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  • 1 Faculty of Chemistry, Institute of Polymer and Dye Technology, Technical University of Łódź, Stefanowskiego 12/16 St., 90-924, Łódź, Poland
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Abstract

New branched polymethylvinylborosiloxanes (PMVBSs) with random structures were prepared, and their chemical structures were studied by spectroscopic methods (FTIR, 1H-, 29Si-, and 11B-NMR) and elemental analysis (% C, % H, % Si, and % B). Average molecular weights Mw and Mn were determined by a size exclusion chromatography (SEC), and dynamic viscosities were measured in Brookfield cone–plate reoviscometer HBDV-II+cP. Thermal properties of PMVBSs were studied under air and under nitrogen atmosphere. Thermal curves were interpreted from the point of view of physical and chemical transitions, taking place during the heating process of PMVBSs. Parameters of their thermal stabilities and glass transition temperatures (Tg) were determined. The synthesized PMVBSs are characterized by low glass transition temperatures (Tg: from −122 to −137 °C) which depend on their chemical structures. It was concluded that gaseous products (such as volatile siloxanes, silanes, CO2, H2O, CH2O, methanol, and formic acid), which could be liberated during the heating process of PMVBSs, promote ceramization processes, leading to the formation of the ceramics of a type SiBCO—a borosilicate glass and silica.

Abstract

New branched polymethylvinylborosiloxanes (PMVBSs) with random structures were prepared, and their chemical structures were studied by spectroscopic methods (FTIR, 1H-, 29Si-, and 11B-NMR) and elemental analysis (% C, % H, % Si, and % B). Average molecular weights Mw and Mn were determined by a size exclusion chromatography (SEC), and dynamic viscosities were measured in Brookfield cone–plate reoviscometer HBDV-II+cP. Thermal properties of PMVBSs were studied under air and under nitrogen atmosphere. Thermal curves were interpreted from the point of view of physical and chemical transitions, taking place during the heating process of PMVBSs. Parameters of their thermal stabilities and glass transition temperatures (Tg) were determined. The synthesized PMVBSs are characterized by low glass transition temperatures (Tg: from −122 to −137 °C) which depend on their chemical structures. It was concluded that gaseous products (such as volatile siloxanes, silanes, CO2, H2O, CH2O, methanol, and formic acid), which could be liberated during the heating process of PMVBSs, promote ceramization processes, leading to the formation of the ceramics of a type SiBCO—a borosilicate glass and silica.

Introduction

The development of a contemporary technique prompts an increase in the demand for polymeric materials with special properties, which are resistant to the influence of low and high temperatures, are slow-burning, and have good mechanical strength. In order to fulfill these requirements and find new materials and technologies of their production, numerous efforts are undertaken. One of such possibilities is the chemical synthesis of new copolymers. In recent years, intensive studies concerning synthesis and applications of hybrid inorganic–organic polymers have been developed. An important group of these polymers are polyborosiloxanes (PBS) [1].

The PBS have thermodynamically stable linkages, but are non-resistant to hydrolysis [2]. Although it is known from the literature information that the presence of trivalent metals causes increase of thermal stability of materials, nevertheless an effect of boron atoms on thermooxidative stability under air atmosphere was studied so far only in a limited range [3]. Thermogravimetric studies proved a high thermal stability of PBS, which is the result of high dissociation energy of Si–O and B–O bonds, and moreover it is the result of high crosslinking degree of these polymers and the presence of phenyl groups in their macromolecules.

The PBS have found many comprehensive practical applications, for instance, as substances for decreasing the flammability of polyethylene terephtalate (PET) [4]. PBS were added to PET, together with montmorillonite nanoparticles. This system of fire retardants substantially decreased the flammability of PET and contributed to a formation of thick multi-cellular borosiloxane-carbon coatings during polymer combustion. These coatings acted as a barrier for a flame, smoke, and oxygen [4]. Marosi and coworkers [5] had applied PBS as flame retardants for polyolefines. The addition of PBS to polypropylene (PP) caused the increase of a viscosity and viscoelasticity during the melting of PP and the decrease of the polymer flammability. PBS cumulated on a PP surface during combustion process and prevented the spreading of a flame, forming a protective coating, and thus deterring any contact with the flame [5]. Other boron compounds (e.g., boric acid and borax) [6, 7]; silanes; silicon-containing polymers: siloxanes, silsesquioxanes [6], and inorganic silicates, e.g., modified montmorillonites [810]; and halloysite nanotubes [11, 12] were successfully used as halogen-free fire retardants. Ammonium polyphosphate, microencapsulated with a low molecular weight polydimethylsiloxane-α,ω-diol, showed enhanced water resistance and significantly improved flame resistance properties as compared with an unmodified ammonium polyphosphate in a thermoplastic polyurethane composites [13].

In this article, we present the results of our studies concerning thermal properties of the synthesized, new branched polymethylvinylborosiloxanes (PMVBSs) which have not been described in the literature so far. We are going to use these copolymers as modifiers of diene elastomers.

Experimental

The focus of our studies are the chosen new branched PMVBSs. Their characteristics are given in Table 1. They were synthesized in the following way. In reactions of boric acid B(OH)3 with a large excess of dichlorodimethylsilane Me2SiCl2, in a dry diethyl ether, a borosiloxane precursor tris(chlorodimethylsilyl)borate B(OSiMe2Cl)3 was prepared. PMVBSs with random, and branched structures were prepared by a hydrolytic copolycondensation of ether solution of the borosiloxane precursor B(OSiMe2Cl)3 and appropriate stoichiometric amounts of chlorosilanes (selected according to predicted chemical structures of PMVBSs): dichlorodimethylsilane Me2SiCl2, trichloromethylsilane, MeSiCl3, chlorotrimethylsilane, Me3SiCl, and methylvinyldichlorosilane, MeViSiCl2 with stoichiometric quantity of water, in the presence of pyridine as HCl acceptor [14, 15].

