2731 Bartram Road, Bristol, PA 19007

800-541-0559
www.unitedchem.com

Formulating
Silicone Adhesives
Gels and Sealants
John H. MacMillan Ph .D.
Ph.D.

1
 Silicone Technology is a wide and mature science spanning the gamut of
materials from commodity lubricants to high performance defense coatings. This paper
will give an overview of the basic technology and classes of silicone fluids. Cure
types,basic formulations,applications,catalyst types and blending methods will all be
discussed. United Chemical Technologies (UCT) is a major manufacturer of high
quality silicones. During the discussions the catalog numbers for the corresponding
UCT product will be introduced when appropriate. In many chemical reactions the
reacting groups are color coded for clarity.
For those wanting additional detail on industrial manufacturing methods for
bulk silicones, the Kirk Othmer Encyclopedia (Ref 1) is an excellent guide. More recent
advances in high performance silicone materials are reviewed by Brook (Ref 2) in an
excellent text.
Before we discuss basic silicone structures and curing mechanisms,it is
necessary that the reader be familiar with simple silicone structural terminology and
other common industrial terms. Figure 1 and Table 1 review the structural features
and industrial terms commonly encountered.

2
 Figure 1
Silicones Me

Si O D unit
INTRODUCTION Me

( )
CH3
CH3 CH3
(Me 3 SiO) M unit
CH3 Si O Si O Si CH3

CH3 CH3 CH3

n O

Me Si O T unit
O

O Si O Q unit
O
3
 Table 1 Common Terms

Basic Terminology
Cure: Crosslink a liquid polymer system to where it forms an elastic gel (
sets up and solidifies).

Addition Cure: Platinum Catalyzed,

Examples: PC072, PC075, PC085

Condensation Cure: Tin, Zinc Catalyzed,

Examples: PC040, PC050

Peroxide Cure: Peroxide Catalyzed,

Example: PC010

RTV : Room Temperature Vulcanizabe (curable) system,

Usually an addition or condensation cure resin.

4
 The most basic class of silicones is the conventional inert
polydimethylsiloxane series. They are trimethylsiloxy terminated and possess no
reactive chemical functionality. These fluids find utility as plasticisers, lubricants,
defoamers, in high temperature baths, and cosmetic products. Typical service
temperatures are to 250° celsius. UCT offers the full line of these materials from very
low to gum like viscosities. Table 2 is a compilation of this series.

5
 Table 2
Specific Refractive Flash Pour
Product# Viscosity Gravity Index Point Point

Polydimethylsiloxanes Trimethylsiloxy Terminated CAS No. (63148-62-9)

PS034 .65 .761 1.3750 -1° -68°

PS035 1.0 .818 1.3825 38° -85°

Conventional
PS036 1.5 .853 1.3880 63° -75°
PS037 2.0 .873 1.3900 79° -80°
PS037.5 3.0 .898 1.3935 100° -70°
PS038 5.0 .918 1.3970 135° -65°
PS038.5 7.0 .930 1.3980 150° -65°
PS039 1.0 .935 1.3990 163° -65°
PS039.5 2.0 .950 1.4000 232° -65°

Silicone PS040
PS041
PS041.2
5.0
100
200
.960
.966
.968
1.4015
1.4025
1.4030
285°
315°
315°
-65°
-65°
-60°
PS041.5 350 .970 1.4031 315° -60°
PS042 500 .971 1.4033 315° -55°
PS043 1,000 .971 1.4034 315° -50°

Fluids
PS044 5.000 .973 1.4035 315° -48 °
PS045 10,000 .974 1.4035 315° -48°
PS046 12,000 .974 1.4035 315° -46°
PS047 30,000 .976 1.4035 315° -43°
PS047.5 60,000 .976 1.4035 315° -42°
PS048 100,000 .977 1.4035 321° -41°
PS048.5 300,000 .977 1.4035 321° -41°
PS049 600,000 .978 1.4035 321° -41°
PS049.5 1,000,000 .978 1.4035 321° -39°
PS050 2,500,000 .978 1.4035 321° -38°

Branched Polydimethylsiloxane CAS No. (68037-74-1)

PS052 50 cSt. 0.97 1.4030 279° -85°

Polydimethylsiloxane Emulsion
PS053.5 30% silicone antifoam in water.
Used to defoam biological mixtures by adding 2-50 mg/liter.

6
 Although conventional fluids are stable thermally to 250° celsius, many high
performance coating applications require higher temperature stability. Introduction of
aromatic groups (phenyl rings) raises thermal stability to greater than 300° celsius. The
indices of refraction and the rigidity of cured resins are also increased over
conventional fluids. Figure 2 describes these materials in more detail. They are
available with curable vinyl terminals at the polymer terminals and containing
variable viscosities and mole percentages of phenyl groups. The most utilized UCT
product line of curable aromatic silicones is the PS732-PS793 series of vinyl terminated
fluids.

7
 Figure 2 Thermal Silicones

( )( ) ( )
CH3 CH3 CH3 CH3 CH3

CH3 Si O Si - O Si O Si CH 3 CH3 Si O Si - O Si CH3

CH3 CH3 CH3 CH3 CH3 n CH3

m n

The most commonly used high temperature silicone fluids are the phenyl containing siloxanes. The phenyl
group is usually incorporated in two ways. It may be introduced as a phenylmethylsiloxane or a
diphenylsiloxane. As phenyl groups replace methyl groups in a polysiloxane, several changes occur.
Lubricity, oxidation resistance, thermal stability and shear resistance are enhanced. For polymethylphenyl
siloxane the service temperature is -55º to 290º C.
In a closed oxygen-free system the polymethylphenylsiloxanes are stable for thousands of hours at 230ºC. The
materials are used in heating baths. The tetrachlorophenyl-dimethylsiloxane copolymer is well-suited for metal
to metal lubrication. They are also used as base oils for high temperature lubrication.

The phenyl group also introduces rigidity in the silicone chain. When substitution exceeds 75 mole percent the
polymers are solid. Diphenylhomopolymers demonstrate liquid crystal behavior between 250ºC and 500ºC.
Silanol terminated polydiphenylsiloxane is a glassy solid useful as a resin intermediate. The refractive index
also increases with phenyl concentration. At 15-20 mole percent phenyl concentrations the refractive index
matches that of amorphous silica and transparent compounds may be prepared.

8
Figure 2 Thermal Silicones (Contd)
At low phenyl concentrations these fluids are dielectric coolants. They also function in place of
standard dimethylfluids where extended service temperature is necessary. One special class of phenyl
fluids are the dimer, trimer and tetramer fluids (see section on diffusion pump fluids). Because the
introduction of a moderate concentration of phenyl groups also improves lubricity, members of the
family have found utilization as lubricants for instruments and timing devices. High phenyl content
fluids are also used as heat transfer media and chromatographic stationary phases. The
polymethylphenylsiloxanes exhibit good radiation resistance by remaining serviceable up to 200
megarads exposure.

The compressibility of phenyl containing siloxanes is reduced in comparison to dimethyl fluids.

Polymethylphenylsiloxane has a compressibility of 5.5% at 20,000 psi. Dimethyl phenylmethylsiloxane
copolymer has a compressibility of 6.5% at 20,000 psi.

9
 Silicone fluids typically show low solubility in petroleum oils. Addition of
long hydrocarbon chains on the backbone increases solubility in these oils and also the
lubricity. The fluids are then of utility as oil well defoamers and cosmetic lubricants.
These fluids are described in detail in Figure 3. The UCT product line is shown in
Table 3.

10
 Figure 3 Polymethylalkylsiloxanes
CH3

( )
CH3 (CH2 )m CH3

CH 3 Si O Si O Si CH3

CH3 CH3 n CH3

Silicones can be modified to impart organic characteristics to their inorganic structure, which makes them more compatible
with organic materials such as petroleum oils and synthetic resins.

Replacement of a methyl group with longer chain aliphatic moieties produces silicones with properties that more closely
resemble hydrocarbons. When compared to polydimethylsiloxanes, methylalkylsiloxanes have greatly improved lubrication
characteristics and greater compatibility with organic materials. The fluids have higher viscosity-temperature coefficients,
lower compressibility and decreased oxidation stability. This last characteristic has been substantially overcome by
compounding the fluids with stabilizers such as BHT or DSTDP or copolymerizing them with aromatic siloxanes as internal
stabilizers.

Lubrication properties are optimized when the alkyl unit is at least eight carbons long. Polymethyloctylsiloxane is useful as a
lubricant for soft metals such as aluminum, zinc and copper. It is also useful as a rubber or plastic lubricant especially when
mated against steel or aluminum. Polymethyloctylsiloxane is also employed in aluminum machining operations.

With increasing length of the alkyl substituent the melting point increases. As the pour point of the alkyl modified siloxanes
increases, the resemblance and compatibility with hydrocarbon oils increase. Polymethyltetradecylsiloxane has a high
degree of hydrocarbon compatibility and maintains liquid behavior at room temperature. Polymethyloctadecylsiloxane is a
creamy solid with a melting point just above room temperature. It is compatible with paraffin wax. It is used as a component
in thread and fiber lubricant formulations and as a process aid in melt spinning. Methylalkylsiloxane reduces the surface
tension of many non-aqueous solvents allowing them to act as wetting and leveling agents in coating and ink formations.

11
 Table 3 Polymethylalkylsiloxanes

Prod# Description [CAS#] Visc.

Visc. SG Rl PP ST

PS130 Polymethyloctadecyl- 250-300 0.89 1.443 50° 39.5

siloxane [68607-75-0]

PS130.5 (70%) Dimethyl (30%) 250-350 0.892 1.44

Methyloctadecyl Siloxane
Copolymer

PS134 Polymethyltetradecyl- 1500-3000 0.89 1.455

siloxane [76684-67-8]

PS134.5 (70%) Dimethyl (15%) 150-200 0.916 1.43

Dodecyl (15%) Tetradecyl
Siloxane Terpolymer

PS134.8 (50%) Dimethyl (25%) 150-200 0.903

Dodecyl (25%) Tetradecyl
Siloxane Terpolymer

PS135 Polymethylhexadecyl- 0.88 1.451 35°

siloxane (50)

PS136.5 (35-40%) 500-600 0.93 1.437

Methyloctyl- (3-4%)
Vinylmethyl (56-64%)
Dimethylsiloxane Terpolymer

PS140 Polymethyloctylsiloxane 600-1000 0.91 1.445 -50° 30.4

PS141 Propylmethyl Homopolymer 200 1.43

Vinyldimethyl Terminated

12
 The most outstanding thermal stability and solvent resistance is imparted by
the inert fluorosilicones (see description in Figure 4). Indices of refraction are
considerably lower than for conventional fluids. See the UCT product catalog for more
information. Curable versions of this series are UCT catalog number PS184.5, a silanol
fluid, and PS185, a vinyl fluid. The curing chemistries for these classes of silicone will
be described later.

