15

Hot Melt Adhesives

15.1 Introduction
Hot melt adhesives set (i.e., transformation of liquid adhesives into solid)
by cooling. Other types of conversion of a liquid adhesive to solid are by
solvent evaporation and by chemical reactions (cross-linking).
Hot melt adhesives basically consists of a polymer, a tackifier, and a
number of functional additives such as antioxidants. These components
are mixed together to produce a hot melt adhesive. The hot melt adhesives
are applied on the substrates in the molten state, and the adhesive bond
formation takes place by rapid solidification of the melt.

15.2 Polymers Commonly Used for Hot Melt Adhesives

While there are many polymers that are used in adhesive applications,
the bulk is served by four types of polymers: styrenic block copolymers
(SBCs), ethylene vinyl acetate copolymers (EVAs), linear low-density
polyethylene, and atactic poly alpha olefins (APAO), reactive PU, and
polyamide.

15.2.1 Ethylene Vinyl Acetate Copolymers

Ethylene copolymers, of which EVA is particularly predominant, are the
most commonly used in HMA formulations [1]. These copolymers are
characterized by their polar (ester) functionality that provides excellent
adhesion to more polar substrates such as paper, wood and metal.
EVA is a copolymer made from two different monomer types: ethylene
and vinyl acetate. The chemical structure of EVA is given in Figure 15.1.
The polymerization of EVA corresponds closely to the polymerization
of low-density poly(ethylene).

R. N. Kumar and A Pizzi. Adhesives for Wood and Lignocellulosic Materials, (347–365) © 2019
Scrivener Publishing LLC

347
348 Adhesives for Wood and Lignocellulosic Materials

CH2-CH2 CH2-CH
n
O

C=O

CH3

Figure 15.1 Ethylene vinyl acetate copolymer.

Ethylene and vinyl acetate are copolymerized by free radical polym-

erization. The options are solution polymerization, suspension polymer-
ization, emulsion polymerization, and bulk polymerization. But solution
polymerization is preferred [2]. A method of either continuous type or
batch type may be employed. Methanol is generally used as the solvent.
Commonly used catalysts are 2,2 azobisisobutyronitrle, or organic perox-
ides. 2,2 -Azobis(4-methoxy-2,4-dimethyl valeronitrile) is the most pre-
ferred catalyst [3]. To stop the polymerization reaction, a polymerization
inhibitor is added to the reaction mixture.
The properties of EVA copolymer can determined by three structural
attributes, namely, the weight percent of vinyl acetate, molecular weight,
and distribution and molecular branching. Vinyl acetate content has two
basic influences on the properties of EVA copolymers.

(1) To disrupt the crystalline regions due to the polyethylene

segments of the copolymer [4].
(2) High vinyl acetate content tends to make the polymer
softer and more rubbery, while low vinyl acetate content
tends to make the polymer harder and more crystalline. If
vinyl acetate exceeds 45%, the crystallinity of the EVA will
be lost [5].

The composition of a hot melt adhesive usually includes a thermoplas-

tic polymer backbone and a diluent system. The diluent system in a hot
melt adhesive can include materials such as wax, tackifier, plasticizer, and
antioxidant.
By adding these materials accordingly, the properties of hot melt adhe-
sives can be modified and customized to a specific end usage.
Generally, hot melt adhesives based on EVA resins contain a vinyl acetate
concentration of 18–40%. A higher vinyl acetate content provides better
adhesion to polar substrates such as aluminum and steel, while the lower
vinyl acetate copolymers are often used for bonding low-energy surfaces.
 Hot Melt Adhesives 349

