Polymer Degradation and Stability 85 (2004) 769e777

www.elsevier.com/locate/polydegstab

Studies on the aminolysis of RTV silicone rubber

and modifications of degradation products
Cheng-Liang Chang, Trong-Ming Don), Howard Shih-Jen Lee, Yi-On Sha
Department of Chemical and Materials Engineering, Tamkang University, Tamsui, Taipei County 25147, Taiwan

Received 26 September 2003; received in revised form 1 December 2003; accepted 2 December 2003

Abstract

The degradation of room temperature vulcanized (RTV) silicone rubbers, swelled in different solvents and followed by the
aminolysis reaction using diethylamine as a nucleophilic reagent, was studied. The reaction was further facilitated with a potassium
hydroxide catalyst dissolved in ethanol. When the silicone rubber swelled in a less polar solvent, toluene, the main product of the
aminolysis reaction was a linear polydimethylsiloxane with hydroxyl and ethoxy end groups (EtOePDMSeOH), and an average
molecular weight of 15,000. On the other hand, when a polar solvent, tetrahydrofuran, was used, the degradation rate was increased,
and significant amount of cyclic compounds were found in addition to the linear PDMS. Furthermore, if different alcohols were
used to dissolve the KOH catalyst, the degradation rate and the product distribution were both changed. The dissolution time
decreased in the following order: glycerol O ethylene glycol O 1,4-butanediol O ethanol. In this study, efforts have also been made
to improve the reusability of the aminolysis products by changing their terminal groups.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Silicone rubber; Polydimethylsiloxane; Aminolysis; Diethylamine; Alcohol

1. Introduction oxide are generally incorporated into the silicone rubbers

[1,2].
Silicone polymers or polysiloxanes possess several It is costly to recycle the RTV silicone rubbers,
unique properties that are retained over a wide temper- because they are thermosets. In addition, the reusability
ature range, such as low temperature flexibility, good of the recycled silicone rubbers is limited. Most methods
dielectric strength and water repellency. Depending on to recycle the RTV silicone rubbers are based on the
the molecular weight and structures, they are produced degradation at high temperatures. However, Pappas and
in the form of fluids, resins, and elastomers. Silicone coworkers [3] have found that aliphatic primary and
elastomers are either room temperature vulcanized secondary amines completely dissolve the crosslinked
(RTV) or heat-cured silicone rubbers, depending on silicone rubbers at room temperature. The dissolution is
whether crosslinking is carried out at ambient or ele- caused by the nucleophilic cleavage of SieO bonds by
vated temperature. Though the mechanical strengths of amines, which occurs selectively at crosslinking sites.
RTV rubbers are generally lower than those of the The selectivity is attributed to the enhanced silicone
corresponding heat-cured silicones, but for many appli- electrophilicity at crosslinking site, where the silicon
cations, their convenience outweighs their reduced me- atom is bonded to four oxygen atoms. In comparison,
chanical properties. To increase their strength or some the other silicon atoms in the main chain are bonded to
specific properties, fillers like silicon oxide and titanium only two oxygen atoms. Their results show the way to
recycle the RTV silicone rubbers at mild conditions.
Later on in 1980, Pappas and Just [4] used various
) Corresponding author. Tel.: C886-2-29068537; fax: C886-2- amines with different functionalities to degrade RTV
26209887. silicone rubbers. They found that the dissolution time,
E-mail address: tmdon@mail.tku.edu.tw (T.-M. Don). the time needed to just dissolve the silicone rubber

0141-3910/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2003.12.001
770 C.-L. Chang et al. / Polymer Degradation and Stability 85 (2004) 769e777