13
 Figure 4 F

Fluorosilicones
F C F

CH 2

( )
CH 3 CH 2 CH 3

CH 3 Si O Si O Si CH 3

CH 3 CH 3 n CH 3

Many advantages of fluorocarbons and silicones are combined in fluorosilicones. Fluorination of compounds usually
enhances their thermal stability. In the case of the polysiloxanes, fluorination usually begins at the gamma position of an
alkyl chain. Due to the electropositive nature of silicon, fluorination at the alpha and beta positions generally results in poor
thermal stability. As a consequence, commercial fluorosilicones are currently limited to trifluoropropyl substituted methyl
fluids. The materials are useful from -40 to 285° C in a wide range of aggressive service environments. The fluids are
excellent lubricants under extreme pressure conditions. Trifluoropropylmethylsiloxane fluids have a compressibility of
7.45% at 20,000 psi. They are not miscible with fuel or oils.
Trifluoropropylsilicone fluids have achieved a number of unique applications due to their chemical and solvent resistance,
lubricity and thermal stability. They have been employed in mechanical vacuum pumps where moisture and high
temperature oxygen exposure is encountered. They are used as defoamers in processes involving solvent-based wash
solutions. They have been employed as grease bases when formulated with thickeners such as PTFE. Their high density
has led to their use as flotation media for inertial guidance systems. Longer chain fluorinated silicone fluids demonstrate
increased solvent resistance and have been employed as partitioning phases in gas chromatography. Acoustic velocities
in fluorosilicones are lower than in conventional silicones, allowing sonar lens development.
Copolymers of fluoroalkylsiloxanes with dimethylsiloxanes exhibit improved boundary lubrication properties while
maintaining excellent solvent and chemical resistance. They also form high performance greases when thickened with
fluoropolymer powders. Such greases have been used in sealed transmissions and other extreme pressure applications.
Other fluorocopolymers have been employed as lubricants for electrical contacts and precision timing devices.

14
 Silicone fluids typically show limited water solubility and must be
emulsified. To impart such solubility long chain polyethylene oxide or polyethylene
oxide/polypropylene oxide chains are grafted on to the silicone backbone. Figure 5 and
accompanying text describes this series. See the UCT product catalog for more
information. Available materials are non curable and are typically used as surfactants
or defoamers.

15
 Figure 5 Hydrophilic Silicones

Hydrophilic silicones are non-reactive fluids that have been modified to give them slight to complete solubility in water.
Their chemical description is polyalkylene oxide modified polydimethylsiloxanes. The typical structure of a hydrophilic
silicone is:

(CH2)3 (OCH2CH2)X OCH3

( )( )
CH3

(CH3)3SiO Si - O Si O Si(CH3)3

CH3 m CH3 n

Polydimethylsiloxanes prepared as copolymers with alkene oxides are widely used as surfactants. By altering the
amounts of alkene oxide (hydrophile) and dimethylsiloxane (lipophile) the desired surfactant properties may be balanced.
The higher the alkene oxide content the higher the hydrophilicity. Materials with ethylene oxide contents 75% and higher
are freely soluble in water, as well as other commonly used organic solvents such as methanol, isopropanol, acetone,
xylene, and methylene chloride. PS071 is a low molecular weight water soluble fluid that is used in lithographic and
photographic plates to facilitate wetting and spreading of developers. It is also used as an anti-fogging treatment for glass
and plastic optical surfaces. PS073 is used as an anti-foam in water-based coatings. PS072 is a water soluble
copolymer employed as a lubricant for fibers and plastics. It also imparts anti-tack and mar resistant qualities coatings.
PS071, PS072 and PS073 all have excellent long term hydrolytic stability. PS071 and PS072 provide slip in flexographic
and gravure inks. PS073.5 reduces the static charge generation of fiber substrates and has been incorporated into rolling
oil formulations for metal drawing and stamping. The coefficient of thermal expansion is 8 x 10°C.

16
 The silicone fluids described to this point are non reactive, that is, they are
not readily cured to solid elastomers. Table 4 summarizes many of the uses of these
materials. Usually applications involve adding the liquid to a formulation as a
plasticiser or stabilizer. Uses also include lubricants in machinery and high
temperature bath oils.

17
 Table 4 Silicone Fluid Selection Guide

Function Application Fluid Class

Performance Surfactant/Antifoam Conventional (Low Viscosity)
Additive Hydrophilic or
Fluorosilicone

Hydrocarbon Compatibility Organic Compatible

Flow Control Conventional (Low Viscosity)

Wetting Hydrophilic

Radiation Resistance Thermal

Acoustical Sonobuoy Conventional (Low Viscosity)

Sound Coupling Fluorosilicone

Optical Optical Coupling Fluid Thermal

Anti-fog Agent Hydrophilic

Heat Transfer Heat Treatment Bath Thermal

Constant Temperature Bath Conventional (Intermediate Viscosity)

or Thermal

Temperature Measurement Conventional (Intermediate Viscosity),

Device Thermal or
Fluorosilicone

Closed Loop Heating Thermal

Refrigerated Systems Low Temperature

18
Silicone Fluid Selection Guide (contd)
Function Application Fluid Class

Working Media Fluid Clutch Conventional or

Thermal
Smart Fluids Conventional or
Organic Compatible
Hydraulic Fluid Low Temperature,
Conventional or
Thermal

Brake Fluid Conventional (Intermediate Viscosity)

Shock Absorber Conventional,

Thermal

General Damping Conventional,

Thermal or
Fluorosilicone

Meter Damping Conventional

Timing Devices Conventional or

Thermal

Magnetic Amplifier Thermal

Diffusion Pump Thermal (Oligomeric)

19
Silicone Fluid Selection Guide (contd)
Function Application Fluid Class
Lubrication Mold Release Conventional
Organic Compatible
Emulsion

Aluminum Machining Organic Compatible

and Extruding

Die Casting Organic Compatible

Ball Bearing and Gear Organic Compatible

Lubrication Thermal or
Fluorosilicone

Airborne Radar Low Temperature

Rubber/Plastic Contact Conventional or

Organic Compatible

Fiber/Plastic Contact Hydrophilic

Metal/Plastic Contact Organic Compatible

Thermal or
Fluorosilicone

Metal/Metal Contact Organic Compatible

Thermal (Chlorophenyl)

Grease Conventional,
Thermal or
Fluorosilicone
20
Silicone Fluid Selection Guide (contd)
Function Application Fluid Class

Dielectric Transformers, Rectifiers Conventional

Coolant/Fluid Capacitors

Magnetron Conventional
Thermal

Dielectric Impregnation Conventional

of Porous Substrate

21
 The basic feed stocks employed in homogeneous platinum catalyzed silicone
resin systems are vinyl fluids, whose structural types are outlined in Figure 6, and
hydrosilicones, outlined in Figure 8. Vinyl fluids are typically blended in the “ base” or
“part A” side while hydrosilicones are put into the “crosslinker” or “part B” side. The
A side and B side convention is sometimes violated and inverted by major turn key
formulation manufacturers. Technical datasheets and MSDS sheets should be reviewed
for unequivocal determination of each sides identity.

United Chemical Technologies is also a major manufacturer of these silicone resins.

Table 5 and Table 6 list these materials and their most common applications.

22
 Figure 6 Vinyl Fluids

( )
Me Me Me

CH 2 CH Si O Si O Si CH CH 2

Me Me n Me

Vinyl Terminated Siloxanes

CH 2

( )( )
Me Me CH Me

Me Si O Si O Si O Si Me

Me Me m Me n Me

Vinyl Functional Copolymers

23
 Vinyl functional silicones are commonly cured by two routes. The “addition
cure” route involves adding a silicon hydride functional group to a terminal “vinyl”
double bond. The catalyst is a homogeneous platinum catalyst of the Karstedt (Ref 4)
type. These cures can be either at room or high temperature, depending on the activity
of the catalyst. We will describe these platinum catalysts in more detail later (see
Figure 15).

The second route involves cures catalyzed by a high temperature radicle

induced polymerization , initiated via decomposition of an organic peroxide. Both of
these routes are illustrated in Figure 7. In a later section we will discuss in detail the
advantages of the platinum catalyzed route over the peroxide route for curing silicone
resins.

24
 Figure 7 Cure of Vinyl Silicones
Si-CH = CH2
VINYL FUNCTIONAL SILICONES
O CH3 O CH3

Pt
O Si H + H2C=CH Si O O Si CH2 CH2 Si O

CH3 CH3 CH3 CH3

addition cure

O CH3 O CH3
RO• •
O Si CH3 + H2C=CH Si O O Si CHCH2 CH2 Si O
- ROH
CH3 CH3 CH3 CH3

peroxide activated cure

25
 The complete product line of United Chemical Technologies vinyl silicones is
listed in Table 5. PS437 through PS449.5 are di-functional at the the polymer
terminals ( the ends). These fluids are the base resins incorporated into the “Part A” of
two part silicones employing platinum catalysis. These formulations will be described
and illustrated in later sections. PS422 through PS488 are poly (>2) functional in
vinyl, either in the backbone or at the terminals. These resins are additives to the di -
functional fluids in Part “A” to impart greater hardness and tear strength.
“Q” resins (see Figure 1 nomenclature) are also used as additives to
improve tear strength and abrasion resistance. PS496 and PS498 are representative
members of this class offered by UCT.

PS437 and PS925 are efficient cure retarders for the platinum based
addition cure silicone curing systems.