Table 1

Results of determination of molecular weights (by SEC method), elemental analysis, and the contents of Si–Vi groups [15]

Predicted composition of PMVBSsMn calc.MnMwMw/Mn% C% H% B% SiThe content of Si–Vi groups/mol/100 g
Calc.FoundCalc.FoundCalc.Found*Calc.FoundCalc.Found**
B3O2D190D19viM′516,237 3,3107,1502.1633.4433.75

33.79
8.068.13

8.32
0.200.1737.0237.210.1170.107
B6O5D180D10viM′815,809 3,0207,4302.4632.9733.15

33.31
8.118.31

8.44
0.410.3137.3637.700.0530.063
B9O8D190D10viM′1116,157 3,2607,0702.1732.9333.30

33.37
8.108.29

8.39
0.580.4636.6837.250.0560.062
B3O8T′6D76D19viM′118,673 1,9004,1802.2034.3434.51

34.74
7.988.14

8.30
0.370.2736.2736.740.2180.240
B3O11T′9D100D25viM′1411,415 2,3704,6901.9834.3034.08

34.27
7.978.08

8.23
0.280.2636.4236.430.2170.239
B6O8T′3D76D19viM′118,576 1,8504,1602.2534.3134.58

34.68
7.978.07

8.15
0.760.4535.7036.670.2220.221
B6O11T′6D100D25viM′1411,318 2,3104,7802.0734.2833.92

34.21
7.967.73

7.83
0.570.5635.9836.470.2200.211
B6O14T′9D124D31viM′1714,059 2,9107,1902.4734.2634.18

34.20
7.968.26

8.13
0.460.3436.1635.730.2190.223
B9O14T′6D124D31viM′1713,962 2,8206,8802.4434.2434.08

34.32
7.957.74

7.93
0.700.5235.8136.110.2220.211

% C, % H, % B, and % Si were calculated for predicted molecular formulas of PMVBSs

D Me2SiO, Dvi Me(CH2=CH)SiO, T′ MeSi, M′ Me3SiO

* % B was determined by ICP-AES method

** The content of CH2=CH–Si groups was calculated on the basis of integration ratio of their signals to CH3–Si signals in the 1H-NMR and compared with theoretical integration ratios of both signals

Synthesis of B9O14T′6D124D31viM17 (B9T6)

To one-necked round bottom flask with a volume 250 ml, equipped with a reflux condenser and a drying tube filled with anhydrous CaCl2, was added 3.34 g (0.054 mol) of boric acid (p.a.), 90.25 ml of Me2SiCl2 (0.744 mol), 30 ml of dry diethyl ether, and a magnetic stirring bar. This mixture of reagents was stirred with a magnetic stirrer for 24 h at room temperature (24 °C). After this time, stirring was stopped, because the entire amount of boric acid had reacted, giving homogeneous solution of borosiloxane precursor, B(OSiMe2Cl)3, and an excess of Me2SiCl2. Then, to a four-necked reactor with a volume 1.5 L (equipped with a mechanical stirrer, thermometer, reflux condenser, and the drying tube filled with anhydrous CaCl2) was added the solution of the borosiloxane precursor, 24.14 ml of MeViSiCl2 (0.186 mol), 4.23 ml of MeSiCl3 (0.036 mol), 12.95 ml Me3SiCl (0.102 mol), and 70 ml of dry diethyl ether. The content of reactor was cooled down to −12 °C in an ice–NaCl bath, and 189 ml of pyridine was added dropwise for 70 min., at temperatures ranging from −12 to −4 °C. Next 34.3 ml (1.91 mol) of distilled water was added dropwise at temperatures ranging from −9 to +6 °C for 200 min. During the addition of water, the reaction system was diluted with 175 ml of dry diethyl ether. The cooling bath was removed, and stirring was continued. When temperature in the reactor reached 13 °C, a vigorous increase of temperature was observed (up to 19 °C), and immediately the cooling bath was applied again for 15 min.

In order to block any unreacted terminal Si–OH groups, 20.25 ml of trimethylchlorosilane (0.16 mol) was added, and the content of reactor was stirred for 10 h. On the next day (day 2), the reaction solution was decanted, transferred to a separation funnel, and quickly washed with 25 ml of distilled water. The solution of products was transferred to an Erlenmeyer flask and dried with anhydrous MgSO4. It was kept in a fridge overnight. On the next day (day 3), the solution of products was filtered off through Schott funnel (G-3), and the precipitate was washed with dry diethyl ether. The solvent was distilled off through fractionation Vigreux column. Traces of ether were removed under reduced pressure (∼30 mmHg). The obtained product was evacuated at 5 mmHg in oil bath at a temperature 150 °C, giving 46.07 g of PMVBSs (with yield 59.7 wt%) as a colorless liquid with dynamic viscosity of 32.3 cP.

Other PMVBSs products were similarly prepared.

Methods

The FTIR spectra were registered on Bio-Rad 175C spectrophotometer for neat samples, placed between NaCl plates.

1H-, 29Si-, and 11B-NMR spectra (in C6D6) were recorded on Bruker DRX 500 machine, at the Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, in Łódź (CBMM PAN). Hexamethyldisiloxane Me3SiOSiMe3 was used as an external standard in the 29Si-NMR (INEPT) (δ = 6.98 ppm, in CDCl3).