through the aminolysis degradation, increased with the the product distribution. Methanol was used to separate
number of carbon atoms in the aliphatic amines. They the polymer products and low-molecular-weight
attributed this to the steric effect on the amine group. oligomers including cyclic compounds. Low-molecular-
They also found that the dissolution is faster for the weight oligomers below approximately 4000 can be
primary amines than the secondary amines. dissolved in methanol, while high-molecular-weight
Shimmel [5e7] found that the addition of potassium polymer products precipitate out. After weighing, it
hydroxide (KOH) could accelerate the aminolysis rate of was found that 90 wt% of the aminolysis product was
silicone rubbers by the secondary amines. Several con- high-molecular-weight polymer. GPC and GC were then
clusions were made on the steric effect and the need for employed to determine the molecular weight distribu-
a base as the catalyst in order to have an effective split- tion of the polymer product and the composition of the
ting reaction in the aminolysis process. However, the cyclic compounds, respectively. FTIR and NMR were
role of the KOH as a catalyst is not clarified. In order to used to investigate the structure of the polymer product.
further reduce the dissolution time, ethanol was em- The effects of different swelling solvents, toluene and
ployed to dissolve KOH in order to ensure a fixed tetrahydrofuran (THF), and different alcohols such as
homogeneous catalyst concentration [8]. In this study, ethanol, ethylene glycol, glycerol and 1,4-butanediol, on
the effects of different swelling solvents on the aminol- the aminolysis of RTV silicones were investigated.
ysis reaction of RTV silicone rubbers were further
examined. In addition, a reaction mechanism was pro-
2.3. Structure analysis of the degradation products
posed to elucidate the need of a base as the catalyst.
Furthermore, in order to improve the functionality for
Gel permeation chromatography (GPC) from Waters
possible applications, various chemical modifications of
501 was used to determine the molecular weight distri-
the degradation products have also been investigated.
bution of the degradation products. Toluene was used as
the mobile phase at a flow rate of 0.6 mL/min. All the
reported molecular weight values are based on poly-
2. Experimental
styrene standards. Fourier transform infrared (FTIR)
spectra were recorded with a Nicolet Magna-IR 550
2.1. Synthesis of RTV silicone rubber
spectrophotometer. The resolution was set at 4 cm
1
and 32 scans were taken to average the signal. Nuclear
Silicone rubber was prepared from Dow Corning
magnetic resonance (NMR) was examined to obtain
Silastic 3481 molding fluid, which is composed of 1
H-NMR and 13C-NMR spectra using a Bruker AC 300
ethoxy-terminated polydimethylsiloxane (PDMS) with
instrument. D-Chloroform and tetramethylsilane were
measured molecular weight of 35,000 and fillers (40%).
used as the solvent and internal standard, respectively.
The silicone fluid underwent vulcanization at ambient
Gas chromatography (GC) from Carlo ERBA HRC
temperature for 8 h with the use of a curing agent, which
5300 was also used to analyze the degradation products,
is a mixture of tetraethoxysilane and organometallic tin
especially the low-molecular-weight oligomers. Hexam-
catalyst. The cured silicone rubber was cut into small
ethylsiloxane (M2), hexamethyl-cyclotrisiloxane (D3),
slabs (15!2!2 mm).
octamethyltrisiloxane (MDM), octamethyl-cyclotetrasi-
loxane (D4), and decamethyltetrasiloxane (D5), were
2.2. Aminolysis of RTV silicone rubber
used as the standards for comparison.
Potassium hydroxide (KOH, 3 g) was dissolved in
ethanol (1 mol, 45.8 g) and then added to 50 g of diethyl- 2.4. Chemical modification of the aminolysis product
amine (DEA) to form a homogeneous solution. The
rubber sample was fist swelled in 200 ml toluene for 8 h The degradation product, EtOePDMSeOH, was
and then added with the amine solution in a four-necked modified to form 1,3-bis(4-hydroxybutyl)-polydimethyl-
reaction vessel. The aminolysis was carried out at 25 (C siloxane (HOBuePDMSeBuOH), 1-ethoxy-3-hydro-
under agitation at a speed of 400 rpm. Products were polydimethylsiloxane (EtOePDMSeH), 1,3-bis
sampled at fixed time intervals from the reaction vessel (hydroxyl)-polydimethylsiloxane (HOePDMSeOH),
after the silicone rubber slabs were completely dissolved and 1,3-bis(hydro)-polydimethylsiloxane (HePDMSeH).
in the amine solution. The product sample was mixed HOBuePDMSeBuOH was synthesized through the
with diethylether and washed with deionized water reaction of EtOePDMSeOH with 1,1-dimethyl-1-sila-
several times. Acetic acid (1 N) was added to neutralize 2-oxa-cyclohexane (DSOH) in 1,4-dioxane. A small
the product solution. Water residue was then salted out amount of hydrochloric acid was also added to catalyze
by washing with saturated NaCl solution. Before the the reaction. The reaction temperature was 85 (C and
cyclic compounds were separated (if any), a small the reaction time was 2 h. After reaction, the solvent was
amount of sample was analyzed by GPC to determine removed through the rotary evaporator. The product
 C.-L. Chang et al. / Polymer Degradation and Stability 85 (2004) 769e777 771

