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Synthesis of a comb-like/bottlebrush-like silicone-epoxy co-

polymer with high thermal stability and mechanical properties for
ablative materials

Youquan Ling, Jiemin Luo, Zhengguang Heng, Yang Chen,

Huawei Zou, Mei Liang

PII: S1381-5148(20)30177-2
DOI: https://doi.org/10.1016/j.reactfunctpolym.2020.104742
Reference: REACT 104742

To appear in: Reactive and Functional Polymers

Received date: 9 February 2020

Revised date: 24 July 2020
Accepted date: 24 September 2020

Please cite this article as: Y. Ling, J. Luo, Z. Heng, et al., Synthesis of a comb-like/
bottlebrush-like silicone-epoxy co-polymer with high thermal stability and mechanical
properties for ablative materials, Reactive and Functional Polymers (2020),
https://doi.org/10.1016/j.reactfunctpolym.2020.104742

This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
not yet the definitive version of record. This version will undergo additional copyediting,
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version to give early visibility of the article. Please note that, during the production
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that apply to the journal pertain.

© 2020 Published by Elsevier.

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Synthesis of a Comb-like/bottlebrush-like Silicone-epoxy Co-polymer with High

Thermal Stability and Mechanical Properties for Ablative Materials

Youquan Ling, Jiemin Luo, Zhengguang Heng, Yang Chen, Huawei Zou, Mei

Liang

(The State Key Lab of Polymer Materials Engineering, Polymer Research Institute

of Sichuan University, Chengdu 610065, PR China)

Abstract

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A comb-like/bottlebrush-like silicone-epoxy co-polymer was prepared by

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synergizing o-allylphenol modified (UC-233) and methoxy-terminated methylphenyl

silicone intermediate (PMPS-S). The SEM and DMA revealed that the
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comb-like/bottlebrush-like silicone-epoxy co-polymer showed better compatibility
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owing to the pre-chemical grafting reaction. Additionally, TGA revealed that the
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carbon residue of the comb-like/bottlebrush-like silicone-epoxy co-polymer reached

45.06% at 800 ℃ in N2, the thermal stability of the A comb-like/bottlebrush-like

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silicone-epoxy co-polymer was improved and maintained the excellent mechanical

properties of epoxy resin. Furthermore, TGA-FTIR shows the thermal degradation

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process that methoxy-terminated methylphenyl silicone intermediate (PMPS-S) and

phenyl hydrogen-containing silicone oil (UC-233) could inhibit the degradation of

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epoxy resin. Therefore, it is believed that comb-like/bottlebrush-like silicone-epoxy

co-polymer, with mechanical properties, thermal stability and high thermal residual

weight and will have application potential in ablative materials.

Keywords

Epoxy resin; organosilicon intermediate; thermal stability; grafted copolymer;


Corresponding author. Tel: +86-28-85408288; Fax: +86-28-85402465.
E-mail address: cy3262276@163.com (Yang Chen)

Corresponding author. Tel: +86-28-85408288; Fax: +86-28-85402465.
E-mail address: hwzou@163.com (Huawei Zou)
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ablative materials

1. Introduction

Ablation thermal protection is a very effective and mature thermal protection

method developed from 1950s. Meanwhile ablative material is one of the most

important material in thermal protection system (TPS), which is widely used to

protect the internal structure and instruments of the space vehicle at high speed. As an

important part of ablative material, resin-based composite materials have been widely

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used in thermal protection system. In resin-based composite materials, resin plays a

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significant role in bonding, transferring and ablating carbon source in components[1,

2]. The residual carbon and the carbon layer construction of materials are very
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important for ablative performance and thermal insulation performance, which is an
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essential index of thermal protection performance of TPS[3]. In some applications,
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such as the shell of a rocket, it is necessary for the material to have both excellent

ablative and mechanical properties.