The materials with high vinyl acetate concentration exhibit reduced crys-
tallinity and increased polarity. At about 50% vinyl acetate content, all
crystallinity is lost.
The properties required for specific end uses of EVA hot melt adhe-
sives depend on the degree of crystallinity of EVA copolymers. Hence,
the degree of crystallinity is responsible for versatility of these products
[4]. The common grades for EVA copolymer have vinyl acetate contents
ranging from 1% to 50% by weight, depending on the application [6].
Acetoxy groups present in the EVA confer polar characteristics on the
hot melt adhesives. As the vinyl acetate content increases, the polarity of
the EVA also increases. This is the second effect of vinyl acetate group
in the EVA-based hot melt adhesives. EVA-based hot melt adhesives are
therefore widely used in various substrates such as paper, wood, plastics,
rubbers, and metals [5].
The domain structure of EVA copolymers consists of stiff and partially
crystalline polyethylene blocks, and flexible, soft and polar amorphous
vinyl acetate blocks [7]. Thus, EVA polymers, like the SBCs, also exhibit
a two-phase morphology. The more crystalline polyethylene segments
segregate upon cooling from the melt from the amorphous domains
formed by the ester-containing segments. The ultimate crystallinity of the
polymer is also affected by branching formed during their free-radical-
catalyzed polymerization. The crystalline polyethylene domains deter-
mine the ultimate melting point of the polymer and contribute to the
hardness and creep resistance of the adhesive. Because they can cocrys-
tallize with the polyethylene regions, waxes are especially effective in
EVAs in enhancing the attributes (e.g., melting point) of these domains.
The amorphous regions are responsible for specific adhesion, tack, and
flexibility.
An example of a general-purpose EVA-based adhesive is shown in
Table 15.1.

Table 15.1 General-purpose EVA-based adhesive.

Components Parts by weight
Ethylene vinyl acetate (Elvax 220, DuPont) 30
Tackifier, polyterpene resin 50
Plasticizer, microcrystalline wax 20
Antioxidant 0.5–1.0
350 Adhesives for Wood and Lignocellulosic Materials

15.2.2 Styrenic Block Copolymers

SBCs are important components in a wide range of hot melt adhesives. As
the name implies, SBC is a copolymer formed when the two monomers,
namely, styrene and butadiene, cluster together and form “blocks” of
repeating units. SBCs are the largest volume and one of the lowest-priced
commercial thermoplastic elastomers. The styrene end blocks are hard
polymers that add strength to an HMA, but do not contribute to the tack
and adhesion properties. On the other hand, the polyisoprene (SIS), poly-
butadiene (SBS), ethylene–butene copolymer (SEBS), and others are the
midblocks. The midblock combined with tackifiers and plasticizers pro-
duce the adhesive properties.
Thus, three segments, styrene–polyolefin–styrene, are needed to attain
the unique properties of this class of polymers. The unique properties of
SBCs are the result of the two-phase morphology they are transformed
into in the solid state. Polystyrene segments are immiscible with poly-
isoprene and polybutadiene and are connected by the rubbery midblock
segments as shown in Figure 15.2 to form what is called thermoplastic
elastomer. The idea of thermoplastic elastomer comes from the concept
of reversible cross-link. Thus, the polystyrene clusters act as cross-links
for the polybutadiene blocks in the solid state. The cross-links however
break up when the SBS is heated, so it can be processed and recycled like
a non-cross-linked polymer.
However, it has to be kept in mind that the double bonds are present
in the midblock structure and are susceptible to thermal and oxidative
degradation. By selective hydrogenation of the midblock, the copolymers
become substantially more stable. These so-called SEBS block copolymers
have much improved thermal and weathering resistance [8].

polystyrene
domain

elastomeric
phase

Figure 15.2 Two-phase morphology of SBC.

 Hot Melt Adhesives 351

This physical cross-link system imparts strength and flexibility to the

thermoplastic elastomer. The midblocks contribute flexibility to the adhe-
sive. It is also the region compatible with tackifiers and provides tack and
adhesion.