was precipitated three times with methanol. The yield Table 1

was calculated as 59.7 wt%. Chemical shift of various hydrogen atoms of the aminolysis product
from RTV silicone rubber with diethylamine and catalyzed by KOH/
EtOePDMSeH was synthesized by the reaction of EtOH (toluene was used to swell silicone rubber)
EtOePDMSeOH with the chlorodimethylsilane cata-
Chemical shift (ppm) Hydrogen atom
lyzed with a triethylamine [2,9]. The distilled ether
(100 mL) and 1.5 mL chlorodimethylsilane were added 0.1 eSieCH3
1.21 eSieOeCH2eCH3
to 500 mL round-bottom flask, purged with nitrogen 1.26 eSieOH
and kept in an ice bath. A mixture containing 20 g 1.60 H2O, CH3OH
EtOePDMSeOH, 22.16 mL distilled triethylamine and 3.48 CH3OH
75 mL diethylether, was slowly dropped into the re- 3.76 eSieOeCH2eCH3
action flask in 40 min. After 1 h in ice bath, the flask was
removed and slowly returned to room temperature. The high-molecular-weight polymer did not change much
total reaction time was 12 h. After reaction, ice water with the degradation time. In addition, cyclic compound
and ice NaCl solution were used to wash the products. was not found suggesting that there was nearly no
Most of the ether was removed by the rotary evapora- backbiting cyclization. The 1H-NMR spectrum of the
tor, and the product was precipitated three times with high-molecular-weight polymer shows the various hy-
methanol. The yield was calculated as 79.3 wt%. drogen absorption peaks of the degradation products.
HOePDMSeOH was synthesized through the hydro- The chemical shift values (d in ppm) of the correspond-
lysis reaction of the ethoxy end group in EtOePDMSe ing hydrogen atoms were listed in Table 1. The peaks at
OH catalyzed by HCl [1]. A round-bottom flask 1.21 and 3.76 ppm were caused by the OeCH2eCH3
containing 10 g EtOePDMSeOH and 150 g 1, and OeCH2e groups, respectively, which implied the
4-dioxane was heated at 90 (C for half an hour and existence of a terminal ethoxy group. The peak at
then 1 g of 12 N HCl and 3 g distilled water were added 1.26 ppm was due to the absorption of the other
to the flask. After 1 h of reaction, 3 g of distilled water was terminal group, SieOH. Therefore, it was presumed
added again and the reaction was continued for another that with toluene as the swelling solvent, the main
half an hour. After reaction, a rotary evaporator was used product of the aminolysis reaction was a linear poly-
to remove the dioxane. The product was precipitated dimethylsiloxane having hydroxyl and ethoxy end
three times with methanol. The yield was 61.3 wt%. groups (EtOePDMSeOH). From the peak areas of
HePDMSeH was synthesized through the reaction of the SieCH3 (0.1 ppm) and eSieOeCH2eCH3
HOePDMSeOH with chlorodimethylsilane [10,11]. The (3.76 ppm) with the assumption that each chain had
reaction procedure was similar to the synthesis of EtOe only one terminal ethoxy group, one thus could
PDMSeH described previously. The yield was 83 wt%. calculate the Mn value of the linear PDMS. The value
was about 9600, which was of the same order as with the
result from GPC analysis. The difference was mainly
3. Result and discussion because the calculated Mn value from GPC was based
on the PS standards. Simultaneously, this proved that
3.1. Degradation of RTV silicone rubber one half of the end groups were the ethoxy group. In the
using toluene solvent FTIR analysis of the degradation product, all the char-
acteristic peaks of linear PDMS were found in the
After 4 h of degradation by the diethylamine (DEA) spectrum including peaks from SieC (800 cm
1 and
with the help of KOH/EtOH catalyst, the originally 1270 cm
1), SieO (1025e1100 cm
1) and CeH (2800e
white RTV silicone rubber, pre-swelled in toluene 3000 cm
1). Yet, the terminal eOH and eOeC2H5
solvent, changed into a white liquid. After separation groups were not revealed in the spectrum, because of the
and purification, the degradation product was analyzed very low concentration of the end groups. In the previous
by several instrumental methods. The results show that paper [8], the ethoxy group (SieOEt) was postulated to
90 wt% of the product was a high-molecular-weight arise mainly through the displacement reaction of SiNEt2
polymer. From GPC results, the number- and weight- groups produced by amine cleavage of SieO bonds at
average molecular weights (Mn, Mw) of the polymer the crosslinking sites. The reaction mechanism of the
product were 7544 and 15,136 g/mol, respectively. The aminolysis of silicone rubber is shown below [8,12].
polydispersity was thus calculated as 2.01. However, the Step 1. The hydrogen bonding between potassium
molecular weight between cross-links of the starting hydroxide and diethyl amine can increase the nucleo-
RTV silicone rubber was 35,000 g/mol. This suggested philic activity of diethyl amine.
that linear PDMS chains between crosslinking points
still had a chance to undergo chain degradation during
the dissolution with a very slow reaction rate. After
dissolution, the molecular weight and the yield of the ð1Þ
772 C.-L. Chang et al. / Polymer Degradation and Stability 85 (2004) 769e777

