REINFORCED PLASTICS SYMPOSIUM

SILANE
COUPLING AGENTS
SAMUEL STERMAN
JAMES G. MARSDEN
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Dual reactivity of silane coupling agents affords

chemical bonding to both the reinforcing agent t’
Ind. Eng. Chem. 1966.58:33-37.

and the resin base and, hence, provides for im-

provement of physical properties of resin-based
composites

coupling agents are used in awide range of

Silane
applications because of their unique ability to bond
polymers with dissimilar materials such as inorganic
oxides—i.e., silica and alumina. The bond thus formed
has good initial strength as demonstrated by failure of the
composite by polymer rupture, and the bond exhibits
excellent retention of strength even after severe environ-
mental aging. The siliceous matter or metal may be in
the form of fibers, particulate fillers, or massive structures.
Almost every type of organic polymer is compatible
with silane coupling agents, ranging from thermoset
resins through elastomers to thermoplastic resins. The
silane may be applied to the substrate as a pretreatment PHOTO COURTESY OF UNION CARBIDE SILICONES DIVISION

or, in many systems, the silane may be added to the resin Electron micrograph of Union Carbide A 1100 silane coupling agent
(72, 14) where it migrates to the substrate during normal on glass cloth shows an effective loading of less than 0.1% silane re-

mixing and application procedures. The application of
silane coupling agents to promote bonding has led to im-
proved physical properties of composite materials such as
filled and reinforced resins, filled elastomers, caulks for
adhesion of metal and glass, and resin-coated and painted
metal. Use of silane coupling agents in glass reinforced
plastics has resulted in a particularly notable improve-
ment of materials performance, and this application is
the subject of this paper.
Development of Coupling Agents
The earliest attempts to apply organic sizes to glass
fiber were carried out in the mid-1930’s by Slayter and
Thomas (4) and were directed primarily toward main-
maining after 4 hr. of water extraction treatment
taming the physical integrity of glass immediately subse-
quent to the drawing operation. A continuation of this
approach led to the development of the starch-oil or No.
630 size. This size not only gave protection to the fiber
after drawing but was also adequate for the weaving op-
eration.
Woven glass fabrics treated with the starch-oil size
were used as reinforcement for phenol-formaldehyde
resins as late as the early 1940’s. During this same
period, Hyde (4) and, shortly thereafter, Biefeld (4)
filed patent applications covering the use of silicon-based