Elementary analysis (% H and % C) was performed at CBMM PAN. The content of Si was determined by the “wet method” with concentrated H2SO4 (p.a.) [16]. The contents of CH2=CH–Si groups were calculated from the integration of signals of CH2=CH–Si and CH3–Si in the 1H-NMR spectra and compared with theoretical integration ratios of both signals. The content of boron was determined by the emission atomic spectroscopy combined with inductive plasma (ICP-AES) in Thermo Jarrell Ash Spectrometer (USA). The calibration of the spectrometer was done with an ICP multi-element standard solution VI for ICP-MS (Merck). Samples for the analysis were dissolved in concentrated acid solutions of spectral grade (HNO3 and H2SO4) in an MLS 1200 device (Milestone, Italy), with the application of microwaves.

Dynamic viscosities (η25) of PMVBSs were measured at 25.0 °C on Brookfield cone–plate reoviscometer HBDV-II+cP with a cone cP40 (Table 2). Because of Newtonian properties of PMVBSs, values of rotational speeds are not given.

Table 2

Yields of PMVBSs, their dynamic viscosities, and chemical shifts in 11B-NMR spectra

Average compositions of PMVBSs (the expected structures)Yields/wt%Dynamic viscosities/cP11B-NMR data
δ/ppm
B3O2D190D19viM574 28.315.0
B6O5D180D10viM875 25.817.2
B9O8D190D10viM1173 16.517.2
B3O8T′6D76D19viM1167 18.415.3
B3O11T′9D100D25viM1458 22.415.0
B6O8T′3D76D19viM1160 32.315.0
B6O11T′6D100D25viM1463 30.417.4
B6O14T′9D124D31viM1769 32.915.2
B9O14T′6D124D31viM1760 34.217.3

The molecular weights (MWs) values of PMVBSs and their polydispersities were analyzed using a size exclusion chromatography (SEC) in toluene solution, using LDC analytic chromatograph equipped with refractoMonitor and two phenogel columns covering the MWs values in the range of 102–105 g mol−1. A calibration was made as per polystyrene standards.

The thermal analysis of PMVBSs under air atmosphere was conducted in Paulik Paulik, Erdey derivatograph within the temperature ranging from 25 to 800 °C. Samples weighing 90 mg each were used. The heating rate was 7.9 °C/min. The thermal analysis under nitrogen was carried out by the method of scanning dynamic calorimetry and thermogravimetry by means of a DSC-204 microcalorimeter of Netzsch and a TG 209 thermobalance of Netzsch, using weighed samples of 5–6 mg. The heating rate was 10 °C/min. DSC curves were recorded for the temperatures ranging from −150 to 500 °C and TG curves under nitrogen atmosphere—for the temperature range of 20–500 °C.

Results and discussion

The prepared branched PMVBSs (with yields: 55–74 %, Table 2) contain linkages Si–O–Si; functional vinylsiloxane groups, –(CH2=CH)Si(Me)–O–; trifunctional branching points, BO3/2; and non-reactive trimethylsiloxane end groups, Me3SiO1/2. Some PMVBSs contain methylsiloxane branching points, CH3SiO3/2 (T), but all the prepared PMVBSs do not have hydroxyl functional groups, B–OH and Si–OH, and also do not have sensitive to hydrolysis linkages B–O–B.

The chemical structure of PMVBSs was first analyzed by elemental analysis (% C, % H, % Si, and % B) and infrared spectroscopy (Fig. 1).

Fig. 1
Fig. 1

FTIR spectrum of B6O11T′6D100D25viM′14 (neat)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2446-8

The absorption bands corresponding to vibrations of the following groups of atoms: Si–CH3 (2967, 2911, 1416, 1261, 845, and 721 cm−1), Si–C (895 cm−1), Si (CH3)3 (769 cm−1), Si–O–Si (1,075–1,009 cm−1), and Si–CH=CH2 (3048, 3007, 1600, 1410, 1275, 970, and 770 cm−1) were present in the FTIR spectra of all the PMVBSs. The absorption bands at 1340 cm−1 correspond to the stretching vibrations of B–O bond in the Si–O–B linkages (according to the literature data: 1500–1300 cm−1). Characteristic absorption bands of B–O–Si linkages at frequencies of 892 and 675 cm−1 overlap with absorption bands of other linkages, existing in the structure of the PMVBSs. The IR data for PMVBSs were consistent with the literature data [3, 1721].

The chemical structure of the PMVBSs was confirmed by 1H-, 29Si-, 11B-NMR methods. In the 1H-NMR spectra of PMVBSs (e.g., Fig. 2) were present the following signals of hydrogen atoms: for groups Si–CH3– in the range δ: 0.14–0.00 ppm; and for Si–CH=CH2 groups in mers Dvi (Dvi = MeViSiO)—at δ ∼6 ppm; these signals (overlapped multiplets) come from hydrogen atoms of vinyl groups CH=CH2 (integration 1:2); the higher signal corresponds to protons of CH2 group, and the lower one—to proton of C–H bond of the vinyl group.

Fig. 2
Fig. 2

1H-NMR spectrum of B6O5T′6D100D25viM′14 (in C6D6)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2446-8

In the 29Si-NMR spectra (e.g., Fig. 3) are present signals of silicon atoms of all units present in the structures of these copolymers: Me3SiO0.5 (δ 8.4 ÷ 7.2 ppm), Me2SiO (δ −17.8 ÷ −23 ppm), MeViSiO (δ ∼−35 ppm), and MeSiO1.5 (δ −62 ÷ −67 ppm). More detailed analysis, of the 1H-NMR and 29Si-NMR spectra, and a very complex microstructure of siloxane chain of randomly branched PMVBSs, is discussed elsewhere [15]. PMVBSs may have many sequences of the siloxane chain. Their tacticity depends on the stoichiometry of monomers, the presence of different structural units, the steric hindrance at silicon atoms, and the reaction conditions [15].