Step 2. The KOH/HeNEt2 degradation agent (eOEt) and hydroxyl group (eOH). He suggested that
diffuses into the swelled RTV silicone rubber and the SeOEt functionality arises mainly through the
undergoes a nucleophilic degradation reaction with displacement reaction of SieNEt2 group with ethanol.
silicone atom, selectively at crosslinking sites (Q
structure).
3.2. Degradation of RTV silicone rubber
using THF solvent

When tetrahydrofuran (THF), a polar solvent, was

used to swell the silicone rubber, it was found that
25 min was enough to completely crack the silicone net-
work by KOH/EtOH, in comparison with 4 h using a
less polar solvent, toluene. The NMR, GPC, FTIR and
GC experiments were used to analyze the composition
of the degradation products. After 1 h, the degradation
products consisted of 83 wt% of the linear HOe
PDMSeOC2H5 chain and 17 wt% of the cyclic com-
pounds. The weight percentage of linear PDMS polymer
decreased to 32% after 25 h of degradation. In the mean
time, the molecular weight of linear PDMS decreased
from 3550 g/mol at 1 h to 1150 g/mol after 25 h of
ð2Þ degradation (Table 2). Simultaneously, the amount of
cyclic compounds produced by backbiting increased
Step 3. Further nucleophilic reaction occurs by the
with degradation time. The composition of the cyclic
KOH/HeNEt2 with the silicone atom and eventually
compounds was analyzed with GC and the results show
linear PDMS chains were produced.
that there were D4 (59%), D5 (30%) and D6 (7%) after
25 h of degradation. From the above results, it was
concluded that with a polar solvent, THF, the de-
gradation rate was increased greatly and backbiting
cyclization occurred, which not only produced cyclic
compounds but also decreased the molecular weight of
linear PDMS. The reaction is shown below.
Step 5. Backbiting reaction by the attack of the
terminal hydroxyl group produces cyclic compounds
ð3Þ and another linear PDMS with lower molecular weight.

Step 4. The terminal diethyl amine group was

replaced through the displacement reaction of SieNEt2
group with ethanol.

ð4Þ
ð5Þ

From the reaction mechanism, it was clearly shown However, previous results show that with a non-polar
that the hydrogen bonding with KOH increased the solvent, toluene, the backbiting reaction was not sig-
nucleophilic nature of DEA. Chen [9] has found that nificant. This was attributed to the polarity of the
without using KOH, the dissolution time was greatly solvent. The non-polar PDMS chain was relatively
increased. The KOH/DEA then attacked the SieO extended in the non-polar solvent, toluene; and this
selectively at crosslinking sites. The nucleophilic cleav- decreased the probability of backbiting. The probability
age resulted in a product of trisiloxane structure and of backbiting increased greatly when the PDMS chain
a linear polydimethylsiloxane. The KOH/DEA could was relatively contracted in the polar solvent THF,
further attack the trisiloxane and produced more linear where the active hydroxyl end group could easily
polydimethylsiloxane. Chang et al. [8] has also found backbite its own chain.
that the end groups of the polymer products using If different alcohols were used as the co-solvent to dis-
KOH/DEA degradation reagent were ethoxy group solve KOH catalyst, the reaction time for the complete
 C.-L. Chang et al. / Polymer Degradation and Stability 85 (2004) 769e777 773

