Introdução

Resin. In polymer technology the term resin usually means a powdered or granular synthetic
polymer suitable for use, possibly with the addition of other nonpolymeric ingredients.
Although the meaning is very ill defined, it is listed here because it is widely used.
“Na tecnologia de polímeros, o termo resina normalmente significa um polímero sintético em
forma de pó ou grãos que é propicio para uso, possivelmente com adição de outros ingredientes
não políméricos. Apesar desse significado ser muito mal definido, é listado por conta de o termo
ser amplamente usado. ”
[Rudin]

Polymer is a large molecule consisting of many repeating subunits. Resin is a solid or viscous
material which gives a polymer after curing.
Resins can be synthetic or natural and generally are mixtures of organic compounds. After
polymerizarion or curing, resins form polymers. Commercially available adhesives and sealants
generally come in two parts- resin and hardener. When both parts are mixed, polymerization
starts, the resin gets cured and the product we get is a polymer. So, according to my
understanding, a resin is an uncured polymer.
[quora – referência não confiável]

PROPERTIES OF RESINS
Resins are amorphous or semi-crystalline solids or highly viscous liquids that can be converted
into plastics. These substances have a polymeric or semi-polymeric structure, and are usually of
natural or (semi-)synthetic origin. They are often treated with plasticizer, stabilizer, filler,
antioxidant, etc. before pelletized, extruded and molded into a myriad of shapes.

Resins encompass a great number of compounds with vastly different properties. For example,
they can be flexible and ductile or hard and stiff. The oldest resins were derived from plants and
animals. Today most natural resins have been largely replaced by synthetic resins, which can be
divided into two major classes:

 Thermoplastic resins

 Thermosetting resins

Thermoplastic resins can be repeatedly melted and solidified by heating and cooling. Generally,
no chemical changes take place during molding so that the mechanical and physical properties
stay the same. Thermoset resins, on the other hand, react during processing and are converted to
cross-linked polymers, which can neither be remolded nor reprocessed (recycled) and which
have very different properties than the resins.

The most important resins in order of demand (production volume) are polyethylene (HDPE,
LDPE, LLDPE), polypropylene (i-PP), polyvinyl chlorides (PVC), polystyrene (PS),
polyethylene terephthalate (PETE), and polyurethane (PUR).

The plastic and rubber industry uses a large variety of methods to convert resins into plastic
products. The method most frequently used for processing resins is injection molding. Other
important methods include casting, blow molding, thermoforming, compression and transfer
molding, extrusion, and reaction injection molding.
Note

Other industries define resins as a sticky substance that oozes out of trees when an injury occurs
to a plant. These substances are usually extracted from fir and pine trees and are used in
medicine, varnishes and other industries. A large portion of these resins are used as tackifiers in
adhesives. Today many of these natural tackifiers have been replaced by synthetic tackifiers
which are produced via cracking of hydrocarbons (naphtha) which are also called resins.

[Polymer Properties Database http://polymerdatabase.com/polymer%20classes/Intro

%20Resins.html]

Propriedades

1.1.3 Thermoplastic versus thermosetting

The resin chemistry employed in polymer matrix composite materialscan be divided into two
types, thermoplastic and thermosetting. This distinction has a very large impact on the
inherent recyclability of a composite material.
Thermoplastic polymer matrices soften and melt with the application of heat. Any process step
throughout a thermoplastic composite’s life cycle, from the initial introduction of reinforcement
fibres to the final moulding of a component, takes place with sufficient heating to melt the
polymer. Although this ability to melt can limit the application of such composites due to
comparatively low maximum in-service temperatures, it does mean that end-of-
life thermoplastic compositecomponents can be shredded/ground and readily re-processed via
heating and moulding. The penalty for repeated processing in this manner is only limited
degradation in matrix properties and reinforcement fibre damage.
However, thermosetting systems undergo a permanent cross-linking reaction when curing that,
although resulting in a stiffer (and more brittle) matrix material, cannot be reversed with the
application of heat. The application of heat after curing only degrades the cross-linked polymer
matrix and will not melt it. This means that practical end-of-life recycling options are limited,
and could more properly be defined as ‘reuse’, such as in the case of incineration with energy
recovery and also the reuse of thermosetting composite (via regrinding) as a low value filler
material.