26
 Table 5 Vinyl Fluids
Description (CAS #) Viscosity Weight % Vinyl SG Primary Use in RTV
Addition Cure Systems

Polydimethylsiloxane, Vinyldimethyl Terminated CAS No. [68951-99-5]

PS437 2-3 10-12 0.919 Cure moderator or as an inhibitor
PS438 4-6 7-9 0.93
PS441 100 12-14 0.97

PS441.2 200 0.97 Base polymer or part of

PS442 500 0.97 Polymer blend of liquid RTV

PS443 1000 0.18-0.26 0.97 systems

PS444 5000 0.97

PS445 10,000 0.97 High strength RTV systems

PS447.6 65,000 0.03-0.07 0.97

PS448 100,000 0.97

PS448.5 165,000 0.97

PS449 600,000 0.98 Main polymer for High

PS449.5 1,000,000 0.01-0.02 0.98 Consistency RTV systems

Polydimethylsiloxane, Monovinyl, Mono n-Butyldimethyl Terminated

PS491 10,000 0.05-0.1 0.98

27
 Table 5 Vinyl Fluids(CONTD)
Description (CAS #) Viscosity Weight % Vinyl SG Primary Use in RTV
Addition Cure Systems
Vinyldimethyl, Dimethylsiloxane Copolymer, Trimethylsiloxy Terminated CAS No. [67762-94-1]
PS422 250 1.0 Peroxide or Pt cure
PS424 1000 7-5
PS426 1000 1.0

Vinyldimethyl, Dimethylsiloxane Copolymer, Vinyl Dimethyl Terminated

PS493 1000
Divinylmethyl Terminated, Polydimethyl Siloxanes
PS483 1000

PS488 100,000

Vinyl Q-resin Dispersion

PS496 4000-6000 1.02 High strength RTV systems

PS498 165,000 1.02

Vinylphenylmethyl Terminated Dimethyl Siloxanes

PS463 1000

T-structure Polydimethylsiloxane with vinyl at branchpoint

PS408 50-75

T-structure Polydimethylsiloxane with vinyl at branch terminus

PS410 300-500 0.99

Cyclic Vinylmethyl, Dimethyl Siloxanes CAS No. [2554-06-5]

PS925 3-7
28
 The other component of the two part RTV platinum curable
silicones is a hydrosilicone crosslinker (see Structure 1 of Figure 8).
This crosslinker typically contains hydrosilicone in the backbone of
the polymer. Silanol fluids (see Structure 2 of Figure 8) may also be
formulated with hydrosilicones and a tin or zinc catalyst. Hydrogen
gas results which blows the polymer matrix on curing. These blown
silicone systems are useful in cushioning materials.

The other major use of hydrosilicones is as selective reducing

agents (Ref 3). Equations for these chemistries are shown in Figure 9.

29
 Figure 8 Structure 1

( )
CH3 H CH3

CH3 Si O Si O Si CH3

CH3 CH3 CH3

n
Organo-Hydrosiloxane Polymers and Copolymers

( )
Me

HO Si O H Structure 2
Me
n
Silanol Terminated and Related Polydimethylsiloxanes
30
 Figure 9

CHEMISTRY OF HYDRIDE FUNCTIONAL POLYMERS

Hydride Functional siloxanes undergo three main classes of reactivity: Hydrosilylation,

dehydrogenative coupling and hydride transfer.

Hydrosilylation
O CH3 O CH3

Pt
O Si H + H 2 C=CH Si O O Si CH 2 CH 2 Si O

O CH3 O CH3

Dehydrogenative Coupling
O CH 3 O CH3
Sn(OOCR) 2
O Si OH + H Si O O Si O Si O + H 2

O CH3 O CH3

Reduction

( ) ( )
CHO CH2OH
H O
Bu3SnH
O Si O + NO2 O Si O + NO2

CH 3 n CH3 n

31
 Table 6 lists the complete line of UCT hydrosilicones. PS118-
PS122 are hydrosilicone homopolymers with trimethylsiloxy
terminals and backbones consisting entirely of methylhydrosiloxy
groups. These are very potent crosslinkers. They also are used as
starting materials to graft on alkyl or other functionalities via the
hydrosilylation reaction. PS122.5-PS124.5 are more moderate
crosslinkers containing varying molar amounts of methyl
hydrosiloxane in the backbone, the remainder being dimethylsiloxane.
Specialized crosslinkers with cyano, octyl or phenyl functionality in
the backbone are offered in PS124 through PS129.5.
Hydrosilicone chain extenders are use extensively to soften
platinum cure formulations and impart greater elongation. They are
di functional in hydride at the polymer terminals. UCT offers a
complete line of these with catalog numbers PS537 through PS545.

32
 Table 6 Hydrosilicones
Description Viscosity Wt% Methyl Specific Refractive Flash Uses
[CAS #] Hydro Gravity Index Point
Polymethylhydrosiloxane, Trimethylsilyl Terminated CAS No. [63148-57-2]
PS118 2-5 1.382 50°
PS119 20 0.99 1.395 100°
PS120 30 0.99 1.396 121° Blowing Agent
Crosslinker
PS122 85 0.99 1.397
Methyl Hydro, Dimethylsiloxane Copolymer, Trimethylsilyl Terminated CAS No. [68037-59-2]
PS122.5 10-15 (50-55%) 0.99 1.394 70°
PS123 25-30 (30-35%) 0.99 1.399 125°
PS123.5 25-35 (15-18%) 0.99 1.400 RTV
Crosslinker for
addition cured
Pt catalyzed
systems
PS123.8 7500± (0.5-1.0%) 0.97 1.404 300°
2500
PS124.5 250-275 (4-6%) 0.97 1.404

33
 Table 6 Hydrosilicones (CONTD)
Description Viscosity Wt% Methyl Specific Refractive Flash Uses
[CAS #] Hydro Gravity Index Point
Methyl Hydro, Cyanopropylmethyl Siloxane Copolymer
PS124 1000-3000 (3-4%) 1.07 1.446
Methyl Hydro, Methyloctyl Siloxane Copolymer
PS125 200-400 (40-60%) 0.93 1.435
PS125.5 300-600 (25-30%) 0.91 1.440
Methyl Hydro, Phenylmethyl Siloxane Copolymer, Dimethylsiloxy Terminated
PS129.5 75-100 (45-50%) 1.500
Polydimethylsiloxane, Hydride Terminated
PS537 2-3 0.905 1.395

PS542 500 0.971 1.403

PS543 1000 0.971 1.403

PS545 10,000 0.974 1.403

34
 The physical properties of silicone resins are intimately related to
the structure of the starting monomer units. Table 7 is a summary of these
structure/property relationships. Trends commonly experienced by polymer
formulators are the increased rigidity and decreased elongation on
introduction of aromatic groups into the backbone of the silicone.

35
 Table 7 Effect of Monomers on the
Properties of Silicone Resin Films

Property CH3SiCl3 C6H5SiCl3 (CH3)2SiCl2 (C6H5)2SiCl2 CH3(C6H5)SiCl2

hardness increase increase decrease decrease decrease

brittleness increase increase decrease decrease decrease

stiffness increase increase decrease decrease decrease

toughness increase increase decrease decrease decrease

cure speed much faster some increase slower much slower slower

tack decrease some decrease increase increase increase

36
 Other monomeric short chain silane end cappers, cross linkers and chain
extenders are employed where the formulator desires a more rigid structure or more
tightly defined stoichiometry. Figure 10 lists the most commonly available commercial
products and their United Chemical Technologies catalog numbers.

37
 Figure 10 Typical Silicone Monomers
Me

Si Me
O
Me O O
Me2
Si
Si O
O O Si O
Me Me2 5
Me2Si Si SiMe2
Me Si O Me2

Me

Hexamethylcyclotrisiloxane Octamethylcyclotetrasiloxane Decamethylcyclopentasiloxane

H7260 O9810 D3770

Ph Ph Ph
Ph Ph
Si OH O Si Me
Si Si Ph Ph
Ph O O Ph Si Si O
Si
Me Me
O O Ph OH
Ph Si O
Ph
Ph

Octaphenylcyclotetrasiloxane Diphenylsilanediol Trimethyltriphenylcyclotrisiloxane

O9817 D6150 T3800

38
 Figure 10 (contd)
O O
H2C CH MeH
Si
SiO O O
CF3 SiO HMeSi Si SiMeH
H3C MeH
Me
3-4
3-4

Vinylmethylcyclosiloxane Trifluoropropylmethylcyclosiloxanes Methylhydrocyclosiloxane

PS925 T2844 T2000

Me Me Me Me
CH3 CH3
Me Si O Si Me H2C = CH Si O Si CH2 = CH2 H Si O Si H

CH3 CH3
Me Me Me Me

Hexamethyldisiloxane Tetramethyldisiloxane
Divinyltetramethyldisiloxane
H7310 T2030
D6210

39
 Typical commercial silicone sealants are formulated to give
high elongation, moderately hard elastomers. Table 8 is an overview
of typical cured rubber physical properties for representative
industrial sealants. UCT silicones are extensively used by these
compounders as base resins for both one and two part systems.

The high gas permeability of silicones is quantitatively

illustrated in Table 9. This property results in their extensive use in
contact lens formulations (Figure 11) to allow oxygen transmission to
the cornea. This property also allows small mammals to breathe in a
low viscosity silicone medium.

40
 Table 8 Cure Properties of Typical RTV
Silicone Rubbers

One-component Two-component Two-component

One-component construction adhesive molding
Property general-purpose sealant sealant compound

hardness, Shore A
durometer 30 22 50 60
tensile strength 2.4 1.0 3.5 5.5
MPa
elongation 400 850 200 220
tear strength 0.80 0.35 0.52 1.75

41
 Table 9 Permeability of Silicone
Elastomers

Permeability
CAS Temperature (cm3-cm)/(s-cm2-kPa)
-7
Type Registry No. °C Gas x 10

Dimethyl silicone (63148-62-9) 25 CO2 405

25 O2 79
25 air 44
30 butane 2.0
70 butane 1.7
fluorosilicones (63148-56-1) 26 CO2 79
26 O2 13
nitrile silicones (70775-91-6) 31 CO2 237
31 O2 40

42
 Figure 11

Hard oxygen-permeable contact lenses allow

correction of a wider range of visual defects
without compromising wearer comfort
(courtesy R. Capozza, Syntex Ophtalmics)

The low toxicity and high gas permeability of silicones

are shown in this experiment, in which snails
completely immersed in 3-5-ctsk polydimethylsiloxane
lived for more than 72 h (author’s experiment
constructed from unpublished work of R. LeVier)

43
 The inertness and low toxicity of silicones allows them to be
used extensively in medical and prosthetic applications, as illustrated
in figures 12 and 13. While UCT does not warrant silicones for
medical use, its customers have qualified a wide variety of
formulations in a plethora of devices. The most recent qualification is
in the “Abiocor™” artificial heart device.

44
 Figure 12

Here actor
Dustin Hoffman
has aged to
121 years for
the film
“ Little Big Man.”