Table 2
The weight percentage (wt%) and molecular weight (MW) of linear PDMS product during degradation of RTV silicone rubber (THF was used to
swell silicone rubber)
Time (h) 1 2 3 4 5 6 7 8 25
Wt% 83 71 62 57 53 49 46 42 32
MW ( g/mol) 3550 2700 2550 2260 1950 1650 1600 1500 1150
Silicone rubber: 42 g, THF: 200 mL, KOH: 3.0 g. Diethyl amine: 50 g. The degradation was carried out at 25 (C in a four-necked reactor with
a stirring speed at 400 rpm.

dissolution and the distribution of the degradation weight percentage was almost 100% at the beginning of
products were found to be different. Table 3 shows the dissolution, and nearly did not change even after 49.5 h.
complete dissolution time with different alcohols, where Fig. 3 shows the Mw values of the high-molecular-weight
the RTV silicone rubber was swelled in THF first and PDMS portion with different degradation times. At the
then degraded by DEA/KOH in a reactor with a stirring time of complete dissolution, the molecular weight was
speed at 400 rpm. As the polarity of alcohol increased, 10,300, 18,000 and 37,800 for the systems with BUD,
the dissolution time increased. The order of the dis- EGD and GLD alcohol, respectively. The composition
solution time was glycerol (GLD) O ethylene glycol of the oligomer from the distillation of the alcohol
(EGD) O butanediol (BUD) O ethanol. Compared with solvent under reduced pressure was analyzed by GC.
other alcohols, it seems that the degradation time with The results showed that the oligomer consisted of
glycerol was much longer. This is because when all the mostly cyclic polysiloxane compounds. For the system
components were mixed together, KOH/glycerol solu- with EGD alcohol, the main compound of the cyclic
tion separated out as an individual liquid phase, where oligomer was D4 (97.3 wt%); where it consisted of
in contrast, KOH/ethanol was miscible with DEA and 64.4 wt% of D4, 27.5 wt% of D5, and 8.1 wt% of D6
THF solvent. The increased phase boundary limited the for the system with BUD alcohol.
diffusivity of reactants and thus decreased the reaction The above results clearly suggested that the degrada-
rate and increased the dissolution time. Fig. 1 shows tion rate and the product composition are both affected
that there were two peaks corresponding to high- by the type of alcohol added to the solution, such as the
molecular-weight linear PDMS and low-molecular- polarity and number of hydroxyl groups in the alcohol.
weight oligomer in the GPC chromatogram. In addition, The solubility of KOH in different alcohols and the
the less polar the alcohol, the more obvious was the miscibility of different alcohols with DEA/THF thus
peak for the oligomer portion. Fig. 2 shows the weight have to be considered. In addition, the polarity of the
percentage of the high-molecular-weight polymer por- mixing solvent was different with different alcohol
tion with the degradation time. At the time that silicone
rubber was completely dissolved in the solution through
DEA/KOH aminolysis using BUD co-solvent, the
weight percentage of high-molecular-weight polymer
was 92.6%, and decreased with the degradation time.
After 49.5 h of degradation, it decreased to 71%. In
comparison, for the system with EGD alcohol, the
weight percentage was 95.8% at the beginning of
dissolution, and decreased to 92.7% after 49.5 h of
degradation. For the system with GLD alcohol, the

Table 3
Effect of different alcohols used to dissolve KOH catalyst on the
dissolution time of silicone rubber by the aminolysis with diethylamine
(THF was used to swell silicone rubber)
Solvent Dissolution time (h)
Ethanol 0.4
Ethylene glycol 4.0
Glycerol 25.5
Butanediol 0.5
Silicone rubber: 42 g, THF: 200 mL, KOH: 3.0 g, DEA: 50 g. All the Fig. 1. GPC chromatogram of the degradation product from the
alcohols have the same amount, 0.222 mol. The degradation was aminolysis of RTV silicone rubber with diethylamine and catalyzed by
carried out at 25 (C in a four-necked reactor with a stirring speed at KOH/butanediol. THF was used to swell the silicone rubber. The
400 rpm. degradation time was 49.5 h.
774 C.-L. Chang et al. / Polymer Degradation and Stability 85 (2004) 769e777

120 tetrakis(trimethylsiloxy)-silane, a structure of M4Q, the

rate of aminolysis reaction was found to be higher than
that of alcoholysis [9].
100

80
3.3. Chemical modification of the aminolysis product
polymer(wt%)