15.3 Polyureathane Reactive Hot Melt Adhesives

Reactive urethanes are the newest and fastest-growing category of hot melt
adhesives meant for high-impact applications. The conventional hot melt
adhesives are not chemically reactive and therefore do not develop sufficient
strength, heat, and chemical resistance required in certain applications.
In order to fulfill these properties, the hot melt adhesives should be
capable of undergoing cross-linking reaction, which will result in the for-
mation of durable bonds. Consequently, such reactive hot melt adhesives
can acquire characteristics significant enough to be used in a number of
performance-driven applications.
Reactive polyurethane hot melt adhesives fall into this category. An
isocyanate terminated polyurethane is first produced by the step-growth
polymerization of a polyol and excess of polyisocyanate to control the
molecular weight and to ensure the availability of moisture curable isocya-
nate end groups in the final product.
The physical properties that are key to performance are the melt vis-
cosity, rheology, and melt stability. The atmospheric moisture as well as
moisture present in the substrates can diffuse into the surface and the bulk
of the adhesive and can cause chemical changes to occur [9] [see reactions
of isocyanates with water in Section 7.3 (“Reactions of isocyanates”)]. The
essential reactions are as follows:

1. Reaction of isocyanate with moisture to form amine and

carbon dioxide.
2. Chain extension by reaction of isocyanate with amine
formed to produce substituted urea.
3. Branching reactions of isocyanate with urethane to produce
allophanate and with urea to produce biuret.

The above sequence of reactions leads to cross-linking. This in turn

confers superior properties on the bonded assembly.
A wide range of hot melt PU adhesives is possible given a wide range of
raw materials that are currently available, namely, polyether polyols such
352 Adhesives for Wood and Lignocellulosic Materials

as poly(propylene glycol) in a range of molecular weights, a wide range of

polyester polyols, and a variety of isocyanates.
Because of the cross-linked structure in the bond line, the reactive PU hot
melt adhesives develop good temperature and chemical resistance, a high
degree of degree of stiffness, as well as toughness. The toughness of polyure-
thane is attributed to the flexibility of the long-chain polyols called “soft seg-
ments”. The stiffness of the polyurethane is attributed to the isocyanates with
relatively short chains and high Tg. This domain is called “hard segments”.
Applied as a drop or a thin bead, high-viscosity reactive urethanes set
quickly, becoming structurally rigid in minutes. The secondary moisture
cure continues for up to 24 h.
Since reactive urethane adhesives are heat resistant, they can be used in
heat-sensitive end-use applications.

15.4 Silane Reactive Hot Melt Adhesives

The silane reactive hot melt adhesive composition comprises one or more
silane-modified polymers. The silane-modified polymer has an organic
backbone, bearing one or more terminal or pendant silane or alkoxylated
silane groups. The silane groups are hydrolyzed by water to silanol groups,
which in turn can condense with one another to form polysiloxane or with
reactive species on the adherent surfaces. The silane-modified polymer
may be prepared with one or more variety of polymer backbones such as
polyurethane, polyether, polyester, polyolefin, polycaprolactone, polyacry-
late, polybutadiene, polycarbonate, polyacetal, polyester amide, polythio-
ether, polyolefin, and the like.

15.5 Polyamide Hot Melt Adhesives

Polyamides are condensation polymers, produced by reacting dibasic acids
with diamines. Examples of dibasic acids and diamines employed for the
production of polyamides are given below:

Dibasic Acids:
Dimer acid (dimerized fatty acids)
Dodecanedioic acid
Sebacic acid
Azelaic acid
Adipic acid
 Hot Melt Adhesives 353

Diamines:
Ethylene diamine
Hexamethylene diamine
Diethylene triamine
Triethylene tetramine

The thermoplastic polyamide resins are amides prepared from dimer

acids and low-molecular-weight aliphatic amines. Dimer acids are the
Diels Alder adducts of an unsaturated aliphatic monocarboxylic acid such
as linolenic or linoleic acid (Figure 15.3).
The amines employed for the preparation of the amides are low-
molecular-weight aliphatic amines containing two terminal -NH2 groups
such as ethylenediamine or hexamethylenediamine.
Thermoplastic polyamides derived from dimer acid and an aliphatic
diamine are shown in Figure 15.4. Polyamides are used as hot melt

(CH2)7-COOH

CH
HC CH (CH2)7 COOH
+
CH CH2 CH=CH (CH2)4 CH3
HC
CH Linoleic acid

(CH2)5 CH3

Isomerized linoleic acid

(CH2)7-COOH

CH
HC CH (CH2)7 COOH

CH CH2 CH=CH (CH2)4 CH3

HC
CH3

(CH2)5 CH3

Dimer acid

Figure 15.3 Formation of dimer acid.