Fig. 3
Fig. 3

29Si-NMR spectrum of B6O5T′6D100D25viM′14 (in C6D6)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2446-8

The studies by 11B-NMR (e.g., Fig. 4) confirmed the presence of boron atoms in the structures of PMVBSs.

Fig. 4
Fig. 4

11B-NMR spectrum of B6O5T′6D100D25viM′14 (in C6D6)

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2446-8

Dynamic viscosities (η25) of the PMVBSs (Table 2), measured at 25.0 °C in Brookfield cone-plate reoviscometer, were quite low and ranged from 16 to 34 cP. Low viscosities of PMVBSs in comparison with linear polysiloxanes having similar Mw presumably result from a globular structure of hyperbranched macromolecules.

The values of number average molecular weights (Mn), determined by the SEC method, are significantly lower than those of the calculated Mw (Mcalc) for the predicted molecular formulas of the PMVBSs (Table 1). Taking into consideration the branched structures of the PMVBSs, we presume that their hydrodynamic volumes are much different from hydrodynamic volumes of polystyrene standards, and this seems to be the main reason responsible for lower Mn values, than expected. In our opinion, interactions of boron atoms with oxygen atom of the siloxane chains strongly affect the formation of globular structures by PMVBSs.

It is commonly known from the literature that dendrimers and hyperbranched polymers have low viscosities in solution and in melt. Their viscosities and Mw are much lower than those for linear analogs and depend on degree of branching, the polarity of the solvent, the kind of functional groups on their “surface,” as well as on the pH value of a polymer solution. Dendritic and hyperbranched polymers have varying hydrodynamic radii depending on the property of solvents, and they are smaller than those of their linear analogs with the same molar mass. The MWs of of dendrimers and hyperbranched polymers determined by SEC using polystyrene standards are regarded with some skepticism. The hydrodynamic radii were also susceptible to the polarity of functional groups on the periphery [2224]. Values of number average molecular weights Mn and weight average molecular weights Mw determined by the SEC method as per polystyrene standards for hyperbranched polysiloxanes were much lower than the MWs values obtained by means of MALLS detectors [2527].

Polydispersity of Mw (expressed by the ratio: Mw/Mn) is quite broad and similar for all PMVBSs and changes from 2.0 (for B3O11T′9D100D25viM′14) to 2.5 (for B6O14T′9D124D31viM′17). Results of the determinations of MWs (by SEC method), elemental analysis, and the contents of functional groups Si–Vi [mol/100 g] are presented in Table 1.

Polysiloxanes have a good thermal stability [2832] which mainly depends on their chemical structure: for instance, the contents of phenyl groups promote improved thermal stabilities of poly(dimethyl diphenyl)siloxanes [33]. The addition of silsesquioxanes caused an improvement in the thermal stabilities of other polymers, e.g., epoxy resins [34].

The thermal decomposition of the studied branched PMVBSs under air atmosphere begins at T = 100 °C and occurs in two stages. As can be seen from derivatographic analysis of the PMVBSs, the characteristics of their thermal transitions are similar, and independent of the boron content (Figs. 5, 6). The results of thermogravimetric analysis under air atmosphere (Table 3) show that the thermal stabilities of the branched PMVBSs determined by the indicator T5 are quite similar and range from 140 to 180 °C, while their thermal stabilities determined using the indicator T50 are distinctly differentiated for the PMVBSs having different molecular formulas (250–405 °C, Fig. 7).

Fig. 5
Fig. 5

TG, DTG, and DTA curves of polymethylvinylborosiloxane, B3O2D190D19viM5, under air atmosphere

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2446-8

Fig. 6
Fig. 6

TG, DTG, and DTA curves of polymethylvinylborosiloxane, B6O11T6D100D25viM14, under air atmosphere

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2446-8

Table 3

Results of derivatographic analysis of polymethylvinylborosiloxanes under air atmosphere

No.Predicted average composition of PMVBSsSample abbrev.T5/°CT50/°CP800/%% BVi groups/mol/100 g
FoundFound
1B3O8T′6D76D19viM11B3T6140 250 25.00.270.240
2B3O11T′9D100D25viM14B3T9151 252 22.20.260.239
3B6O11T′6D100D25viM14B6T6161 375 33.30.560.211
4B6O14T′9D124D31viM17B6T9150 250 22.20.340.223
5B6O8T′3D76D19viM11B6T3152 275 24.40.450.221
6B9O14T′6D124D31viM17B9T6150 285 27.80.520.211
7B3O2D190D19viM5B3D190140 405 28.90.170.107
8B6O5D180D10viM8B6D180180 340 26.90.310.063
9B9O8D190D10viM11B9D190170 332 24.70.460.062

T 5 and T50 temperature of 5 and 50 % of sample mass loss, respectively

P 800 residue after heating of a sample up to 800 °C

Fig. 7
Fig. 7

The thermal stability of polymethylvinyloborosiloxanes with the different boron content, under air atmosphere, determined by the indicators T5 and T50

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2446-8

The PMVBSs: B6O5D180D10viM8 and B9O8D190D10viM11 exhibit the highest thermal stability, determined by the indicators T5: 180 and 170 °C, respectively (Table 3). The highest value of T50 (405 °C) shows PMVBSs with the chemical structure B3O2D190D19viM5 (Table 3; Fig. 7).

It is worthy to stress that quite a large residue after thermooxidative decomposition of PMVBSs (P800) ranged from 22.2 to 33.3 %, and it might be the result of the formation of a ceramic material (a ceramics of a type SiBCO [20, 3537]—a borosilicate glass and silica). The content of boron in macromolecules of PMVBSs does not affect the mass of the residue after thermooxidative decomposition of the samples; however, the largest mass of the residue characterizes the sample corresponding to the molecular formula of B6O11T′6D100D25viM14, with the highest content of boron in the siloxane chain (Table 3).