Reações – Arquivo separado

Aplicações comerciais

Resina epóxi

Applications of Epoxy Resins

Epoxy resins have found a broad range of application, mainly because the proper selection
of resin, modifiers, and cross-linking agent allows the properties of the cured epoxy resin to be
tailored to achieve specific performance characteristics. This versatility has been a major factor
in the steady growth rate of epoxy resins over the years.
Besides this versatility feature, properly cured epoxy resins have other attributes:
1.Excellent chemical resistance, particularly to alkaline environments.
2.Outstanding adhesion to a variety of substrates.
3.Very high tensile, compressive, and flexural strengths.
4.Low shrinkage on cure.
5.Excellent electrical insulation properties and retention thereof on aging or exposure to difficult
environments.
6.Remarkable resistance to corrosion.
7.A high degree of resistance to physical abuse.
8.Ability to cure over a wide range of temperatures.
9.Superior fatigue strength.
[J.L. MASSINGILLJR., R.S. BAUER, in Applied Polymer Science: 21st Century, 2000]

37.1 Introduction
Epoxy resins comprise a group of crosslinkable materials, which all possess the same type of
reactive functional group, the epoxy or oxirane group (1); their chemistry and technology have
been reported in a number of texts.1, 2

The epoxy group is characterized by its reactivity towards

both nucleophilic and electrophilic species and it is thus receptive to a wide range
of reagents or curing agents. Such curing agents are of two types: they may be either catalysts
or hardeners. Catalysts are usually drawn from tertiary amines or Lewis acids, and they function
by initiating the ionic polymerization of the epoxy compound to produce polyether structures.
Typically catalysts are used in low concentrations (< 1% of the resin’s weight). They are often
used in association with hardeners in resin formulations. Common examples of hardeners are
provided by aliphatic and aromatic amines, and carboxylic anhydrides. These types of
compound react directly with the epoxy and other groups of the resin, and so influence the
structure of the cured resin. In resin manufacturers’ recommended formulations resin : hardener
ratios are usually in the band 3:1 to 10:1 by weight.
It is the combination of resin and curing agent which produces the cured thermoset epoxy resin.
The process of curing an epoxy resinconverts the initially low molecular weight resin into its
thermoset form, which is a space network or three-dimensional chemical structure.
The term epoxy resin refers to both the uncured and the cured forms of the resin. Industrial
interest and use of these resins resides in both the valuable properties of the cured resin, which
include good adhesion to many substrates, relatively high toughness (particularly when rubber
modified), good environmental resistance, high electrical resistivity, low shrinkage, etc. and the
ease with which the curing reaction may be adapted to suit the fabricating process. Thus the
curing reaction, which is exothermic, may be induced at room or elevated temperatures or it
may be initiated, in the presence of appropriate catalysts, by UV light. The specific curing
procedure required to produce a cured resin of optimized performance characteristics is
dependent upon the precise combination of resin, curing agent and/or catalyst.
An important technological feature of the curing processes of epoxy resins is that, although they
proceed mostly by step-growth reactions, no volatile by-products are generated. This allows the
production of coherent void-free structures without recourse to applied pressure during forming
or moulding processes.
The combination of good processing characteristics and useful properties has led to the use of
epoxy resins in many applications including adhesives,3 in electronics for encapsulation, potting
and printed circuit boards,4 and in the aerospace industries as matrices for composites.5
To meet the differing requirements of this broad sweep of applications, epoxy resins of many
types are available, and it is these in combination with the variety of curing agents which
contribute the essential versatility of the epoxy system. In the next section some examples of
typical epoxy resins are discussed.
[Kenn Hodd, in Comprehensive Polymer Science and Supplements, 1989]

The epoxide resins (also widely known as epoxy resins and, occasionally, as ethoxyline resins)
are characterised by the possession of more than one 1,2-epoxy group (I) per molecule. This
group may lie within the body of the molecule but is usually terminal.
The three-membered epoxy ring is highly strained and is reactive to many substances,
particularly by with proton donors, so that reactions of the following schematic form can occur:

Such reactions allow chain extension and/or cross-linking to occur without the elimination of
small molecules such as water, i.e. they react by a rearrangement polymerisation type of
reaction. In consequence these materials exhibit a lower curing shrinkage than many other types
of thermosetting plastics.
There is, quite clearly, scope or a very wide range of epoxy resins. The non-epoxy part of the
molecule may be aliphatic, cycloaliphatic or highly aromatic hydrocarbon or it may be non-
hydrocarbon and possibly polar. It may contain unsaturation. Similar remarks also apply to the
chain extension/cross-linking agents, so that cross-linked products of great diversity may be
obtained. In practice, however, the commercial scene is dominated by the reaction products of
bis-phenol A and epichlorohydrin, which have some 80–90% of the market share.
The commercial interest in epoxide (epoxy) resins was first made apparent by the publication of
German Patent 676 117 by I G Farben 1in 1939 which described liquid polyepoxides. In 1943 P.
Castan2 filed US Patent 2 324 483, covering the curing of the resins with dibasic acids. This
important process was subsequently exploited by the Ciba Company. A later patent of
Castan3 covered the hardening of epoxide resins with alkaline catalysts used in the range 0.1–
5% This patent, however, became of somewhat restricted value as the
important amine hardeners are usually used in quantities higher than 5%.
In the early stage of their development the epoxy resins were used almost entirely for surface
coating and developments in this field are to a large extent due to the works of S.O. Greenlee
and described in a number of patents. These included work on the modification of epoxy resins
with glycerol4, the esterifiction of the higher molecular weight materials with drying
oil acids5 and reactions with phenolic6and amino resins.7
Before World War II the cost of the intermediates for the these resins (in most cases
epichlorohydrin and bis-phenol A) would have prevented the polymers from becoming of
commercial importance. Subsequent improvements in the methods of producing these
intermediates and improved techniques of polymerisation have, however, led to wide
commercial acceptance.
By the beginning of the 1980s world capacity for epoxide resins reached about 600 000 tonnes
per annum but at this time plant utilisation was only about 50–60%. Thus with a global
consumption of about 10 million tonnes per annum for thermosetting plastics, epoxide resins
had a share of about 3%. Western Europe and the USA each had about 40% of the market and
Japan a little over 10%. This situation has not greatly changed since then; but by the late 1990s
the world market for epoxide resins had risen to about 750 000 t.p.a.
About half of epoxide resin production is used for surface coating applications, with the rest
divided approximately equally between electronic applications (particularly for
printed circuit boards and encapsulation), the building sector and miscellaneous uses. In tonnage
terms consumption of epoxide–fibre laminates is only about one-tenth that of polyester
laminates, but in terms of value it is much greater.
Whilst the properties of the cross-linked resins depend very greatly on the curing system used
and on the type of resin, the most characteristic properties of commercial materials are
their toughness, low shrinkage on cure, high adhesion to many substrates, good alkali resistance
and versatility in formulation.
[J.A. Brydson, in Plastics Materials (Seventh Edition), 1999]

Epoxi

introdução

Epoxy resins are formed from an oligomer containing at least two epoxide groups and a curing
agent, usually either an amine compound or a diacid compound. A great variety of such resins
is on the market. There are many monographs on epoxy resins available.

hisotria

N. Prileschajew discovered in 1909 that olefins can react with peroxybenzoic acid to epoxides.3
Schlack claimed in 1939 a polymeric material based on amines and multi functional epoxides.4
Castan∗ , in the course of searching for dental materials claimed the preparation of bisphenol A
diglycidyl ether (DGEBA).5, 6 A similar material, but higher in molecular weight, was invented
by S. O. Greenlee.7 Epoxy resins came on the market around 1947. The first major intended
application was as coating material.

3.4 CURING

3.4.1 Initiator Systems

The epoxide group reacts with several substance classes. Only a few of the possible reactions
are used for curing in practice. Curing agents of epoxy resins can be subdivided into three
classes:

1. Compounds with active hydrogens,

2. Ionic initiators, and

3. Hydroxyl coupling agents.

The most commonly used curing reaction is based on the polyaddition reaction, thereby
opening the epoxide ring. The glycidyl group can be cured by amines and other nitrogen-
containing compounds such as polyamides. Many of the amines effect curing at room
temperature. This type of curing is called a cold curing. The reactivity of an epoxy compound
with an amine depends on the structure of the compounds. The relative reaction rates of the
secondary amine to the primary amine can be explained in terms of substitution effects.212
Anhydrides are active only at elevated temperatures. This type of curing is addressed as hot
curing.