354 Adhesives for Wood and Lignocellulosic Materials

(CH2)7-COOH
+ 2 H2N-CH2-CH2-NH2
CH
Ethylenediamine
HC CH (CH2)7 COOH

CH CH2 CH=CH (CH2)4 CH3

HC
CH3

(CH2)5 CH3

Dimer acid
(CH2)7-CO NH-CH2-CH2-NH

CH
HC CH (CH2)7 CO NH-CH2-CH2-NH

CH CH2 CH=CH (CH2)4 CH3

HC
CH3

(CH2)5 CH3

Dimer acid polyamide

Figure 15.4 Dimer acid polyamide.

adhesives, particularly for applications that require good adhesion and

high tensile strength of adhesive bonds.
The thermoplastic polyamide adhesives are available commercially in
three general molecular weight classes. The lowest molecular weight (for
inexpensive equipment), the intermediate molecular weight (for equip-
ment suitable for handling higher melt viscosities), and high molecular
weight (for high-strength applications) [10].
Polyamides are excellent adhesives and can be used under severe envi-
ronmental conditions such as exposure to solvents, gas, or oil. They are
also suitable for applications up to 160°C. They possess superior thermal
stability, good chemical resistance, and strength. They are tough polymers
and are excellent for electrical potting applications. Polyamide hot melts
offer good adhesion to a wide range of substrates including metal, wood,
vinyl, ABS, and treated polypropylene and polyethylene.
 Hot Melt Adhesives 355

15.6 Amorphous Polyolefin (APO/APAO)

Hot Melt Adhesives
The preparation of a high-performance and low-cost hot melt adhesive
based on atactic polypropylene and a minor proportion of different poly-
mers such as isotactic polypropylene and polyethylene has been reported
[11]. The resulting hot melt adhesives have excellent properties for bond-
ing materials, particularly paper. They have light color, making them suit-
able for applications where clarity is important.
Atactic (essentially non-crystalline) polypropylene is formed during the
stereospecific polymerization of propylene using the Ziegler–Natta cata-
lyst system. The polymerization takes place in the presence of a catalyst
comprising a coordination complex of a transition metal halide with an
organometallic compound. Atactic polypropylene usually represents from
about 5% to 15% by weight of the polymerization product, the remainder
being isotactic (essentially crystalline) poly propylene. The solid atactic
polypropylene suitable for the composition of the adhesive has a molecular
weight of 15,000 to 60,000 and more particularly from 16,000 to 20,000. It
is soluble in boiling pentane, hexane, heptanes, and other hydrocarbons.
They have excellent chemical resistance to polar solvents, acids, bases,
esters, and alcohols, but only moderate heat resistance and poor chemical
resistance against nonpolar solvents like alkanes, ethers, and oils. When
compared with EVA and polyamide hot melt adhesives, polyolefins have
extended open times for positioning of parts. They also have lower melt
viscosity and slower set times compared to EVAs. Some APOs can be used
without any additives, but often they are compounded with tackifiers,
waxes, and plasticizers (mineral oil, polybutene oil) [8].
Zhou (2006) reported novel polyolefin hot melt adhesives based on the
blend of amorphous/atactic polypropylene (or copolymers) and crystalline/
isotactic polypropylene as well other additives [11]. The newly formulated
polyolefin-based adhesive made from the PP blends was successfully used as
a multifunctional hot melt adhesive for construction.
Polyolefin hot melts are a unique combination of base resins and tackifi-
ers. This hot melt technology provides superior adhesion to polypropylene,
a good barrier against moisture and water vapor, and excellent chemical
resistance against polar solvents and solutions including acids, bases, and
alcohols.
356 Adhesives for Wood and Lignocellulosic Materials