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As a widely used resin, epoxy resin has excellent bonding strength, low cure

shrinkage, stable chemical structure, high mechanical strength, excellent electrical

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insulation and processing properties [4-7]. Unfortunately, it is impossible to be used in

thermal protection systems (TPS) because of its poor thermal stability and residual
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carbon. However, silicone rubber has high heat resistance and high carbon residue

rate, and it has been widely used in thermal protection systems (TPS)[8-10]. Thus, by

introducing silicone into epoxy resin, an epoxy resin matrix with high residual carbon,

good heat resistance, and utility for ablation materials can be synthesized. The

mechanism of synthesis is through the organic functional group carried by the silicone

molecular chain reacts with the epoxy resin, such as the hydroxyl[11, 12], alkoxy[13,

14], amino[15] , epoxy group[16], ethylene[17, 18], silicon hydrogen bond[19],

carboxyl group[20] on the silicone molecule, and the hydroxyl group[21, 22] on the

epoxy resin molecular chain and epoxy group to synthesis a highly branched
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silicone-epoxy co-polymer[23-27]. These reactions are used to improve the

compatibility of silicone and epoxy resins in the new type of epoxy resin [28, 29]. In

addition, some scholars have prepared silicone-containing carboxylic acid curing

agents[30], acid anhydride curing agents[31], and amine curing agents[32].

Meanwhile, some researchers have introduced silicon-containing substances directly

into the epoxy resin main chain and prepared silicon-containing epoxy resins[33].

Chen[4] synthesized silicone-bridged epoxy resins by reacting hydroxyl-terminated

silicone oligomer with bisphenol-A type epoxy resins, in which the residue carbon of

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the modified epoxy resin at 600°C increased while the mechanical properties greatly

degraded with increasing silicone content.

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In general, many studies have prepared silicone-modified epoxy resins to prepare
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comb-like/bottlebrush-like copolymers to improve the compatibility between silicone
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and epoxy[2, 5, 7]. There are a lot of studies on the toughening of silicone-toughened

epoxy resin [34-37], but only a small amount of silicone is added in these studies. At
lP

the same time, it is difficult to balance both mechanical properties and residual carbon,

in which the toughness will decrease due to the poor compatibility of silicone and
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epoxy resin under high content.

Therefore, in this study, a comb-like/bottlebrush-like silicone-epoxy copolymer

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with high residual carbon and toughness was prepared by the hydrosilylation reactions,
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ring-opening reactions and grafting reactions among methyl phenyl hydrosilicon oil

(UC-233), 2-Allylphenol (AP), epoxy resin, and methoxy-terminated methylphenyl

silicone intermediate (PMPS-S). Based on the substance, the effect of phenyl

hydrogen silicone oil (UC-233) on the compatibility of silicone and epoxy resin was

investigated. The mechanical properties and thermal degradation stability of

comb-like/bottlebrush-like silicone-epoxy resin were studied, the relationship among

molecular structure and macroscopic properties and the thermal degradation

mechanism were explored. Finally, the test results show that we have prepared a resin

matrix with high residual carbon, heat resistance and toughness. It has potential
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applications in thermal protection systems. For example, it can be used in

ablation-resistant coatings for spacecraft, and composited with carbon fiber to prepare

rocket engine shell materials.

2. Experimental procedure

2.1. Materials

Bisphenol-A type epoxy resins (E44) were purchased from Nantong Xingchen

Synthetic Material Co Ltd China. Methyl phenyl hydrosilicon oil (UC-233) and

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methoxy-terminated methylphenyl silicone intermediate (PMPS-S) were purchased

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from China BlueStar Chengrand Research Institute of Chemical Industry.

2-Allylphenol (AP), dibutyltin dilaurate (DBTDL), 4,4'-Methylene bis(2-chloroaniline)

-p
(MOCA), chloroplatinic acid solution, N, N-dimethylbenzylamine (BDMA).
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Dimethylbenzene and acetone were purchased from Chengdu Kelon Chemical
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Reagent Factory, China.