It is beneficial to introduce the desired properties of

60 PDMS by incorporating the degradation product, linear
EtOePDMSeOH, into various copolymers. The termi-
nal groups, EtOeSie and eSieOH, are easy to react
40 EGD with other organic monomers or oligomers having suit-
GLD able functional groups. However, the formed eSie
20
OeCe bond, which binds PDMS and other organic
BUD
polymeric chain together through condensation, is not
stable and the hydrolysis reaction occurs in a humid
0 environment. Therefore, it would be better to replace
0 10 20 30 40 50 60 the terminal groups of EtOePDMSeOH with a more
time(h) stable eSieReX, where X can be OH, OCH3, OeC2H5,
Fig. 2. Weight percentage of the high-molecular-weight PDMS portion H, NH2, eCHaCH2. The degradation product,
of the degradation product from the aminolysis of RTV silicone rubber EtOePDMSeOH, was thus modified to form HO-
in THF solvent with the degradation time. Different solvents for KOH BuePDMSeBuOH, EtOePDMSeH, HOePDMSe
catalyst were used: ethylene glycol (EGD), butanediol (BUD) and OH, and HePDMSeH.
glycerol (GLD). HOBuePDMSeBuOH was synthesized through the
reaction of EtOePDMSeOH with 1,1-dimethyl-1-sila-
added. Another factor that has to be considered is the 2-oxa-cyclohexane (DSOH) in 1,4-dioxane. The reaction
alcoholysis reaction. However, it has been proved [8,9] was catalyzed by HCl. The yield was calculated as
that the alcoholysis reaction is much slower than the 59.7 wt%. The low yield was caused because some low-
aminolysis reaction due to the lower nucleophilicity of molecular-weight oligomers, produced from the HCl-
ethanol compared to that of DEA, and penetrates less catalyzed hydrolysis, were washed away during the
easily into PDMS networks due to the polarity methanol precipitation. The reaction is shown below
difference. In an experiment using a model compound, (Scheme 1).
Table 4 shows various 1H-NMR peaks of the reaction
product. The peak from eSieCH2eCH2eCH2eCH2e
40000 OH overlapped with the one from eSieCH2eCH2e.
Nevertheless, the 1H-NMR spectrum confirmed the
35000 existence of the terminal butanol group. This was also
EGD
evidenced from the 13C-NMR spectrum (Table 5).
30000
GLD Especially, 13C-NMR spectrum clearly showed that the
carbon atom was bonded with the hydroxyl group
polymer(Mw)

25000 BUD
(eSieCH2eCH2eCH2eCH2eOH, 62.0 ppm), which
20000 proved the existence of the butanol group. FTIR
spectrum (Fig. 4) also shows the absorption of the
15000 hydroxyl group at 3500 cm
1, in addition to the other
characteristic absorption peaks of PDMS. The Mn and
10000 Mw values measured from GPC were 11,880 and 19,160,
respectively, where the calculated polydispersity was
5000
1.61. The objective of this substitution is to build
0
a stable SieC linkage, which is believed to be essential
0 10 20 30 40 50 60 for PDMS to copolymerize with other organic mono-
time(h) mers or oligomers, for example, polyurethane.
EtOePDMSeOH was also modified to form
Fig. 3. Mw values of the high-molecular-weight PDMS portion of the
EtOePDMSeH by the reaction of EtOePDMSeOH
degradation product from the aminolysis of RTV silicone rubber in
THF solvent at different degradation times. Different solvents for with the chlorodimethylsilane catalyzed with a triethyl
KOH catalyst were used: ethylene glycol (EGD), butanediol (BUD) amine [1,9]. The yield was calculated as 79.3 wt%. The
and glycerol (GLD). reason for these modifications is that the terminal hydro
 C.-L. Chang et al. / Polymer Degradation and Stability 85 (2004) 769e777 775

CH 3 CH 3
Si
O CH 2 HCl,H 2 O
+ EtO Si-O H HO (CH 2 )4 Si-O Si (CH 2 )4 OH
CH 2 CH 2 n n

CH 2

Scheme 1. Synthesis of HOBuePDMSeBuOH from the reaction of EtOePDMSeOH with 1,1-dimethyl-1-sila-2-oxa-cyclohexane.