15.7 Tackifiers
Tackifiers are chemical compounds used in formulating adhesives to
increase the tack, the stickiness of the surface of the adhesive. They have a
crucial role in providing initial adhesion. They are usually low-molecular-
weight compounds with high glass transition temperature.
Tackifiers function as polymer modifiers. Hence, they should pos-
sess good compatibility with the main polymer for good performance.
Compatibility among two or more materials is governed by their molecular
weights, molecular weight distributions, and solubility parameters (com-
positions). Low molecular weights, narrow molecular weight distributions,
and close solubility parameters result in good tackifier–polymer compati-
bility. The Hildebrand solubility parameter gives an estimate of the degree
of interaction between tackifier and polymer. Materials with similar values
are likely to be miscible and have favorable viscoelastic properties [12].

15.7.1 Aromatic Hydrocarbon Resins

Hydrocarbon resins are amorphous thermoplastic polymers produced by
polymerization of unsaturated hydrocarbons. The feedstock are various
by-products of naphtha crackers, resins from coal tar commonly called
coumarone-indene resin. These resins have typically a low molecular
weight ranging from about 400 to 5000 g/mol. The three main types are C5
aliphatic, C9 aromatic, and DCPD cycloaliphatic resins. These resins are
produced by catalytic solution polymerization of aromatic crude streams
containing indene as the principal polymerizable monomer along with
varying minor percentage of styrene, methyl indenes, methyl styrenes,
coumarone, and dicyclopentadiene. Aromatic resins can be obtained in
various softening points from about 10°C to over 150°C and in colors rang-
ing from pale straw to dark amber. The iodine number generally taken
as a measure of reactivity or unsaturation is relatively low in these resins
ranging from 30 to 60 [13].

15.7.2 Aliphatic Hydrocarbon Resins

Aliphatic hydrocarbon tackifier resins are thermoplastic resins that pro-
mote adhesion and tack in hot melt adhesives. Hydrocarbon tackifier
resins are selected on the basis of the softening point, molecular weight,
molecular weight distribution, and composition of the tackifier. Aliphatic
hydrocarbon resins (C5 resins) are made from C-5 piperylene (cis- and
 Hot Melt Adhesives 357

trans-piperylene) and its derivatives. The most important ones are cis/
trans 1,3-pentadienes, 2-methyl-2-butene, cyclopentene, cyclopenta-
diene, and dicyclopentadiene (see below). The liquid C5 feedstock can
be polymerized to a hard resin using a Lewis acid catalyst and carefully
selecting temperature and pressure to obtain the desired softening point
and molecular weight. The structure of the polymerized resin is difficult
to characterize since the various isomers of the feedstock will combine
unpredictably [13]. Hydrogenation is used after a resin is polymerized
to decrease its color and improve its stability towards heat, oxygen, and
ultraviolet light.

15.7.3 Mixed Aliphatic and Aromatic Resins

C5 aliphatic and C9 aromatic resins can be modified by mixing the two feed
streams together at a carefully chosen ratio to produce hybrid polymers.
This ratio determines the aliphatic/aromatic balance of the resin, which is
an essential determinant of the resin’s compatibility [14]. The polymeriza-
tion is carried out using either AlCl3 or BF3 as required. The MMAP* and
DACP** cloud points are the method used to characterize C5/C9 resins.
As the cloud points decrease, the compatibility with polar and aromatic
polymers increases