VOL. 58 NO. 3 MARCH 1 966 33

 materials as components in sizes. These materials were
potentially capable of reacting with the glass surface, but
not with the matrix resin, and they contributed water
repellency and lubricity to the treated glass.
In the mid-1940'"s, three patent applications were filed
that laid the foundation for coupling agents as we know
them today. Steinman (4) filed on the use of methallyl
silicate, Te Grotenhuis (4) on vinylsiloxanes, and Goebel
and tier (4) on methacrylato chromic chloride. These
patents were all concerned with improving the adhesion
of matrix resins to glass fiber by the use of a coupling
agent.
Mechanism of Adhesion
The study of the theory of mechanism of adhesion has
been pursued from many viewpoints using both empirical
and classical methods. R. M. Vasenin (75), in a recent
article, attempted to classify most of the current theories
of adhesion. His classification is as follows: mechani-
cal, adsorption, diffusion, chemical, and physical. The
first three of these involve intermolecular forces, the
fourth involves chemical bonds, and the fifth, electrostatic
forces.
A recent view (79) is that the relative surface tension of
substrate and adherent is most important, so that an
adhesive of lower surface tension will spread and wet a
substrate of higher surface tension with good adhesion,
but the reverse is not true. A modification of this latter
view has been presented by W. D. Bascom (7). He
assumes the need of a silane coupling agent and proposes
the use of a surfactant to promote better wetting of the
glass fiber by the resin with subsequent reduction of voids
and an increase in strength.
One of the difficulties with much of the classical work
on adhesion is that it has been primarily concerned with
the strength of adhesion under room temperature condi-
tions. While this is an area of importance in glass rein-
forced plastics, of equal importance is the retention of
properties under more severe conditions. It is true that
no clear unequivocal proof for the mechanism of resin
adhesion to glass fiber has been demonstrated; and
while several of the suggested mechanisms may contribute
to adhesion, the majority of available evidence indicates
that the controlling mechanism in most cases is chemical
bonding of the resin to the glass through a coupling
agent. This is a plausible explanation of the good reten-
tion of properties exhibited by reinforced composites
containing silane coupling agents.
The Chemical Bridge
The dual reactivity of a coupling agent permits chemi-
cal bonding to both the glass fiber and resin, thereby
forming a chemical bridge across the glass-resin interface.
This type of bonding, at this critical region of the com-
posite, produces high mechanical strength and good reten-
tion of properties even under severe conditions. Mate-
rials capable of performing this function were introduced
in the mid-1940’s as methacrylato-chromium chloride
complexes and vinylsilanes. Since that time, a number
of new silane coupling agents have been developed which
34 INDUSTRIAL AND ENGINEERING CHEMISTRY
afford higher strengths in the resulting composites and
reactivity with a wider range of resins.
Specific functional requirements of a silane coupling
agent are discussed below.
Silane to Glass Bonding. Silanes bond chemically
to glass by the condensation of an active group on
silicone, such as OH, Cl, OR, or OAc, with a silanol on
the glass surface. Supporting evidence for this type of
reaction is difficult to obtain in practical commercial
systems. This conclusion is based on a large number of
empirical results and a limited amount of more basic
work.
Islinger (6) has studied the vapor phase chemisorption
of chlorosilanes on E-glass fibers and has concluded that
siloxane bonds are formed at the interface. Infrared
techniques have been used by White (77) to study the
reaction of chlorosilanes with high surface silicas. He
concludes that a reversible physical reaction takes place
at room temperature but that irreversible chemisorption
occurs at higher temperatures. Sterman and Bradley
(70) studied the tenacity of the silane glass bond by
aqueous and solvent extraction of silane-finished E-glass
cloth. Their w'ork indicated that some of the finish can
be removed by this technique, but that a tightly bonded
quantity of silicone remains equivalent to two to four theo-
retical monolayers.
Theoretically, one hydrolyzable group per silicon atom
W'ould be sufficient if the coupling agent could be applied
under anhydrous conditions. Obviously, this anhydrous
condition is not present in commercial systems where the
preferred application solvent is water. The use of silanes
in water results in the hydrolysis of the silane to a silanol,