2.2. Synthesis of 2-allylphenol modified methyl phenyl hydrosilicon oil (UAP).

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AP (3.1g) and UC-233 (6.9g) were charged into a 50 ml three-necked flask. The

temperature was increased to 55 °C and purged with Argon for 30 min. The flask was
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submerged into a preheated oil bath at 55 °C and purged with Argon for 30min,
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followed by adding 30 uL of a chloroplatinic acid catalyst. After 1 hour, the UAP was

obtained.

2.3. Preparation of UAP ring-opening epoxy resin (EUAP)

UAP (10g) and E44 (100g) was charged into a 200 ml three-necked flask. The

temperature was increased to 110 °C and purged with Argon for 20 min, followed by

adding 4 wt % of BDMA catalyst. After 2 hours, the UAP was obtained.

2.4. Preparation of PMPS-S modified EUAP prepolymer (EUAPS)

According to the formulations listed in Table 1, EUAP and PMPS-S were added

to a three-necked flask containing xylene. After bubbled for 30min, 3 wt % of

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DBTDL was added. Then the flask equipped with a spherical condenser was

submerged into a preheated oil bath at 140 °C for 5 h. EUAPS copolymers were

obtained after evaporated the solvent. The detailed process was shown in Fig. 1. As a

comparison, ES-70 was also synthesized through a similar process.

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Fig. 1 Preparation process of EUAPS copolymer

2.5. Curing of EUAPS copolymer

The prepolymer (EUAPS) and the curing agent (MOCA) were mixed according

to the ratio (Table 1), stirred uniformly, vacuumed to remove the bubbles, then casted

in a preheated teflon mold, and finally placed in an oven for curing. The curing

conditions were 150 °C/2h+190 °C/3h. The curing process of EUAPS is shown in Fig.
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2.

Table 1 The formulations of the EUAPS system

Code E44/g UC-233 /g AP/g PMPS-S/g MOCA/g

E44 100 0 0 0 28.4

EUAP 100 6.9 2.1 0 28.4

EUAPS-10 100 6.9 2.1 10 28.4

EUAPS-30 100 6.9 2.1 30 28.4

EUAPS-50 100 6.9 2.1 50 28.4

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EUAPS-70 100 6.9 2.1 70 28.4

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ES-70 100 0 0 70 29.4
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Fig. 2 Curing process of the EUAPS system

2.6. Characterization

The ATR-FTIR was measured by using an Infrared Analyzer (Nicolet iS50,

Thermo, USA). The EUAPS and UAP were uniformly coated on the potassium

bromide sheet for infrared test, and the scanning range was 400~4000 cm-1. The NMR

spectrum was tested on a spectrometer (AVII NMR, Bruker Company, Germany).

Deuterated chloroform was used as a solvent to obtain a 400 MHz nuclear magnetic

resonance spectrum at 25 ℃. The impact fracture and carbon layer of the composite

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was observed by means of a scanning electron microscope (JSM-5900, JEOL, Japan)

and the accelerating voltage is 15 kV. The glass transition temperature (Tg), storage

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modulus (E′), and crosslink density (νe) were tested by a dynamic thermomechanical
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analyzer (DMA, Q800, TA, USA). DMA uses a three-point bending test method with
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the condition of 1 Hz test frequency and 20 um amplitude. And the test temperature is

from 40 to 200 ℃ at a heating rate of 3 ℃/min. The tensile strength was measured by
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universal material testing machine (Instron 5567) according to GB/T 528-2008. All

the samples were a dumbbell-shaped spline with a length of 125 mm, a width of 10
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mm and a thickness of 4 mm with a tensile speed of 10 mm/min. The impact strength

was measured using an impact testing machine (ZBC-4B, Xinsansi, China) according
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to GB/T 2567 -2008. All sample sizes are 80 mm long, 10 mm wide.

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Thermogravimetric measurements were recorded using a thermogravimetric analyzer

(TG STA 449 C, NETZSCH, Germany) to investigate the thermal stability of the

samples. Samples of 3-10 mg were heated from 30 to 800 °C at a heating rate of 10

K/min under the nitrogen and air gas flow (60 mL/min). TGA-FTIR were recorded

using a thermogravimetric analyzer (TGA55, TA, USA) and an Infrared Analyzer

(Nicolet iS50, Thermo, USA) to analyze the thermal degradation process. Samples of

5~10 mg are heated from 30 ℃ to 800 ℃ with a heating rate of 10 K/min in N2.