[*MMAP is 1:2 mixture of methylcyclohexane and aniline

**DACP is 1:1 mixture of xylene and di-acetone alcohol
(4-hydroxy-4-methyl-2-pentanone)

Cloud point determination is easy to do and involves weighing a stan-

dard amount of resin that is dissolved in the solvent at high temperature.
When homogeneous, it is allowed to cool, with mixing. The temperature
at which the resin begins to form a separate phase is defined as the cloud
point.]
A study explored the use of dynamic mechanical analysis to qualitatively
show the effects of resin aromaticity, as measured by the modified mixed
aniline point (MMAP), on adhesive properties [15]. Another presentation
described the use of MMAP and a diacetone alcohol cloud point (DACP)
as predictors of tackifier utility in different elastomer systems [16].
These resins are the result of research efforts by various manufactur-
ers to fine-tune the compatibility and tackifying characteristics of heir C-5
resins to produce products with outstanding performance of the hot melt
adhesives [13].
358 Adhesives for Wood and Lignocellulosic Materials

15.7.4 Terpene Resins

Terpene-based resins are important tackifiers, besides rosin esters, derived
from renewable resources. The terpenes used in the tackifier industry are
obtained from turpentine, which can be either gum turpentine or crude
sulfate turpentine (CST) obtained from tall oil during the Kraft pulping of
pine wood. The two major terpenes obtained from turpentine are α-pinene
and β-pinene (Figure 15.5). Another very commonly used terpene for tack-
ifiers that is not derived from turpentine is d-limonene, which is obtained
from citrus sources, i.e., orange peels.
Terpene resins are primarily synthesized by a cationic polymerization
process where a suitable solvent and AlCl3 or other Lewis acid catalysts are
employed. The three major classes of terpene resins in the tackifier indus-
try are polyterpene resins, phenol-modified polyterpene resins (terpene–
phenol resins), and styrene-modified polyterpene resins (styrenated ter-
pene resins) (Figure 15.6). The actual monomers are usually one or a
combination of the terpenes, α-pinene, β-pinene, and dipentene or lim-
onene [17].
Terpene resins are light in color and can be obtained in softening points
10°C to 140°C and molecular weights from about 300 to almost 2000.
Generally speaking, at the equivalent softening points, β-pinene resins
have the highest molecular weights [18].

α−Pinene β−Pinene Dipentene

Figure 15.5 Terpenes for producing tackifiers.

Styrene
Polyterpene Styrenated Terpene Resin

α−Pinene
Phenol

Terpene-Phenol Resin

Figure 15.6 Three major classes of terpene resins.

 Hot Melt Adhesives 359

15.7.5 Terpene–Phenol Resins

The terpene-phenolic tackifier resins are produced by an alkylating reac-
tion of a compound containing at least two phenolic groups with a terpene
in the presence of a Friedel Crafts catalyst. The phenolic compound should
have two phenolic groups and should have at least one ortho or para posi-
tion free for alkylation by a terpene.
A method for making a phenol–terpene resin by reacting phenol or alkyl
phenol and a terpene in the presence of a Friedel Crafts catalyst and an aro-
matic, naphthenic, or paraffinic hydrocarbon solvent has been reported by
Gonzenbach [19].
Wang et al. [20] describe the preparation of terpene–phenol–
aldehyde resin, a copolymer product obtained by cationic copolymeriza-
tion of monoterpene with phenol and aldehyde, as a new modified pheno-
lic aldehyde resin. It is a transparent, light yellow material that is soluble
in most solvents and is compatible with rubber, rosin, and others. The ter-
penes usually used for the synthesis of terpene–phenol–aldehyde resin are
α-pinene, β-pinene, limonene, carene, camphene, and others. The phenols
used are phenol, 3;4-dimethylphenol, 4-methylphenol, and others. The
aldehyde used is mainly formaldehyde. There are two methods for syn-
thesizing the resin. With the first method, phenol is condensed with an
aldehyde in the presence of an acid catalyst and is then alkylated with the
terpene in the presence of Lewis acid or protonic acid. With the second
method, phenol is first polymerized with the terpene in the presence of an
acid catalyst and is then condensed with the formaldehyde [20].