Propriedades

Mechanical properties of epoxy resins can be correlated and traced back to the constituting
monomers. The mechanical properties of epoxy resins depend on the flexibility of the
segments and on the crosslinking density. Epoxy resins shrink in the course of curing less than
vinyl resins. It is important to distinguish between the shrinkage that occurs before gelling and
after gelling. Only a shrinkage that occurs after gelling results in residual stress in the final
product. Epoxy resins can exhibit several thermal transition regions, depending on the chemical
nature of the monomers. These transitions influence the curing. If a glass transition occurs
during curing at the temperature applied, the individual reactive parts of the pendant
molecules can no longer move sufficiently and the curing reaction freezes at this conversion.
However, raising the temperature effects further curing. Cycloaliphatic epoxy resins have a low
viscosity. The cured resins exhibit a high glass transition temperature. On the other hand, they
exhibit low break elongation and toughness because of their high crosslinking density. Epoxy
resins show good electrical properties. Of course, the electrical properties are affected by the
moisture content. On the other hand, the resins can be made electrically conductive, by metal
particles such as silver and copper. Epoxy resins adhere by forming strong bonds with the
majority of surfaces, therefore, an important application is in adhesives. Epoxy resins have
excellent resistance to a acids, bases, organic and inorganic solvents, salts, and other
chemicals.

3.6 APPLICATIONS AND USES

3.6.1 Coatings

The largest applications of epoxy resins are in coatings. Epoxy resin coatings have excellent
mechanical strength and adhesion to many kinds of surfaces. They are corrosion resistant and
resistant to many chemicals. Coatings find applications in various paints, white ware, and
automotive and naval sectors, for heavy corrosion protection of all kinds. Epoxy coating
formulations are available both as liquid and solid resins. Epoxy acrylic hybrid systems are used
as coatings for household applications, e.g., indoor and outdoor furniture and metal products.
Waterborne coatings are dispersions of special formulations of the resins with suitable
surfactants. These materials can be applied by electrodeposition techniques. Powders can be
applied as coatings by fluidizedbed techniques.

3.6.2 Foams

Epoxy resins can be fabricated to make foams. Foamable compositions have been described
from a novolak resin, an epoxy resin, and a blowing agent. Water can act as a blowing agent,
especially when higher density foams are required. Novolak resins are typically suspended in
an aqueous solution, that is the blowing agent. Encapsulated calcium carbonate or anhydrous
sodium bicarbonate are suitable blowing agents. Phosphoric acid is used to catalyze the
polymerization of resin and it also reacts with the carbonate core to generate a blowing gas to
form voids.

3.6.3 Adhesives

Approximately 5% of total epoxy resin production is used in adhesive applications. Epoxide

resin adhesives are formulated two-component systems that cure at room temperature, and as
hot curing systems in the form of films and tapes. Among others, acrylates are suitable
modifiers for epoxy adhesives.

3.6.4 Molding Techniques

Epoxy resins are used in all known reactive molding techniques. Non-reinforced articles can be
molded with aluminum molds. This is used for electrical coil covering, etc. In electronic
industries various embedment techniques, i.e., casting and potting, and impregnation are
important applications. Laminated sheets are used for the fabrication of printed circuit boards
in the electronics industry. Pultrusion and lamination are common techniques. Laminated
articles are also used in building constructions for concrete molds, honeycomb cores,
reinforced pipes, etc. Epoxy resins are superior to polyesters where adhesion and underwater
strength are important.

3.6.5 Stabilizers

for Polyvinyl Chloride Epoxy resins with monofunctional epoxy groups in the prepolymer are
effective in stabilizing polyvinyl chloride against dehydrochlorination during processing and
use, in comparison to tribasic lead sulphate. Lead-based stabilizers for polyvinyl chloride are
mostly banned and only allowed for a few applications. For example, the replacement of lead-
based stabilizers by epoxy stabilizers will improve the environmental toxicity of lead in water
flowing through PVC pipes.
Especialidades

Hyperbranched polymers

Hyperbranched polymers are highly branched macromolecules that are prepared through a
single-step polymerization process.

In composite materials, resins modified by hyperbranched polymers allow higher volume

fractions of fibers for producing void-free laminates in comparison to unmodified resins.

Liquid Crystalline Epoxide Resins

Liquid crystalline polymers exhibit a number of improved properties in comparison with

traditional plastics, in particular increased elastic moduli at high temperatures, reduced
coefficients of thermal expansion, increased decomposition onset temperatures, and reduced
solvent absorption.