group of a siloxane polymer will have a high reactivity The structure of the reaction product was confirmed
toward vinyl groups. The reaction is shown below with the 1H-NMR and 13C-NMR. The hydrogen
(Scheme 2). absorption peaks at 4.72, 3.76 and 1.21 ppm were
assigned to the SieH, eSieOeCH2eCH3 and eSie
OeCH2eCH3, respectively. The carbon absorption
Table 4
Chemical shift of various hydrogen atoms of HOeBuePDMSe peaks due to the SieCH3, eSieOeCH2eCH3 and
BueOH converted from EtOePDMSeOH eSieOeCH2eCH3 were found at 1.0, 18.40 and
Chemical shift ( ppm) Hydrogen atom 65.87 ppm, respectively. In addition to the characteristic
absorption peaks of PDMS observed in FTIR spectrum,
0.09 SieCH3
0.58 eSieCH2eCH2e a very small peak was found at 2160 cm
1, which was
1.23 eSieCH2eCH2eCH2eCH2eOH caused by the SieH. Therefore, the NMR and FTIR
1.41 eSieCH2eCH2e analyses confirmed the structure of EtOePDMSeH.
1.56 eSieCH2eCH2eCH2eCH2eOH The Mn and Mw values were 15,690 and 29,480,
3.68 eSieCH2eCH2eCH2eCH2eOH
respectively, from the GPC results. The calculated
polydispersity was 1.88.
It is easy to convert the EtOePDMSeOH to HOe
Table 5 PDMSeOH through the hydrolysis reaction of the
Chemical shift of various carbon atoms of HOeBuePDMSeBueOH ethoxy end group catalyzed by the HCl [1]. The reaction
converted from EtOePDMSeOH is shown below (Scheme 3). However, PDMS can also
Chemical shift ( ppm) Carbon atom undergo chain scission with the existing HCl during the
1.10 SieCH3 reaction, which would lower the molecular weight of
18.15 eSieCH2eCH2e PDMS. Once the low-molecular-weight PDMS was
19.65 eSieCH2eCH2e produced, it was washed away during the step of
36.36 eSieCH2eCH2eCH2eCH2eOH precipitation with methanol. Therefore, the yield was
62.0 eSieCH2eCH2eCH2eCH2eOH
low at 61.3 wt%. The Mn and Mw values of the high-
molecular-weight part were 8150 and 15,630, respectively.
The polydispersity was 1.92. Again, the structure of
HOePDMSeOH was confirmed with the NMR analysis.
There was no sign of absorption peaks caused by the
ethoxy group and only methyl (eSieCH3) and hydroxyl
(eSieOH) absorptions were found in the spectrum. From
the area ratio of the absorption peaks corresponding

EtO Si O H + C l S iH + (C2H5) N
3
n

EtO Si O Si H + (C2H5)3 N H C l
n

Scheme 2. Synthesis of EtOePDMSeH from the reaction of

EtOePDMSeOH with chlorodimethylsilane.

HCl
HO Si O Et + H2O HO Si O H + EtOH
4000 3500 3000 2500 2000 1500 1000 500 n n
Wavenumbers (cm-1)
Scheme 3. Synthesis of HOePDMSeOH from the hydrolysis reaction
Fig. 4. FTIR spectrum of the reaction product, HOeBuePDMSe of the ethoxy end group in the EtOePDMSeOH catalyzed by the
BueOH, converted from EtOePDMSeOH. HCl.
776 C.-L. Chang et al. / Polymer Degradation and Stability 85 (2004) 769e777

