Synthesis, Characterization and Modification of Silicone Resins - An "Augmented Review"

Progress in Organic Coatings 125 (2018) 287–315
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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat
Review
Synthesis, characterization and modification of silicone resins: An T

“Augmented Review”
Constance Robeynsa, Loïc Picardb, François Ganachauda,
⁎
a
IMP@INSA-Lyon, CNRS UMR 5223, 17 Avenue Jean Capelle, F-69621 Villeurbanne, France
b
Hutchinson SA Centre de Recherche, Rue Gustave Nourry, BP 21, 45120 Châlette-sur-Loing, France
ABSTRACT
This article deals with the preparation and modification of resins, as found in patents and articles and exhaustively reported here, and their characterization and
functionalization, complemented by our own experimental experience. First, we present the different syntheses of resins according to the chosen precursor (e.g.
chlorosilanes, alkoxysilanes, sodium silicate or others…) as well as the microstructure of the copolymers (e.g. MQ, T, MDT...). The few characterizations reported in
the literature on these hybrid molecules are reviewed and completed with our own set of analyses on some commercial resins. Finally, the different methods of
silicone resins modification (condensation, redistribution, functionalization…) are reviewed and also illustrated experimentally using few examples from our side.
1. Introduction groups, “Vi” for vinyl and “OH” for hydroxyl (for other functional
groups, the exponent “R” is used and the formula described in each
Silicone resins were discovered by Eugene G. Rochow in 1941 [1,2]. case). A glossary can be found in the Appendix A at the end of this paper
The absence of carbon-carbon bonds and their high temperatures of as a reminder. Fig. 1 shows different types of amorphous resins found
decomposition, compared with usual organic macromolecules, rapidly commercially. We also include in this schema a model type of T resin, a
made these polymers popular. They currently are used as is in many polysilsesquioxane (TPh8 ), a highly crystalline molecule. This latter type
domains, for instance, in reinforcing or damping agents in polymer of molecules, used either in niche domains (aerospace, for instance) or
compositions [3–10] or in pressure sensitive adhesives (PSAs) [11–13]. mostly for fundamental purposes, will not be considered further here
Other “bulk” applications include anti-foaming or foam stabilization since the literature is too abundant and too far (at least, for the most
[14,15], as well as ceramics, the viscoelastic nature of the resin pre- part) from the coatings applications (for recent reviews on the field, see
cursors allowing improving the mechanical properties of final materials [3,31,32]).
after pyrolysis [3,16,17]. But their main use lies in the coatings industry, Since the 40s, many patents and articles have described methods for
e.g. as varnish in electrical insulations [18,19], in optical devices be- producing silicone resins. The general synthesis protocol is established
cause of their light and heat stability (e.g. LED encapsulation) [20–23], and summarized in Fig. 2. All precursors bearing the different func-
in cosmetic formulations (glossing or tackifying agents, curl retention) tional units are mixed in a reactor with a water-insoluble solvent, a
[24–28], or in masonry paints (as binders or water repellents) [29]. catalyst, water and alcohol. After stopping the condensation reaction,
Silicone resins are tridimensional, highly branched silicone macro- the resin is separated from the aqueous phase, neutralized and dried.
molecules made of different primary units called M, D, T and Q. This The solvent in the organic phase can be evaporated either totally or
notation was first adopted by General Electric [30] and describes a si- partially, if one wishes to keep the resin in solution. A last optional step
licon atom according on the number of oxygen atoms bonded to it: M is the condensation of the residual hydroxyl groups in the resin by
stands for a monofunctional unit (R3SiO1/2), D for a bifunctional unit heating it with a catalyst (vide infra). This step is useful if one seeks a
(R2SiO2/2), T for a trifunctional unit (RSiO3/2) and Q for a tetrafunc- silicone resin keeping a stable structure on a long term.
tional unit (SiO4/2). Subscripts define the number of oxygen linked to The number of patents describing synthesis of silicone resins have
another silicon atom: for instance, Q3 and Q4 stand for tetrafunctional been increasing for the last decades, with various evolutions with time
units with 3 and 4 Si-O-Si bonds, respectively (in the former, the silicon according to the precursors used (Fig. 3). Today, many companies make
atom typically bears one Si-OAlk or SiOH functionality in resins, OAlk and sell their own materials, which do not show exactly the same fea-
being OeC2H5 or OeCH3 for example). Exponents are used to define a ture from one sample to another. We can cite Dow Corning, Shin-Etsu,
specific functionality to a silicon atom: for instance, “Ph” is for phenyl Wacker, Momentive Performance Products (former General Electric
⁎
Corresponding author.
E-mail address: [email protected] (F. Ganachaud).
https://doi.org/10.1016/j.porgcoat.2018.03.025
Received 25 January 2018; Received in revised form 13 March 2018; Accepted 27 March 2018
Available online 15 September 2018
0300-9440/ © 2018 Elsevier B.V. All rights reserved.
C. Robeyns et al. Progress in Organic Coatings 125 (2018) 287–315
Fig. 1. Chemical structures of some conventional silicone resins (a, b, c) and a model polysilsesquioxane (d).
Fig. 2. Schematic summary of the different silicone resins synthesis methods.
Silicones), Elkem Silicones (former Bluestar Silicones/Rhodia Silicones) open papers. In the third part of this review, we make an inventory of
or Gelest, only to mention the most important ones. the modification and functionalization of silicone resins in the litera-
In the same manner as silicone resins are hybrid copolymers in their ture, and challenge the modification of some previously characterized
inorganic silicone backbone and their organic moieties (alkyl or alkoxy commercial silicone resins.
groups), this paper is also ‘hybrid’ in the way that it combines both a
classical literature review and some experimental results from our la-
2. Synthesis of silicone resins
boratory, which we think complete advantageously information given
otherwise. Such ‘augmented review’ has been proposed previously to
2.1. MQ resins
describe the Mullins effect, for instance [33]. After an exhaustive de-
scription of the synthesis of silicone resins, including MQ, DT, three-
The most popular resins found in the market are made of MQ units.
units or more exotic resins, we present a thorough protocol to char-
They are available in a wide range of molar mass or ratios M/Q, as
acterize several commercial resins, not available in most patents or
described below. Note here that we will systematically refer to non-
288
Thirty years later, Blizzard et al. [41,42] used Daudt’s method to get
MQQOH resins with an M:Q ratio of 0.75 and with a hydroxyl content
between 1.9 and 2.6 wt.% (Fig. 5). These resins, kept in solution at
70 wt.% in xylene, were used either in PSAs or as an anti-adhesive agent
in surface coating formulations. Similarly, Wengrovius et al. [43] syn-
thesized an MQQOH resin by mixing sodium silicate, a 16.5 wt.% aqu-
eous HCl solution, isopropanol, trimethylchlorosilane and toluene.
Kobayashi et al. [44] used the same method as Wengrovius et al.,
but replaced the toluene with xylene and obtained a solution of MQQOH
resin with an M:Q ratio of 0.75 and residual silanol according to their
FT-IR analyses. Carpenter et al. [45] used the same method as Ko-
bayashi et al., but replaced the trimethylchlorosilane by hex-
adimethyldisiloxane. They received a 36 wt.% solution of MQQOH in
xylene (with residual M2 inside), exhibiting a number-average mole-
cular weight around 4500 g mol−1. The composition was 50 wt.% of M
units, 12 wt.% of QOH units and 38 wt.% of Q units and the M:Q ratio
was 0.95. The resin was not post-condensed and a white powder was
obtained after spray-drying.
Dexter [46,47] and Currie [48] also used sodium silicate precursors
Fig. 3. Evolution of the number of patents and articles about the synthesis of to create MQQOH resins. Their methods are similar to Daudt’s, except
silicone resins (MQ, MDT, TQ...) based on different precursors. that they used isopropanol instead of ethanol and added both hexam-
ethyldisiloxane and trimethylchlorosilane in the mixture. They ob-
condensed resins (MQQOH) unless cited references expressively de- tained an MQ copolymer solution adjusted to 75–77 wt.% solid in xy-
scribed processes so as to remove excess Si-OH groups or mentioned the lene and with an M:Q ratio of 0.8.
absence of these; in that case, ‘MQ’ resins are quoted. From the years 2000s, patents focused on the improvement of the
processes for silicone resins synthesis, the control of the parameters and
2.1.1. Synthesis from a tetrachlorosilane (SiCl4) precursor the resins compositions. In one of his patents, Wengrovius et al. [49]
The first silicone resins synthesized with SiCl4 were patented in presented a continuous process for producing a silicone resin in a
1941 by Rochow [2], followed by other patents in the 40s and 50s column reactor with the same components as in Daudt et al. patent
[2,34–37]. However, these patents focused on resins with 3 different [39,40]. By controlling the reagents flows, the MQQOH resin composi-
units such as MDT or MDQ resins, and it is only in 1968 that the first tion remained the same in time with an M:Q ratio of 0.8, 2.7 wt.% of
MQ resin was synthesized with this precursor by Lamoreaux et al. [38] silanol groups and a kinematic viscosity of 9.8 mm2 s−1 for the toluene
as shown in Table 1. To do so, they mixed SiCl4 with trimethylsilanol solution at 60 wt.% solids. More recently, Ramdani et al. [50] used the
they had made beforehand by reacting trimethylchlorosilane with Daudt et al. reagents, replaced the ethanol by isopropanol and used a
diethyl ether and a solution of ammonium hydroxide (Fig. 4). Then, tangential-jet intensive mixing tool producing a dissipated power of
they added toluene and methanol to alkoxylate the compound formed 100 kW m−3 and a mixing time of 5 ms to get an MQQOH resin with an
by the addition of the hydrolyzed trimethylchlorosilane to the silicon M:Q ratio of 0.8.
tetrachloride. Finally, water was added to hydrolyze the methoxy Fosdick et al. [52] created a process to improve the resin’s purity
groups and the final compound obtained was an MQQOH resin that had with the use of a fiber bundle. The resin was first made based on Daudt
the appearance of a viscous fluid. This resin was made for medical use, et al. patent, and the obtained resin had an M:Q ratio of 0.8, a weight-
especially as additive of surgical gloves. average molecular weight of 21,000 g mol−1 (which is an exceptionally
The MQ resins synthesis from tetrachlorosilane precursors has not high value) and a silanol content of 3 wt.%. The process involved first
been very popular afterwards, since another method was discovered in flowing water at the upstream-end of Pyrex glass fibers and then, when
1950 which implied the use of another precursor (sodium silicate) that the water flow have started, introducing a second mixture, made of a
we present thereafter. Note anyway, as will be presented below, that solvent (toluene or xylene) containing the MQ resin, hexamethyldisi-
other chlorosilane precursors are still used nowadays in reaction with loxane and residual HCl into the conduit through a side inlet pipe. By
TEOS or silicate precursors. varying the contact and the flow rates, Fosdick et al. could remove up to
99.9 wt.% of HCl impurities.
2.1.2. Synthesis from a sodium silicate precursor In 2009, Berry et al. [51] patented a process to prepare solid sol-
Since 1950, different syntheses of silicone resins using sodium sili- ventless MQ resins. To do so, they first synthesized resins based on
cate as a precursor have been patented, essentially by Dow Corning Daudt’s method and obtained three different MQQOH resins with M:Q
(Table 2). The first researchers who synthesized MQQOH copolymers ratios between 0.80 and 0.95, silanol content between 2.5 wt.% and
with this precursor were Daudt et al. in 1950 and 1951. They hydro- 3.2 wt.% and number-average molecular weights between 2350 and
lyzed sodium silicate to create silica sols that they mixed with tri- 4700 g mol−1. The resins were fed in a twin screw extruder at a velocity
methylchlorosilane or hexamethyldisiloxane [39,40], as shown in of 300 rpm and a single vacuum port operated at 584–635 mm Hg va-
Fig. 5. After washing, neutralization and drying, the MQQOH resin was cuum. The residual solvents decreased from 30 down to 0.05 wt.% and
extracted with chloroform. The soluble fraction of the resin melted the final resins were clear molten extrudates with final Mn between
between 140 °C and 160 °C and had an M:Q ratio of 1.48, while an 2400 and 3850 g mol−1. The new silanol content was not given.
insoluble fraction remained and had an M:Q ratio of 1.13. The sodium silicate-based synthesis has been recently thoroughly
Table 1
Patent describing MQ silicone resins synthesis using a tetrachlorosilane precursor.
Authors M precursor Final resin M:Q ratio Application Ref.
OH
Lamoreaux et al. Trimethylchlorosilane MQQ 0.77–1 Surgical gloves [38]
289
Fig. 4. Synthesis of an uncondensed MQQOH resin described in Lamoreaux et al. patent [38].
investigated by Sun et al. [53]. His team compared the yield as well as several papers have also been published. These patents and papers are
the formation of a gel depending of different parameters such as, the summarized in Table 3.
reaction temperature or reaction time, the feeding order or the type of In Goodwin’s patent, ethyl orthosilicate and trimethylchlorosilane
catalyst. The different catalysts tested were concentrated sulfuric acid, were mixed to create a 30–60 wt.% solution of MQ resin in toluene,
acetic acid and hydrochloric acid, the latter being the most efficient. with residual hydroxyl groups (Fig. 6). This resin was added into an
They observed that the optimum reaction time and temperature were organopolysiloxane fluid to create PSAs. This method was also used by
30 min and 30–40 °C, respectively. They also noticed that in small-scale Modic [56], Lamoreaux [38], Min [57] and Kuo [58]. Modic obtained a
experiments, there was no difference in MQQOH silicone resin yield 60 wt.% solution of MQ resin whose M:Q ratio is 0.5. When condensed
when different feeding orders were applied. However, in larger scales, a with a silanol chain-stopped PDMS, this material could be used for the
better yield was obtained by adding the catalyst first, then the sodium encapsulation of electronic coils as a protection against mechanical
silicate solution, and finally the mixture of hexamethyldisiloxane and shock and vibration. Lamoreaux et al. obtained an MQQOH resin with an
ethanol. The presence of silanol groups was confirmed by the broad M:Q ratio of 0.77 in a 30 wt.% solution of toluene, used to make sur-
absorption band seen at 3487 cm−1 on FT-IR spectra attributed to the gical gloves. Min et al. synthesized an MQQOH resin with the presence
OeH stretching vibration, and a SEC analysis gave a number-average of hydroxyl groups confirmed with FT-IR spectra analyses. Kuo et al.
molecular weight of ca. 2900 g mol−1. synthesized four MQ resins with different M:Q ratio by varying the
In one of his papers, Xu et al. [54] made an MQQOH resin by co- trimethylchlorosilane content, and the M:Q ratios calculated from the
29
hydrolysis and condensation-polymerization of sodium silicate in a Si NMR spectra were found to be slightly higher than the ones cal-
solution of ethanol and hexamethyldisiloxane. After 30 min reaction, culated from the molar ratio of the starting materials. Kuo et al. noticed
toluene was added and the mixture was heated at 70 °C for 2 h. The that when the content of M units increased, the EtO:M and OH:M ratios
organic phase was then dehydrated with anhydrous calcium chloride decreased, indicating that the end-capping was nearly complete.
and the toluene was evaporated. The obtained resin was an MQ resin Moreover, higher contents of M units led to lower molecular weights
with a number-average molecular weight of ca. 2100 g mol−1. and worse thermal stabilities, illustrated by the lower temperatures for
5 to 10 % weight loss. These resins were used as pressure-sensitive
2.1.3. Synthesis from a tetraethoxysilane precursor adhesives components. Traver et al. [59] used trimethylchlorosilane
Tetraethoxysilane is one of the most used precursors in silicone and hexane which implied the continuous addition of water to control
resins synthesis. Since 1944, General Electric, Dow Corning, Wacker the exothermic reaction. The product was a yellow liquid resin with a
and other companies have registered more than 35 patents using this very low dynamic viscosity (6.85 mPa s) and an M:Q ratio of 0.67.
compound. However, it is only from 1958 that the first MQ resins were Other scientists did not use trimethychlorosilane but hexam-
synthesized with this precursor by Goodwin, whose patent opened a ethyldisiloxane to synthesize MQ resins from TEOS, like Shirahata [60]
new research field in MQ resins syntheses [55]. In the last decades, who obtained MQ resins with different M:Q ratios, number-average and
Table 2
Patents and articles describing silicone MQ resins syntheses using a sodium silicate precursor.
Authors M precursors Final resins M:Q ratio Mn, Mw (g mol−1) Other properties Application Ref.
Daudt et al. Trimethylchlorosilane MQQOH 1.48 Waterproof/ Anti-flotation of paint [39,40]