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3. Results and discussion

3.1. Characterization of UAP, EUAP, EUAPS

The FTIR spectrum of UAP was presented in Fig. 3. As shown in Fig. 3 (a), the

characteristic peaks at 1638 cm-1 and 2135 cm-1 were attributed to C=C and Si-H

respectively[38-40]. After the reaction, the peak at 1638 cm-1 disappeared (Fig. 3 b),

suggesting AP were completely consumed. Due to the excessive content of

hydrogen-containing silicone oil, the peak intensity of the Si-H did not disappear. The

peak at 3422 cm-1 belongs to the phenolic hydroxyl group.

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Fig. 3 FTIR spectra of the methyl phenyl hydrosilicon oil by 2-allylphenol (UAP)

Fig. 4 shows the nuclear magnetic resonance spectrum of epoxy resin modified
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by UPA (EUAP) after 0 h and 2 h, recording as EUAP-0h (a) and EUAP-2h(b). The

change in the epoxy group content is characterized by nuclear magnetic resonance

spectroscopy. In Fig. 4, no new peak appeared in the EUAP-0h and EUAP-2h. Due to

the UAP’s content is only 9wt %, there is no obvious peak position is on the epoxy

resin except Si-CH3 (δ:0.0 ppm) of UAP. The EUAP’s chemical structures: δ(ppm):

3.34 (-CH-), 1.63 (-C(CH3)2-) as well as its peak position is shown in Fig.4 (b) [23,

41-43]. Using -C(CH3)2- as the internal standard, the ratio of the area of the peak of

-CH- and CH3-C-CH3 was recorded as H0h and H2h. H2h/H0h=0.2/0.21=0.95, which is

consistent with the theoretical change of epoxy group (theoretical amount of epoxy
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group is 0.42/0.44=0.95), indicating that the epoxy group reacts with the phenolic

hydroxyl group.

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Fig. 4 1H-NMR spectra of the modified-epoxy resin: (a) EUAP-0h, (b) EUAP-2h
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Fig. 5 (a) and (b) shows the FTIR spectrum of EUAPS-30 after reacting for 0 h
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and 5 h. The peaks at 2840 cm-1 and 915/830 cm-1 were attributed to Si-O-CH3 and

epoxy groups respectively. The characteristic peaks of 1183 cm-1, 1038 cm-1 and 3482
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cm-1 belong to Si-O-Si, Si-O-C and -OH respectively. As shown in Fig. 5 (b) , the

peaks at 2840 cm-1 disappeared. It is indicated that the PMPS-S is successfully grafted
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onto EUAP.
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Fig. 5 FTIR spectra of EUAPS copolymer at different reaction time(a) 0 h of

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EUAP and PMPS-S reaction;(b) 5 h of EUAP and PMPS-S reaction

3.2. Micromorphology of the cured system

Fig. 6 shows the scanning electron micrograph (SEM) of the impact profile of

the EUAPS resin. There is no obvious dispersed phase in Fig. 6 (a), which indicates a

good compatibility. It is proved that the phenolic hydroxyl group of the

hydrogen-containing silicone oil is successfully reacted with the epoxy group, and

UAP is successfully grafted on the epoxy resin. From Fig. 6 (a) and (b), the

microcracks generated by the stress of the impact section are connected to each other

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in Fig. 6 (b). The introduction of a silicone intermediate (PMPS-S) makes the impact

energy more easily dissipated. The microcracks in the cross section become less and

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flat with the increase of the PMPS-S, indicating that the toughness of the EUAPS-10
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is best. It is consistent with the impact test results. In the Fig. 6 (e) and (f), it can be
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clearly seen that the ES-70 system has a very rough cross section because of the poor

compatibility of the silicone phase and the epoxy phase. The surface of EUAPS-70 is
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smoother than ES-70, indicating that hydrogen-containing silicone oil can improve

the compatibility of silicone and epoxy resin in the comb-like/bottlebrush-like

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silicone-epoxy co-polymer.
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Fig. 6 SEM images of impact fractured surfaces of samples of EUAPS system: (a)