The mask and other appliances are made of silicone and bonded by PSAs. These materials
are non-sensitizing and used in a wide range of bonding applications, including surgical
dressings, ileostomy and colostomy appliances, and toupes (courtesy Dow-Corning Corp.)
45
 Figure 13

Silicone medical devices and the body:

Numerous medical devices are made from silicone-containing polymers.

46
 Ultraviolet (UV) curable silicones are a specialized application with unique advantage
but also limitations. UV curing allows a continuous curing process by passing the coated substrate
through a high intensity UV light bank. If this technology is available the advantages of no
premixing, humidity effect or heating are obvious. UV technology has the following limitations.

A) Need for thin coats (typically 20 micron or less).

B) Need for high power mercury arc lamp type UV device.
C) Inhibition by oxygen.
D) Need for adding photoinitiator (typically several hundred ppm).

Good photoinitiators are the “Irgacure” series of substituted acetophenones.

The UCT product line of UV curable silicones is summarized in Table 11. Among the
most popular products are:

PS560. Monomethacryl functional silicone for grafting of a silicone backbone into a methacrylate
cure resin.

PS583 Difunctional silicone methacrylate giving soft UV cures.

PS851 Methacrylate with functionality in backbone. Gives moderately hard ( Shore A ~ 20-30) UV
cures. A good photoinitiator is Irgacure 851 (2,2-dimethoxyphenylacetophenone).

PS2067 Cyclic high functionality methacrylate, gives very hard (Shore A > 50) cure with minimal
elongation.

47
Methacrylate & Acrylate-Functional Polymers

Acryloxypropyl-functional silicones undergo UV and visible light

polymerization in the presence of photoinitiators such as
ethylbenzoin.

Methacryloxypropyl-functional silicones undergo the same

general chemistry as the vinylsilicones, but possess several
significant reactivity differences. They copolymerize readily with
methacrylate monomers and undergo light activated
polymerization.

48
 Table 10
Methacrylate & Acrylate-Functional Polymers
Product # Description Viscosity Specific Mole %
Gravity Comonomer

PS560 Polydimethyl siloxane 1000

Monomethacryloxy-
Propyl terminated
PS583 Polydimethyl siloxane 2000 1.00
Methacryloxypropyl-
terminated
Polydimethyl Siloxane, Methacrylate & Acrylate Functional Copolymers
PS802 (Acryloxypropyl) Methyl 80-120 0.98 15-20
PS851 (Methacryloxypropyl) Methyl 1000-2000 0.98 2-3
PS852 (Methacryloxypropyl) Methyl 10000 0.92 5
PS853 (Methacryloxypropyl) Methyl 2500 0.91 8

PS854 (Methacryloxypropyl) Methyl 0.98 16

Methacrylate Functional T-structure
PS406 Methacryloxy Propyl 25-50 0.97
Acrylate Homopolymers
PS 901 Poly(Methacryloxypropylmethyl)Siloxane 25-125
(Includes Cyclics)
PS 901.5 Poly(Acryloxypropylmethyl)-Siloxane 100 1.10-1.12
(Includes Cyclics)

49
 “Lens Monomers” are low molecular weight silane additives
for contact lens formulations. They greatly increase the permeability
of the lens to oxygen and moisture. United Chemical Technologies is a
basic manufacturer of lens monomers. Figure 14 shows the most
common silane lense monomers.

50
 Figure 14 Lens Monomers
O O Me Me
CH2 = CCO(CH2)3Si(OSiMe3)3 CH2 = CCO(CH2)3SiOSiMe
CH3 CH3 Me Me
M8559
M8547
Methacryloxypropyltris Methacryloxypropylpen-
(trimethylsiloxy)silane tamethyldisiloxysilane

O Me Me
CH2 = CCO(CH2)3Si(OSiOSiMe)3

CH3 Me Me

Methacryloxypropyltris(pentamethyl-
disiloxanyl)silane

51
 Figure 14 Lense Monomers (Contd)
O OH OSiMe3
CH2 = CCO(CH2)OCH2CHCH2O(CH2)3SiMe

CH3 OSiMe3
Methylbis(trimethylsiloxy)silylpropylglycerol-
methacrylate

O Me Me O

CH2 = CCO(CH2)4SiOSi(CH2)4OCC = CH2

CH3 Me Me CH3
Bis(Methacryloxybutyl)tetramethyldisiloxane
B2408.5
52
 This article will attempt to highlight the benefits of homogeneous
platinum catalysts of the Karstedt type (Ref 4) over other catalyst
systems commonly used in curing polydimethylsiloxane resins. The
technology is also applicable to organic synthesis where an active silyl
functionality needs to be grafted onto an olefinic moiety. These platinum
catalysts are described in detail in Figure 15 and Table 11 . Advantages
over the older “Speiers” catalyst (chloroplatinic acid in ethanol) are
summarized in Table 12.

Table 13 is a compilation of the many features and benefits offered by the

United Chemical Technologies line of Homogeneous Platinum Catalysts.

53
 Figure 15 Platinum Vinylsiloxane
Catalysts
Application
Platinum vinylsiloxane complexes have found
extensive use as catalysts for promoting
Applications include two part silicone
hydrosilylation reactions. The bond forming chemistry
compositions (RTV addition cure systems)
proceeds according to the following equation:
utilized in dental impression compounds,
prototype molding, sealants, and electronic
Platinum coating applications. Cure time is reduced
SiH + CH2 = CHSi SiCH2CH2Si from hours to minutes in RTV systems due to
Catalyst
the solubility of these catalysts in
dimethylsiloxane polymers.
Typical Properties
Platinum1 For hydrosilylation reactions or two part RTV
Product Content Carrier Cure time2 systems, it is recommended that platinum
PC072 > 2% Xylene 5.0 - 8.5
catalysts be utilized at the 5-50 ppm range
PC075 > 2% Linear Silicone Fluid 5.0 - 10.0 based on total formulation weight. The
PC085 > 2% Cyclic Silicone Fluid 10.0 - 15.0 reactivity of PC072, PC075, and PC085 can
be modified using inhibitors such as UCT’s
products designated D6210 and T4290 to
Assay Test Method No. UCT0001
1
achieve optimum reactivity characteristics.
2 In minutes standard RTV system, Test Method No. UCT0002 Reactivity rates are PC072 > PC075 >
PC085.

54
Table 11 Homogeneous Platinum Catalysts
Minimum
Product Percent Platinum (1) Carrier
PC065 10 Linear Inhibitor
PC072 2 Xylene
PC073 1 Xylene
PC074 (CLEAR) 2 Xylene
PC074.5 2 Octamethylcyclotetrasiloxane
PC075 2 Linear Silicone
PC075.3 3 Linear Silicone
PC075.5 5 Linear Silicone
PC076 1 Linear Silicone
PC085 2 Cyclic Silicone (Ashbey’s Catalyst)
PC085.3 3 Cyclic Silicone
PC086 1 Cyclic Silicone
PC088.3 2.1 Octanol/Octanal (Lamoreaux’s Catalyst)
1. Standard UCT atomic absorption method.
55
 Table 12
Advantages of Platinum (0) Vinyl Siloxane Complexes
PC065-PC086
Over Chloroplatinic Acid, H2PtCl6

1) Homogeneous.
2) Higher reactivity.
3) Reactivity is fine tuned by
choice of solvent and inhibitor.
4) No corrosive HCl or chloride byproducts.
5) Colorless catalyst solutions are available.

56
Table 13 Features and Benefits
Features
• Consistent reactivity profile.
• High Clarity, Low Color.
• Customized platinum levels available.
• Specialized packaging available.
• Wide variety of catalyst activities for room temperature
and high temperature cure profiles.
• Complete catalyst product line to serve Platinum-based,
Peroxide-based, and Condensation-based Silicone cures.

Benefits
• Just in time delivery, very competitive pricing.
• Less customer problems with final cured product.
• Our platinum catalysts are more reactive and selective than chloroplatinic acid.
• Our platinum catalysts require low formulated platinum concentrations (5-30 ppm).
• Platinum catalyzed cures evolve no volatile byproducts.
• Our homogenous platinum catalysts have more consistent reactivity than
heterogeneous catalysts due to irregular surface effects in the latter.

57
 While homogeneous platinum catalyzed resins have many
processing advantages over peroxide cure systems (see Table 14),
United Chemical Technologies is a full service company that offers a
comprehensive line of peroxide catalysts. Figure 16 describes this
product line and gives starting process conditions. The peroxide
catalysts are supplied as pastes in inert silicone to allow easier
compounding into the formulation.

58
 Figure 16 Peroxide Catalysts

Applications
Peroxide catalysts are primarily used for the
cross linking of silicone rubber compounding.
Peroxide catalysts are best used for low vinyl
containing polymers (for example - UCT's
products PS255, PS264, PS268, PS286)
which can be cured at elevated temperatures
using peroxide. The benzoyl peroxide catalyst
Typical Properties has less tendency to scorch than
Chemical dichlorobenzoyl peroxide and is therefore
Product Description Carrier Concentration favored for thin sections.
2,4-Dichloro- Polydimethyl
Peroxide loading is approximately 0.2-1.0%
PC010 benzoyl peroxide siloxane 50% and curing is at 125-150°C.
Benzoyl Polydimethyl
PC020 peroxide siloxane 50%

59
 Table 14
Advantages of Addition Cure (Platinum)
Over Peroxide Cure Systems:

A) Lower curing temperatures possible.

B) No acidic byproducts
(e.g., benzoic acid from benzoyl cure).
C) No “frothing” from oxygen byproduct of cure.
D) No oxidative degradation of elastomer
possible.

60
 High molecular weight silicone gum stock is curable utilizing
both peroxide and platinum based catalysts if the gum contains vinyl
functionality. Table 15 lists the complete UCT product line. Of these
all but PS240 contain vinyl groups and are curable with a
homogeneous platinum catalyst plus hydrosilicone crosslinker.