pigments
Blizzard et al. Trimethylchlorosilane MQQOH 0.75 OH: 1.9–2.6 wt.% PSAs/anti-adhesive agent [41,42]
Wengrovius et al. Trimethylchlorosilane MQQOH 0.65–0.79 PSAs [43]
Kobayashi et al. Trimethylchlorosilane MQQOH 0.75 Mn: 5000 Softening point: Anti-adhesive coating/Electric [44]
200 °C insulation coating
OH
Ramdani et al. Trimethylchlorosilane MQQ [50]
Wengrovius et al. Trimethylchlorosilane MQQOH 0.80 OH: 2.7 wt.% [49]
ν: 9.8 mm2 s−1*
Berry et al. Trimethylchlorosilane MQQOH 0.80–0.95 Mn: 2400–3850 OH: 2.5–3.2 wt.% Blends with thermoplastics or [51]
silicone rubbers
OH
Carpenter et al. Trimethylchlorosilane MQQ 0.95 Mn: 4500 OH: 11.6 wt.% Silicone rubbers/Paint [45]
Hexamethyldisiloxane formulations
OH
Dexter Trimethylchlorosilane MQQ 0.80 PSAs [46,47]
Hexamethyldisiloxane
Currie et al. Trimethylchlorosilane MQQOH 0.80 PSAs [48]
Fosdick et al. Trimethylchlorosilane and/or MQQOH 0.80 Mw: 21000 OH: 3 wt.% [52]
hexamethyldisiloxane
OH
Sun et al. Hexamethyldisiloxane MQQ Mn: 2900 PSAs [53]
Xu et al. Hexamethyldisiloxane MQQOH Mn: 2100 [54]
*
Kinematic viscosity.
290
Fig. 5. MQ resins syntheses described in Daudt et al. and

Blizzard et al. patents [39–42].
Table 3
Patents and articles describing MQ silicone resins syntheses using a TEOS precursor.
Authors M precursors Final resins M:Q ratio Mn, Mw (g mol−1) Other properties Application Ref
OH
Goodwin Trimethylchlorosilane MQQ PSAs [55]
Lamoreaux et al. Trimethylchlorosilane MQQOH Surgical gloves [38]
Traver et al. Trimethylchlorosilane MQQOH 0.7 Skin Care Products [59]
Min et al. Trimethylchlorosilane MQQOH Mn: 4050 PSAs [57]
Mw: 7070
Kuo et al. Trimethylchlorosilane MQQOH 0.7–1.0 Mn: 1430–2620 Softening point: 80–190 °C PSAs [58]
Mw: 1970–7700 OEt: 2.9–3.7 wt.%
OH: 0.4–1 wt.%
Modic Trimethylchlorosilane MQQOH 0.5–1 Damping for electronics [56]
Shirahata Hexamethyldisiloxane MQQOH 1–1.6 Mn: 1100–3200 η: 0.7–15.4 Pa s* Tack or coating agent [60]
Mw: 1200–3600 Softening point: 110–120 °C
Wolfgruber et al. Hexamethyldisiloxane MQQOH [66]
Ekeland et al. Hexamethyldisiloxane MQQOH Mn: 2900 [63]
Mw: 9550
Magee et al. Hexamethyldisiloxane MQQOH 0.2–0.6 Mn: 18000 η: 50–750 mPa s Reinforcing agents/PSAs [65]
Mw: 51000
Butler Hexamethyldisiloxane MQ 0.9–1.6 Mn: 880 OH: 0.3 wt.% [61]
OEt: 2 wt.%
ν: 550 mm2.s−1
Weidner et al. Hexamethyldisiloxane MQ OH: 0.2 wt.% [64]
ν: 3.8 mm2 s−1
Voronina et al. Hexamethyldisiloxane MQ 0.6–1.1 Mw: 3300–61000 Reinforcing agents [62]
Flagg & McCarthy Hexamethyldisiloxane MQ 0.3–1.2 Mn: 2100–15100 Softening point: 100 °C [67]
Mw: 2800–78000
*
Dynamic viscosity.
synthesize a priori MQQOH resins with an unknown silanol content.

In Ekeland et al. patent [63], a continuous process was presented to
produce MQ silicone resins while maintaining a constant ratio of re-
actants, which led to less variation in the final product. They used
heptane in place of toluene and the final resin had number-average and
weight-average molecular weights of 2900 and 9550 g mol−1, respec-
tively. Weidner et al. [64] used the same method to obtain an MQQOH
resin in toluene, and after distilling the mixture with a 25 wt.% solution
Fig. 6. Synthesis of an MQ silicone resin with a TEOS precursor as described in
of NaOH in water, the obtained MQ resin had a content of 50 wt.% in
Goodwin patent [55].
toluene, a kinematic viscosity of 3.8 mm2 s−1 and an OH content of
0.2 wt.%. This low OH content was ascribed to the elimination of water
during the distillation. Magee et al. [65] polymerized ethyl silicate
before using it to synthesize MQ copolymers, leading to 50 wt.% of solid
resin in solution with high molecular weights, low M:Q ratios (between
0.2 and 0.6) and a dynamic viscosity from 50 to 750 mPa s.
In Wolfgruber et al. patent [66], a continuous process was used to
synthesize an MQ resin. In a tubular reactor, an aqueous solution of
Fig. 7. Synthesis of an MQ silicone resin with a TEOS precursor described in
water and emulsifier was added continuously. The organosilicon com-
Shirahata patent [60].
pounds were added continuously at a specified rate. The mixture was
then transferred to a thin-film evaporator where an alkanol/water
weight-average molecular weights, and viscosities (Fig. 7). With the mixture was eliminated. After distillation, the aqueous suspension was
addition of toluene during the reaction, the MQ resin had an M:Q ratio re-injected in the reactor with the organosilicon compounds and after
of 0.7, a softening point between 110 and 120 °C and some residual four passes, a quarter of the volume flow of the colloidal aqueous
ethoxy groups. Based on the same method, Butler [61] synthesized a suspension was removed. This suspension was then spray-dried and an
viscous liquid MQ resin, thanks to its high M:Q ratio of 1.6, at a yield of MQ resin in powder was obtained. The particles diameters fell between
91 wt.%, an OH content of 0.3 wt.%, a content of residual ethoxy groups 5 and 16 μm. The resin characteristics were not described in this patent.
of 2 wt.% and a number-average molecular weight of 880 g mol−1. The Recently, Flagg & McCarthy [67] published an article about the
resins M:Q ratios changed from 1.6 to 0.9 by decreasing the amount of synthesis of MQ resins, including a large literature survey, in which
hexamethyldisiloxane. Voronina et al. [62] used the same precursors to they reported how challenging it can be to prepare the same resin twice
291
in a row. In fact, they tested dozens of syntheses methods at small scale, 2.2.1. Hydrido – functionalized resins
but did not succeed in scaling up the most promising ones. Moreover, Brady [74] synthesized different MMHQ resins by varying di-
they concluded that none of their home-made copolymers properties methylchlorosilane content in the mixtures, as seen in Fig. 9. The resins
could be compared with the literature results, leading to the selection of had an M:Q ratio comprised between 1.68 and 2.14, an MH:Q ratio
a “model” commercial MQ resin used as a reference. They observed that between 0.4 and 1.2 and 0.17–0.40 wt.% silicone-bonded hydrogen
the method based on Goodwin patent [55] led to no molecular weight atoms. When cured with a poly-organosiloxane gum and Pt catalyst,
control and a very high polydispersity index. The method based on these resins could be used in flexible coatings.
Magee patent [65], which is a derivative of Goodwin procedure, was Silicone resins with the formula MMHQ have also been synthesized
also abandoned because of the uncontrollable content of residual with TEOS as a precursor by Kobayashi et al. [44], Hurford et al. [75],
ethoxy groups. They finally presented a new synthesis procedure and Berthiaume et al. [76], Mine et al. [77] and Yoshii et al. [78]. In
obtained different resins that were polydisperse in molecular weights Hurford et al. patent, hexamethyldisiloxane was mixed with tetra-
and M:Q ratios. In their example, they added TEOS in a solution of methyldisiloxane, TEOS and an aqueous solution of hydrochloric acid
water, ethanol and H2SO4, stirred the mixture at 50 °C for a certain to get an uncondensed, colorless liquid MMHQ resin with a dynamic
time, added hexamethyldisiloxane in solution in toluene to form an viscosity of 0.9 Pa.s and an M:Q ratio of 1.2. Kobayashi et al. [44] used
emulsion. The emulsion was progressively heated up to 80 °C, then the a method similar to Goodwin’s but used dimethylchlorosilane in addi-
reaction mixture was transferred to a separatory funnel, rinsed with tion to trimethylchlorosilane. The analyses showed that the resin con-
water, sodium bicarbonate, and finally brine. Once separated, the or- tained only 40 wt.% of the Si-H calculated from the quantity of di-
ganic phase was dried and filtered. Upon removal of solvent by rotary methylchlorosilane. Berthiaume et al. [76] used TEOS and
evaporation, they obtained the MQ resin under the form of a white dimethylchlorosilane to synthesize an MHQ resin whose Si-H bonds
powder. The characterization of those copolymers highlighted their presence were confirmed by FT-IR analysis. This resin was then added
polycyclic silica-like structure. They also condensed one of their MQ in cosmetic formulations for haircare. Yoshii et al. [78] and Mine et al.
resin with trimethylsilyl iodide and noticed that it converted 90% of the [77] used a procedure similar to the ones using TEOS as a precursor and
Q3 units into Q4 units, but did not remove all ethoxy groups. replaced TEOS with tetramethoxysilane (TMOS) to synthesize two MHQ
resins. This precursor was mixed with methanol, hydrochloric acid and
1,1,3,3-tetramethyldisiloxane. Mine et al. confirmed the presence of the
2.1.4. Synthesis with other precursors Si-H group in the final resins by FT-IR analysis. Their resins were used
Although tetraethoxysilane and sodium silicate are the most for surface coatings and as additives in silicone elastomers. Un-
common precursors used in MQ resins synthesis, other reactants have fortunately, these syntheses were not investigated any further due to
been tested to synthesize these copolymers [68–73] (Table 4). For in- the high toxicity of the TMOS.
stance, MQ resins were synthesized in the patent GB 783,868 (author
unknown) [68] by mixing hexamethyldisiloxane with a silica hydrogel
(bringing the Q units) in the presence of ethanol and hydrochloric acid. 2.2.2. C]C – functionalized resins
This resin was used as a reinforcing agent in silicone elastomers. Kuroda Vinyl or alkenyl-modified MQ resins have been prepared from
et al. [73] prepared MQ resins by using calcium silicate, with the same several precursors. For example, Schattenmann et al. [79] used SiCl4,
method as with sodium silicate. Burns et al. [70] used a sol-gel process trimethylchlorosilane and vinyldimethylchlorosilane to synthesize an
to synthesize a solid MQ resin that was also used as a reinforcing agent MMViQQOH resin with 1.7 wt.% silanol content and a weight-average
in silicone elastomers. Mutoh et al. [69] and Huang et al. [71,72] used a molecular weight of 1800 g mol−1. Several patents describe the use of
commercial pre-condensed TEOS precursor named “Ethyl Silicate 40” TEOS as a precursor to synthesize vinyl-modified MQ resins. Mautner
and made it react with hexamethyldisiloxane and an acid (H2SO4 for et al. [80] and Weidner et al. [81] used hexamethyldisiloxane and 1,3-
Mutoh et al., and HCl or H2SO4 for Huang et al.) as shown in Fig. 8. The divinyltetramethyldisiloxane to create MMViQ resins with a good sto-
Ethyl Silicate 40 compound has the general formula EtO[Si(OEt)2O]nEt rage stability. Yoshii et al. [78] also used 1,3-divinylte-
with n = 5. The obtained MQQOH resin could then be condensed by the tramethyldisiloxane to get MViQ resin, as well as tetramethyldisiloxane
addition of sodium hydroxide. Huang et al. also studied the influence of to obtain MHQ resin. Dauth et al. [83] made MMViMHQ resins through
the acid catalyst content on the resins characteristics such as the M:Q condensation of TEOS with different silazanes, such as 1,3-divinylte-
ratio [72] and observed that the acid-catalyzed resins had a narrow tramethyldisilazane, to generate vinyl-functional MVi units, and very
molecular weight distribution according to their GPC chromatograms few dimethylethoxysilane molecules as MH precursor. The final resin
[71]. was a white powder that contained 5.5 wt.% of vinyl groups and 0.1 wt.
% of SiH groups. This resin was used as a filler, adhesive agent and
crosslinking agent.
2.2. Synthesis of functional MQ resins Kobayashi et al. [84] mixed the Q precursor, TEOS, with hex-
enyldimethylchlorosilane (CH2]CHC4H8Me2SiCl), toluene, THF and a
Modified MQ resins comprising SiH, vinyl, phenyl or alkenyl groups solution of hydrochloric acid. After the reaction occurred, the solvent
were also synthesized with the three main Q precursors we presented removal led to transparent, light yellow oil. The presence of C]C bonds
previously. All references are summarized in Table 5. in the resin was confirmed by 29Si NMR analyses and a titration by
Table 4
Patents and articles describing only one line for column titles, please describing MQ silicone resins syntheses using other precursors.
Authors Precursors of Final resins M:Q ratio Mn, Mw(g mol−1) Other Properties Application Ref
Q units M units
Anonymous Silica hydrogel Hexamethyldisiloxane MQQOH Density: 0.12 Reinforcing agent [68]
Kuroda et al. Calcium silicate Hexamethyldisiloxane MQQOH Mw: 2500–7800 [73]
Mutoh et al. Ethyl Silicate 40 Hexamethyldisiloxane MQQOH 2:1 [69]
Huang et al. Ethyl Silicate 40 Hexamethyldisiloxane MQQOH 0.6–1 Mn: 4200–6100 Softening point: 100–230 °C [71]
Huang et al. Ethyl Silicate 40 Hexamethyldisiloxane MQ 0.6–3.5 [72]
Burns et al. Silica hydrosol Hexamethyldisiloxane MQ [70]
292
Fig. 8. Synthesis of an MQ silicone resin with Ethyl Silicate 40