EUAP; (b) EUAPS-10; (c) EUAPS-30; (d) EUAPS-50; (e) EUAPS-70; (f) ES-70
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3.3. Dynamic mechanical analysis

Figure 7 was the DMA results of E44, EUAP, EUAPS and ES-70, and the glass

transition temperature (Tg), storage (E’) and crosslink density (νe) of these materials

were listed in Table 2. It is shown that the Tg of the EUAPS system decreases

gradually. There are three reasons proposed for the downward to the Tg. First, Si-O-Si

and Si-O-C chemical bonds in the molecular chain improve the the flexibility of the

chain. Moreover, the comb-like/bottlebrush-like PMPS-S side chain increases free

volume and makes the segment movement easier. Besides, it can be calculated that

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the crosslinking density (νe) is also gradually decreased compared with EUAP, due to

a decrease in the content of the epoxy group because of the reaction of the phenolic

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hydroxyl group with the epoxy group and the silicone increase the spacing between
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epoxy groups and limit crosslinking. Meanwhile, the storage modulus (E') decreases
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regularly. It is due to that the flexibility of bonds in UC-233 and PMPS-S reduces the

rigidity of epoxy matrix and the large silicon particles decrease the crosslink density.
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Fig. 7 (a) storage modulus (E′) and (b) Tan δ of EUAPS systems

Table 2 Tg, storage modulus (E′) and crosslinking density (νe) of EUAPS systems

Code Tg (℃) E′ (MPa)at 40℃ νe (mol/dm3)

E44 154.2 3225 2.066

EUAP 151.0 3066 1.792

EUAPS-10 146.8 2950 1.747

EUAPS-30 141.1 2724 1.749

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EUAPS-50 133.6 2334 1.512

EUAPS-70 123.9 2028 1.290

ES-70 132.9 2401 1.620

Compared with ES-70, the EUAPS-70 has been grafted with UAP which reduces

the epoxy group content and increases the flexibility of the silicone molecular chain,

so the νe, Tg and E′ have all decreased. Thus, the results of DMA are also consistent

with the results of SEM.

3.4. Thermal stability analysis

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Fig. 8 shows thermogravimetric (TG) curves (a) and differential thermal mass

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loss (DTG) curves (b) of the EUAPS system measured under N2 atmosphere. Table 3

shows the temperature at 5% (T5%) and the maximum weight loss rate (Tmax) of the
-p
EUAPS modified EUAPS system under N2 atmosphere. From Fig. 8 and Table 3, the
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T5% and Tmax of the EUAP did not change much compared to pure epoxy (E44). This

is different from the law of change after adding PMPS-S: the T5% decreases and Tmax
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increases with the increase of PMPS-S, as the degradation mechanism of

hydrogen-containing silicone oil is different[44, 45]. On the one hand, the Si-C
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created by the reaction of the hydrogen-containing silicone oil and the 2-allylphenol is
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more stable because the Si-O bond is prone to rearrangement and cyclization

degradation. On the other hand, the removal of hydrogen has little effect on quality
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and does not trip degradation compared with Si-OCH3 because of the small molecular

weight of hydrogen in free Si-H. Moreover, it is difficult to cyclize the degradation

due to the positional effect of the benzene ring in UC-233, so the T5% and Tmax of

EUAP are basically the same as those of epoxy resin. The low surface energy of

silicone can decomposes SiO2-like protective layer, which tends to flow on the surface

of the substrate and acts as a barrier to the transfer of heat and insulation, isolates the

release of combustible gases, protects its substrate[46, 47]. When PMPS-S was

incorporated, the EUAPS resin can form the protective layer at the initial degradation

temperature, which can slow down the degradation of the matrix and lead to an
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increase in Tmax. When the temperature continues to rise, the excellent thermal

stability of the UC-233 and the PMPS-S results in the decomposition curve of the

modified epoxy resin above that of E44, and finally the thermal residual weight at

800 ℃ is heavier than E44.