61
 Silicone Gums
Silicone gums are high molecular weight linear polydiorganosiloxanes that can be
converted from a highly viscous plastic state into a predominantly elastic state by cross-
linking. They are base stocks for most traditional silicone rubbers. The principal method of
producing rubbers is to cure at elevated temperatures with peroxides. Elevated
temperature cure gums usually have molecular weights ranging from 500,000 to 900,000.
A variety of groups, including trifluoropropyl, cyanopropyl, phenyl, and vinyl, are used to
substitute for methyl groups in order to impart specific cure, mechanical or chemical
properties to silicone rubbers. Introduction of phenyl groups reduces elasticity, increases
radiation resistance and useful temperature range. Phenyl groups reduce crosslinking
efficiency. Trifluoropropyl groups increase solvent resistance. Introduction of low
percentages of vinyl groups reduces the vulcanization temperature and imparts greater
elasticity and lower compression set to rubbers. Peroxide cure gums may be
trimethylsiloxy or vinyldimethylsiloxy terminated. Most gum stocks have
methylvinylsiloxane chain components. The peroxides most commonly used are benzoyl
peroxide and bis(dichlorobenzoyl) peroxide. Other peroxides are restricted to more specific
systems. Dicumyl peroxide, for example, can be used only for vinyl containing polymers.
Generally, peroxide loading is 0.2 to 1.0% and cure is at 125°-155°.
Trifluoropropylmethylsiloxane compounds are often stabilized with red iron oxide.

62
 Table 15 Silicone Gums
Normal Cure
Product # Description System Used

PS240 Poly (Dimethylsiloxane), gum Peroxide

PS255 Peroxide
Poly (Dimethylsiloxane) - (0.1-0.3%)
(Methylvinylsiloxane) Copolymer, Gum

PS264 Poly (Dimethylsiloxane) - (5-6%) - (Diphenyl) - Peroxide

(0.1- 0.3%) - (Methylvinylsiloxane) Copolymer, Gum

PS268
Poly (Dimethylsiloxane) - (15%) - (Diphenylsiloxane) Peroxide
(0.1-0.3%) - (Methylvinylsiloxane) Copolymer, Gum

Peroxide
PS286 Poly (Methyl-3,3,3-Trifluoropropyl) - (1-2%)
(Methylvinylsiloxane) Copolymer, Gum

63
 Typical formulated silicone rubber systems require substantial molar
excesses of hydrosilicone over vinyl fluid to achieve optimal physical properties. The
desired mix ratio depends on the chain length of the vinyl terminated silicone and
percent hydride in the backbone of the crosslinker. Table 16 lists theoretical mix ratios
for three commercial United Chemical Technologies vinyl fluids when compounded
with three hydrosilicones of varying hydride content (refer to tables 4 and 5). Ratios
are computed at a 1.5/1.0 SiH/Vinyl molar ratio. Less potent crosslinkers, such as
PS123.8, and higher viscosity vinyl fluids, such as PS445, give softer cures at equivalent
molar ratios.

64
 Table 16
Starting Ratios of Hydrido Siloxanes (parts)
to 100 parts of Vinylsiloxanes
Vinylsiloxane PS123.8 PS123.5 PS123.0

PS443 80.8 4.2 2.1

PS445 11.5 1.8 0.9

PS735 11.9 1.9 0.9

Formulation is based upon molar ratio of 1.5 Si-H to 1.0 vinyl.

Filled formulations may require up to 3x the amounts listed for

optimal physical properties.

65
 Experienced formulators and compounders can startup new materials
research with little guidance, but for those new to silicone formulation Tables 17-18 are
convenient starting points. The crosslinker, catalyst and plasticiser levels can all be
varied to achieve the formulator’s unique cure profile and physical properties
requirements. Other general guidelines are:

a:) For two part systems, always put the platinum catalyst in the “ A”
(vinyl or base) side to avoid slow reaction of the catalyst with the hydrosilicone.

b:) Plasticiser and vinyl fluid can be partially mixed with the “ B”
(hydrosilicone) side to achieve a better mix ratio. Care must be taken to avoid metal
contamination on the “B” side if this approach is taken.

c:) Avoid:
Contact with platinum catalyst poisons such as tin salts, mercaptans, PVC beakers or
amino compounds.

66
Table 17 Starting Formulation, Molding RTV
Silicone
This formulation has low modulus and durometer but is useful as a molding
compound. No special procedure or apparatus is required and the procedure may
be modified by varying the ratios of concentration to accelerate or retard the cure
rate. Alternatively, the cure rate may be retarded by addition of T2160 inhibitor.

PS443 (Vinyl Fluid) 100 parts

SS0216 (Filler) 50 parts
PS123 (Hydrosilicone) 3-4 parts
PC075 (Catalyst) 150-220 ppm

With a spatula or tongue depressor, stir the PS443 into the SS0216. A plastic
beaker or coffee cup is a convenient disposable recepticle. After producing a
uniform paste, stir in the PS123. This paste is stable at room temperature if stored.
For activation add the platinum solution dropwise with eyedropper or syringe and
rapidly stir with spatula. Expect a 5-10 minute work life. Let cure overnight at room
temperature to optimize physical properties.

67
 Table 18 Starting RTV Formulation

PART A PART B

PS443 (Vinyl Fluid) 82g PS443 (Vinyl Fluid) 90g

SS0216 (Filler) 17.85g PS123 (Hydrosilicone) 10g
PC075 (Catalyst) 0.15g TOTAL: 100g
TOTAL: 100g

Prepare parts A and B separately. Mix 3 parts A with one part B.

Cure at ambient conditions for four hours.

Physical Properties
Shore A 20-30 Tensile Strength 3.5 Mpa (500psi)
Elongation 400-500% Tear Strength 16N/mm(91ppi)

68
 Simple formulating technique for small scale development work is
illustrated in Figure 17. No expensive equipment is required and physical properties
such as Shore A durometer hardness and elongation are easily measured. Other
physical properties such as tear strength or modulus will require more sophisticated
instrumentation.

69
Figure 17 How To Use UCT’s PETRARCH®
Silicones

1. WEIGHING: Weigh A and B in the 2. MIXING: Use a spatula to make a

recommended ratios. homogenous mixture of A and B.

3. DEAIRING: Place the mixed 4. POURING: Pour mix into mold

silicone in a vacuum chamber (desiccator) or form avoiding entrapment of air.
and apply vacuum until foam collapses.

70
 How To Use UCT’s PETRARCH®
Silicones (Contd)

5. CURING: Follow the recommended

cure schedule
6. DEMOLDING
THE FINISHED PART

71
 In contrast, scale up to commercial silicone resin requirements will require
specialized blending equipment to achieve uniform mixing. High viscosities and filler
levels necessitate such an investment. Alternatively, formulations may be sub
contracted to experienced adhesives manufacturers. Figure 18 shows typical large scale
equipment and Figure 19 illustrates intermediate scale equipment for scale up to
kilogram level.

72
 Figure 18 Large Scale Formulation Equipment

“50 gallon high speed disperser – produced by Applied Silicone Corp, Ventura, California”

73
 Figure 19 Kilogram scale
formulation equipment

“Hauschild Speed Mix from FlackTek Inc.,

Landrum South Carolina”

“One gallon Double Planetary Mixer”

produced by Charles Ross & Son
Company, Hauppauge, New York”

74
 While United Chemical Technologies is a major
manufacturer of the basic building blocks for silicone rubber
formulations,UCT also offers “turn-key” pre blended formulations
for those customers who do not want to do their own development
work. Figure 20 begins an extensive discussion of formulation
techniques and also describes our most popular two part kits. PEM10
is a two part RTV platinum catalyzed system that cures to a clear
silicone elastomer. PEG060 is a two part RTV platinum cure system
that cures to a soft silicone gel. Adjusting the crosslinker
(part “B”) level up or down can make the systems harder/softer for
individual specialized requirements.

75
 Figure 20
Two Part Elastomeric Sealant Kits
Prototype and Model Making Silicones
How Modeling Silicones Work

The silicones are supplied as two part kits with “A” and “B” parts, containing at least
three components:

1. Base
2. Crosslinker
3. Catalyst

The base, typically a moderate viscosity vinyl fluid, and crosslinker, typically a hydrosilicone,
combine with each other to form the cured product. The catalyst, often a platinum derivative, is
premixed with the base, so most kits have only two parts. They are referred to as vinyl-addition
silicones.

Other materials can be added by the craftsman to modify the basic properties of the silicones.
These include fillers, softening agents, pigments, dyes, additional catalyst or cure retarders.
The modifiers are added to the base. After mixing these components, the crosslinker is added.
All of UCT’s kits are in ready-to-use form with responses and strengths most widely desired.
Only the experienced modellist should consider blending materials other than pigments and
dyes, such as softening agents and fillers.

76
 Two Part Elastomeric Sealant Kits
Mixing
It is important to obtain a homogenous mix of the silicones and to avoid entrapment of air.
Mixing can be accomplished with a spoon or mixing stick. If air is entrapped as bubbles, cured
rubber will contain weak areas and detail will be lost. In most systems vacuum de-airing is
desirable. Some systems will de-air on standing for 5 to 20 minutes, particularly if the mix
container is tapped sharply or placed on a vibrating surface. Bubbles on mold surfaces can be
reduced by brushing a layer of catalyzed mix over the surface before pouring.

Work Life
All silicone systems are designed to have a work life of 30 to 90 minutes. The work life can be
extended by adding a cure retarder to the initial mix. The work life can be shortened by adding
catalyst or warming the mix.

Curing
Most UCT silicones will cure at room temperature in 24 hours. The cure can be accelerated by
heating the silicones. At a temperature of 110°C(240°F) most will cure within two hours.

Materials to Avoid
The “A” Part, “B” Part and catalyzed mixture of A/B can be cure-inhibited by certain
contaminants. Avoid contamination with amines, sulfur, chloride or tin containing compounds.
These materials are found in epoxy, natural rubber, PVC and moisture cure silicones,
respectively.

77
 Two Part Elastomeric Sealant Kits
PEM-10

Description
PEM-10 silicone elastomer is supplied as a two part kit consisting of liquid base and curing agent. When the
base and the curing agent are thoroughly mixed in a 10:1 weight ratio, the liquid mixture will cure in thick or thin
sections to a flexible, transparent elastomer ideally suited for electrical/electrical potting and
encapsulating`applications.

Uses
Equipment modules
Relays, power supplies and magnetic amplifiers
Transformers, coils and ferrite cores
Connectors
Fiber optic waveguide coatings
Encapsulation of circuit boards

Mixing
PEM-10 silicone elastomer is supplied in two parts, a lot-matched base and curing agent, mixed
in a ratio of 10 parts base to one part curing agent, by weight.

For best curing results, glassware or tinned cans with glass or metal stirring implements should
be used. Mix with a smooth action that will minimize the introduction of excess air.