described by Mutoh et al. and Huang et al. [69,71,72].
sodium thiosulfate determined their content of about 9 wt.%. Their white, opaque dispersion of the resin. This dispersion was used for the
number-average and weight-average molecular weights were 5100 and treatment of surfaces of many materials such as concrete, textile or
5900 g mol−1, respectively. Herzig et al. [82] synthesized original papers. Liu et al. [90] prepared a soluble and meltable phenyl- and
carbosiloxane-based MM’Q resins, where the “M”' precursor bears two amino-functionalized T resins that could be used for the synthesis of
hexenyl groups. By varying the length of the oligomers (Fig. 10), dif- diverse and novel inorganic-organic materials. Lu et al. [91] synthe-
ferent M:Q ratios, ethoxy contents and viscosities were obtained. sized a TTN polysilsesquioxane resin with 3-aminopropyltriethoxysilane
However, the drawback of such a synthesis method was the use of an and methyltrimethoxysilane as precursors. The resin was found to have
important content of basic salts to neutralize the mixture (Fig. 11). a good trapping ability of Cu(II) and Pb(II) ions, permitting them to be
These resins were claimed to be used in anti-adhesive coatings for pa- removed from aqueous solutions. Arimitsu et al. [92] synthesized sili-
pers or films. cone resins that generated aliphatic secondary amines under UV ra-
diation. These resins could be found in photolithography methods for
2.2.3. Phenyl-functionalized resins the production of micropatterns for circuits or electrodes in electronic
Hyde [34] synthesized phenyl-functionalized MQ resin by mixing devices.
dimethylphenylchlorosilane with SiCl4 in a solution of water and di- Rerat et al. [93] synthesized a special sulfur and boron-containing
oxane. A viscous oil was obtained with a MPh:Q ratio of 2:1, and a silicone resin with phenyl-functionalized T units, whose formula is
suspension of formed silica remained in the oil. When this ratio was TPhTSB with a molar ratio of 25:25:50. This resin, a white solid powder,
increased to 3:1, more silica was formed, although this phenomenon resulted from the reaction between boric acid, phenyltrimethoxysilane
could be avoided with the addition of acetic acid in the reactor. The and 3-mercapto-trimethoxysilane and it was used for scratch- or fire-
final MPhQ resin was a medium-viscosity oil. In one of his papers, Xu resistant coatings. Kilinc et al. [94,95] and Backer et al. [96] prepared a
et al. [54] made phenyl- and vinyl-modified MQ resin by cohydrolysis resin containing sulfur and phosphorus atoms. To do so, Kilinc et al.
and condensation-polymerization of sodium silicate in an ethanol so- mixed 3-mercaptotrimethoxysilane and 2-DOPO-ethyltrimethoxysilane
lution of hexamethyldisiloxane, methyldiphenylethoxysilane (MDPES) with distilled water in a reactor under nitrogen atmosphere and the
or dimethylphenylethoxysilane (DMPES) and 1,1,3,3-tetramethyl-1,3- mixture was under reflux for 4 h. The final resin was made of T units
divinyldisiloxane (TMDVS). After 30 min reaction, toluene was added with a TR:TS ratio of 1 and was used in coatings as a flame retardant or
and the mixture was heated at 70 °C for 2 h. The organic phase was then for scratch-resistance enhancement. Backer et al. mixed phenyl-
dehydrated with anhydrous calcium chloride and the toluene was trimethoxysilane, methyltrimethoxysilane, DOPO-trimethoxysilane and
evaporated. The obtained resin was either a transparent liquid or semi- methoxy-benzoxazinepropyltrimethoxysilane to get a T resin with a
solid depending on the M:Q ratio. T:TR:TBz:TPh ratio of 0.20:0.25:0.05:0.50.
2.3. Synthesis of other silicone resins 2.3.2. Synthesis of silicone resins with two (M, D, T, Q) units
2.3.2.1. DQ resins. DQ resins’ syntheses are summarized in Table 7. The
Even though MQ and functionalized-MQ resins are among the most first DQ silicone resin was synthesized in 1944 in the patent GB 603,076
popular silicone copolymers and have been synthesized in many ways (author unknown) [36]. In this patent, diethyldichlorosilane and SiCl4
for several decades, other resins with M, D, T and/or Q units have also were heated in alcohol, creating a viscous fluid that was afterwards
been prepared and published, mainly in patents. We separate here the dissolved in toluene. DQ resins were also synthesized by mixing,
description of the resins according to their increasing degree of com- hydrolyzing and inter-condensing TEOS and dimethyldiethoxysilane;
plexity. the characteristics of these resins were not displayed in the patent.
More recently, Kobayashi et al. [97] synthesized a liquid DQ resin
2.3.1. Synthesis of T resins through the reaction of cyclic dimethylsiloxane and methyl polysilicate
All patents concerning this section are quoted in Table 6. Silicone comprising the partial hydrolysis and condensation product of TMOS.
resins bearing exclusively T units were first made in 1965 by Burzynski When cured, this resin was introduced in a composition forming a
et al. [85] who prepared them with a commercial triethoxymethylsilane water-repellent coating on a variety of substrate surfaces. Chojnowski
purified by distillation with LiAlH4 to mix it afterwards with hydro- et al. [98] synthesized DQ resins with no residual silanol, through the
chloric acid and water (Fig. 12). The resin was synthesized in molds and nonhydrolytic dehydrocarbon polycondensation of TMOS (or TEOS)
a clear, flexible cylinder with a 50 mm diameter and 12.7 mm height with hydrosilanes catalyzed by tris(pentafluorophenyl)boron B(C6F5)3.
was obtained. Finally, Gancberg [37] synthesized DDPhQ resins with SiCl4, TEOS,
Varaprath et al. [28] and Becker et al. [86,87] replaced SiCl4 with diethyldichlorosilane, diphenyldichlorosilane as precursors and FeCl3
other chlorosilanes as precursors and mixed them in a solvent to get and AlCl3 as catalysts.
respectively TTPh resins and a white solid TH resin. Varaprath et al. used
phenyltrichlorosilane and methyltrichlorosilane with toluene and iso- 2.3.2.2. TQ resins. TEOS was the main precursor used to synthesize TQ
propanol, while Becker et al. only used trichlorosilane to get TH resins. resin, as shown in Table 8. Rust [99] used butyltrisiloxane resulting
MacKinnon et al. [88] obtained a TtBuTH resin with t-butyltri- from the hydrolysis of n-butyl silicon trihalide, as shown in Fig. 13. The
chlorosilane and trichlorosilane. The final TtBu:TH ratio was 1. resin was a clear, rubbery gel that became a hard resin when heated at
Bekemeier et al. [89] created a water-dispersible silicone TTN resin 140 °C. This resin was used for coating applications on metal, wood...,
by mixing trimethoxysilane with dimethyloctadecyl[3-(trimethoxysilyl) as well as for electric insulation. Isozaki [100] mixed TEOS with
propyl]ammonium chloride solution in methanol and hydrochloric methyltriethoxysilane with alcohol and a solution of hydrochloric
acid. This resin was then added to deionized water and sheared with an acid, and triethylamine was added to increase the pH to 7 and
ultrasonic converter (a tool based on the piezoelectric principle, used to therefore to improve the condensation reaction, leading to a TQ resin
transform an electrical signal in mechanical vibration) to obtain a with very few residual silanol groups. This resin was transparent and at
293
C. Robeyns et al.
Table 5
Patents describing functional MQ resins syntheses.
Authors Precursors of Final resins M:Q ratio Mn, Mw(g mol−1) Other properties Application Ref.
Q units M units M’ units
Brady et al. Sodium Hexamethyldisiloxane Dimethylchlorosilane MMHQ 1.68–2.14 MH:Q = 0.4–1.2 Clear flexible coatings [74]
silicate
Trimethylchlorosilane Si-H: 0.17–0.4 wt.%
Hurford et al. TEOS Hexamethyldisiloxane Tetramethyldisiloxane MMHQ 0.9 MH:Q = 0.2 Release Compositions [75]
Kobayashi et al. TEOS Trimethylchlorosilane Dimethylchlorosilane MMHQ [44]
Berthiaume et al. TEOS Dimethylchlorosilane MHQ Cosmetic products [76]
Mine et al. TEOS Tetramethyldisiloxane MHQ 0.35–0.5 Mn: 3300–3600 Surface coatings/Silicone [77]
elastomers
Mw: 5760–7060
Yoshii et al. TEOS Tetramethyldisiloxane MHQ Mw: 1800 MH:Q = 1:1 [78]
Schattenmann et al. SiCl4 Trimethylchlorosilane Vinyldimethylchlorosilane MMViQ Mw: 1800 OH: 1.7 wt.% [79]
294
Mautner et al. TEOS Hexamethyldisiloxane Divinyltetramethyldisiloxane MMViQ EtO: 0.7 wt.% Additives for anti-foam [80]
products
Weidner et al. TEOS Hexamethyldisiloxane Divinyltetramethyldisiloxane MMViQ OH: 0.09 wt.% PSAs [81]
Herzig et al. TEOS Hexamethyldisiloxane Complex oligocarbosiloxane oligomer (see MM’Q 0.9–1.2 OEt: 4.5–5.8 wt.% Coatings for release papers [82]
Fig. 10)
ν: 3.2– 7.8 mm2 s−1
Yoshii et al. TEOS Tetramethyldivinyldisiloxane MViQ Mw: 1700 MVi:Q = 1.5 [78]
Dauth et al. TEOS 1,3-divinyltetramethyldisilazane MViMHMNQ Vi: 5.5 wt.% Filler [83]
Dimethylethoxysilane
Hexamethyldisilazane Si-H: 0.1 wt.% Adhesive/Crosslinking
agent
Kobayashi et al. TEOS Hexenyldimethylchlorosilane M’Q Mn: 5100 M’: 9 wt.% [84]
Mw: 5900
Hyde SiCl4 Phenyldimethylchlorosilane MPhQ [34]
Xu et al. Sodium Hexamethyldisiloxane Tetramethyldivinyldisiloxane MMPhMViQ 0.78–1.12 Mn: 1800–7100 Ph: 4.2–30 wt.% Fillers in silicone rubbers [54]
silicate
Dimethylphenylethoxysilane Vi: 0.9–3.2 wt.%
Fig. 9. MMHQ resins synthesis described in Brady patent [74].
Fig. 10. Hexenyl-functionalized carbosiloxane oligomer for-

mula used in Herzig et al. patent [82], with n = 0.5, 0.75 or
1.2.
Fig. 11. Synthesis of an MM'Q silicone resin with a TEOS

precursor described in Herzig et al. patent [82].
40 wt.% solution in benzene, had a dynamic viscosity of 5.8 mPa s and a and SiCl4 to synthesize a TC18THQ resin with TC18 = C18H37SiO3/2.
very good storage stability. It was used to produce inorganic coatings Kurjata et al. [102] synthesized a phenyl-functionalized TQ resin with
with a better resistance to corrosion, solvents, heat and bad weather TMOS and phenylsilane (PhSiH3) as precursors through the method of
than usual silicate coatings. Cheng et al. [101] prepared a TQ resin by Chojnowski & al described previously [98].
hydrolyzing and condensing TEOS and methyltriethoxysilane, and the
final resin was used as transparent coatings.
Eguchi et al. [103] used octadecyltrichlorosilane, trichlorosilane 2.3.2.3. (Functional) MT resins. The synthesis of complex MT resins
have been described by several researchers (Table 9). Lee et al. [104]
Table 6
Patents and articles describing silsesquioxane resins syntheses using different precursors.
Authors Precursors of Final resins Mn, Mw Other Properties Application Ref
(g mol−1)
T units T’ units
Burzynski Methyltriethoxysilane T [85]