The residual weight of EUAPS-70 is up to 45.06% at 800℃ with an increase of

147.3% compared to E44. Compared with ES-70, EUAPS-70 has a lower degradation

rate and a higher thermal residue at temperature above 550 ℃. This indicates that the

introduction of UAP can improves the thermal stability of the EUAPS system.

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Fig. 8 (a) TGA plots and (b) derivative curves of cured EUAPS systems under
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nitrogen atmosphere

Table 3 Thermal stability factors of cured EUAPS systems under nitrogen

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atmosphere
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Solid residue at
Code T5% (℃) Tmax (℃)
800℃ (%)

E44 391.2 413.1 18.6

EUAP 390.6 413.5 20.8

EUAPS-10 376.0 402.0 27.2

EUAPS-30 377.7 407.0 34.6

EUAPS-50 374.1 404.7 40.1

EUAPS-70 374.7 417.5 45.1

ES-70 370.1 410.6 43.7

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Fig. 9 shows the thermal stability of the EUAPS system measured in air:

thermogravimetric (TG) curve (a), and differential thermal mass loss (DTG) curve (b).

Table 4 shows the thermal stability parameters of the EUAPS system under air

atmosphere. From Table 4, the T5% of the EUAP and EUAPS systems introduced with

UC-233 were higher than those of E44 and ES-70 respectively, which were different

from those in the nitrogen atmosphere. It manifests that the initial degradation

mechanism of UC-233 in air atmosphere is different from that in nitrogen

atmosphere[48]. In the air, the epoxy group is more easily degraded to form

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oxygen-containing radicals, and the silicon-hydrogen bonds are easily broken to form

silicon-containing radicals. Therefore, the silicon-containing radical on the UC-233

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can react with the oxygen-containing radical on the epoxy main chain to form a
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Si-O-C bond, and the high bond energy of the Si-O-C bond can improve the heat
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resistance of the matrix, resulting in an increase of T5%.

With the introduction of PMPS-S, the heat resistance of the system increased
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significantly: Tmax3 increased from 546.5 °C to 621.6 °C, and the thermal residual

weight at 800 °C increased from 0% to 15.99%. It is proved that the

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comb-like/bottlebrush-like silicone-epoxy co-polymer has a greatly positive effect on

the heat resistance of the epoxy.

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Fig. 9 (a) TGA plots and (b) derivative curves of cured EUAPS systems under air

atmosphere

Table 4 Thermal stability factors of cured EUAPS systems under air atmosphere

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Solid residue at
Code T5% (℃) Tmax (℃)
800℃ (%)

E44 341.5 321.5/381.5/546.5 0

EUAP 343.3 325.8/383.3/543.3 2.2

EUAPS-10 338.9 321.4/381.4/568.9 4.6

EUAPS-30 341.5 319.0/381.5/594.0 8.2

EUAPS-50 329.1 326.6/386.6/614.1 13.5

EUAPS-70 331.6 386.6/621.6 16.0

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ES-70 326.6 316.6/386.6/621.6 16.0

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3.5. TGA-FTIR analysis of EUAPS system

Fig. 10 (a), (b) and (c) show the FTIR spectra of pyrolysis products of E44,
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ES-70, EUAPS-70 at different stages of thermal degradation respectively to further
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study the thermal degradation process and mechanism.
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Fig. 10 FTIR spectra of volatile products recorded at the indicated temperatures

for the decomposition of silicone modified epoxy resins in a nitrogen atmosphere:

(a) E44, (b) ES-70, (c) EUAPS-70

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As for E44, when the temperature of the sample was 391℃ (Fig 10a), the peaks

at 1400~1800 cm-1, 3500~3900 cm-1 and 2200 ~ 2400 cm-1, which corresponded to

-OH in H2O, phenol and CO2 respectively[49-51], were observed, suggesting water,

phenol and carbon dioxide are produced in the first stage of thermal degradation.