spectrum. Instead, the absorption from eSieH was

HO Si O H + 2ClSiH + 2(C 2 H 5 )N
n 3 observed at 4.72 ppm, in addition to the absorption peak
at 0.09 ppm caused by the SieCH3. Furthermore, a very
H Si O Si H + 2(C 2 H 5 ) 3 N H C l small peak at 1.53 ppm assigned to H2O or CH3OH was
n
observed. However, the peak due to CH3OH (4.08 ppm)
Scheme 4. Synthesis of HePDMSeH from the reaction of HOePDM- was not observed in 1H-NMR and there was only one
SeOH with chlorodimethylsilane. absorption peak at 1.0 ppm in 13C-NMR spectrum. This
was caused by the SieCH3. Therefore, the NMR results
to eSieCH3 and eSieOH, the number average mole- confirmed the structure of HePDMSeH and the eOH
cular weight could be calculated, with an assumption that peak in FTIR spectrum was caused by the absorbed
both end groups were eSieOH. The value was 7880, moisture. From the area ratio of the absorption peaks
which was close to the GPC result. corresponding to eSieCH3 and eSieH, the number
HOePDMSeOH was further converted to average molecular weight was calculated as 9860, which
HePDMSeH through the reaction with chlorodime- was close to the GPC result. This indicates that both end
thylsilane [10,11]. The yield was 83 wt% and the GPC groups (eSieOH) were converted to eSieH.
results revealed the Mn and Mw were 9430 and 17,590,
respectively. The polydispersity was 1.87. The values 4. Conclusions
were close to those of the starting polymer, HOe
PDMSeOH, indicating that acid hydrolysis by HCl The aminolysis reaction of RTV silicone rubbers in
did not occur much. This was probably because the different solvents was studied. Backbiting effect was
condensation by-product HCl reacted with the added found to be important using polar solvents, such as
tertiary amine immediately, and thus maintained the THF, as evidenced by the fact that the main degradation
neutrality of the solution. The reaction is shown in products were cyclic compounds, mostly D4. If less
Scheme 4. polar solvents were employed, such as toluene, the main
Fig. 5 shows FTIR spectrum of the reaction products became linear siloxane polymers with mea-
product. In addition to the absorption peaks from sured molecular weight of 15,000. In this case, the end
SieC (800 cm
1 and 1270 cm
1) and SieO (1025e groups were hydroxyl group and ethoxy group. By
1100 cm
1), the absorption peak caused by SieH was adding ethanol to diethylamine, potassium hydroxide
clearly observed at 2160 cm
1. Simultaneously, the eOH was soluble in the ethanol, which greatly enhanced the
peak near 3400 cm
1 decreased greatly, yet, it did not nucleophilic cleavage reaction of the SieO bond by
disappear completely. This small absorption eOH peak amine. If different alcohols were used to dissolve the
was probably caused by the absorbed moisture and/or KOH catalyst, the degradation rate and the distribution
the residual methanol during the separation procedure. of the products were both changed. The order of the
This assumption was supported by the NMR results. The dissolution time was glycerol (GLD) O ethylene glycol
original absorption peak due to the terminal hydroxyl (EGD) O butanediol (BUD) O ethanol. The reusability
group (eSieOH ) was not found in the 1H-NMR of the aminolysis products of the RTV silicone rubber
was improved by changing their terminal groups. The
main aminolysis product, EtOePDMSeOH, was con-
verted to HOeBuePDMSeBueOH, EtOePDMSeH,
HOePDMSeOH and HePDMSeH. The yield was
between 60 and 80%.

Acknowledgements

The authors wish to express their appreciation for the

financial support of the National Science Council,
Taiwan, Republic of China (Project No: NSC 89-2216-
E-032-009).

4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm-1)
References

Fig. 5. FTIR spectrum of the reaction product, HePDMSeH, [1] Noll WJ. Chemistry and technology of silicones. New York:
converted from HOePDMSeOH. Academic Press; 1968.
 C.-L. Chang et al. / Polymer Degradation and Stability 85 (2004) 769e777 777

[2] Clarson SJ, Semlyen JA. Siloxane polymers. New Jersey: PTR [8] Chang CL, Lee HS, Chen CK. Polym Degrad Stab 1999;65:1e4.
Prentice Hall; 1993. p. 16, 569. [9] Chen JG. Studies on the aminolysis of the room temperature
[3] Hsiao YC, Hill LW, Pappas SP. J Appl Polym Sci 1975; vulcanization silicone rubber. M.S. Thesis, Tamkang University,
19:2817. Taipei, Taiwan; 1996.
[4] Pappas SP, Just RL. J Polym Sci Polym Chem Ed 1980;15:527. [10] Rubinsztajn S, Cypryk M, Chojnowski J. J Organomet Chem
[5] Schimmel KH. Acta Polym 1987;38:495. 1989;367:27.
[6] Schimmel KH, Shulz J. Acta Polym 1987;38:536. [11] Voronkov MG, Mileshkevich VP, Yuzhelecskii YA. The siloxane
[7] Schimmel KH, Schroder E, Shulz J, Souvimonh J. Acta Polym bond. New York: Consultants Bureau; 1978. p. 388.
1988;39:310. [12] Sommer LH, Rasborough KT. J Am Chem Soc 1969;91:7067.