78
 Two Part Elastomeric Sealant Kits
PEM-10

Physical Properties Cured Physical Properties

Base viscosity at 25°C, 5500 centipoise Appearance, Transparent

Specific Gravity at 25°C, 1.05 Hardness Shore A, 40
Tensile Strength MPa (psi), 6.20 (900)
Mixed Viscosity at 25°C, 3900 centipoise
Pot Life at 25°C, 2 hours Elongation Percent, 100
Tear Strength die B kN/m (ppi), 2.6 (15)
Cure Time at 25°C, 24 hours
Brittle Point Centigrade, -65
Refractive Index at 25°C, 1.430

Storage and Shelf Life

When stored in original unopened containers at or below 32°C, PEM-10 has a shelf life of 12 months from date of
shipment from United Chemical Technologies, Inc.

Packaging
PEM-10 silicone elastomer, base and curing agent, is shipped in kits containing both the base and curing agent in
separate containers. Each kit contains the appropriate weight of curing agent for the amount of base. Complete kits
are available in 1.1, 8.8, 44 and 495-lb (0.5, 4, 20 and 225-kg) quantities, net weight.

79
 Two Part Elastomeric Sealant Kits
PEG-60
Description
PEG-60 is a silicone gel. A silicone gel is a solid with fluid characteristics. PEG-60 maintains good
cohesion, high instantaneous deformation and good resilience. It is clear with a range of firmness that
varies from slow flowing to free standing. The temporarily deformable material has found application in
soft tissue prosthesis and shock adsorption. It may be characterized as a viscoelastic substance of which
only a small portion is crosslinked by an addition cure mechanism. Variation of base components gives a
wide range of firmness.

Properties, Mixed
Viscosity, centistokes @25°C, 1000
Specific Gravity @25°C, 0.97
Penetration mm, 150-250

Processing
PEG-60 is a 2 part addition cure system. The system comprises an “A” and “B” which, as supplied, are mixed in a 10
to 1 ratio. After thoroughly mixing 10 parts “A” to 1 part “B”, allow mix to de-air cure at 115-120°C for 30-60 minutes or
at room temperature for 48 hours. If penetration of the cured gel is either too firm or too soft for the given application,
the “A” part to “B” ratio can be changed:
Too firm-low penetration-change “A” to “B” ratio to 11:1, 12:1, 13:1, etc.
Too soft-high penetration-change “A” to “B” ratio to 9:1, 8:1, 7:1, etc.
At each ratio, re-cure and check penetration until desired softness is achieved.

80
 A quite old silicone curing technology involves use of silanol
fluids (Figure 21) cured with a zinc or tin catalyst and a wide variety
of crosslinkers such as polysilicate, oxime or acetate. Figure 21 also
illustrates generation of a moisture curable tetra acetato functional
silicone, by reaction of a silanol fluid with a triacetate functional
silane (UCT number M8980). Table 19 lists the complete UCT line of
silanol fluids. All are difunctional with the silanol groups at the
polymer terminals. Table 20 lists moisture curable silicone
prepolymers with acetoxy or alkoxy functionality. Materials in Table
20 are curable with zinc or tin alkanoate catalysts (see Figure 23).

81
 Figure 21
Si-OH

( )
CH3 CH3 CH3

HO Si O Si O Si OH

CH3 CH3 n CH3

Silanol Functional Polymers

O O O

( ) ( )
CH3 CH3 CH3 OCCH3 CH3CO CH3 CH3 CH3 OCCH3
O

HO Si O Si O Si OH + 2 CH3 Si O CCH3 H3C Si O Si O Si O Si O Si CH3

CH 3 CH3 CH3 OCCH3 CH3CO CH3 CH3 CH3 OCCH3

n n
O O O

Condensation cure

82
 Table 19
Polydimethylsiloxanes,
Silanol Terminated
Product # Viscosity Functionality Specific Uses
[CAS #] Weight % Gravity
Polydimethyl Siloxanes Silanol Terminated CAS No. [7013-67-8]
PS340 15-35 4.0-6.0 0.95 Structure control additive for
Silicone rubber and cure
PS340.5 45-85 0.9-1.2 0.97 Moderator for RTV foams

PS341 100 0.8-0.9 0.97

PS342.5 750 0.2 0.97
PS343 1000 0.1 0.98 One & two part RTV’s

PS343.5 2000 0.09 0.98

PS343.8 3500 0.08 0.98

PS344.5 8000 0.06 0.98
PS345.5 18,000 0.04 0.98

PS347.5 50,000 0.03 0.98

PS348.7 125,000 – 175,000 0.03 0.98
PS349.5 800,000 – 1,200,000 0.01 0.98 Silicone pressure sensitive
adhesives, silicone curable
solvent dispersions.

83
 Table 20
Other Moisture Cure Prepolymers
Product # Viscosity Functionality Specific Uses
[CAS #] Weight % Gravity
Polydimethylsiloxane, Dimethylacetoxy Terminated
PS363.5 2500-3500 0.30 0.98
[68440-60-8]
Polydimethylsiloxane, Methyldiacetoxy Terminated
PS368.5 2500-3500 0.5-0.6 0.99
Polydimethylsiloxane, Dimethylchloro Terminated
PS375 2-5 13-16 1.00
[67923-13-1]
Polydimethylsiloxane, Dimethylamino Terminated
PS383 2-5 13-16 0.98
[67762-92-9]
Polydimethylsiloxane, Dimethylethoxy Terminated
PS393 2-3 20-25 0.92
[70851-25-1]
PS395 6-11 7-13 0.94
Polydimethylsiloxane, Dimethylmethoxy Terminated
PS397 1000 R.I.=1.4040 0.98

84
 Silanol fluids are curable to elastomers by a wide variety of
crosslinkers. Equations listing the most common cure pathways are
listed in Figure 22. All of these cure systems result in elimination of a
volatile byproduct such as acetic acid, an oxime or alcohol. These
systems are thus called “condensation cures”. Metallic corrosion can
result from elimination of acetic acid or to a lesser extent alcohols.
Oxime or enoxy cure systems are preferred if metal contact is
anticipated. Due to the problems with volatile byproducts or
corrosion, the homogeneous platinum catalyzed systems described
earlier have replaced silanol based cure systems in many electronic,
fiber optic or defense applications. The advantages of the platinum
based over the condensation based cure systems are outlined in Table
21.

85
 Figure 22
THE MOST COMMON
CONDENSATION CURE SYSTEMS ARE:
O O
=

=
Acetoxy Si - OH + CH3CO - Si Si - O - Si + CH3COH

CH2 O
=

=
Enoxy Si - OH + CH3CO - Si Si - O - Si + CH3CCH3

C2H5 C2H5
Oxime Si - OH + C=NO - Si Si - O - Si + C=NOH
H 3C H 3C

Alkoxy Si - OH + CH3O - Si Si - O - Si + CH3OH

Amine Si - OH + (CH3)2N- Si Si - O - Si + (CH3) 2NH

86
 Table 21
Advantages of Addition Cure (Platinum)
Over Condensation Cure (Tin, Zinc) Systems:

A) No volatile byproducts.
B) Lower catalyst concentrations
(5-30 ppm vs 100-300 ppm).
C) Less moisture sensitivity
D) Smoother reaction profiles.

87
 Typical one and two part condensation cure RTV systems
are listed in Table 22 and Table 23. For one part moisture cures it is
critical that all components be thoroughly dried to prevent premature
gelation in a dispensing tube or “hot warehouse”. Liquid
components, if low viscosity, can be dried over molecular sieves.
Alternatively, water can be azeotroped off with toluene. Solid fillers
should be oven dried if possible. Untreated silica fillers when
incorporated into one part systems, often cause viscosity buildup or
gelation from active silanols on the surface. Treated fillers, such as
UCT number SS0216, cap off these groups and give more stable
systems.

88
 Table 22
Condensation Cure Silanol System
PART A PART B

PS347.5 (Silanol) 70g PS041 (Plasticizer) 35g

SS0216 (Filler) 28g SS0216 (Filler) 45g
PS9120 (Crosslinker) 2g PC055 (Catalyst) 20g

TOTAL: 100g TOTAL: 100g

Procedure

Prepare parts A and B separately. Mix 10 parts A with one part B.

Cure at ambient conditions.

89
 Table 23
Starting One Part Moisture Cure RTV Formulation
PS347.5 (Silanol) 65.9g
PS043 (Plasticizer) 20.0g
M9220 (Oxime Crosslinker) 5.0g
A0750 (Primer) 1.0
150m2/g Fumed Silica 8.0g
Dibutyl Tin Dilaurate (Catalyst) 0.1g
TOTAL: 100g

Physical Properties

Shore A 22 Tensile Strength 1.9 Mpa

Elongation 550% 100% Modulus 0.4 Mpa
Skin over 10 min Tack Free 60 min
Scratch time 120 min Through cure 2.0 mm (24hr)

90
 Figure 23 describes the tin and zinc alkanoate catalysts
offered by United Chemical Technologies for condensation cure
systems. The catalysts are blended with low viscosity inert silicone to
allow easier compounding. The “octanoate” group is actually 2-ethyl
hexanoate, not a linear C8 carboxylic acid.
Tin salts are generally more reactive than zinc salts. Typical starting
formulations incorporate a minimum of 500 ppm of active metal.

91
 Figure 23
Metal Octanoates (Zinc & Tin)
and Metal Dilaurate (Tin)Catalysts
Applications

Zinc and Tin Octanoates are catalysts used There are several applications for UCT's
independently or together in RTV formulations. metal catalysts. They may be cross-linked
RTV systems are formulated from silanol with small quantities of multifunctional
terminated polymers with a molecular weight of silanes that condense with silanol groups,
26,000 to 200,000. as in the following equation:

Typical Properties Catalyst

Si – OH + MeO – Si Si – O - Si
Chemical
Product Description Carrier Concentration

PC040 Zinc Octanoate

Polydimethyl
siloxane
These catalysts may also be used to apply
50%
silicon elastomers on surface treatments if
PC050 Tin Octanoate
Polydimethyl
siloxane 50%
the surface has an - OH group. Zn and Sn
catalysts also catalyze the reaction
Dibutyl Tin Polydimethyl between a silanol and
PC055 Dilaurate siloxane 25%
hydrosilane.