which is the active species in bonding to glass. Com-
petitive with the condensation of coupling agent silanol
with a silanol on the glass surface is a condensation of
silanols on two coupling agent molecules. Therefore, the
use of a silane coupling agent having one or two hydro-
lyzable groups per silicon atom can result in the forma-
tion of di- or polysiloxanes having little or no ability to
bond to glass under the normal use conditions. For
these reasons and because of the solubility requirement
for aqueous application, all commercially used coupling
agents have three hydrolyzable groups per silicon atom.
The group on silicon that is hydrolyzed to form the
silanol has little effect on the performance of the coupling
agent in the resulting composite. It is, therefore, chosen
on the basis of handling ease, nature of hydrolysis by-
products (HC1, HOAc, or ROH), and, occasionally, by
ease or feasibility of synthesis.
Table I show's the essentially equivalent performance
of a series of trifunctional vinylsilanes in a standard
12-ply 181-style glass cloth reinforced polyester lam-
inate. This equivalency of performance of different
hydrolyzable groups is typical for many types of silanes
in a number of resin systems.
Resin Reactivity. The variety of organofunctional
groups presently available on silanes provides at least
one (and often several) coupling agent that is highly
reactive with all of the current thermoset resin systems. Commercially Available Thermoset Resins
Unlike the hydrolyzable groups discussed in the preced- Silane Coupling Agents of Common Use
ing section, these groups must be bonded to silicon in CH2==CHSi=
a hydrolytically and thermally stable manner. The
ch3o
chemistry and performance of coupling-agent types can
best be discussed in terms of specific resin systems, but the
CH2=C—C—OCH2CH2CH2Si= Polyester, diallyl
following list is representative of silanes that have proved phthalate
commercial utility in glass reinforced plastics and the CH2—CHCH2OCH2CH2CH2Si=
resin systems in which they are commonly used.
O
Polyester, epoxy,
TABLE I. EFFECT OF X ON FLEXURAL STRENGTH —CH2CH2Siss
OF ViSiXs FINISHED GLASS CLOTH REINFORCED
melamine
POLYESTER RESIN COMPOSITES» NH2CH2CH2CH2Si=
Flexural Strength H
CHi—CHSiXz P.S.I. X 70-*
X Dry 8-Hr. Boil NH2CH2CH2NCH2CH2CH2Síe= Epoxy, melamine,
—Cl 68.5 58.1 phenolic
—OCHs 65.0 59.0 The relative performance of a number of silanes in
—OC2H5 66.0 57.0 several resin systems is presented in the following sections,
—och2ch2och3 69.0 61.0 based on results obtained on woven glass cloth rein-
o forced laminates. This choice of composite allows
II
II the use of readily available heat-cleaned glass fabric
—oc—ch3 64.0 57.0
which offers good reproducibility and allows the effect
—N(CH3)2 72.2 57.8
of the silane to be studied free of possible interference by
»
Laminates constructed from 72 plies of glass and a general-purpose other materials. Woven glass reinforced laminates limit
polyester resin. the number of mechanical properties that can be mean-
ingfully tested and the use of a coupling agent as a finish
TABLE II. FLEXURAL STRENGTH OF VARIOUS GLASS does not evaluate its compatibility with and utility in a
REINFORCED POLYESTER RESIN COMPOSITES»
complete binder system.
Flexural
Glass Content, The absolute strength values obtained for a given resin
Type of Glass Strength,
Reinforcement Wt. % P.S.I. X 70-* system depend on the type as well as the amount of glass
Chopped strand mat 35-45 32 reinforcement used. Table II shows the strength values
Woven roving 55 40 obtained with various forms of reinforcements in a poly-
cloth ester resin (3). These values seem somewhat conserva-
Satin weave 62 55
tive when compared to the values obtained with the
Unidirectional roving 70 150
newer coupling agents, but they illustrate the trend of
»
General purpose polyester resin. type of reinforcement vs. mechanical strength.
It has been shown empirically that the relative per-
TABLE III. EFFECT OF R GROUP REACTIVITY ON formance of a series of coupling agents is essentially the
PERFORMANCE OF RSi= ON COUPLING AGENTS IN same regardless of the form of glass used. Therefore, it
GLASS REINFORCED POLYESTER RESIN LAMINATES»
appears that the evaluation of silanes in a woven glass
Flexural Strength, laminate system can provide meaningful design data if
P.S.I. X 70-z
it is realized that additional work is required to convert
Silane Finish Dry 8-Hr. Boil
such systems to a complete binder system.
112 (heat-cleaned cloth) 61.0 23.0
CH3CH2Si= 43.5 29.7 Matrix Resins
CH2=CHSi= 69.0 61.0
The choice of the matrix resin in all-glass reinforced
CHS O composites depends on a great many factors including