et al.
Ph
Varaprath Propyltrichlorosilane Phenyltrichlorosilane TT Hair fixative [28]
et al.
tBu H tBu H
MacKinnon Trichlorosilane t-BuSiCl3 T T T :T = 1 Insulating film [88]
et al.
Becker et al. Trichlorosilane TH OH: 0.1–0.2 wt.% [86,87]
Liu et al. N/A Phenyltriethoxysilane TTPhTN Mw: T:TPh:TN = 0.19:0.70:0.11 [90]
1400–4600
Aminopropyltriethoxysilane
Lu et al. Methyltrimethoxysilane Aminopropyltriethoxysilane TTN NH2: 0.19:0.70:0.11 Cu(II) and Pb(II) [91]
adsorbents
N
Bekemeier Methyltrimethoxysilane 3-(trimethoxysilyl)-propyl-N,N- TT Mn: 390 η: 14 mPa s Surface [89]
dimethyloctadecylammonium chloride treatment
Mw: 440
Arimitsu 3-isocyanatopropyltriethoxysilane Mw: OEt: 0–14 wt.% [92]
et al. TR 2200–4600
Rerat et al. Phenyltrimethoxysilane TPhTSB Flame [93]

retardancy
coatings
3-mercapto trimethoxysilane (+ boric
acid)
Kilinc et al. 3-mercaptotrimethoxysilane TRTS Coatings: flame [94,95]
retardant or
scratch
resistance
2-DOPO-ethyltrimethoxysilane
Backer et al. Methyltrimethoxysilane Phenyltrimethoxysilane TTRTBzTPhT Flame retardant 144]
DOPO-trimethoxysilane
Methoxy-benzoxazinepropyl-
trimethoxysilane
295
Fig. 12. T resin synthesis described in Burzynski et al. patent

[85].
synthesized an MVi3TPh resin with phenyltrichlorosilane and [116] synthesized DTTPh resins containing 2.1–5.7 wt.% and 1.3–4.6 wt.%
trivinylchlorosilane as precursors. Next, they made this resin react silanol groups, respectively. Those resins were used for electrical
with trivinylchlorosilane and 1,1,3,3-tetramethyldisilazane to obtain an insulation (Fig. 14).
MHMVi3TPh resin. This resin had a lower silanol content than the initial Horstman et al. [117] generated phenyl- and aminofunctional
MVi3TPh resin (< 1.5 and 5 wt.%, respectively). The others patents and DPhTTN silicone resins by using a mix of diphenyldimethoxysilane,
articles describe syntheses with trialkoxysilanes as precursors, such as methyltrimethoxysilane and aminopropyltriethoxysilane. Xie et al. [6]
trimethoxysilane or triethoxysilane. For instance, Johnson et al. [105] and Chen et al. [118] prepared DViDPhTPh and DPhTPhTVi resins re-
used a triethoxyphenylsilane to create an MT resin. In this patent, they spectively, by hydrolysis-condensation of several alkoxysilanes in the
mixed this component with sulfonic acid and water with a nitrogen presence of KOH catalyst. Xie et al. then mixed their resins with bis
inlet, and added hexamethyldisiloxane and 3- (hydridodimethylsilyl)-m-carborane (HCB) and cured with H2PtCl6
aminopropyltriethoxysilane. The result is an amino-functional catalyst through a hydrosilylation reaction, as shown in Fig. 15. The
MTPhTN resin used in cosmetic formulations with a refractive index of obtained macromolecules had better thermal properties compared with
1.5 and a viscosity at room temperature of 2.9 Pa.s. Gordon et al. [106] the initial resins, and their maximum tan δ values make them inter-
synthesized SiH and phenyl functional MT resins that can be modified esting for damping applications.
in carbinol functional MPrOHTTPh resin where MPrOH denotes HO(CH2)3) Among the different kinds of DT resins, some epoxy-functionalized
(CH3)2SiO1/2. DT resins were prepared few years ago. Lee et al. [119] synthesized DT
Bailey et al. [107] also synthesized a functionalized MT resin in resins with different functional groups, such as epoxy, phenyl or vinyl
their patent by co-hydrolyzing trimethoxyphenylsilane, tetra- depending on the reagents. They tested several combinations of pre-
methyldivinyldisiloxane, dimethylvinylchlorosilane and using tri- cursors among six different alkoxysilanes. The D:T ratio varied from
fluoromethanesulfonic acid as a catalyst. This resin had a silanol con- 0.5:0.5 to 0:1. The weight-average molecular weights were comprised
tent of 0.6 wt.% and was used to create reinforced silicone films for between 2800 and 34000 g mol−1. Only the resins with a molecular
coatings. Horstman et al. [108] synthesized MPrOHTTPh resins by re- weight between 5000 and 20000 g mol−1, and 60–88 wt.% T units,
acting an MHTTPh resin with allyl alcohol in presence of a catalyst Pt showed good properties as a coating composition once mixed with
(Al2O3). More recently, Zhang et al. [109] synthesized an end-capped propylene glycol monomethyl ether acetate.
hydrogen-functionalized hyperbranched polysiloxane (MTHTPh resin)
made by the reaction of phenyltrimethoxysilane in anhydrous me-
thanol, trimethoxysilane and hexamethyldisiloxane. Its appearance was 2.3.3. Synthesis of silicone resins with three or four (M, D, T, Q) units
a transparent and oily product, and the FT-IR analyses underlined the 2.3.3.1. MDT resins. At the beginning of the research on silicone resins,
absence of residual silanol groups. Finally, Xie et al. [110] synthesized most of these synthesized copolymers were made of three functional
an amino MTN silicone resin with a three-step method that included an units (Table 11). Rochow [2] and Meadowcroft [120] patented
acid-catalyzed prehydrolysis step, dialysis purification and alkali cata- syntheses of MDT resins, while functionalized resins were described
lyzed re-equilibrium. The precursors were (3-aminopropyl)triethox- by Mu et al. [121].
ysilane, methyltrimethoxysilane, and trimethylchlorosilane. The final Rochow was the first in 1941 [2] to use methyl magnesium bromide
resins had low molecular weights and low silanol contents due to the and SiCl4 as a precursor to create an MDT resin, as shown in Fig. 16.
post-condensation step with a Dean-Stark apparatus. Meadowcroft et al. [120] synthesized an MDT silicone resin by using
ethyl bromide, diethyl ether and magnesium with TEOS. The reaction
released MgBr2 and Mg(OH)2 and a viscous resin was obtained when
2.3.2.4. (Functional) DT resins. All references are listed in Table 10. Liu the ethyl bromide to TEOS ratio was 3, and a solid resin was obtained
et al. [111] synthesized a DT resin by using triethoxysilanes and when this ratio was 1. An intermediate ratio led to a mixture of a solid
trimethoxysilanes, while Itoh et al. [112] used dichlorosilanes and and an oil. Indeed, the decrease of the content of ethyl bromide pro-
trichlorosilanes. Phenyl-functionalized DT resins syntheses are described moted the formation of T units that led to a tridimensional network and
in many patents and articles, as summarized in Table 10. Fenn et al. [113] therefore to a solid copolymer. More recently, Roca-Ortega et al. [122]
used triethoxymethylsilane, diethoxymethylphenylsilane and synthesized MDT resins by mixing several chlorosilanes (CH3SiCl3,
phenyltriethoxysilane with alcohol and oxalic acid. Hunter et al. [114] (CH3)2SiCl2 and (CH3)3SiCl) with toluene and a 37 wt.% solution of
and Varaprath et al. [28] replaced SiCl4 with other chlorosilanes mixed in hydrochloric acid. The 29Si NMR analyses confirmed the composition of
a solvent to get respectively DTTPh and DDPhTTPh resins, as seen in Fig. 14, this resin, which was 13.8 wt.% of M units, 27 wt.% of D units and
with R = CH3 or C5H6. In the same way, Porte [115] and Zhang et al. 59.2 wt.% of T units and the presence of residual silanol, around 0.8 wt.
Table 7
Patents and articles describing DQ resins syntheses using different precursors.
Authors Precursors of Final resins Mn, Mw (g mol−1) Other properties Application Ref.
Q units D units
Anonymous SiCl4 Diethyldichlorosilane DQ [36]

Kobayashi et al. TMOS Cyclic dimethylsiloxanes DQ Mw: 3500 ν: 24 mm2 s−1 Water-repellent coating [97]
OMe: 27 wt.%
Chojnowski et al. TMOS Tetramethyldisiloxane DQ Mw: 3500–55500 [98]
TEOS
Gancberg SiCl4 Dimethyldichlorosilane DDPhQ [35]
TEOS Diphenyldichlorosilane
296
Table 8
Patents and articles describing TQ resins syntheses using different precursors.
Authors Precursors of Final resin Properties Application Ref.
Q units T,T’ units
Rust TEOS n-butyl silicone trihalide TQ Coating applications/Electrical insulation [99]

Isozaki TEOS Methyltriethoxysilane TQ η: 5.8 mPa s Inorganic coatings [100]
Cheng et al. TEOS Methyltriethoxysilane TQ [101]
Kurjata et al. TMOS Phenylsilane (PhSiH3) TPhQ Mw: 3400 g mol−1 Coating applications [102]
Eguchi et al. SiCl4 Octadecyltrichlorosilane TC18THQ TC18:TH:Q = 0.52:0.36:0.12 Insulating films [103]
Trichlorosilane
1
%. This resin had good storage stability and was mixed with other H and 29Si NMR spectra gave the general formula
components to create an emulsion that was used in paint formulations. (HSiMe2O1/2)0.9(SiMe2O)0.5(SiMeViO)1(SiPhO3/2)3.1 with a Si-H to Si-
Horstman et al. [108] and Gordon et al. [123] synthesized phenyl CH]CH2 ratio of 0.9, and other characteristics shown in Table 11. This
and aminofunctional MDT resins through the hydrolysis-condensation resin was then blended with diglycidyl ether of hydrogenated bisphenol
of several precursors such as phenyltrimethoxysilane, aminopro- A (DGEBA) and cured to create optically clear silicone resin/epoxy resin
pyldiethoxymethylsilane, γ-aminopropyltriethoxysilane (APTES) or hybrids for LEDs.
trimethylethoxysilane. Yang et al. [124,125] mixed methyltriethox- Zhang et al. [109] synthesized an MDPhTTVi resin made from the
ysilane, dimethyldiethoxysilane and 1,4-bis(ethoxydi-methylsilyl)ben- reaction between methyltrimethoxysilane, vinyltrimethoxysilane, di-
zene (BEDMB) to obtain a carbosiloxane-functionalized MDT resin phenyldimethoxysilane and hexamethyldisiloxane with anhydrous
using the aforementioned method. These resins had a better thermal ethanol. This resin was then blended with an MTHTPh resin in the
stability than MDT resins without aromatic rings, due to the silpheny- presence of a Karstedt catalyst to create a resin with very interesting
lene units. Mu et al. [121] and Zhan et al. [127] used several dis- dielectric properties and thermal resistance. Chen et al. [118] synthe-
iloxanes, ethoxy- and methoxysilanes with a catalyst to create an MDT sized vinyl-terminated (and sometimes vinyl-capped) phenyl-silicone
resin with vinyl and phenyl groups. The resin was then used as a re- resins MDT (Fig. 17) through the co-condensation of several disiloxanes
inforcing agent in PDMS-based silicone rubbers. and methoxysilanes. They synthesized two resins: MViDPhTPh and
Zhang et al. [126] synthesized a phenyl- and vinyl-functionalized MViDPhTPhTVi with different M:D:T ratio, vinyl contents and viscosities.
MDT resin through hydrolytic condensation of 1,3-dihydrote-
tramethyldisiloxane and three different alkoxysilanes. 2.3.3.2. MDQ resins. All results are summarized in Table 12. Hyde [35]
Fig. 13. Synthesis of a TQ silicone resin described in Rust pa-

tent [99].
Table 9
Patents and articles describing MT resins syntheses using different precursors.
Authors Precursors of Final resin Mn, Mw Other properties Application Ref.
(g mol−1)
T, T’ units M, M’ units
Lee et al. Phenyltrichlorosilane Trivinylchlorosilane MHMe2MVi3TPh Mn: 930 OH: < 1.5 wt.% Microelectronic [104]
packaging
Me2 Vi3 Ph
Tetramethyldisilazane Mw: 1310 MH :M :T =
0.13:0.23:0.64
Jonhson Phenyltriethoxysilane Hexamethyldisiloxane MTPhTN η: 2900 mPa s Cosmetic [105]
et al.
3-aminopropyltriethoxysilane
Gordon Phenyltrimethoxysilane Tetramethyldisiloxane MHTTPh M:T:TPh = 0.4:0.5:0.1 Thin films adhesive [106]
et al. applications
Methyltrimethoxysilane
Bailey et al. Phenyltrimethoxysilane Tetramethyldivinyldisiloxane MViTPh Mn: 1440 M:T = 25:75 Reinforced silicone [107]
resin films
Mw: 1700
Horstman Phenyltrimethoxysilane Tetramethyldisiloxane MPrOHTTPh MPrOH:T:TPh = 0.35:0.3:0.3 Coating [108]
et al. Allyl alcohol compositions
Methyltrimethoxysilane
Zhang et al. Phenyltrimethoxysilane Hexamethyldisiloxane MTHTPh Mw: 3700 [109]
Trimethoxysilane
Xie et al. (3-aminopropyl) triethoxysilane Hexamethyldisiloxane MTN Mn: [110]
580–830
Methyltrimethoxysilane M w:
730–940
297
Table 10
Patents and articles describing DT resins syntheses using different precursors.
Authors Precursors of Type of resin M n, M w Other properties Application Ref.
(g mol−1)
T, T’ D, D’
Itoh et al. Methyltrichlorosilane Dimethyldichlorosilane DT Mn: 1040 [112]