15.7.6 Rosin and Rosin Derivatives

The use of wood resins in connection with the construction of early sailing
ships led to the general term naval stores for rosin, turpentine, and tall
oil, which are the most important group of materials today with regard to
commercial production. These naval stores are obtained either by tapping
living pine trees (gum resin, oleo resin), by solvent extraction of stumps
of coniferous trees (wood rosin), or as a by-product of pine and softwood
kraft pulping (tall oil rosin) [21].
Tall oil rosin, the third type of rosin, is obtained from the tall oil, which
is a by-product of the paper industry. During the pulping operation, wood
chips are cooked under heat and pressure in the alkaline medium. The pulp
is removed by filtration and washing, and the liquid portion is concen-
trated, resulting in a precipitate that is removed and acidified to give crude
360 Adhesives for Wood and Lignocellulosic Materials

tall oil. Crude tall oil consists mainly of fatty acids and rosin acids that are
separated by distillation.
While the production of oleo resins is generally stagnant, the produc-
tion of tall oil and sulfate turpentine in connection with the kraft pulping
of pines and other coniferous woods remains the dominant source of naval
stores [21].
Rosin from any of the above sources is a mixture of organic acids called
rosin acids. Minor components consist of rosin esters and anhydrides,
unsaponifiable matter, and fatty acids.
Rosin acids can be divided into two types. These are the abietic acid type
and pimaric acid type (Figure 15.7). Unmodified rosin consists primarily
of abietic acid type. The figure shows some of the more common members
of these two types.
It can be seen that the difference in the two types is the substitution
pattern at the C13 position. Abietic acid types have an isopropyl group at
the C13 and pimaric acid types have instead a methyl and a vinyl group.
Rosin by itself is generally unsuitable for use in modern adhesive sys-
tems because it is prone to oxidation and further reactions as well as
crystallization.

Abietic acid type

COOH COOH COOH

COOH
Abietic acid Neo-abietic acid Dehydroabietic acid Dihydroabietic acid

Pimeric acid type

COOH
COOH
Palustric acid Isopimeric cid

Figure 15.7 Rosin acids.

 Hot Melt Adhesives 361

Most rosins for adhesive use are modified to give rosin derivatives
through disproportionation, polymerization, hydrogenation, and esterifi-
cation reactions.
Disproportionation takes place when rosin is heated to about 270°C.
The reaction may be accelerated by use of various catalysts such as plati-
num or iodine. The result is a hydrogen exchange between the rosin acids.
Accordingly, two abietic acids are converted into dihydroabietic acid and
dehydroabietic acid.
Polymerization is carried out by treating a solution of rosin in an
inert solvent with an acid catalyst such as boron trifluoride or sulfuric
acid. Removal of solvent and the catalyst results in a product composed
largely of rosin dimer and having a higher softening point than unmod-
ified rosin. Hydrogenation using Raney nickel or a similar catalyst can
be tailored to give products that are only partially saturated such as
dihydroabietic acid or completely saturated such as tetrahydroabietic
acid [13].
Rosin acids react with a variety of alcohols to form esters. Because
of steric hindrance, however, the esterification requires higher tempera-
ture, but the resulting esters are quite stable and resistant to hydroly-
sis. Usually, polyhydric alcohols are used for esterification in order to
give products with higher softening points and higher molecular weight.
Ethylene glycol, glycerol, and pentaerythritol are the most common alco-
hols for the purpose. Rosin esters are compatible with a broad range of
polymers, including high and low vinyl acetate EVA, acrylics, SBR, SIS,
and SBS. This characteristic enables formulation flexibility in various hot
melt, water-based, and solvent-based adhesive applications. Solid rosin
esters can be formulated into SBC- or EVA-based adhesives for packag-
ing, PSA, and woodworking applications. In addition to these end uses,
liquid rosin esters can also be used in water-based acrylic for construc-
tion adhesives [12].