strength requirements, method of fabrication, electrical

1 II
CH2=C—C—OCH2CH2CH2Si== 87.0
»
Laminate constructed from 12 plies of glass and
polyester resin.
AUTHORS Samuel Sterman is Supervisor, Product Development,
Resins, Monomers, and Functional Fluids; and James G.
Marsden is Group Leader of the Product Development Group for
Resins and Monomers at Union Carbide's Silicones Division
Research and Development Laboratories in Tonawanda, N. Y.
79.0
requirements, use conditions (temperature, humidity),
a general-purpose and cost. Silane coupling agents have demonstrated sig-
nificant improvements in and retention of general me-
chanical and electrical properties in glass reinforced
composites of all thermosetting resins. In some of these
systems the improvement of a specific property is of equal
or greater importance than over-all performance improve-
ment. For example, the use of y-aminopropyltriethoxy-
silane as a finish in glass cloth reinforced phenolic resin
laminates produces dry and wet strength improvements

VOL. 58 NO. 3 MARCH 19 6 6 35

 TABLE IV. PERFORMANCE OF NONOLEFIN 1C SI LANES
AS COUPLING AGENTS FOR GLASS REINFORCED
POLYESTER RESIN LAMINATES"
Silane Finish
112 (heat-cleaned cloth)
but its more important contribution may be the retention
of strength at elevated temperatures.
The two thermoset resins that command the greatest
Flexural Strength,
P.S.I. X 7CM attention in the field of glass reinforcement today are
Dry 8-Hr. Boil polyester and epoxy resins. Polyester resins comprise
61.0 23.0 a major part of the reinforced plastics market today and

CH2—CH—CH2OCH2CH2CH2Si= 76.0 58.0 epoxy resins represent the highest strength systems.
\ Z Polyester Resins. The free radical initiated polym-
O erization of unsaturated polyester resins lends itself
to modification of the resin by copolymerization with
71.0 58.0 other materials of appropriate reactivity. Indeed, the
oc(¡jrCH‘CH‘Si· commercial form of most polyester resins contains a
°
Laminates constructed from 72 plies of glass and a general-purpose reactive monomer, such as styrene, that serves to reduce
polyester resin. the viscosity of the resin and to copolymerize during the
cure. Silane coupling agents can react with unsaturated
components of polyester resins by the same copolymeriza-
TABLE V. EFFECT OF SILANES ON THE MECHANICAL tion mechanism.
PROPERTIES OF 181-TYPE GLASS CLOTH REINFORCED
EPOXY RESIN LAMINATES" Current theories of double bond polymerization pre-
dict that optimum copolymerization is obtained from
Flexural Strength,
P.S.I. X 70"3 monomers that have similar orders of reactivity. The
Silane Finish Dry 72-Hr. Boil relative reactivity of monomers may be estimated from
112 (heat-cleaned
cloth) 78.0 29.0 q-e values derived by Schwan and Price (9). In this sys-
90.0 54.0 tem, q represents the resonance stabilization of a radical
NH2CH2CH2CH2Si=
by adjacent groups and ranges 0 to —4.4 kcal./mole,
while e indicates the polarity of monomer radical forming
ocJ+T^011·*- 101.0 66.0
the end of a grow-ing chain. These e values range from
CH2—CHCH2— OCH2CH2CH2Si= 87.0 56.0 —
0.61 X 10-10 to +0.76 X 10-10 in electrostatic units.
\ Z The results obtained using silanes of varying reactivity
o
as finishes for glass cloth reinforced polyester laminates
(HOCH2CH2)2NCH2CH2CH2Si== 96.0 65.0
are shown in Table II. Because ethyl silane has no
Laminates constructed from 12 plies of glass and
°
an amine-hardened double bond reactivity, it is ineffective. Vinylsilane is
glycidyl ether-type epoxy resin.
relatively unreactive and produces marginal improve-
ment in dry strength and good wret strength, while the
highly reactive methacryloxypropylsilane produces ex-
TABLE VI. EFFECT OF SILANE FINISHES ON ME- cellent dry and wet values. Plueddmann et al. (S) have
CHANICAL PROPERTIES OF GLASS CLOTH RE-
INFORCED THERMOPLASTIC RESINS" evaluated a number of silanes as finishes in glass cloth
reinforced polyester resin and compared the results with
Flexural Strength
% Improvement Over ControD the q-e values of Schwan and Price (9). Good agree-
Resin Silane Dry Wet° Temp.,
0
F. ment is obtained between the results predicted from q-e
CH3 O values and those actually obtained. It would appear
\ ¡1 from these results that good coreactivity with styrene is
Polystyrene ch2=c—c— 100.0 95.0 70.0 (200) more important than coreactivity with the maleate por-
och2ch2ch2-
Si= tion of the polyester resin.
(HOCH2CH2)2- 83.0 100.0 There is another group of silanes that does not contain
Polyvinyl
chloride nch2ch2ch2- any double bonds, yet is effective as coupling agents in
81
polyester resin systems. Many of these compounds are
Nylon (HOCH2CH2)2- 110.0 160.0 150.0 (400) believed to interact with the resin by chain transfer (76).
nch2ch2ch2- Two such materials are -glycidoxypropyltrimethoxy-
Si=
silane and /3-(3,4-epoxycyclohexyl)ethyltrimethoxy-
Polycar- nh2ch2ch2ch2- 30.0 60.0 20.0 (250)
bonate Si= silane. They are about as effective as vinylsilanes as
finishes for glass reinforced polyesters. Typical values
Polymethyl nh2ch2ch2ch2- 45.0 90.0 25.0 (200)
meth- SlE= are shown in Table IV.
acrylate Epoxy Resins. The silane coupling agents that are
Acrylo- ch2—chch2- 145.0 228.0 145.0 (150) effective in epoxy resins can be divided into two types:
nitrile- \z (1) those that have the same chemical reactivity as the
buta- o
diene— OCH2CH2CH2- resin and react with the hardner in the same way,
styrene Si= such as the epoxysilanes, and (2) those that are chemi-
cally similar to the hardner and react with the epoxy
°
Laminates contain 11 plies of 181-type glass cloth, 40-45% resin.
6
Control is heat-cleaned glass cloth reinforcement. c Immersion for 16 groups of the resin, such as the aminoalkylsilanes.
hr. in water at 120° F. Neither type is preferred over the other on a general

