copolymer

Acrylonitrile Butadiene Styrene

Acrylonitrile-butadiene-styrene copolymer

TFE HFP
Tetrafluoroethylene (TFE)-Hexafluoropropylene (HFP) copolymer
Fig. 2-4. Carbon “backbone” copoloymers

the bonds between portions of the polymer In addition, the properties of a polymer may
molecule. In some cases the polymers are be radically altered by mixing it with non-
formed by molecular rearrangements (in the polymeric materials and chemicals. In fact,
case of polyurethanes and epoxies) and in other some polymers would be worthless to the
cases by condensation reactions (some nylons). molder or extruder if additives were not used
Other condensation polymers are illustrated to modify them before they were processed into
in Fig. 2-7, which shows some of the complex finished products.
structures proposed for the more common types For example, phenolic, urea, and melamine
of thermosets. Note that the thermosets always resins, as they come out of the polymerization
have more than two linkages connecting the kettle, are largely brittle, frangible solids with
various structural units in the polymer, and they low impact strength. To make them usable,
are commonly referred to as cross-linked ma- such materials must be mixed with a filler of
terials involving a networklike molecular struc- some kind to reinforce the strength of the poly-
ture. mer. In the case of the three thermosets men-
There are at least 30 to 40 different families tioned, cellulose fillers made from wood flour
of thermoplastics now offered and about 10 dif- or cotton are necessary to make the resins com-
ferent basic families of thermosets. And this mercially moldable. Similarly, cellulosics and
takes into account only the more common types vinyl resins must also be mixed with semisol-
of polymers. It should also be noted that co- vents, called plusticizers, to soften them to
polymers, mixtures, and chemically modified some degree (so they may be molded or ex-
versions of the polymers listed make the total truded) o r to modify their properties (to make
number of polymeric materials that are theo- them soft and pliable, rather than hard and
retically possible entirely too great to list them stif).
in any one place. In actual practice, the number of different
 POLYMER CHEMISTRY 43

CH20H
I

f H < Z H +

iy Polyacetal resin

c---c-c4
H - r

H H-C-H
c1
y

H
Cellulose (natural polymer)

Chlorinated polyether Phenoxy resin (polyhydroxyether)

Polycarbonate Polyphenylene oxide

Fig. 2-5. Polymers with opygen in the chain.

Nylon 6/10 Nylon 11

t 0-(C H2 ),-O--C-N-(C
0
I1
I
H
Polyurethanes
Hz )y -N-C
H
I
“f
Fig. 2-6. Polymers with nitrogen in the chain
44 SPI PLASTICS ENGINEERING HANDBOOK

Phenol-formaldehyde resin

Urea-formaldehyde

I
CH2
I
N-H
I

H N N H

II 1
N N

I I
N-H N-H
I I
CH2 CH2
I I
Melamine-formaldehyde

Fig. 2-7. Thermoset structures

 POLYMER CHEMISTRY 45

types of chemical additives and fillers that are a polymer to significantly increase the strength
mixed with the fundamental polymer is so large of the polymer in the direction of the orienta-
that the chemistry of plastic compounds be- tion. Chemical or irradiation methods also can
comes extremely complex. be used to cross-link a plastic (such as polyeth-
It also is possible to vary existing polymers ylene) to improve its toughness and chemical
by any number of chemical, mechanical, or ir- resistance. Nucleation techniques and chemical
radiation techniques to change the structure of modification (as in the case of chlorinated poly-
the polymer. During processing, for example, ethylene) are further adaptable to changing
it is possible to align or orient the molecules in polymer structures.