15.8 Antioxidants [22]

Adhesives and their raw materials react like other organic materials with
oxygen in a process called “autoxidation”. Autoxidation is initiated by heat,
light, mechanical stress, catalyst residues, or impurities.
Free radicals are formed and react in the presence of oxygen to form
peroxy radicals, which further react with other hydrogen donors present,
leading to hydroperoxides (ROOH).
362 Adhesives for Wood and Lignocellulosic Materials

All these reactions ultimately lead to a change in chemical composition

and such polymer properties as molecular weight, which has immediate
impact on polymer degradation affecting the service life of an adhesive.
Some results of adhesive degradation are as follows:

• discoloration
• viscosity changes
• char formation
• cracking and
• loss of adhesion

Antioxidants are used in a variety of adhesive formulations to protect

against degradation caused by reaction with atmospheric oxygen. The
introduction and type of antioxidant will depend on the nature of the base
polymer, the processing parameters, and the end-use application. The anti-
oxidant or stabilizer maintains viscosity, color, and physical properties and
prevents thermal degradation.
Excessive oxidation generally results in undesirable changes in the
adhesive’s mechanical, aesthetic, or bonding properties. Oxidation can
occur at all stages of an adhesive’s life from synthesis to final end use. It is
usually recognized at high processing temperatures such as during mixing,
compounding, or extrusion (in the case of hot melt adhesives). However,
oxidation can also occur at relatively low temperatures including ambient
storage and also on exposure to UV light.

15.8.1 Oxidation-Sensitive Components in Hot Melts

Adhesive components especially susceptible to oxidation include base syn-
thetic polymers such as ethylene vinyl acetate and styrene block copoly-
mers, polyolefins, polyamides, and polyurethane. Hydrocarbon additives,
such as tackifiers and waxes, are also vulnerable to oxidation and can actu-
ally contribute to the oxidation of the base polymer. Metallic and other
impurities in the adhesive can accelerate the oxidation process. Depending
on the aging environment, most adhesives can benefit from antioxidants.

15.8.2 Antioxidants Used in Hot Melts

Hindered phenols, amines, phosphites, and thioester are commonly used
stabilizers for hot melt adhesives. The chemical types of common antioxi-
dants that are most often used in hot melt adhesive applications are shown
in Table 15.2 [22]. The hot melt adhesive composition includes from about
 Hot Melt Adhesives 363

Table 15.2 Common antioxidants by chemical type with major resin applications.
Types Common resin applications
Amine Rubber, some pigmented
polymers, and
polyurethane polyols
Phenolic Polyolefins, styrenics, and
most engineering resins
Organo-phosphite Polyolefins, styrenics, and
most engineering resins
Thioester Polyolefins and styrenics
Comments
Arylamines tend to
discolor and cause
staining
Phenolics are generally
stain resistant
and include
simple phenolics
(BHT), various
polyphenolics, and
bisphenolics
Phosphites can improve
color stability and
property retention,
but can be corrosive
if hydrolyzed
The major disadvantage
with thioesters is
their odor, which is
transferred to the
host polymer

0.1% to about 1.0% by weight antioxidant. There are numerous antioxi-

dants and blends of antioxidants that have proven beneficial for various
types of adhesives.

15.9 Plasticizers
Apart from the basic polymers and the tackifiers, plasticizers are the other
most common additive in hot melt adhesive formulations. The purpose of
adding the plasticizers is to impart flexibility and toughness to the product.
When the base resin is excessively stiff, it is often blended with an elasto-
meric to obtain a tough material with improved energy dissipation and
reduced glass transition temperature. These materials act opposite to the
tackifiers in that they decrease Tg. The plasticizer must be completely solu-
ble in the base resin and be sufficiently nonvolatile. The addition of a plas-
ticizer promotes wetting and reduces the melt viscosity of the formulation.
364 Adhesives for Wood and Lignocellulosic Materials

15.10 Mineral Oil and Wax

Mineral oil and wax are commonly employed as diluents [23]. When added
to the matrix polymer, wax and oils can negatively affect the adhesion
properties because of the shrinkage of the adhesive. Waxes are often used
in hot melt formulations to lower surface tension and decrease melt vis-
cosity. Certain waxes such as microcrystalline waxes also reinforce the hot
melt by forming crystallites that resist deformation under load. These are
used in formulations that require a relatively high degree of creep strength.
They are performance-enhancing additives.

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