A comparative analysis of the results from Table 3 leads to a conclusion that both the content of boron and a length of the siloxane chain may affect the thermal stability of a PMVBSs (Fig. 7). The thermal stabilities of the studied PMVBSs, as determined by the indicator, T5, are not straight dependent on the boron content (which was analyzed by ICP-AES method) (Fig. 7). The highest thermal stability (T5 = 180 °C) shows PMVBSs of the chemical structure B6O5D180D10viM8 (B6D180) with the content of boron being only 0.31 wt%, having the long siloxane chains, i.e., 14–15 siloxane units (D and Dvi) between boron atoms. On the other hand, the lowest thermal stability (T5 = 140 °C) have two PMVBSs with the same functionality (D19vi): B3O8T′6D76D19viM11 (B3T6) and B3O2D190D19viM5 (B3), with the lower contents of boron among the discussed PMVBSs (0.27 and 0.17 wt%, respectively) and with the different lengths of the siloxane chains (5 and ∼30 siloxane units, respectively) between branching points (boron atoms and MeSiO1.5 units) (Table 3; Fig. 7).

The increase of the thermal stability with the increasing boron content, as determined by the indicator T50, was also observed—in the following order of PMVBSs: B3O11T′9D100D25viM14, B3O8T′6D76D19viM11, B6O14T′9D124D31viM17, B6O8T′3D76D19viM11, B9O14T′6D124D31viM17, and B6O11T′6D100D25viM14. Unexpectedly, the highest thermal stability, as determined by the indicator T50, was found for the PMVBSs with the predicted chemical structure B3O2D190D19viM5, with the lowest content of boron (0.17 wt%), and long siloxane chains between boron atoms, were in the order of the PMVBSs: B9O8D190D10viM11, B6O5D180D10viM8, and B3O2D190D19viM5 the T50 values (332, 340, and 405 °C, respectively) increased with the growing length of siloxane chains between boron atoms (∼22, ∼32, and ∼30 siloxane units, respectively). The highest value of T50 (405 °C) obtained for B3O2D190D19viM5 may have resulted from the higher content of vinyl groups, in comparison with B9O8D190D10viM11 and B6O5D180D10viM8. It seems that, for these three PMVBSs, the content of boron does not affect T50 values.

On the basis of the obtained results, it can be stated that the thermal stability of the synthesized branched PMVBSs is affected not only by the content of boron, but also by their chemical structure: degree of branching (3–15) [i.e., the number of boron atoms and methylsiloxane units MeSiO3/2 (T) in macromolecules]; their functionalities (the number of vinylsiloxane groups in the molecule); and—very likely—the length of the siloxane segments between branching points, which is the same for most of the studied PMVBSs ([Me2SiO]/[MeViSiO] = 4), except for those with three structures: B3O2D190D19viM5, B6O5D180D10viM8, and B9O8D190D10viM11.

From a comparison of the values, T5 and T50, we obtain that under air atmosphere PMVBSs characterize lower thermal stabilities than for the polymethylsiloxanes bearing only methyl groups or functional hydrosiloxane or vinylsiloxane groups in macromolecules [38].

The thermal properties of PMVBSs were also studied by the thermogravimetric method under oxygen-free atmosphere. The indicators of the thermal stabilities, T5 and T50, as determined from TG curves under nitrogen atmosphere, show higher values (Table 4) than those under air atmosphere (Table 3). The thermal decomposition of the PMVBSs under nitrogen atmosphere begins at T ≥ 140 °C, which is higher temperature than that under air atmosphere (Figs. 5, 6, 8). The values of the indicators of the thermal stabilities, T5 and T50, of PMVBSs under nitrogen atmosphere are distinctly higher than those under air atmosphere (Tables 3, 4). One may judge that as a result of the heating process of PMVBSs under air atmosphere more volatile products (such as siloxanes, silanes, CO2, H2O, and even formaldehyde CH2O, methanol, and formic acid) are formed [2834, 38], in comparison with the heating process under nitrogen atmosphere. A liberation of these products promotes ceramization processes: the formation of the ceramics of the type SiBCO [19, 3638]—a borosilicate glass and silica. Apparently, these processes occur more intensively under air atmosphere than under nitrogen atmosphere, which leads to the distinctly higher value of the residue after thermooxidative decomposition of PMVBSs (P800), as compared with the residue after thermal decomposition (P500) (Tables 3, 4).

Table 4

Results of derivatographic analysis of PMVBSs under nitrogen atmosphere

Predicted average composition of PMVBSsSample abbrev.T5/°CT50/°CP500/%wt% of BVi groups/mol/100 g
FoundFound
B3O8T′6D76D19viM11B3T6156 304 13.50.270.240
B3O11T′9D100D25viM14B3T9195 358 16.50.260.239
B6O8T′3D76D19viM11B6T3188 385 15.00.450.211
B6O11T′6D100D25viM14B6T6241 438 25.50.560.223
B6O14T′9D124D31viM17B6T9240 427 12.50.340.221
B9O14T′6D124D31viM17B9T6263 412 12.50.520.211
B3O2D190D19viM5B3D190230 450 13.50.170.107
B6O5D180D10viM8B6D180213 381 10.00.310.063
B9O8D190D10viM11B9D190225 398 8.00.460.062

T 5 and T50 temperature of 5 and 50 % of sample mass loss

P 500 residue after heating of a sample up to 500 °C

Fig. 8
Fig. 8

TG curves of two PMVBSs (B3O2D190D19viM5 and B6O11T′6D100D25viM14) determined under nitrogen atmosphere

Citation: Journal of Thermal Analysis and Calorimetry J Therm Anal Calorim 109, 2; 10.1007/s10973-012-2446-8

A comparative analysis of the obtained results leads to a conclusion that, regardless of experimental conditions, the content of boron does not affect the systematic influence, both on the indicator T5, as well on the T50 values of the studied polymers, and on the residue after the thermooxidative destruction (P800 = 22.2–33.3 %) and the thermal destruction (P500 = 8.0–16.5 wt%, except for B6T6: P500 = 25.5 wt%, see: Tables 3, 4). Nevertheless, also under oxygen-free atmosphere, the highest values of the thermal stability and the highest values of the residue after the thermal decomposition showed the branched PMVBSs with the structure, B6O11T′6D100D25viM14, with the highest content of boron and the quite high content of vinyl groups in macromolecules of the polymer (Table 4).