36 INDUSTRIAL AND ENGINEERING CHEMISTRY

basis, although in a specific resin there may be unex-
pectedly wide variations in results. Table V shows the
results obtained when silanes of both types were used as
finishes in an amine-hardened glycidyl ether bisphenol-
A-type epoxy resin.
New Systems
The foregoing discussion has been directed primarily
at glass reinforced thermosetting resins because they
represent the bulk of the present market. There are,
however, two new areas that are relatively small now but
represent tremendous growth potentials. These are
glass reinforced thermoplastics and elastomers.
Thermoplastics. Thermoplastics offer many attrac-
tive properties including relatively low cost, great
versatility of chemical type, and ease of fabrication into
end-use products. Several resins have been limited in
structural and engineering applications because of low
mechanical properties, especially modulus. These de-
ficiencies can be overcome by the use of glass fiber
treated with silane coupling agent without adversely
affecting the processing characteristics of the polymers.
The mechanism of silane-resin interaction has been
reported on by Sterman and Marsden {11), and while it
is not completely understood, empirical results indicate
that, in at least some systems, chemical coreaction sim-
ilar to that discussed for thermoset resin is operative.
In the case of polystyrene, those silanes capable of
undergoing addition polymerization or chain transfer
reaction perform best. Processing temperatures of poly-
styrenes are such that chain scission and free radical gen-
eration can occur, and it is suggested that the reaction of
the silane is with these active polymer fragments.
Nylon, on the other hand, is a “reactive” thermo-
plastic. The silanes that are the most useful with nylon
are capable of reacting either with the amido hydrogen
of the polymer or by rearrangement of the amide linkage.
However, many anomalies remain. Table VI shows
the results obtained by reinforcing a series of thermo-
plastic resins with 181-style glass cloth with and without
silane coupling agent. These results show that the in-
corporation of glass typically doubles the flexural strength
of a given resin, while the use of glass with the proper
coupling agent doubles this value again. Also of con-
siderable interest is the retention of mechanical strength
at higher temperature produced by the use of coupling
agents. Composites containing glass and silane typically
have flexural strengths at 200° F. and higher, equivalent
to the flexural strength of composites without silane at
room temperature. This can possibly increase the useful
temperature range of many thermoplastics.
While these results were obtained with woven glass
cloth, and the market appears to be moving in the direc-
tion of chopped glass reinforcement, they are useful in
indicating the kind of improvement that is possible.
Obviously, there is need for much additional work, par-
ticularly in the systems closer to the conditions of actual
use.
Elastomers. The use of glass, with its low elonga-
tion and high tensile strength, as a reinforcement for
rubber has been a long sought goal. However, the lack
of adhesion of rubber to glass and the destructive seif-
abrasion of the glass fibers have prevented realization of
this goal. Recent developments appear to have over-
come these problems and offer the promise of glass rein-
forcement in a variety of rubber mechanical goods, in-
cluding tires.
Marzocchi and Lachut (7) reported the development of
a rubber-impregnated glass yarn suitable as reinforcement
for several rubber stocks. The use of silane coupling
agents to improve the adhesion of a variety of rubbers