Application is from a dilute (0.5 - 2%)

hydrocarbon or chlorinated hydrocarbon
solution and cured at 110 - 150°C.
92
 UCT also offers an extensive line of one part heat or moisture
curable pre formulated systems under the Glassclad® product line. These are
described in detail in Figures 24-29. Brief overviews of these coatings are
given below.
PS252, a one part moisture cure silicone described in Figure 24. Cure
generates a clear soft shiny hydrophobic silicone coat.
PS200 , a one part coating applied in water to glass or other active substrate
to generate a highly hydrophobic deactivated surface. Technically a silane as
it is C18 functional. See detailed information in Figures 25 and 26.
PS216, described in Figure 27. A one part reactive chloro silicone applied in
dry alcohol or aprotic solvent. Generates a permanently bonded hydrophobic
silicone surface to glass, with lower critical surface tension than PS200
coatings.
PS220,PS225 and PS233, all one part solvent applied thermally cured
silicones, described in Figure 28. All generate hard abrasion resistant clear
films.
PS222 and PS225, are one part neat or solvent applied silicones thermally
generating thin silicon dioxide films. For detailed description see Figure 29.
PR6772, a water borne protective coating for masonry. Refer to Figure 30.
93
 Figure 24
PS252 Glassclad FF
®

Applications
®
PETRARCH FF (PS252) is a source of filler-free silicone rubber in a tough
bulk film. It exhibits high bond strength to a wide range of substrates
including other silicones, silica, metals and solvent compatible plastics and
fibers. In biomedical equipment, PETRARCH® FF coatings reduce
physiological interaction including protein adsorption and clot initiation. In
optical devices it provides a clear mechanical barrier that seals and gaskets
without scratching or initiation notch failure.

Description
®
PETRARCH FF (PS252) is a moisture-activated silicone RTV dispersed in
a solution of tetrahydrofuran/dioxane. In the presence of atmospheric
moisture a condensation of silicone prepolymers to a high molecular weight
rubber occurs. The byproduct of the reaction is acetic acid, which imparts a
vinegar-like odor. The system is designed for wet out and adhesion to polar
substrates.

94
 Figure 24 PS252 PETRARCH FF (Contd)
®

Cured Properties Uncured Properties

Tensile Strength >100psi Percent 48-52%
Elongation >150% Viscosity 350-400 ctsks
Durometer, Shore A >8 Specific gravity 0.97
Tear Strength >5psi Skin over time 30-45 min
Cure time (10 mls) 6-8 hours
Flash Point 0°

Application Methods
®
PETRARCH FF is applied by dipping or brushing. Solvent is allowed to
evaporate. Cure is at room temperature.

Caution:
Use in a well ventilated area. Flammable. Keep away from open flame.

95
 Figure 25 PS200 Glassclad®-18
Hydrophobic Coating
® = Trademark of Sivento, Inc.
PS200 (Glassclad® -18) Imparts the Following Properties to Treated Surfaces
• Non-adherent, non-oily surfaces
• Greater scratch resistance
• Easier cleaning, improved appearance
• Reduces the number of surface polar sites

PS200 = Glassclad® 18

Uses
Applications where Glassclad® 18 has been used successfully include:

Laboratory glassware - improves drainage, reduces breakage.

Porcelain ware - provides a glide surface and reduces adhesion to other porcelain ware.
Optical fibers - provides lubricity and reduces breakage during fabrication and in
operational flexing.
Clinical analysis - treatment of analytical equipment extends clotting time of blood,
reduces hemolysis, reduces protein adsorption. Glassclad® 18 is not
for food or drug use.
Fluorescent light bulbs - increases scratch resistance, reducing breakage,
increases surface resistivity.
96
 Figure 25 PS200, Glassclad®-18 Hydrophobic
Coating (Contd)

Properties of Treated Surface

Values reported are for glass slides dipped in 1 % solution of Glassclad® 18 (PS200) and cured at
100°C.
Surface resistivity
Critical surface tension 12
Untreated 1 x 10 ohms
Untreated γc =78 dynes/cm 13
Treated 1.2 x 10 ohms
Treated (hydrophobic) γc =31 dynes/cm

Coefficient of friction, static

Blood protein adsorption
Untreated 0.9-1.0
(glass slide on glass slide)
Treated 0.2-0.3
comparative 100 hour adsorption values for whole
human blood on borosilicate glass surfaces
2
Untreated 0.13mg/mm
2
Treated 0.01-0.02mg/mm

These results are not meant to suggest “in vivo” application of Glassclad® 18. Glassclad® 18 should be
used only in treatment of diagnostic apparatus for clinical analysis in outside the human body application.

97
Figure 25 PS200, Glassclad®-18 Hydrophobic
Coating (Contd)

Description
Glassclad® 18 (PS200) is a monomeric octadecylsilane derivative in a solution of t-
butanol and diacetone alcohol that reacts with water to form a silanol-rich prepolymer
and an alcohol. The silanol-rich prepolymer is able to condense with available hydroxy
groups of glass or other siliceous materials to form a chemically bound alkylsilicone.

Typical Properties of Glassclad® 18 (PS200)

% active 20%
Color, Gardner scale 8
Flashpoint 10°C
Specific gravity 0.88
Solidification point -30°C

98
 Figure 26
®
PS200Application Methods
Glassclad 18 (PS200) is most frequently used as a dilute aqueous solution containing 0.1%-1.0% of
reactive silicone prepolymer. A 0.2% solution of active chemical can be easily prepared by adding one
part by weight of the product as supplied to 99 parts of water while stirring. The following procedure is
frequently employed.

1. Thoroughly clean objects with an alkaline detergent. Used-glass surfaces may require immersion in
2-3% sodium hydroxide. All detergent or alkali should be removed with a final rinse.
®
2. Prepare a 1% solution of Glassclad 18 in water. Ordinary tap water, but not “hard water,” is
acceptable.

3. Immerse the glass or vitreous surface in the solution for 5-10 seconds, ensuring that all surfaces are
wetted by the solution. Agitation of the solution or the part generally results in more uniform deposition.
®
After immersion remove the part and thoroughly rinse with water to remove excess Glassclad 18 from
the surface.
®
4. Cure Glassclad 18 coatings by bringing surface temperature to 100°C for 3-5 minutes. Room
temperature cure may be accomplished by air drying for 24 hours if relative humidity is 65% or less.

Each liter of solution will coat approximately 80 one liter beakers or 600 15cm test tubes. It will coat
approximately 250 m2 of surface.
®
Stability of Glassclad 18 and Solutions
®
Aqueous solutions of Glassclad 18 are not stable indefinitely and may turn cloudy and precipitate after
standing for several days. The solution stability can be optimized by adjusting the pH of the solution to
4.5-5.
®
PS200 = Glassclad 18
99
 Figure 27 Glassclad 6C®
PS216 = Glassclad® 6C

Uses
®
Applications where Glassclad 6C (PS216) has been used successfully include:
Laboratory glassware - improves drainage, reduces breakage.
Fiberoptics -reduces moisture adsorption and surface fracture.
Clinical analysis - reduces protein and lipid adsorption of diagnostic glassware:
®
Glassclad 6C (PS216) is not for food or drug use.
Electronic glassware - reduces surface tracking in mercury switches and optical displays.

Properties of Treated Surface

®
Values reported are for glass slides dipped in 1 % solution of Glassclad 6C (PS216) and cured at 100°C.

Critical surface tension

Untreated γc =78 dynes/cm
Treated (hydrophobic) γc =25 dynes/cm

Description
®
Glassclad 6C (PS216) is a chlorine terminated polydimethylsiloxane telomer. The chlorines react with
hydroxy and silanol groups of glass or other siliceous surfaces to form a chemically bound
polydimethylsiloxane “siliconized” surface.

Typical Properties of Glassclad® 6C (PS216)

% active 100%
Flashpoint 5°C
Specific gravity 0.98-1.00
100
 PS216
Application Methods
Glassclad® 6C(PS216) is a chlorinated polysiloxane and is corrosive. Avoid skin
and eye contact. Use in a well ventilated area.

1. Glassclad® 6C (PS216) is most frequently applied as a 2-10% solution in “dry” solvents

such as hexane, methylene chloride, or 1, 1,1-trichloroethane. Articles are dipped or wiped.
The articles can be cured by air drying for 24 hours at conditions of less than 75% relative
humidity. Heat curing at 110°C for 15-20 minutes in an exhausted oven provides the most
effective surface treatment.

2. A master batch of Glassclad® 6C (PS216) in isopropanol or ethanol is desirable when

large surfaces are to be treated and the acidic byproducts are difficult to handle. A 0.5 to
2% solution of Glassclad® 6C (PS216) in isopropanol is prepared in a well ventilated area.
Hydrogen chloride fumes issue during this stage. Acidic character is reduced for
subsequent surface treatment. Overtreatment results in a cloudy surface. The concentration
of Glassclad® 6C (PS216) should be reduced to eliminate this effect.

101
 Figure 28
Protective Hard Coatings
®
Glassclad HT(PS220) is a high temperature modified phenylsiloxane resin which has a continuous use
temperature exceeding 350°C. It is used both as a thin film coating and for the production of laminated
structures. It has a tensile strength of 3,500 psi and a hardness of 120R (R=Rockwell). Parts are dipped or
sprayed with undiluted resin and cured 20 to 30 minutes at 240°C.

®
PS220 = Glassclad HT
20% solids in xylene.
®
Glassclad EG (PS225) is a thermally stable resin which forms a moderately flexible film with excellent
adhesion and low chloride content. It provides an oxidation and mechanical barrier for resistors and circuit
boards. Part application is by spraying or dipping. Cure is 20 minutes at 220°C.

®
PS225 = Glassclad EG
20 % solids in xylene.
®
Glassclad RC (PS233) is a methylsilicone resin which forms a coating with high temperature (250°C)
serviceability. Its high dielectric strength, thermal resistance
®
and mechanical strength make it ideal as an
electrical component and circuit board coating. Glassclad RC reacts covalently with glass and siliceous
surfaces to form a permanent bond. It has excellent abrasion resistance properties and can be applied to
materials as a protective coating. It is typically applied by dipping or brushing followed by air dry and final
cure at 150°C for one hour.
®
PS233 = Glassclad RC
50% solution in isopropanol

102
 Figure 29

Silicon Dioxide (SiO2) Sources

®
Glassclad TF(PS235) is employed as a source of thick film (0.2-0.4 micron) coatings of silicon
®
dioxide. Glassclad TF (PS235) is a polymeric precursor of silicon dioxide. Silica formation begins
o o
at 110-120 C and is complete by 220 C. The polymer converts to approximately 36% SiO2.
®
Applications for Glassclad TF include dielectric layers, abrasion resistant coatings, and
translucent films.