Mw: 4220
Porte Trimethyl-1,1,2-trichlorodisilane Dimethyldichlorosilanes DT OH: 2.1–5.7 wt.% Electrical [115]
DTTPh insulation
Fenn et al. Methyltriethoxysilane Methylphenyldiethoxysilane DPhTTPh Insulating bars [113]
Phenyltriethoxysilane
Ph
Hunter et al. Methyltrichlorosilane Dimethyldichlorosilane DTT Electrical [114]
Phenyltrichlorosilane insulation
Varaprath Methyltrichlorosilane Methylphenyldichlorosilane DPhDPhTTPh Hair fixative [28]
et al. Phenyltrichlorosilane
Zhang et al. Methyltrichlorosilane Dimethyldichlorosilane DTTPh Mn: OH: 1.3–4.6 wt.% [116]
2300–5500
Phenyltrichlorosilane
Horstman Methyltrimethoxysilane Diphenyldimethoxysilane DPhTTN DPh:T:TN = 0.23:0.48:0.29 Coating [117]
et al. Aminopropyltriethoxysilane η: 280 mPa s compositions
Xie et al. Phenyltrimethoxysilane Methylvinyldimethoxysilane DViDPhTPh η: 5700–62000 mPa s [6]
Diphenyldimethoxysilane
Vi: 1.5–4.4 mmol g−1
Ph: 39 wt.%
Chen et al. Vinyltrimethoxysilane Phenylvinyldimethoxysilane DPh,ViTPhTVi η: 5800–14500 mPa s LED packaging [118]
Phenyltrimethoxysilane D:T = 0.6:0.4 to 1:0
Ep Ph Ep
Lee et al. 3-glycidoxypropylmethyl 3-glycidoxypropylmethyl DD T T M w: D:T = 0.5:0.5 to 0:1 Coatings [119]
trimethoxysilane dimethoxysilane 2800–34000
Phenyltrimethoxysilane Dimethyldimethoxysilane
2-(3,4-epoxycyclohexyl) ethyl
trimethoxysilane
Liu et al. Methyltrimethoxysilane Octamethylcyclotetrasiloxane DTTC8 D:T = 0.16:0.84 Coating [111]
compositions
n-octyltriethoxysilane OR: 18 wt.%
mixed diphenyldichlorosilane, trimethylethoxysilane and TEOS in MDHQ resins, as shown in Fig. 18. Griswold et al. [131] used
water to get a viscous MDPh2Q resin, which was solid after heating. dimethyldimethoxysilane, dimethylethoxysilane, trimethylchlorosilane
By using SiCl4 instead of TEOS as a precursor, and mixing and TEOS to obtain an MMHDQ resin that was used in silicone release
phenylethyldichlorosilane and triethylchlorosilane, Hyde also coatings. Cray et al. [132] synthesized branched vinyl-functionalized
synthesized an MEtDPhQ resin as an oily liquid with a kinematic MDQ resins by using tetrakis(vinyldimethylsiloxy)silane,
viscosity of 11780 mm2 s−1 and molar ratio MEt:Q and DPh:Q of 0.33 octamethylcyclotetrasiloxane (D4) and tetrakis(trimethylsiloxy)silane.
and 1, respectively. Dexter [46,47] and Flannigan [15,129,130]
synthesized MDQ resins with hydrosol Si(OH)4, which was made by 2.3.3.3. MTQ resins. Flannigan [15], in addition to MDHQ resins,
mixing sodium silicate with hydrochloric acid (concentrated or in synthesized MTQ resins by adding sodium methylsiliconate to sodium
solution). This hydrosol was then mixed with a chlorosilane, a silicate, and the obtained resin of 50 wt.% solids in xylene had a M:T:Q
dichlorosilane, and sometimes hexamethyldisiloxane, to get MDQ or ratio of 0.65:0.2:0.8, as shown in Table 13. In the patent GB 783,867
Fig. 14. Syntheses of phenyl-functionalized DT resins described in Hunter and Varaprath patents [28] (R = CH3 or C5H6).
Fig. 15. Curing process of silicone resin with HCB described in Xie et al. article [6].
298
C. Robeyns et al.
Table 11
Patents and articles describing the syntheses of MDT resins with different precursors.
Authors Precursors of Final resins Other Properties Application Ref.
T units D units M units
Rochow TEOS + EtMgBr TEOS + EtMgBr TEOS + EtMgBr MDT Density: 1.19 gcm−3 [2]
Refractive index: 1.423
Meadowcroft TEOS + EtMgBr TEOS + EtMgBr TEOS + EtMgBr MDT ν: 1.9–4.1 mm2 s−1 [120]
Mn: 200–880 g mol−1
Roca-Ortega et al. Methyltrichlorosilane Dimethyldichlorosilane Trimethylchlorosilane MDT ν: 1209 mm2 s−1 [122]
Gordon et al. Phenyltrimethoxysilane Phenylmethyldimethoxysilane Trimethylethoxysilane MDPhTPh M:DN:DPh:TPh = 0.08:0.2:0.15:0.6 [123]
Aminopropyltriethoxysilane Hexamethyldisilazane Ph: 73 wt.%
NH2: 2.6 wt.%
Horstman et al. Phenyltrimethoxysilane Aminopropyldiethoxymethylsilane Trimethylethoxysilane MDNTPh M:DN:TPh = 0.1:0.4:0.5 Coating [108]
Methylphenyldimethoxysilane MDNDPhTPh M:DN:DPh:TPh = 0.2:0.4:0.2:0.3 compositions
299
Yang et al. Methyltriethoxysilane Dimethyldiethoxysilane 1,4-bis(ethoxydimethylsilyl) benzene “MPh”DT [124,125]
Zhang et al. Phenyltrimethoxysilane Methylvinyldimethoxysilane 1,3-dihydrotetramethyldisiloxane MHDDViTPh Mn: 650 g mol−1 [126]
Dimethyldimethoxysilane
Ð: 1.43
η: 1500 mPa s
Si-H:Si-Vi = 0.9
Mu et al. Phenyltrimethoxysilane Dimethyldimethoxysilane Hexamethyldisiloxane MMViDTPh R:Si = 1.36–1.65 Reinforcing filler [121]
1,3- divinyl-1,1,3,3- Ph:R = 41–60
tetramethyldisiloxane Vi: 3.5–3.7 wt.%
Zhan et al. Phenyltrimethoxysilane Phenylmethyldimethoxysilane Dimethylvinylethoxysilane MViDViDPhTPh Vi: 3.5 wt.% LED packaging [127]
Methylvinyldiethoxysilane
Zhang et al. Methyltrimethoxysilane Diphenyldimethoxysilane Hexamethyldisiloxane MDPhTTVi Mw: 6700 g mol−1 [109]
Vinyltrimethoxysilane
Yang et al. Phenyltriethoxysilane Phenylmethyldiethoxysilane Dimethylvinylethoxysilane MViDPhTPh M:D:T = 3.3:1.7:1 LED packaging [128]
η: 4800 mPa s
Vi Ph Ph
Chen et al. Vinyltrimethoxysilane Phenylmethyldimethoxysilane Tetramethyldivinyldisiloxane M D T M:D:T = 10:8:2 LED packaging [118]
Phenyltrimethoxysilane MViDPhTPhTVi η: 2900–5400 mPa s
Fig. 16. Synthesis of an MDT siliconeresin described in the

first Rochow patent [2].
[133], an MTQ resin with propyl groups was synthesized through the by adding dropwise a TiO2 sol into the MQ-toluene solution and then
reaction of hexamethyldisiloxane and a co-hydrogel containing Q units stirring for 6 h at 60 °C. The Ti:MQ ratio was 1:1 to 4:1, and FT-IR
and TPr units. The resin was a powder with molar ratios M:Q of 0.29 and analyses showed the presence of Ti-O-Si covalent bonds. The hybrid
TPr:Q of 0.04 and it was used as a filler in silicone elastomers. Vinyl- nanocomposite could then be used in LED encapsulating materials or in
functionalized silicone resins with three units have been synthesized by solar cell materials. Wang et al. [142] synthesized titanium-doped si-
Butler [134,135] in 1992. To do so, he used a method similar to licone resins with two triethoxysilanes and tetrabutyl titanate. The re-
Shirahata’s one (Fig. 7) and added vinyltrichlorosilane under an inert sins with higher Ti contents showed better thermal and storage stabi-
atmosphere (nitrogen) to get white liquid MTViQ resins with vinyl lities, due to the Ti-O bond dissociation energy that is higher than Si-O
content around 4.7 wt.%. In his paper, Kuo et al. [136] synthesized an bond corresponding one.
MTPhQ resin by mixing TEOS, phenyltriethoxysilane and Kwon et al. [144] synthesized a TQ resin with vinyl groups, hy-
chlorotrimethylsilane with ethyl acetate and water under heating. droxyl groups and a zirconium atom instead of a silicon atom in some T
The molar ratio M:[T+Q] was 0.8 with few residual hydroxyl and units. To do so, they mixed a vinyltriethoxysilane with TEOS in pro-
ethoxy groups, as shown in Table 13. pyleneglycol monomethylether acetate as a solvent and zirconium (IV)
Chevalier et al. [137] synthesized vinyl and phenyl-functionalized butoxide. The resin was used in silicone compositions as protective
MTQ resins through a hydrolysis-condensation reaction between layers for displays and semiconductor devices.
chlorosilanes, followed by a cure with a platinum complex as the cat-
alyst in order to enhance their thermo-mechanical properties. Issari
3. Characterization of silicone resins
[138] prepared several fluorinated reactive MTQ silicone resins with
TEOS as a precursor and a minimum fluorine content of 55 wt.%. These
3.1. Characterization of silicone resins in the literature
resins were used for liquid optically clear adhesives.
Since the 40s, more than one hundred patents and articles de-
2.3.3.4. Others. Table 14 presents few studies where complex resins scribing the synthesis of silicone resins have been published. Still, little
were synthesized. In the patent GB 603,076 [36], a mixture of characterization was done, according to the different tables given
phenyltrichlorosilane, phenylmethyldichlorosilane and TEOS are above. From this compilation of results, we observed that most of the
dissolved in dioxane to synthesize a solid DPhTPhQ resin, as shown in MQ resins have an M:Q ratio between 0.5 and 1 and a number-average
Table 14. Zhu [139] synthesized a special resin containing a disilane of molecular weight between 2000 and 5000 g mol−1, as shown in Fig. 20.
the formula O3-aRaSi-SiRbO3-b with a = 0, 1 or 2 and b = 0, 1, 2 or 3 Flagg & McCarthy [67] observed a clear trend of decreasing M:Q ratio
and R is H, methyl, ethyl or phenyl. The resin was used to form a cured with increasing molecular weight, and it is noteworthy that this cor-
coating on substrates employed in electronic devices for instance relation was also seen when all the results of the literature are com-
(Table 15). bined, as shown in Fig. 21. In the analyzed patents and articles, molar
ratios are almost systematically determined. When specified, the mo-
2.3.4. Metal-mixed silicone resins lecular masses are usually calculated based on polystyrene standards,
Q-Ti silicone resins were made by Boisvert et al. [140], by com- except for few articles like the article of Flagg & McCarthy [67] where
bining di-t-butoxydiacetoxysilane, THF, water, tetra-t-butoxytitanium poly(methylmethacrylate) (PMMA) standards were used.
and toluene and heating the mixture to 35 °C under reduced pressure. When the M:Q ratio is higher than 1, the resins are in a viscous state,
After a distillation with a Dean-Stark trap, the solution was filtered and whereas for a ratio lower than 1, they come as a solid white powder.
concentrated under reduced pressure at 33 °C, and finally further con- This observation was made in several papers [51,54,67] and can be
centrated under high vacuum in a rotary-evaporator to give a silicone explained by the organization of the resin network induced by the
resin with a low molecular weight, as shown in Fig. 19. The Q-Ti resin tetrafunctional Q units. The more Q units, the more packed and orga-
synthesis is schematically shown in Fig. 19. nized configuration, which favors a solid state. The viscosity was not
Xiang et al. [141] created TiO2/MQ hybrid nanocomposites by first one of the most studied characteristics since little reported resins are
synthesizing an MQ resin in toluene with TEOS as a precursor, and then liquid; however, it can be seen from Fig. 21 that the viscosity
Fig. 17. Schematized structure of the DT and MDT resins synthesized in Chen et al. article [118].
300
dramatically decreases when the M:Q ratio increases. The thermal
[129,130]
stability of resins has not been studied in the majority of the patents,
[46,47]
[131]
[132]
but the softening points were often determined. It appeared that soft-
[35]
Ref.
ening points are not correlated with the M:Q ratios, but it seems that
MQ resins with high molar masses lead to higher softening points. For
Anti-adhesive compositions
instance, one of the resins prepared by Kuo et al. [58] has a molar mass
Release compositions
Release compositions
1400 g mol−1 and a softening point around 80 °C, while Huang et al.
Electric insulation
[71] prepared a resin with a molar mass around 5000 g mol−1 that had
a softening point around 220 °C.
Application
In their paper about MQ copolymers, Flagg & McCarthy [67] com-

pared the 1H and 29Si NMR spectra of the MQ resins characterized in the
PSAs
literature, and observed that for similar resins the spectra were almost
identical. The presence of silanol groups could not be confirmed by
Mw: 9100 g mol−1
ν: 11780 mm2 s−1
Mn: 920 g mol−1

Other Properties
NMR since the silanol proton is not apparent, but it could be seen on the
ν: 600 mm2 s−1
infrared spectra with the peak of the Si-OH stretching, around

Vi: 0.6 wt.%
3100–3800 cm−1. They also observed that the Diffusion NMR (or D-
NMR) was a useful technique to characterize the copolymers in solu-
tion, and that the curves of the diffusion coefficient were steeper for low
molecular weight and low dispersity resins. Note that this analysis was
M:MH:D:Q = 0.02:0.20:0.54:0.24
not used extensively in the literature.