to glass was reported by Vanderbilt and Clayton {13).
This work states that the use of the proper coupling agent
produces excellent bonding to glass for 11 different rub-
ber stocks. In five types of rubber the bonding to glass
was strong enough to result in cohesive failure of the
rubber on rupture. A companion paper by Clayton and
Kolek {2) describes the application of these results to
binder compositions and yarn constructions necessary to
optimize results in a practical continuous process.
While the final and optimum glass reinforcement for
rubber has not been developed, great progress has been
made and it appears that silane coupling agents will be
an important component of the final system.
In addition to glass reinforced systems, silanes are
applied in some filled elastomers. They are particularly
effective in mineral-filled compositions of the newer
ethylene-propylene copolymers and terpolymers. Fusco
(5) has reported on the tensile strength improvements
obtained by the use of vinyl silanes in silica-filled EPR,
and Wolfe and Roche {18) describe the retention of elec-
trical properties under wet conditions and the higher
modulus with vinylsilanes in clay-filled EPT.
REFERENCES
(1) Bascom, W. D., “Some Surface Chemical Aspects of Glass-Resin Composites;
Part I—Wetting Behavior of Epoxy Resins on Glass Filaments,” 20th Annual
SPI Preprints, February 1965.
(2) Clayton, R, E., Kolek, R. L., Rubber World 151 (5), 95 (1965).
(3) De Dani, A., “Glass Fibre Reinforced Plastics,” Interscience, New York, 1960
(4) Eakins, William J., “Glass/Resin Interface: Patent Survey, Patent List and
General Bibliography,” Plastics Technical Evaluation Center, Picatinny Arsenal,
Dover, N. J., September 1964.
(5) Fusco, J. V., “New Cures for EPR,” Rubber World, pp. 48—54 (February 1963),
(6) Islinger, J. S., et al., “Mechanism of Reinforcement of Fiber-Reinforced Struc-
tural Plastics and Composites,” WADC Technical Report 59-600. Part I.
(7) Marzocchi, A., Lachut, F. J., “Glass Fiber for Reinforcement,” Rubber World,
pp. 62-64 (December 1962).
(8) Plueddmann, E. P., “Evaluation of New Silane Coupling Agents for Glass
Fiber Reinforced Plastics,” 17th Annual SPI Preprints, February 1962.
(9) Schwan, T. C., Price, C. C., J. Polymer Sci. XL, 457-68 (1959).
(10) Sterman, S., Bradley, . B., “Evaluation of Existing and Development of New
Analytical Procedures for Use in the Analysis of Finishes for Glass Fabric Ma-
terial,” WADD Technical Report 60-318, (April 1960).
(11) Sterman, S,, Marsden, J. G., “The Effect of Silane Coupling Agents in Im-
proving the Properties of Filled or Reinforced Thermoplastics,” 21st Annual
SPE Preprints, March 1965.
(12) Sterman, S., Marsden, J. G., “Silane Coupling Agents as ‘Integral Blends’ in
Resin Filler Systems,” 18th Annual SPI Preprints, February 1963.
(13) Vanderbilt, B. M., Clayton, R. E., Ind. Eng. Chem. Prod. Res. Develop.
4 (1), 18 (1965).
(14) Vanderbilt, B. M., Clayton, R. E., “Premixes Based on Hydrocarbon Resins,”
16th Annual SPI Preprints, February 1961.
(15) Vasenin, R. M., Adhesives Age 8 (5, 6), 18—22 (1965).
(16) Wallace, T., Gretter, R., “Free Radical Rearrangement of Epoxides,” Ab-
stract, 142nd ACS Meeting, 65Q No. 118.
(17) White, T. E., “A Study of the Reactions of Surface Hydroxyl Groups of Silica
by Means of Infra-Red Spectroscopy,” 20th Annual SPI Preprints, February
1965.
(18) Wolfe, J. R., Jr., Roche, I. D., “Factors Influencing the Electrical Properties
of Ethylene-Propylene Terpolymer Vulcanízales,” presented at 145th Meeting
AGS, September 1963, New York.
(19) Zisman, W. A., “Surface Chemistry of Glass Fiber Reinforced Plastics,”
19th Annual Meeting SPI, February 1964.
VOL. 58 NO. 3 MARCH 1 966 37