When the temperature of the sample was further increased to 413 ℃ at the second

stage of thermal degradation, the characteristic peaks of water remained. These water

vapors may be generated by the reaction between the residual hydroxypropyl groups

in the epoxy resin. The peak intensity of the characteristic peak of carbon dioxide at

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2358 cm-1 reached the highest. It shows that in the second stage of degradation, the

degradation rate of epoxy resin reaches the maximum. In the third stage of thermal

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degradation, at 600 ℃, the characteristic peaks around 3500~3900 cm-1 still exist,
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making clear that there is still a dehydration reaction. In addition, there are new

characteristic peaks around 2180cm-1, and 2180cm-1 is related to the absorption of CO.
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The peak at 745 cm-1 in the spectrum is related to the hydrogen on the benzene ring in
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the aromatic hydrocarbon. The peaks at 3011 cm-1 and 1180 cm-1 correspond to CH4.

It is proved that water, phenol, benzene, and CO, CO2, and CH4 are formed in the
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third stage of thermal degradation.

As shown in Fig. 10 (b) and (c), the pyrolysis gas analysis for ES-70 and
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EUAPS-70 exhibited bands of compounds containing Si-O (1058 cm-1 ,1055 cm-1),
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CO2 (2347cm-1, 2322cm-1), CO (2175cm-1, 2180cm-1), benzene (1178cm-1, 670cm-1,

1186cm-1, 676cm-1), CH4 (3070cm-1, 2963cm-1). The new pyrolysis gas containing

Si-O is attributed to the rearrangement and cyclization degradation of the Si-O bonds

in PMPS-S and UC-233.

Fig. 11 shows the gram Schmidt (GS) curves and functional group profile (FGP)

of E44 (a), ES-70 (b) and EUAPS-70 (c) made by Omnic series software. GS curve is

the quantitative measurement of total infrared absorption, which is expressed as the

curve of the concentration of the escaping gas changing with time. In addition, FTIR

can display the curve of the infrared absorption intensity changing with time in
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multiple areas of each spectrum, that is, the functional group profile[52].

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Fig. 11 Curves of Gram-Schmidt (GS) and functional group profile (FGP) for

E44 (a), ES-70 (b) and EUAPS-70 (c)

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From the GS diagram in Fig. 11, the peak intensity of benzene (1178 cm-1, 670

cm-1, 1186 cm-1, 676 cm-1) and CH4 (3070 cm-1, 2963 cm-1) of ES-70 and EUAPS-70
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are significantly stronger than that in E44. And the release curves of CO (2347 cm-1,
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2322 cm-1) and CO2 (2175 cm-1, 2180 cm-1) in ES-70 and EUAPS-70 with silicone

added were significantly slower, and there was no sharp pyrolysis peak compared to

E44. It was revealed that the silicone can the release of decomposition gas, inhibit the

degradation of epoxy resin and improve the heat resistance of the EUAPS system.

Based on the above results, it was proved that the degradation mechanism of

ES-70 and EUAPS-70 was the different with E44. The mainly pyrolysis gas of

EUAPS-70 and ES-70 was water, phenol, benzene, and CO, CO2, and CH4 during the

stages of thermal degradation. But EUAPS has a better thermal stability and less

release of CO and CO2 compared with E44. The thermal degradation mechanism of

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the EUAPS system is shown in Fig. 12 according to the FTIR spectra of the pyrolysis

products.

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Fig. 12 Thermal degradation reactions occurred in the curing system.

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(a) Thermal degradation in epoxy resin components;(b) and (c) Thermolysis

reactions occurred in the silicone component

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3.6. Mechanical properties

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Fig. 13 shows tensile strength (a) and elongation at break (b) of the EUAPS

system. Compared with E44, the tensile strength and the elongation at break of EUAP

reached 84.3MPa and 7.38%, respectively. The improved tensile strength and

elongation at break of the EUAP proved that the reaction between a small amount of

phenolic hydroxyl groups and the epoxy group will not have a significantly negative

impact on the mechanical properties of the EUAPS system. The UC-233 contains

more than two functional silicon hydrogen bonds (Si-H), which can be chemically

linked by reacting 2-allylphenol with an epoxy group, and finally the UAP works as a

crosslinker, so that the stress can be dissipated through the softer silicone region and

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resulting in an increase in toughness.