The properties of phenyl- and/or vinyl-functionalized MQ resins
were even less characterized, except for the content of vinyl, phenyl,
ethoxy or hydroxyl groups that are almost systematically calculated.
For those resins, the vinyl content goes from 0.86 to 9 wt.% while the
MEt:Q = 0.33
phenyl content goes from 4.2 up to 30 wt.% [54,83,84]. Among the

M:Q = 0.57
D:Q = 0.13
Molar ratio
DPh:Q = 1
other resins (T, DT, MTQ...), only few patents characterized them, de-
termining essentially their molar mass or their viscosity. Depending on
the resins, either the kinematic or dynamic viscosity was determined,
with values comprised between 2 and 11800 mm2.s−1 and between 6
Final resins
and 15000 mPa s, respectively.

MEtDPhQ
MViDViQ
MMHDQ
MDPh2Q
MDHQ
MDQ
In a general way, each resin synthesized in a patent or article is

unique and there is no guarantee in their reproducibility, even for
commercial resins whose molar composition and properties can vary
Tetrakis(vinyldimethyl siloxy)silane
from one batch to another. The next part will focus on the character-
Tetrakis(trimethyl siloxy)silane
ization of some commercial resins that was performed in our labora-

tory.
Trimethylethoxysilane
Trimethylchlorosilane
Trimethylchlorosilane
Dimethylethoxysilane
Triethylchlorosilane
3.2. Our characterization process of commercial silicone resins
In this study, we selected 15 commercial resins and characterized

Patents and articles describing the syntheses of MDQ resins with different precursors.
M units
them. The technical data sheets provided by the suppliers give little
information about the molar composition and the structure of the sili-
cone resins. In the following experiments, the resins were labelled
Phenylethyldichlorosilane
Dimethyldimethoxysilane
RES1, RES2 and so on until RES15. Resins RES1 to RES9 were said to be
Dimethyldichlorosilane
Diphenyldichlorosilane
silanol-functional MQ resins, also referred as MQ or MQQOH resins.

Methyldichlorosilane
RES10 was sold as a polyphenylsilsesquioxane resin, resins RES11-

RES13 as MDViQ resins, and resins RES14-RES15 as MMViQ resins.
When in solution, the resins were dried on rotary evaporator and va-
D units
cuum oven before being analyzed.

D4
3.2.1. Experimental
Tetrakis(vinyldimethyl siloxy)silane
1
H and 13C NMR spectra were acquired on a Bruker AVANCE III
Tetrakis(trimethyl siloxy)silane
400 MHz spectrometer using toluene-d8 or CDCl3 as a solvent, while

29
Si NMR were carried out on a Bruker AVANCE III 500WB spectro-
meter. Size Exclusion Chromatography (SEC) was conducted on a
Shimadzu/toluene GPC equipped with three SODEX KF-804, KF-605
and KF-806 columns and a refractive index detector. Toluene was the
Sodium silicate
Sodium silicate
mobile phase with a flow rate of 1 ml.min−1. The resins were dissolved
Precursor of
TEOS SiCl4
in toluene at a concentration of 2–3 mg ml−1. The thermal transitions of

Q units
TEOS
the resins were determined on a TA differential scanning calorimetry

(DSC) Q22 instrument. The DSC instrument was calibrated according to
the melting temperature of indium (Tm = 156.63 °C). The temperature
Griswold et al.
was increased at a constant rate of 10 °C min−1 from −150 °C to 180 °C

Cray et al.
Flannigan
and then decreased down back to −150 °C. The thermogravimetric

Table 12
Authors
Dexter
Hyde
analysis (TGA) measurements were carried out on a TA instrument

Q500 with a nitrogen flow rate of 90 ml min−1. The temperature was
301
Fig. 18. Synthesis of MDQ silicone resins described in Dexter [46,47] and Flannigan patents [15,129,130].
Table 13
Patents and articles describing the syntheses of MTQ resins with different precursors.
Authors Precursors of Final resins Molar ratio Other Properties Application Ref.
Q units T units M units
Flannigan Sodium Sodium Trimethylchlorosilane MTQ M:T:Q = 0.65:0.2:0.8 Foam stabilizer [15]
silicate methylsiliconate
solution
Anonymous Co- Co-hydrogel Hexamethyldisiloxane MTPrQ [133]
hydrogel
Butler TEOS Vinyltrichlorosilane Hexamethyldisiloxane MTViQ M:Q = 1.6 ν: 300–400 mm2 s−1 [134,135]
TVi:Q = 0.4
Ph
Kuo et al. TEOS Phenyltriethoxysilane Chlorotrimethylsilane MT Q M:[T + Q] = 0.8 Mn: PSAs [136]
3000–4300 g mol−1
OH:M = 0.0059–0.0063 Mw:
4200–7100 g mol−1
OEt:M = 0.047–0.060 Softening Point:
130–150 °C
Chevalier et al. SiCl4 Phenyltrichlorosilane Dimethylvinylchlorosilane MViTHTPhQ M:T:Q = 0.2:0.7:0.1 Mw: 2500 g mol−1 Microeletronic [137]
packaging
Trichlorosilane
Issari TEOS (tridecafluoro 1,1,2,2- (tridecafluoro 1,1,2,2- MFTFQ Refractive index: Optically clear [138]
tetrahydrooctyl) tetrahydrooctyl) 1.35 adhesives
triethoxysilane dimethylchlorosilane
Table 14
Patents and articles describing the syntheses of other resins with three or four units.
Authors Precursors of Type of resin Other Properties Application Ref.
Q units T units D, M units
Anonymous TEOS Phenyltrichlorosilane Phenylmethyldichlorosilane DPhTPhQ Electric insulation [36]

Zhu Dimethyltetrachlorodisilane Trimethyltrichlorodisilane Butylmethyldichlorosilane M’xMaDbTcQd Mn: Coatings for electronic [139,143]
1740 g mol−1 devices
Tetramethyldichlorodisilane M w:
3500 g mol−1
increased at a constant rate of 10 °C min−1 from room temperature to spinning sidebands.

800 °C. The structures of resins RES1 to RES8 are in agreement with the
suppliers information, however it is not the case for RES9. Indeed, this
resin was not made of M and Q units but of D and T units, as shown on
3.2.2. NMR characterization
the 29Si NMR spectrum in Fig. 24. In the same way, the NMR analyses
Fig. 22 gives 29Si and 1H NMR spectra for RES1, shown as an ex-
confirmed the MViQ structure of RES11 and RES12 and the MDViQ
ample. Those spectra are representative of all the MQ copolymers RES1
structure of RES14 and RES15. However, resin RES13 does not possess
to RES8. On the 1H NMR spectrum, the peaks at ca. 1.5 and 4 ppm are
any DVi units, contrary to the supplier’s data sheet information, which
attributed to the protons of ethoxy groups, and the high peak at 0 ppm
means this is an MMViQ resin instead of an MDViQ resin. Indeed, the
corresponds to the methyl monofunctional M units of the resin. On the
29 peaks for vinyl-D unit are usually seen around −35 ppm, which is not
Si NMR spectrum, the peak at ca. 12 ppm is characteristic of M units,
consistent with the peak at 0 ppm seen on the NMR spectra in Fig. 24.
while peaks at −100 and −108 ppm are assigned to the Q3 and Q4
The 1H NMR spectra of the MQ and MViQ resins revealed the pre-
units, respectively.
sence of ethoxy groups, but the proton of the hydroxyl groups was not
The 29Si NMR confirmed the structure of RES10 via the presence of
seen on the spectra. Therefore, the silanol content was calculated from
characteristic T unit peaks between −60 and −80 ppm, in Fig. 23. The
13 the combination of 29Si and 1H NMR analyses. Indeed, in MQ and
C NMR spectrum highlighted the presence of phenyl groups at
MMViQ silicone resins, the total molar percentage of Q3 units measured
130 ppm. On this spectrum, the peaks at 30 and 220 ppm correspond to
302
Table 15
Patents and articles describing the syntheses of metal-mixed silicone resins.
Authors Precursors of Final resin Mn, Mw (g mol−1) Application Ref.
Q units others
Boisvert et al. Di-t-butoxydiacetoxysilane Tetra-t-butoxytitanium Q-Ti Mn: 980–1100 Electronic devices coatings [140]
Mw: 1500–1550
Xiang et al. TEOS Tetra-n-butyl titanate TiO2/MQ Mn: 2300 LED packaging [141]
Hexamethyldisiloxane Mw: 5500
Wang et al. N/A Silane monomers T-Ti Mw: 3180–3550 [142]
Tetrabutyl titanate
Kwon et al. TEOS Vinyltriethoxysilane TQZr Mw: 4700 Insulation [144]
Zirconium (IV) butoxide
by NMR can be separated into the contribution of hydroxyl (Q3/OH) and the presence of hydroxyl groups increases the polarity of the resin, and
alkoxyl (Q3/OX) functionalized units (Eq. (1)). The percentage of Q3 thus its affinity with the SEC columns. Such interactions induce a delay
units is directly determined by 29Si NMR (Eq. (2)), whereas 1H NMR in the retention volume peak and the calculation of an even more down-
only gives the molar percentage of alkoxyl function in the silicone re- estimated molecular weight.
sins (Eq. (3)). In the case of ethoxy functions, this percentage was
calculated from the average of the integration values of eCH2 and
eCH3 corresponding peaks in 1H NMR spectra. These molar percen- 3.2.4. Thermal analyses
tages of Q3 and ethoxy functions were normalized towards the molar The Differential Scanning Calorimetry results (not shown) revealed
percentages of M units whose (CH3)3 peak was integrated on the 1H no transitions for RES1 to RES7 and RES13 resins, but the phenyl-
NMR and 29Si NMR spectra. Q3/OX is then calculated according to Eq. functionalized RES10 resin showed a transition around 66 °C that could
(4) and Q3/OH mol.% from the Eq. (1). be linked to the temperature range of the softening point (54–70 °C)
according to the supplier’s data sheet.
%Q3 = %Q3/ OH + %Q 3/ OX (1)
The thermal stabilities of the different resins were studied with the
%Q 3 help of thermogravimetric analysis (TGA) in an inert atmosphere.
29
%Q 3 = = x (from SiN MR) Residual weights vary broadly, from 6 to 72% depending on the resin
%(CH3)3 (2)
structure (Table 16). The highest residual weight for RES10 could be
% alkoxyl function explained by its phenyl groups, which make this particular resin more
%Q3/ OX = = y (from 1 H NMR)
%(CH3)3 (3) stable to temperature [136]. Only MQ resins data are shown in Fig. 27.
A clear difference between RES6-RES7 and the other resins was also
%Q3*y seen. Indeed, their onset temperatures, corresponding to temperatures
%Q3/ OX =
x (4) when the degradation begins, are much lower compared with the other
Vi resins, as well as the residual weights. At a similar silanol content, the
The values of silanol content obtained for the MQ and M Q resins
resins with M:Q ratios higher than 1 are less thermally stable than MQ
vary from 01 up to 7.5 wt.%, as reported in Table 16. The M:Q ratio is
resins with lower M:Q ratios. Xu et al. [54] and Kuo et al. [58] observed
different for each MQ or MQQOH resin and varies from 0.71 to 1.4.
a similar correlation between the M:Q ratio and the thermal stability,
showing that the thermal decomposition rate of MQ copolymers slows
3.2.3. SEC characterization
down with the reduction of the content of organic groups moieties. The
While SEC analyses give a molar mass in polystyrene standards that
condensation of active silanol occurs while increasing temperature,
is relatively close to the actual molar mass for linear PDMS, the molar
leading to a higher crosslinking density and making the resin more
masses for silicone resins, a 3D complex and compact structure, are
thermally stable. It was also said that the lower the M:Q ratio, the
generally under-estimated. The “apparent” molar masses for MMViQ
higher the silanol content, which leads to more condensation of silanol
and MDViQ resins are shown in Fig. 25 after peak areas were normal-
[54]. In Fig. 27, the correlation between the degradation of M:Q resins
ized. A larger mass distribution with three peaks was seen for MDViQ
and their silanol content was not found as obvious as results in Xu’s or
resins RES14 and RES15, while only two peaks were seen for MMViQ
Kuo’s papers.
resins RES11 and RES13. RES11 had a weak peak of hydrodynamic
volume, seen around 1000 g mol−1. Between the MDViQ resins, a higher
polydispersity index was seen for RES15 (Ð = 3) compared with RES14
3.2.5. Conclusions
(Ð = 2.4), which indicated a more important heterogeneity of hydro-
In summary, the characterization of commercial resins showed
dynamic volumes for RES15. Hydrodynamic volumes of MDViQ resins
different molar compositions, silanol and ethoxy contents as well as
are logically higher than MMViQ ones because of the DVi units that give
molecular weights and residual weights. Some resins were found to
a more spacious structure compared with MVi units, as schematically
have conventional characteristics (e.g. MQ resins RES1 and RES4, or
shown in Fig. 26 [145].
RES6 and RES7), and some others have unique structures (e.g. DT and
The resins average molecular weights were measured between 800
TPh for RES9 or RES10). The analyses of these resins revealed that
and 3300 g mol−1, as shown in Table 16. No correlation was observed
sometimes, their composition was different from the suppliers’ in-
between molecular weights of a resin and its type (MQ, DT, TPh or
formation, which is a good reminder of the importance of character-
MMViQ) or its M:Q ratio, but the polydispersity index is higher when
izing commercial resins before using them. In a general way, many
the molar masses increase. It is important to note that the silanol
resins of different structures and molecular weights are commercially
content has an incidence on the calculated molecular weights. Indeed,
available. Nevertheless, it can be difficult to find all the wanted char-
acteristics in a single commercial resin, leading one to modify com-
1
In some cases, calculus gave slightly negative values for OH contents, be- mercial resins, as shown hereafter.
cause of the uncertainty on both proton and silicon NMRs. In all instances
anyway, it was admitted that the silanol content was nil in these (rare) cases.
303
Fig. 19. Synthesis of a Q-Ti silicone resin described in Boisvert et al. patent [140].
Fig. 20. Distributions of the M:Q ratios and the number-average molecular weights of MQ resins versus the number of patents and articles where they are described.
Fig. 21. Correlation between the number-average molar mass and the M:Q ratio of synthesized MQ resins as described in patents and articles (left) and relationship
between the viscosity and the M:Q ratio of liquid resins (right).
4. Modification and functionalization of silicone resins The final MQ resin only contained 0.24 wt.% silanol. Butler [61] iso-
lated the silicone resin using distilled water and toluene, and then
4.1. Modification of silicone resins in the literature neutralized and dried the organic phase (containing the silicone resin)
with NaHCO3 and MgSO4. Then he filtered the organic phase and re-
4.1.1. Post-condensation of MQQOH into MQ resins moved the solvent under reduced pressure at 130 °C. The final resin
During the synthesis of MQ resins, most of the final products contain only had 0.3 wt.% residual silanol. Voronina et al. [62] washed the
residual silanol. Therefore, some patents and articles described a post- organic phase with water to remove the excess of acetic acid they used
condensation of these MQQOH resins. For example, Weidner et al. [64] for the resin synthesis, and dried the organic layer with Na2SO4. After
mixed a 25 mol.% solution of NaOH, a mixture of water and ethanol the solvent evaporation, the final resin did not have any residual silanol
and the resin in solution in toluene and heated under reflux for 2.5 h. groups according to the FT-IR spectroscopy results. Burns et al. [70]
304
Fig. 22. 1H (a) and 29