A rating of thermal properties of studied PMVBSs is quite complicated because of the many differences in their chemical structures:

  1. The presence of two kinds of branching units (boron atoms and methylsiloxane units CH3SiO1.5),
  2. The different degrees of branching (3–15),
  3. The different contents of boron,
  4. The different values of MWs,
  5. The lengths of the siloxane chains between branching points (boron atoms and MeSiO1.5 units), and
  6. The different functionalities (the contents of vinylsiloxane groups).

We are aware that more detailed studies of thermal stabilities of PMVBSs need to be carried out, with the application of a much wider family of model polymers having very well “tailored” structures.

A characteristic feature of macromolecular compounds is the temperature of transition into a glass state. The temperature of this phase transition determines the thermal resistance of the polymer to an influence of low temperatures. From the analysis of DSC data of the synthesized PMVBSs, it results that their glass transition temperatures (Tg) are different (Table 5), but they are distinctly lower than those for polydimethylsiloxanes (PDMS). In the case of most PDMS (oils with linear structure and silicon rubbers), the values of Tg are usually close to −122 °C [29, 32, 39]. The lowest known value of Tg among polysiloxanes (Tg = −152 °C) was observed for crosslinked polycyclic products of the hydrolytic polycondensation of pentamethylcyclopentasiloxane (MeHSiO)5, occurring toward Karstedt catalyst [40]. The lowest value of Tg among PMVBSs (−137 °C), during cooling process, shows B3O8T′6D76D19viM11 with shorter dimethylsiloxane segments ([Me2SiO]/[MeViSiO] = 4) present between three branching points BO3/2 and six points MeSiO3/2, whereas the highest value of Tg (−122 °C) was found for PMVBSs B3O2D190D19viM5 with the longer (Me2SiO)n segments ([Me2SiO]/[MeViSiO] = 10) and the low branching degree. This polymer statistically contains only three branching units BO3/2 and six branching points MeSiO3/2 in the macromolecule (Table 5).

Table 5

Results of DSC analysis of PMVBSs under inert gas atmosphere (N2)

Tg/°CTemperature range of glass processwt% of B (found)
B3O2D190D19viM5−122−128 ÷ −1160.17
B3O11T′9D100D25viM14−124−136 ÷ −1280.26
B6O11T′6D100D25viM14−128−135 ÷ −1210.56
B6O14T′9D124D31viM17−129−132 ÷ −1250.34
B9O14T′6D124D31viM17−126−132 ÷ −1200.52
B6O5D190D10viM8−133−137 ÷ −1290.31
B9O8D190D10viM11−133−139 ÷ −1280.46
B6O8T′3D76D19viM11−134−140 ÷ −1270.45
B3O8T′6D76D19viM11−137−145 ÷ −1280.27

One may judge that distinct differences of Tg values result from the branched structures and rich structural possibilities of the analyzed PMVBSs, including their tacticity [15]. Space interactions of boron atoms with silicon atoms could also affect the Tg values of the studied PMVBSs.

Conclusions

  1. The residues after the thermooxidative decomposition of branched PMVBSs (P800) ranged from 22.2 to 33.3 %. It results from the formation of the ceramics of the type SiBCO—the borosilicate glass and silica.
  2. The glass temperatures (Tg) of the branched PMVBSs change from −122 to −137 °C, depending on their chemical structures, and especially on the lengths of dimethylsiloxane segments, on the contents of boron, and on the degrees of branching of macromolecules. The Tg values of the most PMVBSs are lower than those for PDMS (oils with linear structure and silicone rubbers).

References

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  • 12. Rybiński, P, Janowska, G, Jóźwiak, M, Pająk, A 2012 Thermal properties and flammability of nanocomposites based on diene rubbers and naturally occurring and activated halloysite nanotubes. J Therm Anal Calorim 107:12431249 .

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    • Export Citation
  • 14. Chruściel, J, Fejdyś-Kaczmarek, M, Michalska, Z 2011 New liquid, branched, hybrid poly-(methylvinylborosiloxanes) and method of their preparation. Pat PL 209514:B1.

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  • 19. Soraru, GD, Babonneau, F, Gervais, C, Dallabona, N 2000 Hybrid RSiO1.5/B2O3 gels from modified silicon alkoxides and boric acid. J Sol–Gel Sci Technol 18:1118 .

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  • 20. Schiavon, MA, Gervais, C, Babonneau, F, Soraru, GD 2004 Crystallization behavior of novel silicon boron oxycarbide glasses. J Am Ceram Soc 87:203208 .

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    • Search Google Scholar
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  • 22. Morikawa, A, Kakimoto, M, Imai, Y 1991 Synthesis and characterization of new polysiloxane starburst polymers. Macromolecules 24:34693474 .

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    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Paulasaari, JK, Weber, WP 2000 Base catalyzed proton transfer polymerization of 1-hydroxy-pentamethylcyclotrisiloxane. Comparison of hyperbranched polymer microstructure and properties to those of highly regular linear analogs. Macromol Chem Phys 201:15851592 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Jikei, M, Kakimoto, M 2001 Hyperbranched polymers: a promising new class of materials. Prog Polym Sci 26:12331285 .