Fig. 13 (a) Tensile strength and (b) Elongation at break of cured EUAPS systems

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The elongation at break of EUAPS-10 reached to 8.26% increased by 39.1%

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compared with E44. And the elongation at break of EUAPS-50 is 6.64 %, which is
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still higher than that of the pure sample. The tensile strength of the EUAPS resin

gradually decreases with an increase of PMPS-S. However, the tensile strength of

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EUAPS-70 was 50 MPa or more. Comparing with ES-70, the tensile strength and
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elongation at break of EUAPS-70 is 54.2 MPa and 4.71% increased by 40.1% and

51.9%, respectively. There are two reasons for this result. First, the introduction of
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UC-233 increases the compatibility of silicone with epoxy resin. Second, the reaction

of UAP with the epoxy resin matrix produces new hydroxyl groups which increase the
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hydroxyl content of the matrix, resulting in a better reaction of epoxy with PMPS-S.
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Fig. 14 shows the effect of PMPS-S content on the impact strength of the

EUAPS modified system. The impact strength increases with the introduction of

UC-233 and PMPS-S, and the impact strength of EUAPS-10 reaches the maximum,

which is 65.4% higher than E44. Compared with the ES-70, the impact strength of the

EUAPS-70 is increased by 43.3%. This proves that the modification of UAP and

PMPS-S can effectively improve the toughness of epoxy resin. And EUAPS system

have achieved the toughening of epoxy resin with a high addition of silicone.

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Fig. 14 Impact strength of cured EUAPS systems

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4. Conclusion

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In this work, the comb-like/bottlebrush-like silicone-epoxy co-polymer was

successfully prepared. It was found that the highly branched reaction could effectively
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improve the thermal properties of epoxy resin while not significantly reduce the
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mechanical performance. The residual carbon of EUAPS-70 at 800 ℃ under nitrogen

atmosphere was increased up to 45.06%, which was 141.7% improved compared with
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E44. The degradation mechanism of the comb-like/bottlebrush-like silicone-epoxy

co-polymer revealed that the PMPS-S and UC-233 could effectively inhibit the
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degradation of epoxy resin. These results indicated that a method of synergistically

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modifying an epoxy resin by UAP and UC-233 to improve the compatibility of the

silicone with the epoxy resin matrix is feasible and the comb-like/bottlebrush-like

silicone-epoxy co-polymer have practical application potential in ablative materials

which needs excellent mechanical properties or the matrix of composite in TPS.

Acknowledgements

We are grateful for financial support by National Natural Science Foundation of

China (Grant No. 51703137), the State Key Laboratory of Polymer Materials

Engineering (Grant No. sklpme 2018-2-10 and sklpme 2019-2-02), and the Testing
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Center of State Key Laboratory and Analytical and Testing Center of Sichuan

University for providing NMR, FTIR, TGA, DMA, SEM and the mechanical

performance testing.

Data availability

The raw/processed data required to reproduce these findings cannot be shared at

this time due to technical or time limitations.

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Youquan Ling: Conceptualization, Methodology, Software, Writing-Original

draft preparation. Jiemin Luo: Data curation, Writing-Original draft preparation.

Zhengguang Heng: Visualization, Investigation. Yang Chen: Supervision, Software,

Validation. Huawei Zou: Supervision.: Mei Liang: Writing-Reviewing and Editing.

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Highlights:

 The compatibility of silicone and epoxy resin was improved by introducing the

pre-reactive phenyl silicone oil containing phenolic hydroxyl groups.

 A comb-like/bottlebrush-like silicone-epoxy copolymer with high residual carbon

and mechanical performance was prepared.

 The hyperbranched structure of silicone in epoxy resin could effectively improve

thermal stability and inhibit the degradation of epoxy resin.

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