Si (b) NMR spectra of the RES1 resin.
13 29
Fig. 23. C (a) and Si (b) NMR spectra for the silsesquioxane RES10 resin.
29
Fig. 24. Si NMR spectra of resins RES8, RES9 (a) and RES11-RES15 (b).
condensed a resin through a toluene reflux with HCl and a Dean-Stark ((CH3)3Si)2NH in toluene. The final MM’Q resin had a molar ratio
trap, which led to the elimination of the water and then prevented the M:M’:Q of 0.27:0.08:0.65, a vinyl content of 8.4 wt.% and number-
formation of new Si-OH bonds. Finally, Flagg & McCarthy [67] elimi- average and weight-average molecular weights of 4500 and
nated the residual silanols by making reacting an MQQOH resin with 10000 g mol−1, respectively. Rivers-Ferrell et al. [147] added 6-hex-
trimethylsilyl iodide, which converted 90% of the Q3 to Q4, and dra- enyldimethylchlorosilane to a xylene solution of MQQOH resin with an
matically attenuated the OeH absorption band on the FT-IR spectra. M:Q ratio of 0.9 and a silanol content of 6.2 wt.%. The final resin was a
xylene solution of hexenyl-functionalized MM’Q resin, a vinyl content
4.1.2. Modification of silicone resins by capping of 1.58 wt.% and a silanol content of 3.4 wt.%, as well as the byproduct
Capping is a process used to reduce the silanol content of MQ resins 1,1,3,3-tetramethyl-1,3-dihexenyldisiloxane. The molar ratio of the
by M precursors (Table 17). In Wright et al. patent [146], amine-capped final resins are displayed in Table 17. Finally, Vincent [93] modified an
resins were prepared by reacting MQQOH resins with a cyclic silazane MTOHQ resin into an MTQ powder resin with a higher content of M
called 1,2,2,4-tetramethyl-1-aza-2-silacyclopentane. Kobayashi et al. units. The initial MTOHQ resin had number and weight-average molar
[84] synthesized an M’QQOH resin where M’ = (CH2]CHC4H8) masses of 4550 and 17760 g mol−1, respectively. This resin was mixed
(CH3)2SiO1/2 and then added M units by mixing this resin with with trimethylmethoxysilane in presence of sodium methoxide basic
305
Table 16
Molar composition and characteristics of commercial silicone resins.
Resin Resin type ‘M’ (mol.%) ‘D’ (mol.%) ‘T’ (mol.%) ‘Q’ (mol.%) M:Q ratio Mn (g mol−1) Mw (g mol−1) Ð –OH (%) –OEt (%) Residual weight (%) Tonset (°C)
RES1 MQ 46 54 0.86 2200 6800 3.1 0 4.6 59 220

RES2 MQQOH 48 52 0.93 2200 4700 2.1 7.5 1.3 47 170
RES3 MQQOH 49 51 0.95 2300 4800 2.1 6.5 4.9 58 150
RES4 MQ 47.5 53 0.90 1900 3400 1.7 0 6.7 45 210
RES5 MQQOH 45 57 0.75 1200 1900 1.6 3.7 17.3 57 160
RES6 MQQOH 58 42 1.4 800 1300 1.6 6.5 10.7 6 80
RES7 MQQOH 52 48 1.1 800 1300 1.6 4.3 19.3 13 100
RES8 MQ 41.5 58.5 0.71 3300 9240 2.8 0.3 4.1 48 NA
RES9 DT 16 84 2700 6210 2.3 6.4 6.5 59 NA
RES10 TPh 100 800 1500 1.9 21 4 72 70
RES11 MMViQ 40 (M) 51.7 0.93 2000 3600 1.8 1.1 6.2 NA NA
8.3 (MVi)
RES12 MMViQ 39.8 (M) 51.9 0.93 2000 3800 1.9 0.7 4.1 NA NA
8.3 (MVi)
Vi
RES13 MM Q 50 (M) 41 1.5 2400 5000 2.1 3.7 0 59 200
9.5 (MVi)
Vi Vi
RES14 MD Q 42.4 6.6 (D ) 51 0.83 2600 6240 2.4 0.6 4.4 NA NA
RES15 MDViQ 41.6 6.8 (DVi) 51.6 0.81 2800 8400 3.0 1 3.2 NA NA
Fig. 25. SEC curves for MMViQ RES11 and RES12 resins and for MDViQ RES14
and RES15 resins.
catalyst. After the reaction, trimethylchlorosilane was added to in- Fig. 27. TGA curves of RES1-RES7 resins.
activate the catalyst and an MTQ resin was obtained with Mn and Mw of
2980 and 5100 g mol−1, respectively, and the residual presence of
Fig. 26. Schematic structures of silicone resins (a) MDViQ and (b) MMViQ.
306
Table 17
Patents describing the modification of silicone resins by capping.
Authors Initial resins Final resins Molar ratio Other Properties Application Ref.
OH N
Wright et al. MQQ MM Q Si-OH = 0.85 wt.% PSAs [146]
Kobayashi et al. MM’Q M:M’:Q = 0.27:0.08:0.65 Mn: 4500 g mol−1 [84]
M’QQOH Mw: 10000 g mol−1
Vi: 8.4 wt.%
Rivers-Ferrell MQQOH MM’QQOH M:Q = 0.9 Alk: 1.6 wt.% Silicone release coatings [147]
(M’=C6H12) M’:Q = 0.09 -OH: 3.4 wt.%
OH
Vincent MT Q MTQ Before: [148]
M:TOH:Q = 0.43:0.12:0.45 Mn: 2980 gmol−1
After:
M:T:Q = 0.48:0.03:0.5 Mw: 5100 gmol−1
Fig. 28. Functionalization of MQ silicone resins described in Kobayashi, Butler and Rubinsztajn's patents [44,61,149].
hydrochloric acid and isopropanol. After a refluxing for a certain time,

they post-introduced a PDMS inside the reactor and the heating con-
tinued. They isolated an MQ-PDMS resin in 46 wt.% in hexamethyldi-
siloxane and used it in hair products formulations. Juen et al. [151]
prepared an MQ-PDMS copolymer by mixing an MQ resin and PDMS in
xylene and heating under reflux for a certain time. They evaluated two
different condensation catalysts (ammonia and potassium acetate) and
the final products had a very high weight-average molecular weight
comprised between 73.2 and 2450 kg mol−1. The MQ-PDMS resin is
schematically shown in Fig. 29.
Cook et al. [24,27] and Li et al. [152] modified MQQOH resins into
propyl-functionalized MTPrQ resins through the condensation of an
MQQOH resin and a propyl-silsesquioxane resin in a xylene solution in
the presence of a basic catalyst (a KOH solution) and a Dean-Stark trap.
Fig. 29. MQ-PDMS silicone resin synthesized in Juen’s patent [151]. Li et al. [152] capped the new resin with M units by adding chloro-
trimethylsilane in a solution of xylene and deionized water, and ob-
methoxy groups. tained a light yellow product solution with a weight-average molecular
weight of 377 kg mol−1 and a silanol content of 1 wt.%. The molecular
weight increased up to 415 kg mol−1 after 78 h of ageing at 110 °C
4.1.3. Modification of silicone resins by condensation/redistribution (Table 18). Cook et al. also created MTPrTPhQ and MDTPrQ resins by
reactions adding respectively a phenyl-silsesquioxane resin or a PDMS fluid to an
One can also functionalize the resins by a simple condensation/re- initial mixture of MQQOH and TPr resins. The MTPrTPhQ and MDTPrQ
distribution step, using this time at least divalent precursors (Table 17). resins had a silanol content of 0.8–1.6 and 1.8 wt.%, respectively.
Butler [61], Rubinsztajn et al. [149] and Kobayashi et al. [44] mixed an
MQ resin with tetramethyldisiloxane to get an MMHQ resin, as shown in
Fig. 28. In two cases, an acid was used to eliminate the silanols by post- 4.1.4. Functionalization of (M)MHQ silicone resins by hydrosilylation
condensation. These acids could be either trifluoromethane sulphonic Hydrosilylation is one of the current methods found in literature to
acid (Butler), Filtrol 20 (Kobayashi) or acid clay (Kobayashi). Su- modify silicone resins (Table 19). Riding [150] prepared a MMHQ resin
perbases such as linear phosphonitrilic chloride Cl3P(NPCl2)nNPCl3PCl6 (vide supra) and reacted it with 4-vinylcyclohexeneoxide and a Pla-
(with n = 1 or 2) were also used by Rubinsztajn et al. [149]. His team tinum catalyst to obtain an epoxy-functionalized MMepoxQ resin
also created an MMViQ resin by using tetramethyldivinyldisiloxane, and (Fig. 30). This resin was used in UV-curable anti-adhesive formulations.
Kobayashi D/DH functionalized resins by adding (HMeSiO)(Me2SiO), in Hurford et al. [75], Ekeland et al. [153], Burkus-II et al. [154] and
place of tetramethyldisiloxane. In Varaprath et al. [28] patent, MQQOH Murai et al. [155] functionalized MHQ resins with specific reagents to
resins are modified to create amine-functionalized MQ resins through get resins of the general formula MM’Q, where M’ is either an oxyalk-
the reaction with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane as enyl group [CH2]CH(CH2)8][CH3]2SiO1/2, a polyoxyalkylene group
a T precursor. Riding [150] mixed an MQ resin with tetra- HO-(OCH2CH2)12-(CH2)3SiO1/2, a 3-methacryloxy-propyltrimethox-
methyldisiloxane and an acid catalyst to get an MMHQ resin. ysilane or an ethyltrimethoxysilane, respectively.
Varaprath et al. [28] also synthesized an MQ-PDMS resin based on Yoshii et al. [78] prepared cured MQ resin films containing mole-
the Daudt et al. method [40]. They mixed sodium silicate and tri- cularly dispersed azobenzene by mixing MHQ and MViQ resins with a
methylchlorosilane as precursors for Q and M units, respectively, with toluene solution of platinum-divinyltetramethyldisiloxane complex and
307
Table 18
Patents describing the modification of MQQOH silicone resins by exchange reaction.
Authors Initial resins Final resins Molar ratio Other Properties Application Ref.
OH H
Butler MQQ MM Q Si-H: 6.2 wt.% [61]
Rubinsztajn et al. MQQOH MMHQ [149]
MMViQ
Kobayashi et al. MQQOH MMHQ M:Q = 0.75 Si-H: 0.09 wt.% Electrical-insulating varnish [44]
Mn: 4900 gmol−1
MDDHQ M:Q = 0.75 Si-H: 0.07 wt.%
D:Q = 0.2 Mn: 5100 g mol−1
H
MD Q M:Q = 0.75 Si-H: 0.14 wt.%
D:Q = 0.19 Mn: 5000 gmol−1
OH
Varaprath et al. MQQ MTNQ Hair fixative [28]
Cook et al. MMQOH MTPrQ M:Q = 0.71–0.78 Mn: 5140–7600 g mol−1 Hair fixative [24,27]
TPr MTPhTPrQ
MDTPrQ
Li et al. MQ MTPrQ OH: 1 wt.% Protective coatings [152]
TPr Mw: 377000–415000 g mol−1
Varaprath et al. MQ MQ-PDMS Hair fixative [28]
Juen et al. MQ MQ-PDMS Mw: 73200–2.45*106 g mol−1 [151]
Table 19
Patents describing condensed silicone resins.
Authors Initial resins Final resins Molar ratio Viscosity Application Ref.
H epox
Riding MM Q MM Q UV-curable anti-adhesive formulations [150]
Hurford et al. MHQ MM’Q M:Q = 1.2 750 mPa s [75]
M’:Q = 0.2
Ekeland et al. MHQ MM’Q M:Q = 0.63–1.42 100–10000 mm2 s−1 [153]
M’:Q = 0.37–0.58
Yoshii et al. MHQ MQ [78]

MViQ
Burkus-II et al. MHQ H
M M’Q Adhesive agent [154]
Murai et al. MHQ PSAs [155]
M’Q
Fig. 31. Condensation reaction of an MQQOH silicone resin.