  • 28. Liptay, G, Nagy, J, Borbély-Kuszman, A, Weis, JC 1987 Thermal analysis of silicone caoutchouc polymers and silicone rubbers II. J Therm Anal Calorim 32:16831691 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 29. Dobkowski, Z, Zielecka, M 2002 Thermal analysis of the polysiloxane-poly(tetrafluoroethylene) coating system. J Therm Anal Calorim 68:147158 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 30. Budrugeac, P, Racles, C, Cozan, V, Cazacu, M 2008 Thermal and thermooxidative stabilities of some poly(siloxane-azometine)s. J Therm Anal Calorim 92:263269 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 31. Zeldin, M, Quian, BR, Choi, SJ 1983 Mechanism of thermal depolymerization of trimethylsiloxy-terminated polydimethylsiloxane. J Polym Sci 21:13611369.

    • Search Google Scholar
    • Export Citation
  • 32. Dvornic PR . Chapter: high temperature stability of polysiloxanes. Gelest Catalog 4000-A: silicon compounds, silanes, and silicones; 2008. p. 441454.

    • Search Google Scholar
    • Export Citation
  • 33. Chou, C, Yang, MH 1993 Structural effects on the thermal properties of PDPS/PDMS copolymers. J Therm Anal Calorim 40:657667 .

  • 34. Ramirez, C, Abad, MJ, Barral, L, Cano, J, Diez, FJ, Lopez, J, Montez, R, Polo, J 2003 Thermal behavior of a polyhedral oligomeric silsesquioxane with epoxy resin cured by diamines. J Therm Anal Calorim 72:421429 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 35. Peňa-Alonso, R, Mariotto, G, Gervais, C, Babonneau, F, Soraru, GD 2007 Chem Mat 19:56945702 .

  • 36. Siqueira, RL, Yoshida, IVP, Pardini, LC, Schiavon, MA 2007 Poly(borosiloxanes) as precursors for carbon fiber ceramic matrix composites. Mat Res 10:147151 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 37. Schiavon, MA, Armelin, NA, Yoshida, VP 2008 Novel poly(borosiloxane) precursors to amorphous SiBCO ceramics. Mater Chem Phys 112:10471054 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 38. Chruściel, J, Janowska, G, Rybiński, P, Ślusarski, L 2006 Effect of the top layer modification of polymers on their thermostability and flammability. J Therm Anal Calorim 84:339344 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 39. Brook MA . Silicon in organic, organometallic and polymer chemistry. New York: Wiley; 2000.

  • 40. Kurian, P, Kennedy, JP, Kisliuk, A, Sokolov, A 2002 Poly(pentamethylcyclopentasiloxane). I. Synthesis and characterization. J Polym Sci Part A 40:12851292 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 1. Nalwa H , editors. In: Handbook of organic-inorganic hybrid materials and nanocomposites, Hybrid materials; nanocomposites, vol. 1; vol. 2. New York: American Science Publication; 2003.

    • Search Google Scholar
    • Export Citation
  • 2. Salamone JC , editor. In: Abe Y, Gunji T, editors. Polymeric materials encyclopedia: polyborosiloxanes, vol. 7. New York: CRC Press; 1996.

    • Search Google Scholar
    • Export Citation
  • 3. Wang, Q, Fu, L, Hu, X, Zhang, Z, Xie, Z 2006 Preparation and properties of borosiloxane gels. J Appl Polym Sci 99:719724 .

  • 4. Huo, Y, Fan, Q, Dembsey, N, Patra, PK 2007 Influence of polyborosiloxane on the flame retardancy of polyethylene terephthalate-clay nanocomposite. Polym Mat 96:528530.

    • Search Google Scholar
    • Export Citation
  • 5. Anna, P, Marosi, G, Bourbigot, S M Le Bras Delobel, R 2002 Intumescent flame retardant systems of modified rheology. Polym Degrad Stab 77:243247 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Lu, SY, Hamerton, I 2002 Recent developments in the chemistry of halogen-free flame retardant polymers. Prog Polym Sci 27:16611712 .

  • 7. Rybiński, P, Janowska, G, Kucharska-Jastrząbek, A 2010 Influence of surface modification on thermal stability and flammability of cross-linked rubbers. J Therm Anal Calorim 100:10371044 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Achilias, DS, Nikolaidis, AK, Karayannidis, GP 2010 PMMA/organomodified montmorillonite nanocomposites prepared by in situ bulk polymerization. J Therm Anal Calorim 102:451460 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Lalikova, S, Pajtasova, M, Ondrusova, D, Bazylakova, T, Olsovsky, M, Jona, E, Mojumdar, SC 2010 J Therm Anal Calorim 100:745749 .

  • 10. Janowska, G, Kucharska-Jastrząbek, A, Rybiński, P 2011 Thermal stability, flammability and fire hazard of butadiene-acrylonitrile rubber nanocomposites. J Therm Anal Calorim 103:10391046 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 11. Zhao, M, Liu, P 2008 Halloysite nanotubes/polystyrene (HNTs/PS) nanocomposites via in situ bulk polymerization. J Therm Anal Calorim 94:103107 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. Rybiński, P, Janowska, G, Jóźwiak, M, Pająk, A 2012 Thermal properties and flammability of nanocomposites based on diene rubbers and naturally occurring and activated halloysite nanotubes. J Therm Anal Calorim 107:12431249 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. Chen, X, Jiao, C, Zhang, J 2011 Microencapsulation of ammonium polyphosphate with hydroxyl silicone oil and its flame retardance in thermoplastic polyurethane. J Therm Anal Calorim 104:10371043 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14. Chruściel, J, Fejdyś-Kaczmarek, M, Michalska, Z 2011 New liquid, branched, hybrid poly-(methylvinylborosiloxanes) and method of their preparation. Pat PL 209514:B1.