®
Glassclad TF (PS235) can be applied without solvent or in chlorinated hydrocarbon and ester
vehicles. Specific gravity is 1.13. It is 100% solids.
®
PS235 = Glassclad TF

®
Glassclad SO (PS222) is specifically formulated for the deposition of silicon dioxide. Undoped films
are useful as protective films and as getter layers; doped silicon oxide film as getter layers. Cure is
o o
accomplished in two steps:1) 2-5 mins at 200 C; 2) final cure at 500 C. S.G=0.84

®
PS222 = Glassclad SO

103
 Figure 30
PR6772 Hydrophobic Masonry Coating
®
Glassclad MS (PR6772) is an alkaline resinous silicone solution that reacts with siliceous substrates
including stone and masonry.

Uses
Masonry - renders surface water repellent.
Ceramics - increases green strength and green storage life.

Description
®
Glassclad MS (PR6772) is a 30% sodium methyl siliconate solution in water.

Application
®
Glassclad MS (PR6772) is diluted 10:1 with water then sprayed or brushed onto surfaces. The
solution should be air-dried 24 to 36 hours prior to immersion in water.

Caution
®
Avoid skin contact, Glassclad MS (PR6772) is alkaline.
®
PR6772 = Glassclad MS

104
 Another class of silicones which has found extensive use as
photocopy releasing agents or additives for epoxies are the amino functional
silicones. The basic structure of a typical amino terminated silicone is
illustrated in Figure 31. Typical cure chemistries when used as additives in
urethanes or epoxy formulations involve reaction of the amine with an
isocyanate group in a curing urethane polymer, or the three membered epoxy
ring in a curing epoxy resin. A typical reaction with the isocyanate group is
illustrated in Figure 32. Silicone additives impart greater flexibility and
lower glass transition temperatures to epoxy and urethane resins.

105
 Figure 31
Aminofunctional Silicones

( )
CH3 CH3 CH3

H2NCH2CH2CH2 Si O Si O Si CH2CH2CH2NH2

CH3 CH3 CH3

n

106
 Figure 32
Reactions of Amino Functional Silicones
Aminopropyl-terminated siloxanes are used to form a variety of block copolymers including
polyamides, polyurethanes and polycarbonates. A typical reaction is shown below:

Me Me O

Si CH2 CH2 CH2 NH2 + RNCO SiCH2 CH2 CH2 NHCNR

Me Me H

The silicone is employed to produce silicone modified epoxy resins. It also has improved
adhesion to both painted and unpainted metal surfaces allowing use in corrosion resistant
coatings and polishes.

Amino functional silicones are reactive additives to both epoxy and urethane formulations.

Aminoalkyl functional T-structure polymers demonstrate the same range of chemical

reactivity as the aminopropyl-terminated siloxanes (reactivity with epoxides, isocyanates,
carboxylic acids, etc.). The branched polymers are more likely to find application as
formulative additives rather than as prepolymers. Typical applications include detergent
polishes, leather finishes, and internal mold releases for nylon.

107
 The UCT product line of aminosilicones is summarized in
Table 24. PS509-PS513 are difunctional in primary amine at the
polymer terminals. These silicones are useful as photocopy releasing
agents or chain extending additives for commercial epoxies or
urethanes. PS806-PS810 are copolymeric materials with varying
molar amounts of ethylenediamine functionality in the backbone. The
PS811-PS820 series is similar except that the amino groups are all
primary aminopropyl. All of the PS806-PS820 series are curable with
atmospheric oxygen to inert films. The films have excellent adhesion
to steel and have found application as syringe needle coatings.

108
 Table 24 Amino Functional Silicones
Product # Description Viscosity Specific Mole% 100 g 1 Kg
[CAS #] Gravity Comonomer
Polydimethylsiloxane, Aminopropyldimethyl Terminated
PS509 10-15 0.98 X X
PS510 50 0.98 X X
[106214-84-0]
PS511 100-120 0.98 X X
PS512 1000 0.98 X X
PS513 2000 0.98 X X
Polydimethylsiloxane, Amino Functional Copolymers COMONOMER = (Aminoethylaminopropyl) Methyl
PS804 100 0.97 1 X X
PS805 2500 0.97 2.5 X X
PS806 50-90 0.96 3-5 X X
PS807 50 0.97 4 X X
PS808 100 0.97 4 X X
PS809 250 0.97 10 X X
PS810 2500 0.97 10 X X
COMONOMER = (Aminopropyl) Methyl
PS811 12500 2.5 X X

109
 Table 24 Amino functional silicones (contd)
Product # Description Viscosity Specific Mole% 100 g 1 Kg
[CAS #] Gravity Comonomer
COMONOMER = (Aminopropyl) Methyl
PS811.5 35000 2.5 X X
PS812 70-110 0.98 3-5 X X
PS813 100-200 3-5 X X
PS814 250 4 X X
PS815 750 4 X X
PS816 2500 4 X X
PS817 5000 4 X X
PS818 7500 4 X X
PS819 12500 0.974 4 X X
PS820 750 0.97 10 X X
Amino Functional T-Structure
PS401 200-600 0.97 X X
[71750-80-6

110
 Amino functional T-structures containing both alkoxy and
amino functionality are one part moisture curable systems. They self
catalyze by the amino groups first promoting hydrolysis to silanols,
then also catalyzing crosslinking of these silanols. PS401 is a
representative and popular member of this series, represented in
Figure 33.
Other potential chemistries applicable to aminosilicones are
incorporation into polyester or urethane compositions as illustrated in
Figure 34.
The only drawback to use of aminosilicones is phase
incompatibility with many industrial resins. In many cases emulsified
mixes still react on heating and impart the desired softening to the
resin.

111
 Figure 33

PS401

CH3 CH3

O CH3 O

NH2C2H4NHC3H6Si O Si O Si C3H6NHC2H4NH2

O CH3 O
n
CH3 CH3

112
 Figure 34 Reactions of Aminosilicones
SiCH2CH2CH2NH2

CH 3 O
OCNR
Si CH 2CH 2CH 2NCNR
CH 3
CH 3
Si CH 2CH 2CH 2 NH2 O
CH 3
CH3
Si CH 2CH 2CH 2N
O
CH 3
O
O

113
 Amino functional silicones have also found utility in the
Rimplast® line of thermoplastic interpenetrating network (IPN)
composites. Typical physical properties for these composites are listed
in Table 25. Figure 25, although now dated, depicts high performance
medical devices that have in the past been fabricated with these
materials.

114
 Table 25
Properties of Rimplast
silicone-thermoplastic IPNs
Aliphatic Nylon Nylon SEBS
Property urethane 12 6/6

Tensile strength, MPa 34.5 35.9 69.6 8.3

Elongation, % 350 20 5 1200

Flexural strength, MPa - 55 96.5 400

Flexural modulus, MPa - 1380 2482 3.5 at 300%

Tear strength, kN/m >60 - - 25

115
 Figure 35
Intra-aortic balloon pumps, requiring
mechanical and fatigue strength along with
physiological inertness, are fabricated from
silicone-urethanes (courtesy Kontron
Cardiovascular)

This artificial heart, a totally implantable,

hydraulically driven total cardiac prosthesis,
is constructed with silicone-urethanes
(courtesy R. Ward, Thoratec Laboratories)

116
 Other silicone functionalities available in a more limited
selection are carbinol (C-OH terminated) and carboxy (COOH
terminated) materials. Carbinol silicones are very reactive additives
in epoxy or urethane resins while carboxy silicones can react directly
into a polyester polymer matrix. Phase incompatibility again limits
additive amounts, but low addition levels or emulsification still can
allow usage.
The UCT offerings include PS555 (carbinol terminated) and PS563
(carboxy terminated) silicones. Contact UCT technical support for
more information. The chemical reactions described above are shown
in Figure 36.

117
 Figure 36
Miscellaneous Functionalities
Me O Me OH

Si R OCH2 CH 2OH + CH2CHR Si R OCH2 CH2OCH2CHR

Me Me
Carbinol Terminated

Me O Me O

SiCH 2CH 2CH2COH + HOR SiCH 2 CH 2 CH 2 COR + H O

H
Me Me

Carboxypropyl Dimethyl Terminated

118
 The wide range of curable silicone functionality available is
summarized in Figure 37. Certain functionalities such as mercapto
have not been covered here due to space limitations. See the UCT
product catalog or contact technical service for more informationon
these silicone materials.

119
 Figure 37
Functional Silicone Reactivity Guide
Class Reactivity / Product Class

peroxide activated cure

Vinyl (heat cured rubber)

vinyl addition (platinum cure)

Hydride
dehydrogenative coupling (metal salt cure)
(foamed silicones, water repellent coatings)

Silanol moisture cure 1-part RTV’s

condensation cure 2-part RTV’s

Alkoxy/Polymeric Alkoxide sol-gel (ceramics, ormosil)

120
 Figure 37
Functional Silicone Reactivity Guide (Contd)
Class Reactivity / Product Class
polyureas, polyimides
Amine
epoxy addition

Epoxy cationic UV

polyester
Carbinol
polyurethane

Methacrylate/Acrylate radical (including UV) cure

thiol-ene UV cure
Mercapto thermal cure

Acetoxy/Chlorine/Dimethylamine moisture cure

121
 In summary, this article has attempted to give the scientist,
industrial chemist and formulator a basic understanding of silicone
functionality, curing chemistries, catalysts and formulation
techniques.

The overview has used the extensive line of United Chemical

Technologies silicones as reference points. UCT is a major
manufacturer of the complete line of curable and non curable silicone
fluids, gums, T-resins and curing catalysts. Contact UCT at 800-541-
0559 for ordering, pricing and technical support on these materials.

122
 REFERENCES

1) Kirk Othmer, “Encyclopedia of Chemical Technology”, Third

Edition, Volume 20, John Wiley and Sons, 1982.

2) Michael A. Brook, “Silicon in Organic,Organometallic and

Polymer Chemistry”, Wiley Interscience, 2000, ISBN 0-471-19658-4.

3) I. Koga, “Reductions Using Hydrosilanes”, Silicon Compounds

Registry and Review, Second Edition, 1982, 36-45.
Paper available from United Chemical Technologies.

4) Bruce D. Karstedt, “Platinum-Vinyl Siloxanes”, U.S. Patent

3,715,334, Feb 6, 1973.

123