Fig. 30. Modification of MQQOH and MMHQ resins described in Riding et al.
patent [150].
with 2.5 ml of ethanol and 1 mg of solid KOH in a one-necked round-
bottom flask equipped with a magnetic stirrer, a reflux condenser and a
dichloromethane solution of azobenzene. The azobenzene was then Dean-Stark apparatus, and the mixture was heated at 95 °C for 4 h. The
photoisomerized in order to study the local free volume in MQ silicone appearance of water in the Dean-Stark indicated that the condensation
resins. happened. The mixture was allowed to cool down to room temperature
and washed with diethyl ether. The organic layer was placed in a rotary
4.2. Post-condensation of commercial MQQOH resins evaporator to remove all the solvents, and the new condensed resin was
placed in an oven under vacuum at 80 °C overnight to remove any re-
It can be sometimes difficult to find, in the market, silicone resins sidual water and solvent. All the condensed resins were at the same
with both low silanol content and desired molecular weight. Here, we state (solid or viscous) before and after the reaction. The condensation
modified RES2 and RES5-RES7 resins through a post-condensation re- reaction is shown in Fig. 31.
action, using either acid or basic catalyst [84,150]. The condensed resins were analyzed via Fourier-Transformed
InfraRed Spectroscopy. Depending on the resin state, it was placed ei-
4.2.1. Experimental ther between two KBr pellets (if viscous), or mixed in a KBr pellet (if
3 g of an MQQOH resin were dissolved in 10 ml of xylene and mixed solid). The quantitative analysis of the M:Q ratio or the silanol content
308
Fig. 32. FT-IR spectra of the RES2 and RES5-RES7 resins before and after the condensation reaction.
Table 20
Characteristics of the post-condensed resins.
Resin Mn (g mol−1) Mw (g mol−1) –OH (wt.%) –OR (wt.%) Q2,3/Q4 ratio Residual weight (%) Tonset (°C)
RES2 Before condensation 2200 4700 7.5 1.3 0.21 47 170

After condensation 3100 5300 3.3 0 0.07 49 150
After condensation 1600 2700 0 18.7 0.49 51 140
was calculated with 29Si and 1H NMR. The molecular weights were
determined by SEC with the same parameters as the ones described in
the previous section.
4.2.2. FT-IR spectroscopy

FT-IR spectra (Fig. 32) showed the disappearance of the eOH ab-
sorbance peak around the wavelength 3500 cm−1 for RES6 and RES7
resins, which confirmed that the condensation happened and that water
was eliminated during the reaction. This was not the case for resins
RES2 and RES5 that did not totally condensate, since the eOH absor-
bance peak did not disappear, but slightly decreased in intensity.
4.2.3. NMR spectroscopy

The silanol and ethoxy contents of the modified resins were calcu-
lated with the help of 29Si NMR and 1H NMR, and the values are
summarized in Table 20. As one can see, the silanol content did not
decrease to zero for the RES2 resin, which is consistent with its FT-IR
spectrum, meaning that the condensation reaction was not complete; on
the other hand, the ethoxy content decreased dramatically to zero. The
Fig. 33. TGA curves of modified silicone resins RES2 and RES5-RES7. nil eOH content for RES6 and RES7 is consistent with the absence of
the large absorbance peak around 3500 cm−1 on the FT-IR spectra. The
309
Fig. 34. Functionalization of an MQ silicone resin into an MDViQ resin [145].
condensation are believed to be closer to the actual molar mass, and can
be compared with other resins with a very low silanol content such as
RES1 or RES4. Note that the polydispersity indexes changed after the
condensation reaction: they decreased for RES2 (2.1–1.7), RES6
(1.5–1.3) and RES7 (1.6–1.3) and slightly increased for RES5 (1.6–1.7).
4.2.5. TGA
The residual weights did not vary much after the RES2, RES5 and
RES6 condensation, but it increased a lot for RES7 resin (Fig. 33), which
would mean that the condensation improved the thermal properties of
this resin. This was confirmed with the onset temperature that in-
creased from 100 °C up to 130 °C after condensation (Table 20). In a
general way, the condensation worked best for RES6 and RES7 resins
whose M:Q ratio was the highest among the commercial resins we
tested and they were more thermally stable even after being condensed.
4.3. Functionalization of commercial MQ resins with vinyl groups

Fig. 35. 29Si NMR of the white solid created during the MQ resin functionali-
zation with a basic catalyst. The functionalization of MQ resins into MDViQ resins is shown here
for RES5 and RES8 resins. The parameters are based on Riding’s patent
[150], where an acid catalysis was considered, and Kobayashi’s patent
results are different between FT-IR and NMR for RES5. This could be
[84], who used a basic catalyst.
explained by the uncertainty of the calculations based on the integra-
tions of the NMR peaks. In every case, we observed a decrease in the
Q2,3/Q4 ratio (Table 20), signifying that there was a condensation for 4.3.1. Experimental
every resin, if not totally, at least partially. 3 g of an MQQOH resin dissolved in 10 ml of xylene were mixed with
vinylmethyldiethoxysilane, 2.5 ml of ethanol, a basic catalyst (a 1 M or
5 M aqueous solution of KOH for RES8 and RES5 resins, respectively) or
4.2.4. SEC and acidic one (37 wt.% purity HCl for both resins) in a one-necked
Molecular weights increased after the condensation reaction flask equipped with a magnetic stirrer, a reflux condenser, and the
(Table 20), but as it was explained previously, this does not mean that mixture was heated for 4 h. The alcohol is known to promote the phase
the absolute molecular weights actually increased. It may rather be due transfer between the organic phase (containing the silicone resin) and
to the decrease of column affinity of the resins with the disappearance the aqueous phase (containing the catalyst). The mixture was allowed
of silanol groups. Therefore, the molecular weights measured after to cool down to room temperature and the resin was extracted with
Fig. 36. 29Si NMR analyses of the commercial MDViQ resin (black), functionalized RES8 (red) and functinoalized RES5 (blue) (basic catalyst). (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)
310
Fig. 37. Reactions occurring with a basic catalyst on silicone resins [145].
Fig. 38. 29Si NMR analyses of the commercial MDViQ resin (black), functionalized RES8 (red) and functionalized RES5 (blue) (acidic catalyst). (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)
diethyl ether. The organic layer was neutralized and placed in a rotary 1700 g mol−1 for RES5 resin; this proves that the structure of the resins
evaporator to remove all the solvents, and the new condensed resin was changed with the basic catalyst. Nevertheless, when comparing the 29Si
placed in an oven under vacuum at 80 °C for one night to remove any NMR spectra of the modified resins with a commercial MDViQ resin
residual solvent. The vinyl-functionalization reaction is schematically used as a reference (Fig. 36), the DVi peaks did not appear at −32 ppm.
shown below in Fig. 34. 29Si NMR and SEC analyses were run to This proved that the basic catalyst did not afford a successful redis-
characterize the modified resins with the same parameters as pre- tribution. In fact, in a basic solution, the scission reactions, redistribu-
viously. tion and condensation of siloxane chains are favored, which lead to the
formation of precipitated silica as schematically shown on Fig. 37.
4.3.2. Basic conditions
When a basic catalyst was used, a white solid appeared in the round- 4.3.3. Acidic conditions
bottom flask during the reaction. This white solid was not soluble in The same reaction was conducted this time with an acid catalyst.
water or in usual organic solvents. The solid 29Si NMR of this pre- Here, no white solid appeared in the flask. The SEC analyses showed
cipitate showed that it was made of Q units only, which meant that that the hydrodynamic volume distributions were similar for the resins
silica was generated (Fig. 35). before and after the reaction. The average molar mass (in polystyrene
The average molecular weights of the resins evolved after reaction standards) was 1500 and 3300 g mol−1 for RES5 and RES8 before the
from 3300 to 2800 g mol−1 for RES8 resin, and from 1500 to functionalization, respectively, and it was 2600 g mol−1 for the
311
Fig. 39. Reactions occurring with an acid catalyst on silicone resins [145].
hydrochloric acid plays a key role in the functionalization. Indeed,

when the quantity of catalyst increased up to a concentration of
0.01 mol of hydrochloric acid, the reaction of the vinylmethyldiethox-
ysilane was improved, which led to the decrease of Q3 units and the
increase of the Q4 units of the silicon resin (Fig. 40).
Two functionalization reactions were made with the RES5 resin and
0.01 mol of acid catalyst: one with 1.5.10−3 mol and the other with
3.10−3 mol of vinylmethyldiethoxysilane. The 29Si NMR and SEC
analyses showed that the percentage of grafted DVi increased (from 2.8
to 3.3 wt.%) with the increase of vinylmethyldiethoxysilane, and the
DVi:M ratio doubled from 0.092 to 0.172. Therefore, it is possible to
optimize the functionalization reaction by choosing the right quantities
of catalyst and vinylmethyldiethoxysilane.
5. Conclusion
Since the first patent written by Rochow in 1941, more than 150
patents and articles describing silicone resins synthesis methods have
Fig. 40. Influence of HCl quantity added in the mixture on the yield of grafted been published. The tetrachlorosilane was the first precursor used for
DVi on silicone resins. the synthesis of silicone resins, but it was replaced in the 50s with so-
dium silicate and tetraethoxysilane, both of which have been ex-
tensively used since then. The study of the literature underlined the
modified RES5 resin and 3500 g mol−1 for the modified RES8 resin.
great variety of silicone resins that can be synthesized or modified
Moreover, the 29Si NMR spectra showed a D peak at −32 ppm for both
nowadays. It seems that it is then possible to have resins with any
modified resins and the reference commercial MDViQ resin, which
wished composition based on the rich literature available. Nevertheless,
means that the redistribution was effective for both resins (Fig. 38).
the reproducibility of the resins characteristics is hardly guaranteed,
Based on the integration of the M and D peaks, the DVi:M ratio was
according to the study of Flagg & McCarthy [67]. We made this ob-
calculated for the modified resins: 0.092 for RES5 resin and 0.075 for
servation for commercial resins too: we selected some commercial re-
RES8, which is lower than the reference commercial MDViQ resin
sins, characterized them and modified some of them. The character-
(DVi:M = 0.176). More vinyl groups were grafted on RES5 because it
ization showed that differences could stand between the suppliers’
exhibits a higher content of available silanol site for reaction, as shown
technical data sheets and the actual properties of the resins. In con-
on Fig. 39. Contrary to a basic environment, the reaction in an acid
clusion, the versatility of silicone resins is the insurance of a never-
environment did not lead to the siloxane chains scission but enhanced
ending story of researches, discoveries and improvements for the sci-
the functionalization of the silicone resin.
ence of materials.
During these experiments, it was observed that the quantity of
312
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Progress in Organic Coatings 125 (2018) 287–315

Contents lists available at ScienceDirect

Progress in Organic Coatings

Synthesis, characterization and modification of silicone resins: An T

Fig. 2. Schematic summary of the different silicone resins synthesis methods.

Daudt et al. Trimethylchlorosilane MQQOH 1.48 Waterproof/ Anti-flotation of paint [39,40]

Fig. 5. MQ resins syntheses described in Daudt et al. and

synthesize a priori MQQOH resins with an unknown silanol content.

Fig. 8. Synthesis of an MQ silicone resin with Ethyl Silicate 40

Q units M units M’ units

Fig. 9. MMHQ resins synthesis described in Brady patent [74].

Fig. 10. Hexenyl-functionalized carbosiloxane oligomer for-

Fig. 11. Synthesis of an MM'Q silicone resin with a TEOS

Burzynski Methyltriethoxysilane T [85]

Rerat et al. Phenyltrimethoxysilane TPhTSB Flame [93]

Fig. 12. T resin synthesis described in Burzynski et al. patent

Anonymous SiCl4 Diethyldichlorosilane DQ [36]

Q units T,T’ units

Rust TEOS n-butyl silicone trihalide TQ Coating applications/Electrical insulation [99]

Fig. 13. Synthesis of a TQ silicone resin described in Rust pa-

Itoh et al. Methyltrichlorosilane Dimethyldichlorosilane DT Mn: 1040 [112]

T units D units M units

Fig. 16. Synthesis of an MDT siliconeresin described in the

dramatically decreases when the M:Q ratio increases. The thermal

In their paper about MQ copolymers, Flagg & McCarthy [67] com-

Mn: 920 g mol−1

infrared spectra with the peak of the Si-OH stretching, around

not used extensively in the literature.

phenyl content goes from 4.2 up to 30 wt.% [54,83,84]. Among the

and 15000 mPa s, respectively.

In a general way, each resin synthesized in a patent or article is

ization of some commercial resins that was performed in our labora-

3.2. Our characterization process of commercial silicone resins

In this study, we selected 15 commercial resins and characterized

silanol-functional MQ resins, also referred as MQ or MQQOH resins.

RES10 was sold as a polyphenylsilsesquioxane resin, resins RES11-

cuum oven before being analyzed.

400 MHz spectrometer using toluene-d8 or CDCl3 as a solvent, while

in toluene at a concentration of 2–3 mg ml−1. The thermal transitions of

the resins were determined on a TA differential scanning calorimetry

was increased at a constant rate of 10 °C min−1 from −150 °C to 180 °C

and then decreased down back to −150 °C. The thermogravimetric

analysis (TGA) measurements were carried out on a TA instrument

Q units T units M units

Q units T units D, M units

Anonymous TEOS Phenyltrichlorosilane Phenylmethyldichlorosilane DPhTPhQ Electric insulation [36]

increased at a constant rate of 10 °C min−1 from room temperature to spinning sidebands.

Fig. 22. 1H (a) and 29

RES1 MQ 46 54 0.86 2200 6800 3.1 0 4.6 59 220

hydrochloric acid and isopropanol. After a refluxing for a certain time,

Yoshii et al. MHQ MQ [78]

Murai et al. MHQ PSAs [155]

Fig. 31. Condensation reaction of an MQQOH silicone resin.

RES2 Before condensation 2200 4700 7.5 1.3 0.21 47 170

4.2.2. FT-IR spectroscopy

4.2.3. NMR spectroscopy

Fig. 34. Functionalization of an MQ silicone resin into an MDViQ resin [145].

4.3. Functionalization of commercial MQ resins with vinyl groups