    • Search Google Scholar
    • Export Citation
  • 15. Chruściel J , Fejdyś M, Fortuniak W. Synthesis and characterization of new, liquid, branched poly(methylvinylborosiloxanes). e-Polymers. 2011 (submitted for publication).

    • Search Google Scholar
    • Export Citation
  • 16. Smith AL . Analysis of silicones. Wiley, New York. 1974.

  • 17. Zha, C, Atkins, GR, Masters, AF 1998 A spectroscopic study of an anhydrous tetraethyl orthosilicate-boric acid-ethanol system. J Sol–Gel Sci Technol 13:103107 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Kaşgöz, A, Misono, T, Abe, Y 1999 Sol-gel preparation of borosilicates. J Non-Cryst Solids 243:168174 .

  • 19. Soraru, GD, Babonneau, F, Gervais, C, Dallabona, N 2000 Hybrid RSiO1.5/B2O3 gels from modified silicon alkoxides and boric acid. J Sol–Gel Sci Technol 18:1118 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Schiavon, MA, Gervais, C, Babonneau, F, Soraru, GD 2004 Crystallization behavior of novel silicon boron oxycarbide glasses. J Am Ceram Soc 87:203208 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21. Peňa-Alonso, R, Rubio, J, Rubio, F, Oteo, JL 2004 Characterisation of the pyrolysis process of boron-containing ormosils by FT-IR analysis. J Anal Appl Pyrolysis 71:827845 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22. Morikawa, A, Kakimoto, M, Imai, Y 1991 Synthesis and characterization of new polysiloxane starburst polymers. Macromolecules 24:34693474 .

  • 23. Chang, H-T, Frechet, JMJ 1999 Proton-transfer polymerization: a new approach to hyper-branched polymers. J Am Chem Soc 121:23132314 .

  • 24. Innoue, K 2000 Functional dendrimers, hyperbranched and star polymers. Prog Polym Sci 25:453571 .

  • 25. Paulasaari, JK, Weber, WP 2000 Synthesis of hyperbranched polysiloxanes by base-catalyzed proton-transfer polymerization. Comparison of hyperbranched polymer microstructure and properties to those of linear analogues prepared by cationic or anionic ring-opening polymerization. Macromolecules 33:20052010 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Paulasaari, JK, Weber, WP 2000 Base catalyzed proton transfer polymerization of 1-hydroxy-pentamethylcyclotrisiloxane. Comparison of hyperbranched polymer microstructure and properties to those of highly regular linear analogs. Macromol Chem Phys 201:15851592 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Jikei, M, Kakimoto, M 2001 Hyperbranched polymers: a promising new class of materials. Prog Polym Sci 26:12331285 .

  • 28. Liptay, G, Nagy, J, Borbély-Kuszman, A, Weis, JC 1987 Thermal analysis of silicone caoutchouc polymers and silicone rubbers II. J Therm Anal Calorim 32:16831691 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 29. Dobkowski, Z, Zielecka, M 2002 Thermal analysis of the polysiloxane-poly(tetrafluoroethylene) coating system. J Therm Anal Calorim 68:147158 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 30. Budrugeac, P, Racles, C, Cozan, V, Cazacu, M 2008 Thermal and thermooxidative stabilities of some poly(siloxane-azometine)s. J Therm Anal Calorim 92:263269 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 31. Zeldin, M, Quian, BR, Choi, SJ 1983 Mechanism of thermal depolymerization of trimethylsiloxy-terminated polydimethylsiloxane. J Polym Sci 21:13611369.

    • Search Google Scholar
    • Export Citation
  • 32. Dvornic PR . Chapter: high temperature stability of polysiloxanes. Gelest Catalog 4000-A: silicon compounds, silanes, and silicones; 2008. p. 441454.

    • Search Google Scholar
    • Export Citation
  • 33. Chou, C, Yang, MH 1993 Structural effects on the thermal properties of PDPS/PDMS copolymers. J Therm Anal Calorim 40:657667 .

  • 34. Ramirez, C, Abad, MJ, Barral, L, Cano, J, Diez, FJ, Lopez, J, Montez, R, Polo, J 2003 Thermal behavior of a polyhedral oligomeric silsesquioxane with epoxy resin cured by diamines. J Therm Anal Calorim 72:421429 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 35. Peňa-Alonso, R, Mariotto, G, Gervais, C, Babonneau, F, Soraru, GD 2007 Chem Mat 19:56945702 .

  • 36. Siqueira, RL, Yoshida, IVP, Pardini, LC, Schiavon, MA 2007 Poly(borosiloxanes) as precursors for carbon fiber ceramic matrix composites. Mat Res 10:147151 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 37. Schiavon, MA, Armelin, NA, Yoshida, VP 2008 Novel poly(borosiloxane) precursors to amorphous SiBCO ceramics. Mater Chem Phys 112:10471054 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 38. Chruściel, J, Janowska, G, Rybiński, P, Ślusarski, L 2006 Effect of the top layer modification of polymers on their thermostability and flammability. J Therm Anal Calorim 84:339344 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 39. Brook MA . Silicon in organic, organometallic and polymer chemistry. New York: Wiley; 2000.

  • 40. Kurian, P, Kennedy, JP, Kisliuk, A, Sokolov, A 2002 Poly(pentamethylcyclopentasiloxane). I. Synthesis and characterization. J Polym Sci Part A 40:12851292 .

    • Crossref
    • Search Google Scholar
    • Export Citation

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Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
Foundation
1969
Volumes
per Year
4
Issues
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24
Founder Akadémiai Kiadó
Founder's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
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ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)